CN113428889B - A kind of layered structure CuS nanoflower, preparation method and application thereof - Google Patents
A kind of layered structure CuS nanoflower, preparation method and application thereof Download PDFInfo
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- 239000002057 nanoflower Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 28
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical group [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- BRWIZMBXBAOCCF-UHFFFAOYSA-N thiosemicarbazide group Chemical group NNC(=S)N BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 3
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- 229930195722 L-methionine Natural products 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 229940108925 copper gluconate Drugs 0.000 claims description 3
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 3
- 229960004452 methionine Drugs 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- -1 Transition metal sulfides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
Description
技术领域technical field
本发明属于微纳米材料领域，尤其是一种分层结构CuS纳米花、制备方法及其应用。The invention belongs to the field of micro-nano materials, in particular to a layered structure CuS nano flower, a preparation method and application thereof.
背景技术Background technique
钠离子电池由于钠资源储量比较丰富，价格相对较低，在新能源领域受到广泛关注。过渡金属硫化物环境友好，制备简单，与钠离子反应活性较大，因此是一类比较有应用前景的钠离子电池负极材料。CuS的电导率为10-3S·cm-1，理论比容量高达560mAhg-1，放电平台较平坦，稳定性较好，因此，CuS也经常被用作钠离子电池负极材料进行研究。目前研究人员采用化学气相沉积法、模板法以及水热法等多种手段制备出了具有纳米颗粒、纳米线、纳米片、纳米花等多种CuS纳米材料。由于花状结构特殊，CuS纳米花近年来受到比较多的关注。Due to the abundant reserves of sodium resources and the relatively low price of sodium-ion batteries, they have received extensive attention in the field of new energy. Transition metal sulfides are environmentally friendly, simple to prepare, and have high reactivity with sodium ions, so they are a class of promising anode materials for sodium ion batteries. The electrical conductivity of CuS is 10-3S·cm -1 , the theoretical specific capacity is as high as 560mAhg -1 , the discharge platform is flat, and the stability is good. Therefore, CuS is often used as the anode material for sodium-ion batteries for research. At present, researchers have prepared a variety of CuS nanomaterials with nanoparticles, nanowires, nanosheets, nanoflowers and other methods by chemical vapor deposition, template method and hydrothermal method. Due to the special flower-like structure, CuS nanoflowers have received more attention in recent years.
如中国专利CN201210043760.1采用化学气相沉积法，通过控制反应体系的温度、压力以及产物收集区域，制备硫化铜纳米晶体、纳米棒、纳米薄片以及纳米花簇多种不同形貌。在功能性半导体器件，光电转化，催化等领域具有较大的应用前景。中国专利CN201910736092.2利用水热法制备出一种3D花状硫化铜，制备的花状硫化铜尺寸均匀、形貌规整，在光催化、电容器、传感器等领域具有一定的应用前景。中国专利CN202010120786.6利用水热法制备出一种石墨烯/硫化铜锌花状微米球光催化剂，制备的产品复合效果好，比表面积大，抗光腐蚀能力强，可见光光催化活性高，能充分利用太阳光对环境污染物进行光催化降解。上述公开的CuS纳米材料在制备过程中反应能耗偏大，制备工艺也比较复杂。For example, Chinese patent CN201210043760.1 adopts chemical vapor deposition method to prepare copper sulfide nanocrystals, nanorods, nanosheets and nanoflower clusters with various morphologies by controlling the temperature, pressure and product collection area of the reaction system. It has great application prospects in functional semiconductor devices, photoelectric conversion, catalysis and other fields. Chinese patent CN201910736092.2 uses a hydrothermal method to prepare a 3D flower-shaped copper sulfide. The prepared flower-shaped copper sulfide has uniform size and regular morphology, and has certain application prospects in the fields of photocatalysis, capacitors, and sensors. Chinese patent CN202010120786.6 utilizes a hydrothermal method to prepare a graphene/copper sulfide spangle microsphere photocatalyst. The prepared product has good composite effect, large specific surface area, strong photocorrosion resistance, high visible light photocatalytic activity, and can Make full use of sunlight for photocatalytic degradation of environmental pollutants. The CuS nanomaterial disclosed above has a relatively large reaction energy consumption during the preparation process, and the preparation process is also relatively complicated.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服上述现有技术的缺点，提供一种分层结构CuS纳米花、制备方法及其应用。The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and to provide a layered structure CuS nanoflower, a preparation method and an application thereof.
为达到上述目的，本发明采用以下技术方案予以实现：To achieve the above object, the present invention adopts the following technical solutions to realize:
一种分层结构CuS纳米花的制备方法，包括以下步骤：A preparation method of layered structure CuS nanoflowers, comprising the following steps:
1)将铜源和金属盐加入1,4-丁二醇中，配制成溶液A，铜离子浓度为0.01～0.04mol/L，另一种金属离子浓度为0.005～0.02mol/L；1) adding copper source and metal salt into 1,4-butanediol, and preparing solution A, the copper ion concentration is 0.01～0.04mol/L, and the other metal ion concentration is 0.005～0.02mol/L;
将硫源加入去离子水中，配制成浓度为0.01～0.03mol/L的溶液B；Add sulfur source into deionized water to prepare solution B with a concentration of 0.01-0.03 mol/L;
2)将溶液B按照体积比1：(0.4～1)滴加至溶液A中，得到混合液；2) Add solution B dropwise to solution A according to a volume ratio of 1:(0.4～1) to obtain a mixed solution;
3)将混合液在40～70℃加热8～11小时，反应结束后，进行洗涤干燥，得到分层结构CuS纳米花。3) The mixed solution is heated at 40-70° C. for 8-11 hours, and after the reaction is completed, washing and drying are performed to obtain CuS nanoflowers with a layered structure.
进一步的，在步骤1)中，铜源为三氟甲磺酸铜、酒石酸铜或者葡萄糖酸铜。Further, in step 1), the copper source is copper trifluoromethanesulfonate, copper tartrate or copper gluconate.
进一步的，在步骤1)中，所述金属盐为氯化镍、氯化钯或二氯化锡。Further, in step 1), the metal salt is nickel chloride, palladium chloride or tin dichloride.
进一步的，在步骤1)中，所述硫源为硫代氨基脲、L-甲硫氨酸或2-硫脲嘧啶。Further, in step 1), the sulfur source is thiosemicarbazide, L-methionine or 2-thiouracil.
进一步的，所述步骤2)中，滴加时间为10～30分钟，滴加完成后搅拌0.5～1小时。Further, in the step 2), the dropwise addition time is 10 to 30 minutes, and the stirring is performed for 0.5 to 1 hour after the dropwise addition is completed.
进一步的，所述步骤3)中，洗涤3～6次，真空干燥温度为50～80℃，干燥时间为9～12小时。Further, in the step 3), washing is performed for 3 to 6 times, the vacuum drying temperature is 50 to 80° C., and the drying time is 9 to 12 hours.
一种分层结构CuS纳米花，根据本发明的方法制备得到。A layered structure CuS nanoflower is prepared according to the method of the present invention.
本发明的分层结构CuS纳米花作为钠离子电池负极材料的应用。The application of the layered structure CuS nanoflower of the present invention as a negative electrode material for a sodium ion battery.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明的分层结构CuS纳米花的制备方法，所用原料价格低廉，所用设备常见易得，制备过程简便，整体能耗较低，有利于工业化生产。不同于常见CuS纳米材料制备过程中经常用到模板，或采用高温煅烧，本发明采用金属离子掺杂在较低温度下即可调节CuS纳米材料的形貌与结构。另外，本发明的制备方法，通过改变反应参数还可以对CuS纳米花中纳米片的尺寸进行调控，根据需要制备出电化学性能较好的产品。The method for preparing the layered structure CuS nanoflowers of the invention has the advantages of low price of raw materials, common and readily available equipment, simple and convenient preparation process, low overall energy consumption, and is favorable for industrialized production. Unlike common CuS nanomaterials that often use templates or high-temperature calcinations in the preparation process, the present invention adopts metal ion doping to adjust the morphology and structure of the CuS nanomaterials at a lower temperature. In addition, in the preparation method of the present invention, the size of the nanosheets in the CuS nanoflowers can also be regulated by changing the reaction parameters, and a product with better electrochemical performance can be prepared as required.
本发明的分层结构CuS纳米花，形貌特征鲜明，较薄的纳米片自组装成分层的CuS纳米花。The layered structure CuS nanoflowers of the present invention have distinct morphological features, and the thinner nanosheets self-assemble into layered CuS nanoflowers.
本发明的分层结构CuS纳米花作为钠离子电池负极材料的应用，CuS独特的分层结构，可以提供更多的活性位点，缩短钠离子扩散路径，进一步提高离子或电子的传输效率。The application of the layered structure CuS nanoflower of the present invention as a negative electrode material of a sodium ion battery, the unique layered structure of CuS can provide more active sites, shorten the diffusion path of sodium ions, and further improve the transmission efficiency of ions or electrons.
附图说明Description of drawings
图1为实施例1的CuS纳米花的XRD图；Fig. 1 is the XRD pattern of the CuS nanoflower of
图2为实施例1的CuS纳米花的扫描电镜图；Fig. 2 is the scanning electron microscope picture of the CuS nanoflower of
图3为实施例1的CuS纳米花的透射电镜图；Fig. 3 is the transmission electron microscope picture of the CuS nanoflower of
图4为实施例1的CuS纳米花的EDS图；Fig. 4 is the EDS figure of the CuS nanoflower of
图5为实施例1的CuS纳米花的充放电图。FIG. 5 is a charge-discharge diagram of the CuS nanoflowers of Example 1. FIG.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to make those skilled in the art better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only Embodiments are part of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。It should be noted that the terms "first", "second" and the like in the description and claims of the present invention and the above drawings are used to distinguish similar objects, and are not necessarily used to describe a specific sequence or sequence. It is to be understood that the data so used may be interchanged under appropriate circumstances such that the embodiments of the invention described herein can be practiced in sequences other than those illustrated or described herein. Furthermore, the terms "comprising" and "having", and any variations thereof, are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device comprising a series of steps or units is not necessarily limited to those expressly listed Rather, those steps or units may include other steps or units not expressly listed or inherent to these processes, methods, products or devices.
下面结合附图对本发明做进一步详细描述：Below in conjunction with accompanying drawing, the present invention is described in further detail:
实施例1Example 1
1)将三氟甲磺酸铜和氯化镍加入1,4-丁二醇中，配制成溶液A，铜离子浓度为0.01mol/L，镍离子浓度为0.005mol/L；1) adding copper trifluoromethanesulfonate and nickel chloride into 1,4-butanediol, and preparing solution A, the copper ion concentration is 0.01mol/L, and the nickel ion concentration is 0.005mol/L;
将硫代氨基脲加入去离子水中，配制成浓度为0.01mol/L的溶液B；Add thiosemicarbazide into deionized water to prepare solution B with a concentration of 0.01mol/L;
2)将溶液B按照体积比1：0.4滴加至溶液A中，得到混合液；滴加时间为10分钟，滴加完成后搅拌0.5小时；2) The solution B was added dropwise to the solution A according to the volume ratio of 1:0.4 to obtain a mixed solution; the dropwise addition time was 10 minutes, and the stirring was performed for 0.5 hour after the dropwise addition was completed;
3)将混合液在40℃加热11小时，反应结束后，去离子水、乙醇洗涤3次，50℃真空干燥12小时，得到分层结构CuS纳米花。3) The mixed solution was heated at 40° C. for 11 hours. After the reaction, the mixture was washed three times with deionized water and ethanol, and vacuum-dried at 50° C. for 12 hours to obtain CuS nanoflowers with a layered structure.
参见图1，图1为本发明制备的CuS纳米花的XRD图，从图1可以确定CuS纳米花物相组成，具有较高的纯度。Referring to FIG. 1, FIG. 1 is the XRD pattern of the CuS nanoflowers prepared by the present invention. From FIG. 1, the phase composition of the CuS nanoflowers can be determined, and the CuS nanoflowers have high purity.
参见图2，图2为实施例1产物的扫描电镜图，其中制得的CuS纳米材料形貌特征鲜明，呈规整的纳米花状，直径大约为400nm。Referring to FIG. 2, FIG. 2 is a scanning electron microscope image of the product of Example 1, wherein the prepared CuS nanomaterial has a distinct morphology, is in the shape of regular nanoflowers, and has a diameter of about 400 nm.
参见图3，图3为产物的透射电镜图，从图中可以看出CuS二维纳米片自组装成独特的分层结构CuS纳米花。Referring to Fig. 3, Fig. 3 is a transmission electron microscope image of the product. It can be seen from the figure that the CuS two-dimensional nanosheets self-assemble into a unique layered structure of CuS nanoflowers.
参见图4，图4为CuS纳米花的EDS图，从图中可以看出，Cu、S、Sn元素分布比较均匀，Sn元素在图1中并未出现，因此，推测Sn元素可能是以离子的形式掺杂到了CuS晶格中。Referring to Figure 4, Figure 4 is the EDS image of CuS nanoflowers. It can be seen from the figure that the distribution of Cu, S, and Sn elements is relatively uniform, and the Sn element does not appear in Figure 1. Therefore, it is speculated that the Sn element may be an ion doped into the CuS lattice.
参见图5，图5给出了CuS纳米花作为钠离子电池负极材料的充放电图，其中，在电流密度为1.0A/g下，放电比容量、充电比容量分别为478mAh/g、471mAh/g。Referring to Figure 5, Figure 5 shows the charge-discharge diagram of CuS nanoflowers as the anode material for sodium-ion batteries, in which, at a current density of 1.0A/g, the discharge specific capacity and charge specific capacity are 478mAh/g and 471mAh/g, respectively. g.
实施例2Example 2
1)将酒石酸铜和氯化钯加入1,4-丁二醇中，配制成溶液A，铜离子浓度为0.02mol/L，钯离子浓度为0.01mol/L；1) copper tartrate and palladium chloride are added in 1,4-butanediol, mixed with solution A, the copper ion concentration is 0.02mol/L, and the palladium ion concentration is 0.01mol/L;
将L-甲硫氨酸加入去离子水中，配制成浓度为0.02mol/L的溶液B；Add L-methionine into deionized water to prepare solution B with a concentration of 0.02mol/L;
2)将溶液B按照体积比1：0.6滴加至溶液A中，得到混合液；滴加时间为20分钟，滴加完成后搅拌1小时；2) The solution B was added dropwise to the solution A according to the volume ratio of 1:0.6 to obtain a mixed solution; the dropwise addition time was 20 minutes, and the stirring was performed for 1 hour after the dropwise addition was completed;
3)将混合液在50℃加热10小时，反应结束后，去离子水、乙醇洗涤6次，60℃真空干燥11小时，得到分层结构CuS纳米花。3) The mixed solution was heated at 50° C. for 10 hours. After the reaction, the mixture was washed 6 times with deionized water and ethanol, and vacuum-dried at 60° C. for 11 hours to obtain CuS nanoflowers with a layered structure.
实施例3Example 3
1)将葡萄糖酸铜和二氯化锡加入1,4-丁二醇中，配制成溶液A，铜离子浓度为0.03mol/L，锡离子浓度为0.02mol/L；1) adding copper gluconate and tin dichloride into 1,4-butanediol, and preparing solution A, the copper ion concentration is 0.03mol/L, and the tin ion concentration is 0.02mol/L;
将2-硫脲嘧啶加入去离子水中，配制成浓度为0.03mol/L的溶液B；Add 2-thiouracil to deionized water to prepare solution B with a concentration of 0.03mol/L;
2)将溶液B按照体积比1：0.8滴加至溶液A中，得到混合液；滴加时间为30分钟，滴加完成后搅拌0.5小时；2) The solution B was added dropwise to the solution A according to the volume ratio of 1:0.8 to obtain a mixed solution; the dropwise addition time was 30 minutes, and the stirring was performed for 0.5 hour after the dropwise addition was completed;
3)将混合液在60℃加热9小时，反应结束后，去离子水、乙醇洗涤4次，70℃真空干燥10小时，得到分层结构CuS纳米花。3) The mixed solution was heated at 60° C. for 9 hours, after the reaction was completed, washed with deionized water and ethanol for 4 times, and vacuum-dried at 70° C. for 10 hours to obtain CuS nanoflowers with a layered structure.
实施例4Example 4
1)将三氟甲磺酸铜和氯化镍加入1,4-丁二醇中，配制成溶液A，铜离子浓度为0.04mol/L，镍离子浓度为0.01mol/L；1) adding copper trifluoromethanesulfonate and nickel chloride into 1,4-butanediol, and preparing solution A, the copper ion concentration is 0.04mol/L, and the nickel ion concentration is 0.01mol/L;
将硫代氨基脲加入去离子水中，配制成浓度为0.01mol/L的溶液B；Add thiosemicarbazide into deionized water to prepare solution B with a concentration of 0.01mol/L;
2)将溶液B按照体积比1：1滴加至溶液A中，得到混合液；滴加时间为10分钟，滴加完成后搅拌1小时；2) The solution B was added dropwise to the solution A according to the volume ratio of 1:1 to obtain a mixed solution; the dropwise addition time was 10 minutes, and the stirring was performed for 1 hour after the dropwise addition was completed;
3)将混合液在70℃加热8小时，反应结束后，去离子水、乙醇洗涤5次，80℃真空干燥9小时，得到分层结构CuS纳米花。3) The mixed solution was heated at 70° C. for 8 hours, after the reaction was completed, washed with deionized water and ethanol for 5 times, and vacuum-dried at 80° C. for 9 hours to obtain a layered structure of CuS nanoflowers.
本发明利用廉价易得的原料及简便高效的制备条件完成了CuS纳米花的制备，并得到了独特的一种金属离子掺杂分层结构CuS纳米花，作为钠离子电池负极材料，具有较好的电化学性能。The invention utilizes cheap and readily available raw materials and simple and efficient preparation conditions to complete the preparation of CuS nanoflowers, and obtains a unique metal ion-doped layered structure CuS nanoflowers, which is used as a negative electrode material for sodium ion batteries and has good performance. electrochemical performance.
以上内容仅为说明本发明的技术思想，不能以此限定本发明的保护范围，凡是按照本发明提出的技术思想，在技术方案基础上所做的任何改动，均落入本发明权利要求书的保护范围之内。The above content is only to illustrate the technical idea of the present invention, and cannot limit the protection scope of the present invention. Any modification made on the basis of the technical solution proposed in accordance with the technical idea of the present invention falls within the scope of the claims of the present invention. within the scope of protection.
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