CN110327913A - A kind of nano-sheet tungsten oxide/graphene oxide Core-shell structure material and the preparation method and application thereof - Google Patents

A kind of nano-sheet tungsten oxide/graphene oxide Core-shell structure material and the preparation method and application thereof Download PDF

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CN110327913A
CN110327913A CN201910706959.XA CN201910706959A CN110327913A CN 110327913 A CN110327913 A CN 110327913A CN 201910706959 A CN201910706959 A CN 201910706959A CN 110327913 A CN110327913 A CN 110327913A
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graphene oxide
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王文静
刘柏雄
万长茂
王子璇
孙强
陈宜
戴天翔
程斌
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Abstract

一种纳米片状氧化钨/氧化石墨烯核壳结构材料及其制备方法与应用。将钨粉和氟化钠混合均匀得到混合粉体A；取H2O2和HNO3混合均匀得混合溶液B；向混合溶液B中加入氧化石墨烯水溶液得混合溶液C；将混合粉体A缓慢加入混合溶液C中得溶液E；将溶液E置于水热反应釜内进行水热反应，冷却，洗涤、收集、烘干，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。该核壳结构材料为方形单层薄片状结构，内层核为方形氧化钨纳米片，外层为氧化石墨烯，其中氧化钨单层薄片的厚度为10～30nm，长宽为100～250nm，外层氧化石墨烯的包覆厚度为5～20nm。应用于钠/锂/镁离子电池、超级电容器及光催化领域，表现出了优异的性能。A nano-flaky tungsten oxide/graphene oxide core-shell structure material and its preparation method and application. Mix tungsten powder and sodium fluoride uniformly to obtain mixed powder A; take H 2 O 2 and HNO 3 and mix uniformly to obtain mixed solution B; add graphene oxide aqueous solution to mixed solution B to obtain mixed solution C; mix mixed powder A Slowly add mixed solution C to obtain solution E; put solution E in a hydrothermal reaction kettle for hydrothermal reaction, cool, wash, collect, and dry to obtain nano-flaky tungsten oxide/graphene oxide core-shell structure material. The core-shell structure material is a square single-layer flake structure, the inner core is a square tungsten oxide nanosheet, and the outer layer is graphene oxide. The thickness of the tungsten oxide single-layer flake is 10-30nm, and the length and width are 100-250nm. The coating thickness of the outer graphene oxide is 5-20nm. It is used in the fields of sodium/lithium/magnesium ion batteries, supercapacitors and photocatalysis, showing excellent performance.

Description

一种纳米片状氧化钨/氧化石墨烯核壳结构材料及其制备方 法与应用A kind of nano flake tungsten oxide/graphene oxide core-shell structure material and preparation method thereof Law and Application

技术领域technical field

本发明涉及一种核壳结构纳米片层材料的制备方法，具体涉及一种一种原位合成纳米片状氧化钨/氧化石墨烯核壳结构材料的制备方法。The invention relates to a preparation method of a core-shell structure nano-sheet material, in particular to a preparation method of in-situ synthesis of a nano-sheet-like tungsten oxide/graphene oxide core-shell structure material.

背景技术Background technique

三氧化钨是稳定的n型半导体材料，被广泛应用于光催化和电化学催化等方面。近年来，随着锂/钠离子电池研究的深入，三氧化钨也被广泛应用在电化学储能方面，主要作为锂/钠离子电池的负极材料被研究。然而，纳米三氧化钨存在电荷转移速率慢、表面反应活性位少以及容易发生光生电子空穴对易复合等缺陷，极大地限制了它的适用领域。氧化石墨烯作为新型二维碳材料，具有大的比表面积，优越的导电性、良好的力学性能以及高的化学和热稳定性，在电化学领域被广泛应用。Tungsten trioxide is a stable n-type semiconductor material, which is widely used in photocatalysis and electrochemical catalysis. In recent years, with the in-depth study of lithium/sodium ion batteries, tungsten trioxide has also been widely used in electrochemical energy storage, mainly as the negative electrode material of lithium/sodium ion batteries. However, nano-tungsten trioxide has defects such as slow charge transfer rate, few reactive sites on the surface, and easy recombination of photogenerated electron-hole pairs, which greatly limits its application field. Graphene oxide, as a new type of two-dimensional carbon material, has a large specific surface area, superior electrical conductivity, good mechanical properties, and high chemical and thermal stability, and is widely used in the field of electrochemistry.

近年来，三氧化钨/氧化石墨烯复合材料作为电池负极材料受到了研究者们的广泛研究，但是到目前为止，关于以三氧化钨为核、氧化石墨烯为壳的二维纳米复合材料的报道几乎没有。In recent years, tungsten trioxide/graphene oxide composite materials have been extensively studied by researchers as battery anode materials, but so far, there are no studies on two-dimensional nanocomposites with tungsten trioxide as the core and graphene oxide as the shell. Reports were barely there.

发明内容Contents of the invention

本发明的目的在于提供一种操作简单，且反应温度低、反应周期短的原位合成纳米片状氧化钨/氧化石墨烯核壳结构材料的制备方法，制得的氧化钨/氧化石墨烯核壳结构材料结构单一，纯度高。The object of the present invention is to provide a method for preparing in-situ synthesis of nano-flaky tungsten oxide/graphene oxide core-shell structure material with simple operation, low reaction temperature and short reaction period, and the prepared tungsten oxide/graphene oxide core The shell structure material has a single structure and high purity.

为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:

1)将钨粉和氟化钠按10:1～10:3的质量比混合均匀得到混合粉体A；1) Mix tungsten powder and sodium fluoride uniformly at a mass ratio of 10:1 to 10:3 to obtain mixed powder A;

2)分别取5～15ml质量浓度为30％的H2O2和5～15ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 5-15ml of H2O2 with a mass concentration of 30% and 5-15ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入2～6ml质量浓度为0.05％～0.15％的氧化石墨烯水溶液，得混合溶液C；3) Add 2 to 6 ml of graphene oxide aqueous solution with a mass concentration of 0.05% to 0.15% into the mixed solution B to obtain a mixed solution C;

4)取1～8g混合粉体A缓慢加入混合溶液C中，搅拌待其充分溶解后得溶液E；4) Take 1-8g of mixed powder A and slowly add it to mixed solution C, stir until it is fully dissolved to obtain solution E;

5)将溶液E置于水热反应釜内于120～200℃进行水热反应，反应结束后，冷却，洗涤、收集、烘干，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put solution E in a hydrothermal reaction kettle for hydrothermal reaction at 120-200°C. After the reaction, cool, wash, collect, and dry to obtain nano-flaky tungsten oxide/graphene oxide core-shell structure material .

所述钨粉的尺寸2～3μm。The size of the tungsten powder is 2-3 μm.

所述氧化石墨烯为微米级单层氧化石墨烯结构。The graphene oxide is a micron-scale single-layer graphene oxide structure.

所述的搅拌为磁力搅拌或超声分散。The stirring is magnetic stirring or ultrasonic dispersion.

所述溶液E置于水热反应釜内的填充比为35～75％。The filling ratio of the solution E in the hydrothermal reactor is 35-75%.

所述反应时间为20～35h。The reaction time is 20-35 hours.

所述洗涤采用无水乙醇离心洗涤3～5次，所述收集为离心收集。The washing is performed by centrifugal washing with absolute ethanol for 3 to 5 times, and the collection is centrifugal collection.

所述烘干温度为50～80℃，时间为12～16h。The drying temperature is 50-80° C., and the drying time is 12-16 hours.

由以上制备方法制成的核壳结构材料为方形单层薄片状结构，内层核为方形氧化钨纳米片，外层为氧化石墨烯，其中氧化钨单层薄片的厚度为10～30nm，长宽为100～250nm，外层氧化石墨烯的包覆厚度为5～20nm。The core-shell structure material made by the above preparation method is a square single-layer flake structure, the inner core is a square tungsten oxide nanosheet, the outer layer is graphene oxide, and the thickness of the tungsten oxide single-layer flake is 10-30nm, long The width is 100-250 nm, and the coating thickness of the outer graphene oxide is 5-20 nm.

由以上制备方法制成的纳米片状氧化钨/氧化石墨烯核壳结构材料应用于钠/锂/镁离子电池、超级电容器及光催化领域。The nano-flaky tungsten oxide/graphene oxide core-shell structure material prepared by the above preparation method is applied in the fields of sodium/lithium/magnesium ion batteries, supercapacitors and photocatalysis.

相对于现有技术，本发明至少具有以下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:

本发明采用原位一步合成氧化钨/氧化石墨烯核壳结构纳米粉体，该方法不需要大型设备和苛刻的反应条件，无需形貌控制剂，原料易得，成本低，产率高，无需后期处理，对环境友好，可以适合大规模生产。The present invention adopts in-situ one-step synthesis of tungsten oxide/graphene oxide core-shell nanopowder. Post-processing is environmentally friendly and can be suitable for mass production.

且通过该方法制备的氧化钨/氧化石墨烯核壳结构纳米粉体，具有以氧化钨为核、氧化石墨烯为壳的核壳结构。该核壳结构的纳米粉体应用于钠/锂/镁离子电池以及光催化领域，表现出了优异的性能。And the tungsten oxide/graphene oxide core-shell nanopowder prepared by the method has a core-shell structure with tungsten oxide as the core and graphene oxide as the shell. The nanopowder with the core-shell structure is applied in the fields of sodium/lithium/magnesium ion batteries and photocatalysis, and exhibits excellent performance.

附图说明Description of drawings

图1为本发明实施例1制备的纳米片状氧化钨/氧化石墨烯核壳结构材料粉体的X-射线衍射(XRD)图谱；Fig. 1 is the X-ray diffraction (XRD) pattern of the nano-flaky tungsten oxide/graphene oxide core-shell structure material powder prepared in Example 1 of the present invention;

图2和图3为本发明实施例1制备的纳米片状氧化钨/氧化石墨烯核壳结构材料粉体的扫描电子显微镜(SEM)照片和透射电子显微镜(TEM)照片。2 and 3 are scanning electron microscope (SEM) photos and transmission electron microscope (TEM) photos of the nanosheet tungsten oxide/graphene oxide core-shell structure material powder prepared in Example 1 of the present invention.

具体实施方式Detailed ways

下面结合附图及实施例对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.

实施例1：Example 1:

1)将2～3μm钨粉和氟化钠按10:1的质量比混合均匀得到混合粉体A；1) Mix 2-3 μm tungsten powder and sodium fluoride uniformly at a mass ratio of 10:1 to obtain mixed powder A;

2)分别取5ml质量浓度为30％的H2O2和5ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 5ml of H2O2 with a mass concentration of 30 % and 5ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入2ml质量浓度为0.05％的微米级单层结构的氧化石墨烯水溶液，得混合溶液C；3) adding 2ml of graphene oxide aqueous solution with a mass concentration of 0.05% in the mixed solution B to obtain a mixed solution C;

4)取1g混合粉体A缓慢加入混合溶液C中，磁力搅拌待其充分溶解后得溶液E；4) Take 1g of mixed powder A and slowly add it to mixed solution C, and magnetically stir until it is fully dissolved to obtain solution E;

5)按35％的填充比将溶液E置于水热反应釜内于160℃水热反应22h，反应结束后，冷却，采用无水乙醇离心洗涤3次、离心收集、于50℃烘干12h，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put solution E in a hydrothermal reaction kettle at 160°C for 22 hours at a filling ratio of 35%. After the reaction, cool down, wash with absolute ethanol for 3 times, collect by centrifugation, and dry at 50°C for 12 hours. , that is, a nano-flaky tungsten oxide/graphene oxide core-shell structure material is obtained.

通过该方法原位合成的核壳结构材料为方形单层薄片状结构，内层核为方形氧化钨纳米片，外层为氧化石墨烯，其中氧化钨单层薄片的厚度为10～30nm，长宽为100～250nm，外层氧化石墨烯的包覆厚度为5～20nm。该核壳材料应用于钠/锂/镁离子电池以及光催化领域。尤其是当其应用于钠离子电池时，表现出了优异的电化学性能。The core-shell structure material synthesized in situ by this method is a square single-layer flake structure, the inner core is a square tungsten oxide nanosheet, and the outer layer is graphene oxide. The width is 100-250 nm, and the coating thickness of the outer graphene oxide is 5-20 nm. The core-shell material is applied in the fields of sodium/lithium/magnesium ion batteries and photocatalysis. Especially when it is applied to Na-ion batteries, it exhibits excellent electrochemical performance.

从图1中可以看出，所制备的复合材料为三氧化钨和氧化石墨烯的复合材料。It can be seen from Figure 1 that the prepared composite material is a composite material of tungsten trioxide and graphene oxide.

从图2中可以清楚的看到所制备纳米粉体为大小均匀的单层片状结构，其尺寸为100-200nm，厚度约为20-30nm。It can be clearly seen from Fig. 2 that the prepared nanopowder is a uniform single-layer sheet structure with a size of 100-200nm and a thickness of about 20-30nm.

从图3中可以进一步看到，所制备的纳米单层片长宽为100nm左右的氧化钨，外层均匀包覆厚度约为15nm的氧化石墨烯层。进一步证实了所制备的材料为核壳结构。It can be further seen from FIG. 3 that the prepared nano single-layer sheet is tungsten oxide with a length and width of about 100 nm, and the outer layer is evenly coated with a graphene oxide layer with a thickness of about 15 nm. It is further confirmed that the prepared material has a core-shell structure.

实施例2：Example 2:

1)将2～3μm钨粉和氟化钠按10:1.5的质量比混合均匀得到混合粉体A；1) Mix 2-3 μm tungsten powder and sodium fluoride uniformly at a mass ratio of 10:1.5 to obtain mixed powder A;

2)分别取8ml质量浓度为30％的H2O2和8ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 8ml of H2O2 with a mass concentration of 30 % and 8ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入2.5ml质量浓度为0.1％的微米级单层结构的氧化石墨烯水溶液，得混合溶液C；3) Adding 2.5ml of graphene oxide aqueous solution with a micron-scale single-layer structure with a mass concentration of 0.1% to the mixed solution B to obtain a mixed solution C;

4)取2.5g混合粉体A缓慢加入混合溶液C中，超声分散待其充分溶解后得溶液E；4) Take 2.5g of mixed powder A and slowly add it to mixed solution C, and ultrasonically disperse it until it is fully dissolved to obtain solution E;

5)按75％的填充比将溶液E置于水热反应釜内于180℃水热反应24h，反应结束后，冷却，采用无水乙醇离心洗涤3次、离心收集、于60℃烘干14h，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put the solution E in a hydrothermal reaction kettle at 180°C for 24 hours at a filling ratio of 75%. After the reaction, cool down, wash with absolute ethanol for 3 times, collect by centrifugation, and dry at 60°C for 14 hours. , that is, a nano-flaky tungsten oxide/graphene oxide core-shell structure material is obtained.

实施例3：Example 3:

1)将2～3μm钨粉和氟化钠按10:3的质量比混合均匀得到混合粉体A；1) Mix 2-3 μm tungsten powder and sodium fluoride uniformly at a mass ratio of 10:3 to obtain mixed powder A;

2)分别取10ml质量浓度为30％的H2O2和10ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 10ml of H2O2 with a mass concentration of 30 % and 10ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入4ml质量浓度为0.13％的微米级单层结构的氧化石墨烯水溶液，得混合溶液C；3) Adding 4ml of graphene oxide aqueous solution with a mass concentration of 0.13% in the mixed solution B to obtain a mixed solution C;

4)取5.2g混合粉体A缓慢加入混合溶液C中，磁力搅拌待其充分溶解后得溶液E；4) Take 5.2g of mixed powder A and slowly add it to mixed solution C, and magnetically stir until it is fully dissolved to obtain solution E;

5)按35％的填充比将溶液E置于水热反应釜内于160℃水热反应30h，反应结束后，冷却，采用无水乙醇离心洗涤5次、离心收集、于80℃烘干16h，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put the solution E in a hydrothermal reaction kettle at a filling ratio of 35% and conduct a hydrothermal reaction at 160°C for 30 hours. After the reaction, cool down, wash with absolute ethanol for 5 times, collect by centrifugation, and dry at 80°C for 16 hours. , that is, a nano-flaky tungsten oxide/graphene oxide core-shell structure material is obtained.

实施41：Implementation 41:

1)将2～3μm钨粉和氟化钠按10:2的质量比混合均匀得到混合粉体A；1) Mix 2-3 μm tungsten powder and sodium fluoride uniformly at a mass ratio of 10:2 to obtain mixed powder A;

2)分别取15ml质量浓度为30％的H2O2和12ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 15ml of H2O2 with a mass concentration of 30 % and 12ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入5ml质量浓度为0.08％的微米级单层结构的氧化石墨烯水溶液，得混合溶液C；3) Adding 5ml of graphene oxide aqueous solution with a mass concentration of 0.08% in the mixed solution B to obtain a mixed solution C;

4)取8g混合粉体A缓慢加入混合溶液C中，超声分散待其充分溶解后得溶液E；4) Take 8g of mixed powder A and slowly add it to mixed solution C, and ultrasonically disperse it until it is fully dissolved to obtain solution E;

5)按50％的填充比将溶液E置于水热反应釜内于120℃水热反应35h，反应结束后，冷却，采用无水乙醇离心洗涤4次、离心收集、于70℃烘干13h，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put solution E in a hydrothermal reaction kettle at 120°C for 35 hours at a filling ratio of 50%. After the reaction, cool down, wash with absolute ethanol for 4 times, collect by centrifugation, and dry at 70°C for 13 hours. , that is, a nano-flaky tungsten oxide/graphene oxide core-shell structure material is obtained.

实施例5：Example 5:

1)将2～3μm钨粉和氟化钠按10:2.5的质量比混合均匀得到混合粉体A；1) Mix 2-3 μm tungsten powder and sodium fluoride uniformly at a mass ratio of 10:2.5 to obtain mixed powder A;

2)分别取12ml质量浓度为30％的H2O2和15ml质量浓度为69％的HNO3混合均匀得混合溶液B； 2 ) Take 12ml of H2O2 with a mass concentration of 30 % and 15ml of HNO3 with a mass concentration of 69% and mix them uniformly to obtain a mixed solution B;

3)向混合溶液B中加入6ml质量浓度为0.15％的微米级单层结构的氧化石墨烯水溶液，得混合溶液C；3) Adding 6ml of graphene oxide aqueous solution with a mass concentration of 0.15% in the mixed solution B to obtain a mixed solution C;

4)取6g混合粉体A缓慢加入混合溶液C中，超声分散待其充分溶解后得溶液E；4) Take 6g of mixed powder A and slowly add it to mixed solution C, and ultrasonically disperse it until it is fully dissolved to obtain solution E;

5)按60％的填充比将溶液E置于水热反应釜内于200℃水热反应20h，反应结束后，冷却，采用无水乙醇离心洗涤5次、离心收集、于80℃烘干12h，即得到纳米片状氧化钨/氧化石墨烯核壳结构材料。5) Put solution E in a hydrothermal reaction kettle at 200°C for 20 hours at a filling ratio of 60%. After the reaction, cool down, wash with absolute ethanol for 5 times, collect by centrifugation, and dry at 80°C for 12 hours. , that is, a nano-flaky tungsten oxide/graphene oxide core-shell structure material is obtained.

相对于现有技术，本发明至少具有以下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:

本发明采用原位一步合成氧化钨/氧化石墨烯核壳结构纳米粉体，该方法不需要大型设备和苛刻的反应条件，无需形貌控制剂，原料易得，成本低，产率高，无需后期处理，对环境友好，可以适合大规模生产。The present invention adopts in-situ one-step synthesis of tungsten oxide/graphene oxide core-shell nanopowder. Post-processing is environmentally friendly and can be suitable for mass production.

且通过该方法制备的氧化钨/氧化石墨烯核壳结构纳米粉体，具有以氧化钨为核、氧化石墨烯为壳的核壳结构。该核壳结构的纳米粉体应用于钠/锂/镁离子电池以及光催化领域，表现出了优异的性能。And the tungsten oxide/graphene oxide core-shell nanopowder prepared by the method has a core-shell structure with tungsten oxide as the core and graphene oxide as the shell. The nanopowder with the core-shell structure is applied in the fields of sodium/lithium/magnesium ion batteries and photocatalysis, and exhibits excellent performance.

Claims (10)

1. a kind of preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material, it is characterised in that:
1) tungsten powder and sodium fluoride are uniformly mixed by the mass ratio of 10:1~10:3 and obtain mixed powder A；
2) taking 5~15ml mass concentration respectively is 30% H2O2The HNO for being 69% with 5~15ml mass concentration3It is uniformly mixed Mixed solution B；
3) graphene oxide water solution that 2~6ml mass concentration is 0.05%~0.15% is added into mixed solution B, obtains mixed Close solution C；
4) 1~8g mixed powder A is taken to be slowly added in mixed solution C, stirring obtains solution E to it after completely dissolution；
5) solution E is placed in hydrothermal reaction kettle in 120~200 DEG C of progress hydro-thermal reactions, after reaction, cooling, washing is received Collection is dried to get nano-sheet tungsten oxide/graphene oxide Core-shell structure material is arrived.
2. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: 2~3 μm of the size of the tungsten powder.
3. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: the graphene oxide is micron order single-layer graphene oxide structure.
4. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: the stirring is magnetic agitation or ultrasonic disperse.
5. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: it is 35~75% that the solution E, which is placed in the packing ratio in hydrothermal reaction kettle,.
6. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: the reaction time is 20~35h.
7. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: the washing uses dehydrated alcohol centrifuge washing 3~5 times, described to be collected as being collected by centrifugation.
8. the preparation method of nano-sheet tungsten oxide/graphene oxide Core-shell structure material according to claim 1, special Sign is: the drying temperature is 50~80 DEG C, and the time is 12~16h.
9. a kind of nano-sheet tungsten oxide made from preparation method as described in claim 1/graphene oxide core-shell structure material Material, it is characterised in that: the Core-shell structure material is rectangular single thin layer laminated structure, and internal layer core is rectangular tungstic oxide nano-sheets, outside Layer is graphene oxide, wherein monolayer of tungsten oxide thin slice with a thickness of 10~30nm, length and width are 100~250nm, outer oxide stone The cladding of black alkene is with a thickness of 5~20nm.
10. a kind of nano-sheet tungsten oxide made from preparation method as described in claim 1/graphene oxide core-shell structure material Material, it is characterised in that: the nano-sheet tungsten oxide/graphene oxide Core-shell structure material be applied to sodium/lithium/Magnesium ion battery, Supercapacitor and photocatalysis field.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111974377A (en) * 2020-09-01 2020-11-24 陕西科技大学 High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805023A (en) * 2010-04-01 2010-08-18 中国科学院宁波材料技术与工程研究所 Method for preparing tungstic oxide nano-sheets
CN106872063A (en) * 2017-01-17 2017-06-20 中国电子科技集团公司第四十九研究所 A kind of preparation method and application of tubulose tungsten oxide graphene composite material
CN108855047A (en) * 2018-08-29 2018-11-23 河南师范大学 A kind of flower-shaped tungstic acid/graphene composite photocatalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805023A (en) * 2010-04-01 2010-08-18 中国科学院宁波材料技术与工程研究所 Method for preparing tungstic oxide nano-sheets
CN106872063A (en) * 2017-01-17 2017-06-20 中国电子科技集团公司第四十九研究所 A kind of preparation method and application of tubulose tungsten oxide graphene composite material
CN108855047A (en) * 2018-08-29 2018-11-23 河南师范大学 A kind of flower-shaped tungstic acid/graphene composite photocatalyst and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
JINGJING GUO ET AL.: "Synthesis of WO3@Graphene composite for enhanced photocatalytic oxygen evolution from water", 《RSC ADVANCES》 *
付长璟编: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 *
李嘉胤: "氧化钨水合物微/纳米材料的可控合成及其性能研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 *
谷一冉: "纳米三氧化钨的制备及其光催化性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 *
黄猛: "石墨烯基复合材料的合成及相关电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
黎先财等: "H2O2氧化-水热结晶法合成纳米WO3的研究", 《稀有金属》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111974377A (en) * 2020-09-01 2020-11-24 陕西科技大学 High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof
CN111974377B (en) * 2020-09-01 2022-11-18 陕西科技大学 High-activity high-stability tungsten oxide hydrogen production catalyst with carbon-coated defects and preparation method thereof

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