WO2017004892A1 - 石墨烯/多孔氧化铁纳米棒复合物及其制备方法 - Google Patents

石墨烯/多孔氧化铁纳米棒复合物及其制备方法 Download PDF

Info

Publication number
WO2017004892A1
WO2017004892A1 PCT/CN2015/089491 CN2015089491W WO2017004892A1 WO 2017004892 A1 WO2017004892 A1 WO 2017004892A1 CN 2015089491 W CN2015089491 W CN 2015089491W WO 2017004892 A1 WO2017004892 A1 WO 2017004892A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
iron oxide
porous iron
oxide nanorod
nanorod composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2015/089491
Other languages
English (en)
French (fr)
Inventor
盛卫琴
吕强
朱鹤孙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to US15/536,204 priority Critical patent/US10131544B2/en
Publication of WO2017004892A1 publication Critical patent/WO2017004892A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Definitions

  • the invention belongs to the technical field of material chemistry, and in particular relates to a graphene/porous iron oxide nanorod composite and a preparation method thereof.
  • Lithium batteries are the main energy source for portable devices, and their applications are growing, including electronic engines and green energy. Although lithium batteries have made some progress in the business, their low energy storage and weak cycle stability limit their application to a wider range. Therefore, many studies are currently trying to find a highly efficient lithium battery electrode material, such as low-dimensional metal oxide materials.
  • a highly efficient lithium battery electrode material such as low-dimensional metal oxide materials.
  • Fe 2 O 3 one of the transition metal oxides, is receiving more and more attention because its theoretical capacity (1007 mAh g -1 ) is much higher than that of graphite and other transition metal oxides (SnO 2 , etc.) ), and its low price, abundant reserves and environmental friendliness.
  • the Fe 2 O 3 material has poor conductivity and large volume expansion during charge and discharge, which hinders its practical application in lithium batteries.
  • the way to overcome this problem is to find an active material with a high specific surface area and a short diffusion path combined with it.
  • the large specific surface area allows the metal oxide to have more lithium storage sites and a larger electrode-electrolyte contact area that facilitates lithium ion diffusion. Therefore, considering its large specific surface area and good electrical conductivity, graphene is an ideal candidate material.
  • silk proteins can regulate their nanostructures and affinity and hydrophobicity by controlling the self-assembly process of nanomaterials, thus providing a controllable template for the synthesis of copper oxide, silver, and other inorganic nanoparticles.
  • Materials such as ⁇ -Fe 2 O 3 /graphene, ⁇ -Fe 2 O 3 /CNTs, ⁇ -Fe 2 O 3 /carbon have been reported to be synthesized, but silk proteins regulate porous Fe 2 O 3 nanorod/graphene composites. Synthesis has not been reported.
  • an object of the present invention is to provide a graphene/porous iron oxide nanorod composite and a preparation method thereof, which are low in cost, easy to obtain, and simple in synthesis method.
  • the present invention provides a graphene/porous iron oxide nanorod composite comprising graphene and Fe 2 O 3 nanoparticles supported on the graphene, the Fe 2 O 3 nanoparticles having a honeycomb porous structure .
  • the morphology of the Fe 2 O 3 nanoparticles is rod-shaped.
  • the invention also proposes a preparation method of graphene/porous iron oxide nanorod composite, comprising the following steps:
  • the mass ratio of the graphene oxide to the silk protein is not more than 1:4.
  • the mass ratio of the graphene oxide to hydrazine hydrate is 1: (0.0004-20).
  • the iron source is FeCl 3 ⁇ 6H 2 O
  • the mass ratio of the graphene oxide to FeCl 3 ⁇ 6H 2 O is 1: (20-60).
  • the pH in the step (1) is 8-11.
  • the present invention has at least the following advantages: the present invention combines iron oxide nanoparticles with graphene, graphene has a large specific surface area and good electrical conductivity, and enhances the discharge capacity of the iron oxide material;
  • the pore structure increases the specific surface area of the iron oxide nanoparticles, so that it has more lithium storage sites and a larger contact area;
  • the silk protein induces the iron oxide nanoparticles to form a rod-like structure and a honeycomb-shaped pore, which is low in cost. It is easy to obtain, has good biocompatibility, no pollution to the environment, and the method of removal is simple.
  • Figure 2 is a transmission electron micrograph of a sample in the first embodiment of the present invention.
  • Figure 3 is an XRD chart of the sample in the first embodiment of the present invention.
  • Figure 4 is a Raman spectrum diagram of a sample in Example 1 of the present invention.
  • Figure 5 is a scanning electron micrograph of a sample in the second embodiment of the present invention.
  • Figure 6 is a scanning electron micrograph of a sample in the third embodiment of the present invention.
  • Figure 7 is a scanning electron micrograph of a sample in the fourth embodiment of the present invention.
  • Figure 8 is an XRD chart of a sample in Example 4 of the present invention.
  • FIG. 1 to 4 are respectively a scanning electron microscope image, a transmission electron microscope image, an XRD pattern and a Raman spectrum of the sample in the first embodiment of the present invention. It can be seen from FIG. 1 and FIG. 2 that the sample prepared by the method is one-dimensional. Rod-like structure, as can be seen from Fig. 2, the rod-shaped iron oxide nanoparticles have honeycomb-like pores. Figure 3 shows that the sample is iron oxide, and Figure 4 further shows that the product is a composite of iron oxide and graphene.
  • Fig. 5 is a scanning electron micrograph of the sample, and it can be seen from the figure that the composite portion is rod-shaped and partially irregular.
  • Figure 6 is a scanning electron micrograph of the sample, and it can be seen from the figure that the composite is rod-shaped.
  • Step (5) is omitted in the first embodiment, that is, the synthesis method of the present embodiment.
  • Figure 7 is a scanning electron micrograph of the sample. It can be seen from the figure that the composite is also a rod-like structure before calcination, and Figure 8 is an XRD pattern of the sample.
  • the product before calcination of the surface composite is FeOOH.
  • the present invention provides a method for preparing a graphene/porous iron oxide nanorod composite, which has wide sources of raw materials, low cost, and simple synthesis process; the present invention combines iron oxide nanoparticles with graphene.
  • Graphene has a large specific surface area and good electrical conductivity, which enhances the discharge capacity of the iron oxide material; and the pore structure of the iron oxide increases the specific surface area of the iron oxide nanoparticles, so that it has more lithium storage sites.
  • the point and the larger contact area; the silk protein-induced iron oxide nanoparticles form a rod-like structure and a porous structure, and the method is low in cost, easy to obtain, good in biocompatibility, no pollution to the environment, and the removal method is simple.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种石墨烯/多孔氧化铁纳米棒复合物及其制备方法，该复合物包括石墨烯及负载在所述石墨烯上的Fe 2O 3纳米粒子，所述Fe 2O 3纳米粒子具有蜂窝状的多孔结构；该复合物的合成方法简单，原料的成本低廉。

Description

石墨烯/多孔氧化铁纳米棒复合物及其制备方法
本申请要求了申请日为2015年07月03日，申请号为201510382555.1，发明名称为“石墨烯/多孔氧化铁纳米棒复合物及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于材料化学技术领域，尤其涉及一种石墨烯/多孔氧化铁纳米棒复合物及其制备方法。
背景技术
锂电池作为可携带设备的主要能源，其应用领域正在不断壮大，包括电子引擎、绿色能源等。尽管锂电池在商业上已经取得了一些进展，但是它们储能低，循环稳定性弱等缺点限制了其在更大范围上的应用。因此，目前很多研究都在努力寻找一种高效的锂电池电极材料，例如低维的金属氧化物材料。在可替代负极材料中，过渡金属氧化物之一的Fe2O3受到越来越多的关注，因为它理论容量(1007mAh g-1)远高于石墨及其他过渡金属氧化物(SnO2等)，且其价格低廉、储量丰富、环境友好。
然而Fe2O3材料电导率差且充放电过程中体积扩张大，阻碍了其在锂电池中的实际应用。克服此问题的方法是寻找一种具有高比表面积、短扩散路径的活性材料与之复合。比表面积大可使金属氧化物具有更多的锂存储位点和更大的便于锂离子扩散的电极-电解质接触面积。因此，考虑到其具有巨大的比表面积和良好的电导率，石墨烯是一种理想的备选材料。
此外，大量研究表明，丝蛋白可通过控制纳米材料自组装过程来调控其纳米结构及亲、疏水性，从而提供可控模板来合成氧化铜、银、 及其他无机纳米颗粒。α-Fe2O3/graphene、α-Fe2O3/CNTs、α-Fe2O3/carbon等材料已被报道合成，但丝蛋白调控多孔Fe2O3纳米棒/石墨烯复合材料的合成尚未有报道。
有鉴于上述的缺陷，本设计人，积极加以研究创新，以期创设一种石墨烯/多孔氧化铁纳米棒复合物及其制备方法，使其更具有产业上的利用价值。
发明内容
为解决上述技术问题，本发明的目的是提供一种石墨烯/多孔氧化铁纳米棒复合物及其制备方法，合成原料的成本低廉，容易获得，合成方法简单。
本发明提出了一种石墨烯/多孔氧化铁纳米棒复合物，包括石墨烯及负载在所述石墨烯上的Fe2O3纳米粒子，所述Fe2O3纳米粒子具有蜂窝状的多孔结构。
进一步的，所述Fe2O3纳米粒子的形貌为棒状。
本发明还提出了石墨烯/多孔氧化铁纳米棒复合物的制备方法，包括以下步骤：
(1)将氧化石墨烯与丝蛋白溶液混合，调pH为碱性，加入水合肼进行还原，从而获得石墨烯/丝蛋白复合物；
(2)向上述复合物中加入铁源，继续搅拌至完全溶解；
(3)将上述混合物倒入反应釜中，于120～200℃反应8～36h；
(4)反应结束后自然冷却到室温，离心，将产物干燥，得到固体粉末；
(5)将上述固体粉末于320～450℃下的惰性气氛中煅烧3～8h，然后自然冷却至室温。
进一步的，所述氧化石墨烯与丝蛋白的质量比不大于1∶4。
进一步的，所述氧化石墨烯与水合肼的质量比为1∶(0.0004-20)。
进一步的，所述铁源为FeCl3·6H2O，所述氧化石墨烯与FeCl3·6H2O的质量比为1∶(20-60)。
进一步的，所述步骤(1)中的pH为8～11。
借由上述方案，本发明至少具有以下优点：本发明将氧化铁纳米粒子与石墨烯复合，石墨烯具有较大的比表面积和良好的电导率，增强了氧化铁材料的放电容量；而氧化铁的孔结构增大了氧化铁纳米粒子的比表面积，使其具有更多的锂存储位点和更大的接触面积；丝蛋白诱导氧化铁纳米粒子形成棒状结构和蜂窝状的孔洞，其成本低廉、容易获得、生物相溶性好、对环境无污染，而且去除的方法简单。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1是本发明实施例一中样品的扫描电镜图；
图2是本发明实施例一中样品的透射电镜图；
图3是本发明实施例一中样品的XRD图；
图4是本发明实施例一中样品的拉曼光谱图；
图5是本发明实施例二中样品的扫描电镜图；
图6是本发明实施例三中样品的扫描电镜图；
图7是本发明实施例四中样品的扫描电镜图；
图8是本发明实施例四中样品的XRD图。
具体实施方式
下面将参考附图并结合实施例，来详细说明本发明。
实施例1
石墨烯/多孔氧化铁纳米棒复合物的制备方法：
(1)将0.05g氧化石墨烯与16mL质量分数为5.06％的丝蛋白溶液混合，调pH为10，并加入0.2mL水合肼进行还原诱导，从而获得石墨烯-丝蛋白纳米纤维复合物；
(2)向上述复合物中加入2.15g FeCl3·6H2O，继续搅拌至完全溶解；
(3)将上述混合物倒入反应釜中，于160℃下反应20小时；
(4)反应结束后自然冷却到室温，并离心洗涤，最后将产物真空干燥；
(5)将上述所得的固体粉末于真空管式炉中在400℃的氩气气氛中煅烧5小时，然后自然冷却至室温。
图1至4分别是本发明实施例一中样品的扫描电镜图、透射电镜图、XRD图和拉曼光谱图，从图1和图2可以看出，该方法下制备得到的样品呈一维棒状结构，从图2可以看到，棒状的氧化铁纳米粒子上有蜂窝状的孔洞，图3表明了该样品为氧化铁，图4进一步表明了产物是氧化铁与石墨烯的复合物。
实施例2
石墨烯/多孔氧化铁纳米棒复合物的制备方法：
(1)将0.05g氧化石墨烯与0.19mL质量分数为5.06％的丝蛋白溶液混合，调pH为10，并加入1mL水合肼进行还原诱导，从而获得石墨烯-丝蛋白纳米纤维复合物；
(2)向上述复合物中加入1g FeCl3·6H2O，继续搅拌至完全溶解；
(3)将上述混合物倒入反应釜中，于120℃下反应36小时；
(4)反应结束后自然冷却到室温，并离心洗涤，最后将产物真空干燥；
(5)将上述所得的固体粉末于真空管式炉中在320℃的氩气气氛中煅烧8小时，然后自然冷却至室温。
图5是样品的扫描电镜图，从图中可以看出，复合物部分呈棒状，部分呈不规则状。
实施例3
石墨烯/多孔氧化铁纳米棒复合物的制备方法：
(1)将0.05g氧化石墨烯与10mL质量分数为5.06％的丝蛋白溶液混合，调pH为10，并加入20μL水合肼进行还原诱导，从而获得石墨烯-丝蛋白纳米纤维复合物；
(2)向上述复合物中加入3g FeCl3·6H2O，继续搅拌至完全溶解；
(3)将上述混合物倒入反应釜中，于200℃下反应8小时；
(4)反应结束后自然冷却到室温，并离心洗涤，最后将产物真空 干燥；
(5)将上述所得的固体粉末于真空管式炉中在450℃的氩气气氛中煅烧3小时，然后自然冷却至室温。
图6是样品的扫描电镜图，从图中可以看出，复合物呈棒状。
实施例4
石墨烯/多孔氧化铁纳米棒复合物的制备方法：
实施例一中将步骤(5)省略，即为本实施例的合成方法。
图7是样品的扫描电镜图，从图中可以看出，复合物煅烧之前也是棒状结构，图8是样品的XRD图，表面复合物煅烧前的产物是FeOOH。
综上所述，本发明提出了一种石墨烯/多孔氧化铁纳米棒复合物的制备方法，该方法的原料来源广泛，成本低廉，合成工艺简单；本发明将氧化铁纳米粒子与石墨烯复合，石墨烯具有较大的比表面积和良好的电导率，增强了氧化铁材料的放电容量；而氧化铁的孔结构增大了氧化铁纳米粒子的比表面积，使其具有更多的锂存储位点和更大的接触面积；丝蛋白诱导氧化铁纳米粒子形成棒状结构和多孔结构，而且其成本低廉、容易获得、生物相溶性好、对环境无污染，去除的方法简单。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种石墨烯/多孔氧化铁纳米棒复合物，其特征在于：包括石墨烯及负载在所述石墨烯上的Fe2O3纳米粒子，所述Fe2O3纳米粒子具有蜂窝状的多孔结构。
  2. 根据权利要求1所述的石墨烯/多孔氧化铁纳米棒复合物，其特征在于：所述Fe2O3纳米粒子的形貌为棒状。
  3. 根据权利要求1或2所述的石墨烯/多孔氧化铁纳米棒复合物的制备方法，其特征在于：包括以下步骤：
    (1)将氧化石墨烯与丝蛋白溶液混合，调pH为碱性，加入水合肼进行还原，从而获得石墨烯/丝蛋白复合物；
    (2)向上述复合物中加入铁源，继续搅拌至完全溶解；
    (3)将上述混合物倒入反应釜中，于120～200℃反应8～36h；
    (4)反应结束后自然冷却到室温，离心，将产物干燥，得到固体粉末；
    (5)将上述固体粉末于320～450℃下的惰性气氛中煅烧3～8h，然后自然冷却至室温。
  4. 根据权利要求3所述的石墨烯/多孔氧化铁纳米棒复合物的制备方法，其特征在于：所述氧化石墨烯与丝蛋白的质量比不大于1∶4。
  5. 根据权利要求3所述的石墨烯/多孔氧化铁纳米棒复合物的制备方法，其特征在于：所述氧化石墨烯与水合肼的质量比为1∶(0.0004-20)。
  6. 根据权利要求3所述的石墨烯/多孔氧化铁纳米棒复合物的制备方法，其特征在于：所述铁源为FeCl3·6H2O，所述氧化石墨烯与FeCl3·6H2O的质量比为1∶(20-60)。
  7. 根据权利要求3所述的石墨烯/多孔氧化铁纳米棒复合物的制备方法，其特征在于：所述步骤(1)中的pH为8～11。
PCT/CN2015/089491 2015-07-03 2015-09-14 石墨烯/多孔氧化铁纳米棒复合物及其制备方法 Ceased WO2017004892A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/536,204 US10131544B2 (en) 2015-07-03 2015-09-14 Graphene/porous iron oxide nanorod composite and manufacturing method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510382555.1A CN104986759B (zh) 2015-07-03 2015-07-03 石墨烯/多孔氧化铁纳米棒复合物及其制备方法
CN201510382555.1 2015-07-03

Publications (1)

Publication Number Publication Date
WO2017004892A1 true WO2017004892A1 (zh) 2017-01-12

Family

ID=54298689

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/089491 Ceased WO2017004892A1 (zh) 2015-07-03 2015-09-14 石墨烯/多孔氧化铁纳米棒复合物及其制备方法

Country Status (3)

Country Link
US (1) US10131544B2 (zh)
CN (1) CN104986759B (zh)
WO (1) WO2017004892A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335496A (zh) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 氧化铁单晶纳米管与氮掺杂石墨烯轴向复合纳米材料的制备及产品和应用
CN114597432A (zh) * 2022-03-23 2022-06-07 合肥工业大学智能制造技术研究院 一种四氧化三钴@三氧化二铁异质结构复合材料及其制备方法和应用
CN117861458A (zh) * 2023-11-24 2024-04-12 广东石油化工学院 光催化双电极一体化石墨烯复合薄膜、制备方法及应用

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106929830B (zh) * 2017-03-07 2019-01-25 湘潭大学 一种高温下纳米结构可控的金属氧化物半导体薄膜电极材料的制备方法
CN108445070A (zh) * 2018-03-14 2018-08-24 杭州电子科技大学 氮掺石墨烯-多孔氧化铁纳米棒检测体液过氧化氢的方法
CN110152569B (zh) * 2018-04-28 2022-07-08 浙江大学 一种纳米FeO(OH)复合气凝胶、其制备方法和用途
CN108584938B (zh) * 2018-06-11 2020-03-20 中国科学院高能物理研究所 一种多孔氧化石墨烯的制备方法
CN109095440A (zh) * 2018-09-12 2018-12-28 杭州电子科技大学 一维多孔过渡金属氧化物纳米材料的制备方法
CN110078049A (zh) * 2019-05-27 2019-08-02 杭州电子科技大学 一种空心纳米过渡金属氧化物/碳复合材料及其制备方法
CN111606325A (zh) * 2020-06-12 2020-09-01 东华大学 一种具有吸波功能的石墨烯-铁氧基纳米功能子的制备方法
CN113332983B (zh) * 2021-04-29 2022-06-03 杭州师范大学 一种多孔棒状Fe21.34O32/C纳米棒复合材料的制备方法
US12551142B2 (en) 2021-05-22 2026-02-17 Tao Treasures, Llc Noninvasive device for monitor, detection, and diagnosis of diseases and human performance
KR102724437B1 (ko) * 2022-12-29 2024-10-31 중앙대학교 산학협력단 바이오 소재 기반 웨어러블 센서 제조 방법
CN117263172B (zh) * 2023-09-22 2025-12-05 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) 一种结构增强的磁性石墨烯气凝胶吸波材料的制备方法
CN117894598B (zh) * 2024-01-24 2025-01-03 重庆文理学院 一种储能电极复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543270A (zh) * 2012-01-31 2012-07-04 苏州大学 基于石墨烯的复合膜及其制备方法、导电电极及其制备方法
CN102649589A (zh) * 2012-05-24 2012-08-29 复旦大学 一种丝蛋白调控的α型三氧化二铁纳米材料及其制备方法
CN103367720A (zh) * 2013-07-09 2013-10-23 上海交通大学 石墨烯与多孔氧化铁复合材料的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103011303B (zh) * 2013-01-07 2014-12-03 云南云天化股份有限公司 氧化铁粒子的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543270A (zh) * 2012-01-31 2012-07-04 苏州大学 基于石墨烯的复合膜及其制备方法、导电电极及其制备方法
CN102649589A (zh) * 2012-05-24 2012-08-29 复旦大学 一种丝蛋白调控的α型三氧化二铁纳米材料及其制备方法
CN103367720A (zh) * 2013-07-09 2013-10-23 上海交通大学 石墨烯与多孔氧化铁复合材料的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHOU, QINGLIANG: "Synthesis of Nanocomposites of Iron Oxides and Graphene and Their Supercapacitor Properties", SCIENCE -ENGINEERING (A), CHINA MASTER'S THESES FULL-TEXT DATABASE, 15 August 2012 (2012-08-15), pages B020 - 126 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335496A (zh) * 2021-12-29 2022-04-12 上海纳米技术及应用国家工程研究中心有限公司 氧化铁单晶纳米管与氮掺杂石墨烯轴向复合纳米材料的制备及产品和应用
CN114597432A (zh) * 2022-03-23 2022-06-07 合肥工业大学智能制造技术研究院 一种四氧化三钴@三氧化二铁异质结构复合材料及其制备方法和应用
CN114597432B (zh) * 2022-03-23 2023-11-21 合肥工业大学智能制造技术研究院 一种四氧化三钴@三氧化二铁异质结构复合材料及其制备方法和应用
CN117861458A (zh) * 2023-11-24 2024-04-12 广东石油化工学院 光催化双电极一体化石墨烯复合薄膜、制备方法及应用

Also Published As

Publication number Publication date
CN104986759B (zh) 2017-06-09
CN104986759A (zh) 2015-10-21
US20170352446A1 (en) 2017-12-07
US10131544B2 (en) 2018-11-20

Similar Documents

Publication Publication Date Title
WO2017004892A1 (zh) 石墨烯/多孔氧化铁纳米棒复合物及其制备方法
Zheng et al. Nano electrochemical reactors of Fe 2 O 3 nanoparticles embedded in shells of nitrogen-doped hollow carbon spheres as high-performance anodes for lithium-ion batteries
Li et al. Engineering coordination polymer-derived one-dimensional porous S-doped Co 3 O 4 nanorods with rich oxygen vacancies as high-performance electrode materials for hybrid supercapacitors
CN106410145A (zh) 一种分级结构金属化合物/多孔碳纳米棒的制备方法
CN106654192B (zh) 一种硫化锡/石墨烯钠离子电池复合负极材料及其制备方法
CN103985884A (zh) 一种氮掺杂碳纳米材料、其制备方法及应用
CN103956473A (zh) 一种CuO-Cu2O/石墨烯纳米复合材料及其制备方法
CN110600697B (zh) 一种具有核壳结构的硫正极材料及其制备方法、锂硫电池正极极片和锂硫电池
CN108598431A (zh) 石墨烯泡沫-氧化镍复合电极材料及其制备方法
CN105293483A (zh) 一种原位制备过渡金属掺杂多孔石墨烯的方法
CN105826527A (zh) 一种多孔硅-碳复合材料及其制备方法和应用
CN108807882B (zh) 一种具有多孔八面体结构的Fe2O3/Fe3O4@C/G复合材料的制备方法
CN109904418B (zh) 一种锂离子电池负极材料及其制备方法
CN105460917A (zh) 一种具有分级结构的氮掺杂碳纳米管及制备方法
CN104773762A (zh) 一种生长在碳纤维布上的NiCo2O4介孔纳米管材料及其制备方法
CN109346702A (zh) 一种锂电池的负极材料及其制备方法
CN108997971A (zh) ZIF-67还原氧化石墨烯基吸波复合材料(CoC-rGo)的制备方法
CN110265225A (zh) 制备氮掺杂三维多孔碳微球负载碳化钼/氮化钼和铁纳米颗粒复合材料的方法
Tang et al. Improved chemical precipitation prepared rapidly NiCo2S4 with high specific capacitance for supercapacitors
CN106450305A (zh) 一种锂离子电池负极材料CoP/C的制备方法
WO2019127031A1 (zh) 用于锂电池的能源复合材料及其制备方法
CN109192952A (zh) 一种二硫化钴/碳纳米纤维复合材料及其制备方法
CN110400918B (zh) 一种钴硫化合物/硫掺杂碳复合材料的制备方法
CN104795557A (zh) 多孔金属掺杂锰酸锂/碳复合锂电池正极材料及制备方法
CN109399722B (zh) 一种多孔棒状二氧化钼/碳复合材料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15897548

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15536204

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15897548

Country of ref document: EP

Kind code of ref document: A1