CN114229896B - 一种三维结构的MoS2/Carbon/FeOx复合材料及其制备方法 - Google Patents
一种三维结构的MoS2/Carbon/FeOx复合材料及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 39
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000000463 material Substances 0.000 claims abstract description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 14
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
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- -1 transition metal sulfide Chemical class 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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- 125000006850 spacer group Chemical group 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明提供一种三维结构的MoS2/Carbon/FeOx复合材料及其制备方法,通过将氧化石墨烯粉末超声分散于水中,加入钼酸钠以及硫脲,然后进行水热反应,得到MoS2/graphene复合粉末。将二茂铁溶解于乙腈中,然后加入上MoS2/graphene粉末,超声分散均匀,然后微波反应。最后将收集到的粉末在氩气保护下高温煅烧后得到了由零维FeOx纳米颗粒、一维CNTs、二维graphene纳米片以及二维MoS2纳米片所构成的具有分级结构的三维复合纳米材料MoS2/Carbon/FeOx。
Description
技术领域
本发明涉及电化学材料技术领域,具体涉及一种三维结构的MoS2/Carbon/FeOx复合材料及其制备方法。
背景技术
锂离子电池(LIBs)由于其高能量密度、高功率密度、长循环寿命和低电池记忆效应,是最有前途的储能系统之一。负极材料作为锂离子电池的重要组成部分,对锂离子电池的电化学性能有重要影响。可逆容量大、循环寿命长、倍率性能好、安全性高的新型电极材料是未来高性能锂离子电池的要求(ACS Nano 2015,9,3369)。
二硫化钼(MoS2)作为一种典型的过渡金属硫化物,具有层状结构,在光催化、电子器件、电催化、储能等领域显示出显著的优势(Chemical Society Reviews 2015,44,2713)。MoS2通常被认为是由范德华力堆积在一起的少量S-Mo-S分子层。这种层状结构使得在MoS2中插入锂离子具有较低的体积膨胀率。最近的研究结果表明,MoS2基负极材料能够提供900~1300mAh·g-1的可逆容量,远远高于传统商业石墨负极。(ChemicalCommunications 2011,47,4252)。
然而,MoS2导电性差,不利于锂离子电池的应用。因此,为了解决这一问题,将MoS2与碳材料(包括石墨烯、碳纳米管等)进行复合。同时,将MoS2与具有储锂性能的纳米颗粒复合,以提高MoS2的锂存储性能。这些纳米颗粒不仅作为锂存储容器,而且作为间隔层,避免了MoS2纳米片在充放电过程中重新堆积。MoS2纳米片可以同时有效地缓解MoS2的体积变化。此外,由于特殊的分子机制将电磁能转化为热能,微波加热可以在快速的时间急剧升温到1000℃,因此被广泛应用于碳材料的合成。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种三维结构的MoS2/Carbon/FeOx复合材料及其制备方法
为实现上述目的,本发明采取的技术方案为:
一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法,包括以下步骤:
(1)将氧化石墨烯分散于去离子水中,然后加入钼酸钠和硫脲,搅拌;
(2)将步骤(1)所得混合溶液进行水热反应,反应结束后经过冷却、抽滤、洗涤、干燥和研磨后得到MoS2/graphene复合粉末;
(3)将二茂铁超声溶解于乙腈中,然后再加入MoS2/graphene复合粉末,超声分散均匀;在本发明制备方法中,乙腈首先作为溶剂溶解二茂铁,因此二茂铁可以在反应体系中均匀分布;其次,乙腈也可以作为碳源在高温下裂解形成碳。
(4)然后将步骤(3)所得混合溶液转移至微波下反应;
(5)微波结束后,将得到的材料在惰性气体或氮气保护下高温煅烧,即得所述三维结构的MoS2/Carbon/FeOx复合材料。
本发明制备方法将氧化石墨烯粉末超声分散于去离子水中,然后加入钼酸钠以及硫脲,搅拌均匀,氧化石墨烯含有大量羧基、羟基等含氧基団,通过配位作用吸附水中MoO4 2-离子,水热过程中,硫脲分解产生具有还原性的H2S,并进一步将MoO4 2-还原成MoS2。因此MoS2纳米片就生长在氧化石墨烯表面,命名为MoS2/graphene复合粉末。将二茂铁超声溶解于装有乙腈的坩埚中,然后加入上述得到的MoS2/graphene粉末,超声分散均匀,然后快速将坩埚转移至微波炉中,在微波反应过程中,由于温度急剧上升,吸附在MoS2/graphene表面的二茂铁分子分解,其中铁元素逐渐被氧化成FeOx纳米颗粒,而余下的茂基作为碳源,在高温环境中由铁催化反应快速生长成CNTs。最后将收集到的粉末在氩气保护下高温煅烧后得到了由零维FeOx纳米颗粒、一维CNTs、二维graphene纳米片以及二维MoS2纳米片所构成的具有分级结构的三维复合纳米材料MoS2/Carbon/FeOx。
进一步地,所述氧化石墨烯采用hummer法制备制得。发明人通过研究发现,hummer法制备氧化石墨烯是单层的或者是少层的,而市售的氧化石墨烯品质差,是许多层的。因此,如果用市售的氧化石墨烯作为原料,那么合成的复合材料性能较差。
进一步地,步骤(1)中的氧化石墨烯是通过超声分散于去离子水中。发明人通过研究发现,超声振动传递到液体中,从而在液体中产生大量的空化气泡,随着这些空化气泡产生和爆破,产生出微射流可以将氧化石墨烯的固体颗粒击碎,由于超声波的振动和分散作用,可以使氧化石墨烯和水更加充分的混合,利于后续反应的均匀性和充分性。
进一步地,步骤(1)中,氧化石墨烯的质量浓度为0.1~0.3mg/mL、钼酸钠的质量浓度为8~12mg/mL,硫脲的质量浓度为20~30mg/mL。
进一步地,步骤(2)中,水热反应温度为180~210℃,反应时间为12~36h。
硫脲在水中长时间受热分解产生具有还原性的H2S,并进一步将MoO4 2-还原成MoS2。发明人通过研究发现,上述反应温度和反应时间可以保证硫脲的充分分解及H2S对MoO4 2-的还原反应。
进一步地,步骤(3)中,每2~8mL乙腈中加入二茂铁100~200mg,每2~8mL乙腈中加入MoS2/graphene复合粉末200~400mg。发明人通过研究发现,如果加入的二茂铁过多,那么复合材料中形成的FeOx纳米颗粒以及碳纳米管过多,复合材料的比容量会降低;如果加入的二茂铁过少,那么复合材料中形成的FeOx纳米颗粒以及碳纳米管过少,复合材料的循环稳定性变差。
进一步地,步骤(4)中,微波功率为600~1000W,反应时间为30~60s。发明人通过研究发现,在微波反应过程中,由于温度急剧上升,吸附在MoS2/graphene表面的二茂铁分子分解,其中铁元素逐渐被氧化成FeOx纳米颗粒,而余下的茂基作为碳源,在高温环境中由铁催化反应快速生长成CNTs。更进一步优选的,微波功率选用800W,反应既温和又彻底。
进一步地,步骤(5)中,高温煅烧温度为400~500℃,煅烧时间为2~4h。
第二方面,本发明还提供一种上述的制备方法制得的三维结构的MoS2/Carbon/FeOx复合材料。本发明所述复合材料既包括零维FeOx纳米颗粒、一维CNTs,又包括二维graphene纳米片以及二维MoS2,是一种具有分级结构的三维复合纳米材料。
第三方面,本发明还提供上述的三维结构的MoS2/Carbon/FeOx复合材料在锂离子电池中的应用。
与现有技术相比,本发明具有以下有益效果:
(1)本发明制备的比容量高、倍率好、循环稳定性好的三维分级纳米结构的MoS2/Carbon/FeOx复合材料应用于锂离子电池负极材料未见文献报道,具有很好的应用发展前景。
(2)本发明微波法制备了三维分级纳米结构的MoS2/Carbon/FeOx复合材料。此种三维分级杂化结构材料可以提高MoS2/Carbon/FeOx材料的比表面积、力学稳定性和导电性,有利于提高MoS2/Carbon/FeOx材料的储锂比容量,有助于电解液的渗透,防止了MoS2纳米片以及FeOx纳米颗粒在充放电过程中的团聚,重叠,从而提高MoS2/Carbon/FeOx的循环稳定性,为寻求新型锂离子电池负极材料提供研究思路。
附图说明
图1为本发明对比例1所制得的复合材料的扫描电镜图(SEM);
图2为本发明实施例1所制得MoS2/Carbon/FeOx复合材料的扫描电镜图(SEM);
图3为本发明实施例1所制得MoS2/Carbon/FeOx复合材料的透射电镜图(TEM);
图4为本发明实施例3所制得MoS2/Carbon/FeOx复合材料的XRD图谱;
图5为本发明实施例1制备的MoS2/Carbon/FeOx复合材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试曲线;
图6为MoS2/graphene复合粉末在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试曲线;
图7为本发明对比例1所制备的复合材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试曲线;
图8为本发明实施例2所制得的复合材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试曲线;
图9为本发明实施例1和对比例1所制得的复合材料在0.01~3.0V电压下的倍率放电循环曲线。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
实施例1
本发明所述一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法,包括以下步骤:
将5.0mg氧化石墨烯粉末超声分散于30mL去离子水中,然后加入300mg钼酸钠以及600mg硫脲,搅拌30min,然后将混合溶液转移至50mL水热釜中,密封后在210℃下反应24h,反应结束后经过冷却、抽滤、洗涤、干燥、研磨后得到MoS2/graphene复合材料。氧化石墨烯粉末可选用市售产品也采用hummer法制备氧化石墨烯粉末,优选采用hummer法制备的氧化石墨烯粉末。
将150mg二茂铁超声溶解于装有5ml乙腈的坩埚中,然后加入上述得到的MoS2/graphene复合材料300mg,超声分散均匀,然后快速将坩埚转移至微波炉中,在微波功率为800W条件下反应40s,最后将收集到的粉末在氩气保护下450℃煅烧2h后得到三维分级纳米结构的MoS2/Carbon/FeOx复合材料。
实施例2
本发明所述一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法,包括以下步骤:
将6.0mg氧化石墨烯粉末超声分散于30mL去离子水中,然后加入250mg钼酸钠以及500mg硫脲,搅拌30min,然后将混合溶液转移至50mL水热釜中,密封后在210℃下反应18h,反应结束后经过冷却、抽滤、洗涤、干燥、研磨后得到MoS2/graphene复合材料。氧化石墨烯粉末可选用市售产品也采用hummer法制备氧化石墨烯粉末,优选采用hummer法制备的氧化石墨烯粉末。
将180mg二茂铁超声溶解于装有5.5mL乙腈的坩埚中,然后加入上述得到的MoS2/graphene复合材料350mg,超声分散均匀,然后快速将坩埚转移至微波炉中,在微波功率为800W条件下反应60s,最后将收集到的粉末在氩气保护下450℃煅烧2h后得到三维分级纳米结构的MoS2/Carbon/FeOx复合材料。
实施例3
本发明所述一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法,包括以下步骤:
将8.0mg氧化石墨烯粉末超声分散于30mL去离子水中,然后加入350mg钼酸钠以及700mg硫脲,搅拌30min,然后将混合溶液转移至50mL水热釜中,密封后在200℃下反应30h,反应结束后经过冷却、抽滤、洗涤、干燥、研磨后得到MoS2/graphene复合材料。氧化石墨烯粉末可选用市售产品也采用hummer法制备氧化石墨烯粉末,优选采用hummer法制备的氧化石墨烯粉末。
将200mg二茂铁超声溶解于装有6mL乙腈的坩埚中,然后加入上述得到的MoS2/graphene复合材料400mg,超声分散均匀,然后快速将坩埚转移至微波炉中,在微波功率为800W条件下反应50s,最后将收集到的粉末在氩气保护下480℃煅烧2h后得到三维分级纳米结构的MoS2/Carbon/FeOx复合材料。
对比例1
本发明所述一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法的一种对比例,包括以下步骤:
将5.0mg氧化石墨烯粉末超声分散于30mL去离子水中,然后加入300mg钼酸钠以及600mg硫脲,搅拌30min,然后将混合溶液转移至50mL水热釜中,密封后在210℃下反应24h,反应结束后经过冷却、抽滤、洗涤、干燥、研磨后得到MoS2/graphene复合材料。
称取90mg上述得到的MoS2/graphene材料超声分散于15mL乙醇及15mL乙二醇的混合溶剂中,然后再加入45mg二茂铁及1mL含量为30wt%的过氧化氢溶液,搅拌均匀后将混合溶液转移至50mL水热釜中,密封后在210℃下反应24h,最后经冷却、抽滤、干燥,并在氩气保护下经450℃煅烧2h后得到MoS2/graphene/FeOx负极材料。
效果例
SEM分析所用的仪器为德国蔡司Sigma型扫描电子显微镜,加速电压为10KV。TEM分析所用的仪器为日本电子公司的JSM-2010型投射电子显微镜(TEM)观察试样表面的微观形貌,加速电压为200KV,制样采用无水乙醇分散后滴加铜网上,空气中干燥。使用日本电子公司JSM-6380F型扫描电子显微镜(SEM)对材料进行形貌观察。
XRD分析所用的仪器为北京普析通用仪器有限公司XD-2型X射线衍射仪(XRD)表征所制备最终产物的晶相结构材料。测试条件为Cu靶,Kα辐射,36kV,30mA,步宽0.02°,扫描范围10~80°。样品为粉末置于样品台凹槽压平,直接检测。
充放电测试所用的仪器为深圳市新威尔电子有限公司的BTS51800电池测试系统,型号为CT-3008W,在0.01~3.0V电压范围内进行电化学测试。
利用实施例1~3及对比例1制备的复合材料分别制作扣式电池,测试充放电性能。包括以下步骤:
将MoS2/Carbon/FeOx复合材料与导电碳黑、粘结剂聚偏氯乙烯(PVDF)按质量比8∶1∶1混合,再加入适量N-甲基吡咯烷酮(NMP)搅拌均匀,涂布到铜箔上,在真空烘箱中于90℃下烘干,在冲片机上剪片得纳米二氧化钛/石墨烯材料电极片。将所得电极做正极,金属锂片为负极(在这个纽扣电池里面,因为金属锂的电势比MoS2/Carbon/FeOx低,所以在这个纽扣电池里面负极是金属锂,这个纽扣电池仅仅是用来测试我们制备的MoS2/Carbon/FeOx复合材料的各种性能的。在实际应用中MoS2/Carbon/FeOx复合材料作为负极,对应的正极材料一般是钴酸锂,磷酸铁锂等),电解液为含有1M LiPF6/(EC+DMC)(体积比为1∶1)混合体系,隔膜为微孔聚丙烯膜(Celgard 2400),在充满氩气(Ar)的手套箱内组装成2025型扣式电池。用深圳市新威尔电子有限公司BTS51800电池测试系统进行充放电性能测试。
图1表明对比例制备的MoS2/graphene/FeOx呈三维的纳米花瓣状,没有CNTs生成。
图2表明实施例1制备的MoS2/Carbon/FeOx复合材料具有是三维的片层结构,并且可以观察到一维的CNTs存在。
图3进一步表明实施例1制备的MoS2/Carbon/FeOx复合材料是由零维FeOx纳米颗粒、一维CNTs、二维graphene纳米片以及二维MoS2纳米片所构成的具有分级级结构的三维复合纳米材料。
图4中是实施例3制备的MoS2/Carbon/FeOx复合材料的XRD图谱。其中,2θ角在14.0°、33.2°、58.8°的衍射峰依次对应于MoS2(JCPDS 37-1492)的(002)、(101)、(110)晶面。2θ角在34.4°出现明显尖峰,这说明了Fe3O4(JCPDS 28-0491)的存在。同时在32.8°及60.5°都有微弱的峰出现,这两个峰分别对应于Fe2O3(JCPDS 16-0653)和FeO(JCPDS 06-0711),这说明了MoS2/graphene/FeOx/CNTs复合材料中的铁氧化合物是以混晶存在,铁元素存在多种价态。
从图5中可以看出,实施例1制备的MoS2/Carbon/FeOx复合材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试100次之后比容量1012mAh g-1,是初始容量的90.3%。
从图6中可以看出,MoS2/graphene负极材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试100次之后比容量542mAh g-1,是初始容量的54.8%。
从图7中可以看出,对比例制备的MoS2/graphene/FeOx负极材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试100次之后比容量745mAh g-1,是初始容量的75.1%。
从图8中可以看出,实施例2制备的MoS2/Carbon/FeOx复合材料在0.01~3.0V、0.2A·g-1电流密度下的循环充放电测试100次之后比容量805mAh g-1,是初始容量的81.5%。
从图9中可以看出,实施例1制备的MoS2/Carbon/FeOx复合在0.01~3.0V、不同电流密度下的倍率放电性能比对比例MoS2/graphene/FeOx复合材料的好。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (9)
1.一种三维结构的MoS2/Carbon/FeOx复合材料的制备方法,其特征在于,包括以下步骤:
(1)将氧化石墨烯分散于去离子水中,然后加入钼酸钠和硫脲,搅拌;
(2)将步骤(1)所得混合溶液进行水热反应,反应结束后经过冷却、抽滤、洗涤、干燥和研磨后得到MoS2/graphene复合粉末;
(3)将二茂铁超声溶解于乙腈中,然后再加入MoS2/graphene复合粉末,超声分散均匀;
(4)然后将步骤(3)所得混合溶液转移至微波下反应;微波功率为600~1000W,反应时间为30~60s;
(5)微波结束后,将得到的材料在惰性气体或氮气保护下煅烧,即得所述三维结构的MoS2/Carbon/FeOx复合材料。
2.根据权利要求1所述的制备方法,其特征在于,所述氧化石墨烯采用hummer法制备制得。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中的氧化石墨烯是通过超声分散于去离子水中。
4.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,氧化石墨烯的质量浓度为0.1~0.3mg/mL、钼酸钠的质量浓度为8~12mg/mL,硫脲的质量浓度为20~30mg/mL。
5.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,水热反应温度为180~210℃,反应时间为12~36h。
6.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,每2~8mL乙腈中加入二茂铁100~200mg,每2~8mL乙腈中加入MoS2/graphene复合粉末200~400mg。
7.根据权利要求1所述的制备方法,其特征在于,步骤(5)中,煅烧温度为400~500℃,煅烧时间为2~4h。
8.一种如权利要求1~7任一项所述的制备方法制得的三维结构的MoS2/Carbon/FeOx复合材料。
9.一种如权利要求8所述的三维结构的MoS2/Carbon/FeOx复合材料在锂离子电池中的应用。
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CN105140475A (zh) * | 2015-07-28 | 2015-12-09 | 哈尔滨工程大学 | 一种Fe3O4/MoS2锂离子电池负极材料的制备方法 |
CN105576212A (zh) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | 一种锂离子电池二氧化钛纳米片包覆石墨烯负极材料的制备方法 |
CN106410132A (zh) * | 2016-11-09 | 2017-02-15 | 上海大学 | 二维片状MoS2@石墨烯复合纳米材料及其制备方法 |
CN106783201A (zh) * | 2016-12-02 | 2017-05-31 | 东华大学 | 一种硫化钼/三氧化二铁复合材料及其制备方法和应用 |
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CN105140475A (zh) * | 2015-07-28 | 2015-12-09 | 哈尔滨工程大学 | 一种Fe3O4/MoS2锂离子电池负极材料的制备方法 |
CN105576212A (zh) * | 2016-02-19 | 2016-05-11 | 东莞市迈科科技有限公司 | 一种锂离子电池二氧化钛纳米片包覆石墨烯负极材料的制备方法 |
CN106410132A (zh) * | 2016-11-09 | 2017-02-15 | 上海大学 | 二维片状MoS2@石墨烯复合纳米材料及其制备方法 |
CN106783201A (zh) * | 2016-12-02 | 2017-05-31 | 东华大学 | 一种硫化钼/三氧化二铁复合材料及其制备方法和应用 |
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