WO2019075953A1 - 一种三维花瓣状镍钴硫化物电极材料的制备方法和应用 - Google Patents
一种三维花瓣状镍钴硫化物电极材料的制备方法和应用 Download PDFInfo
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- WO2019075953A1 WO2019075953A1 PCT/CN2018/074218 CN2018074218W WO2019075953A1 WO 2019075953 A1 WO2019075953 A1 WO 2019075953A1 CN 2018074218 W CN2018074218 W CN 2018074218W WO 2019075953 A1 WO2019075953 A1 WO 2019075953A1
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- nickel
- electrode material
- cobalt
- cobalt sulfide
- solution
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- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 238000000576 coating method Methods 0.000 claims abstract 2
- 238000003825 pressing Methods 0.000 claims abstract 2
- 238000001291 vacuum drying Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 229910001429 cobalt ion Inorganic materials 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- -1 H + Chemical class 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the invention belongs to the field of nano materials and electrochemistry, and particularly relates to a preparation method and application of a three-dimensional petal-like nickel-cobalt sulfide electrode material.
- Metal sulfide is a metal compound with good electrochemical activity which exhibits a highly reversible redox reaction under alkaline conditions. Sulfides have a lower band gap than oxides of the same metal and therefore have better electrical conductivity.
- the nanostructured metal sulfide has a large specific surface area and can be sufficiently contacted with the electrolyte. During the charging process, more ions (such as H + , OH - , K + or Li + ) can diffuse into the electrolyte to the electrolyte.
- the electrode/solution interface enters the metal sulfided phase by performing a redox reaction at the interface, thereby allowing more charge to be stored in the electrode for higher energy density.
- the object of the present invention is to provide a method and application for preparing a three-dimensional petal-like nickel-cobalt sulfide electrode material in view of the deficiencies of the prior art.
- the composite electrode material has a larger specific capacitance.
- the present invention adopts the following technical solutions:
- a method for preparing a three-dimensional petal-like nickel-cobalt sulfide electrode material comprising the following steps:
- the ultrasonic process parameters are: ultrasonic power of 200 W, ultrasonic temperature of 25 ° C, and ultrasonic time of 1 h.
- the molar ratio of nickel nitrate: cobalt nitrate 1: (0.5 ⁇ 2); the concentration of the nickel nitrate solution and the cobalt nitrate solution are both 10 g / L.
- the concentration of the hexamethylenetetramine solution is 10 g/L, and the addition amount is 20 to 40 mL.
- the pretreatment process of the nickel foam is: cutting a graphite felt having a thickness of 0.5 mm into a L-shaped strip of 1 cm ⁇ 1 cm, followed by washing with dilute hydrochloric acid, acetone, and ethanol to remove surface oxidation. The materials and other contaminants were finally ultrasonically washed with a large amount of deionized water and finally dried under vacuum at 60 ° C for 24 hours.
- the electrode material prepared by the present invention uses a secondary hydrothermal reaction, the first hydrothermal reaction synthesizes a manganese sulfide precursor, and then grows on the manganese sulfide precursor by a second hydrothermal reaction.
- Nickel-cobalt sulfide while manganese particles and nickel-cobalt particles undergo a Kirkendall effect to obtain a porous structure, thereby preparing a nickel-cobalt sulfide of a three-dimensional petal nanosphere structure;
- the high temperature calcination is not required in the preparation process of the invention, and the temperature of the hydrothermal reaction is relatively mild, and the electrode material synthesized at a relatively low temperature has a high specific surface area, an appropriate pore size distribution, a high specific capacity, and excellent Cycle stability energy, low energy consumption;
- the water solvent is used in the preparation process of the invention, and the chemical reagent used is less polluted and friendly to the environment.
- Figure 1 is an XRD pattern of the material prepared in Example 1 of the present invention.
- Example 2 is a scanning electron microscope image of a material prepared in Example 1 of the present invention.
- Example 3 is a graph showing cyclic volt-ampere characteristics of a three-dimensional petal-like nickel-cobalt sulfide electrode material prepared in Example 1 of the present invention
- Fig. 4 is a graph showing charge and discharge curves of a nickel-cobalt sulfide electrode material prepared in the present invention.
- a method for preparing a three-dimensional petal-like nickel-cobalt sulfide electrode material is as follows:
- Ni 2 CoS 4 nickel cobalt sulfide
- NMP N-methylpyrrolidone
- the pretreatment process is: cutting the graphite felt with a thickness of 0.5 mm into L-shaped strips of 1 cm ⁇ 1 cm, followed by washing with dilute hydrochloric acid, acetone and ethanol to remove surface oxides and other pollutants, and finally using a large amount of The deionized water was ultrasonically washed and finally dried under vacuum at 60 ° C for 24 hours.
- a method for preparing a three-dimensional petal-like nickel-cobalt sulfide electrode material is as follows:
- NiCoS 4 nickel cobalt sulfide
- NMP N-methylpyrrolidone
- the pretreatment process is: cutting the graphite felt with a thickness of 0.5 mm into L-shaped strips of 1 cm ⁇ 1 cm, followed by washing with dilute hydrochloric acid, acetone and ethanol to remove surface oxides and other pollutants, and finally using a large amount of The deionized water was ultrasonically washed and finally dried under vacuum at 60 ° C for 24 hours.
- a method for preparing a three-dimensional petal-like nickel-cobalt sulfide electrode material is as follows:
- NiCo 2 S 4 nickel cobalt sulfide
- NMP N-methylpyrrolidone
- the pretreatment process is: cutting the graphite felt with a thickness of 0.5 mm into L-shaped strips of 1 cm ⁇ 1 cm, followed by washing with dilute hydrochloric acid, acetone and ethanol to remove surface oxides and other pollutants, and finally using a large amount of The deionized water was ultrasonically washed and finally dried under vacuum at 60 ° C for 24 hours.
- Figure 1 is an XRD pattern of the material prepared in Example 1; compared with a standard PDF card, it was confirmed that the material prepared was a nickel-cobalt sulfide electrode material.
- Example 2 is a scanning electron micrograph of the material prepared in Example 1. It can be seen from FIG. 2 that the prepared nickel-cobalt sulfide electrode material has a three-dimensional petal-like structure.
- Example 3 is a cyclic voltammetry characteristic chart of the three-dimensional petal-like nickel-cobalt sulfide electrode material prepared in Example 1. It can be seen from FIG. 3 that the synthesized electrode material has a distinct Faraday reaction during charging and discharging, and exhibits a tantalum capacitance characteristic.
- FIG. 4 is a graph showing charge and discharge curves of the nickel-cobalt sulfide electrode materials prepared in Examples 1 to 3; FIG. 4 shows that the Ni 2 GoS 4 electrode material has the longest discharge time and better specific capacitance.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明属于纳米材料和电化学领域，具体涉及一种三维花瓣状镍钴硫化物电极材料的制备方法。以硝酸镍和硝酸钴为镍源和钴源，硫化锰为前驱体，六次甲基四胺为表面活性剂，在水热合成反应釜下反应一段时间得到镍钴硫化物，并将其涂覆在泡沫镍表面，经真空干燥后压制成电极材料。在本发明中，一次水热反应过程中，合成硫化锰前驱体，二次水热过程中，在表面活性剂的协同下，硫化锰前躯体上生长出镍钴氧化物纳米片，同时，同时锰离子和镍钴离子发生柯肯达尔效应得到中空结构。所得电极具备较高的比电容，可用于超级电容器电极材料。
Description
本发明属于纳米材料和电化学领域，具体涉及一种三维花瓣状镍钴硫化物电极材料的制备方法和应用。
在21世纪，“能源”已经成为国家间竞争的焦点。面对即将到来的能源危机，在试图找到新能源的同时，科学家们正积极研发节能、高效的储能器件。在新型储能器件中，超级电容器因其功率密度大、充放电速度快和循环寿命长等优点，正受到越来越多的关注。在超级电容器的众多组成部分中，电极材料的特性和组合对超级电容器的性能具有很大影响。
金属硫化物是一种具有良好电化学活性的金属化合物，其在碱性条件下呈现高度可逆的氧化还原反应。相比同种金属的氧化物，硫化物具有更低的能带间隙，因此具有更好的导电性。纳米结构的金属硫化物具有较大的比表面积，能够充分与电解液接触，在充电过程中，电解液中能够有更多的离子（如 H
+、 OH
-、 K
+或 Li
+）扩散到电极/溶液界面，通过在界面上进行氧化还原反应进入金属硫化物体相，从而使更多的电荷存储在电极中，获得更高的能量密度。
[0003] 利用纳米金属硫化物构建具有理想结构的复合材料，从而得到低廉的价格、较高的能量密度和优异的循环稳定性等综合性能的电极材料，是一种有效的途径之一。
本发明的目的在于针对现有技术不足，提供一种三维花瓣状镍钴硫化物电极材料的制备方法和应用。通过调控Ni和Co等原子的比例，使得复合电极材料具备更大的比电容。
为实现上述目的，本发明采用如下技术方案：
一种三维花瓣状镍钴硫化物电极材料的制备方法，包括以下步骤：
（1）将氯化锰和柠檬酸钠溶解在30~50L去离子水中；随后，在磁力搅拌下将20~40mL的0.1mol/L
的硫化钠水溶液滴加到混合溶液中；
（2）将步骤（1）得到的混合物转移到100mL特氟隆内衬的不锈钢高压反应釜中，在120℃下保温12小时；
（3）取出高压反应釜并自然冷却至室温后，离心得到粉红色沉淀，将所得沉淀用去离子水洗涤数次后，超声分散在30~50mL去离子水中；
（4）将硝酸镍溶液和硝酸钴溶液混合均匀，并逐滴加入到步骤（3）的溶液中，磁力搅拌20分钟后，再将配置好的六次甲基四胺溶液逐滴加入溶液中；
（5）将步骤（4）得到的混合物转移到100mL特氟龙内衬的不锈钢高压反应釜中，在120℃下保温24小时；
（6）取出高压反应釜并自然冷却至室温后，将得到的产物离心、洗涤、真空干燥后得到镍钴硫化物；
（7）将步骤（6）的镍钴硫化物与导电极乙炔黑和粘结剂PVDF混合均匀，然后滴加适量的N-甲基吡咯烷酮 ( NMP) 溶剂，配制成均匀的粘稠浆料，将其均匀地涂覆在预处理好的泡沫镍集流体上，真空干燥并压制成片，即制得所述三维花瓣状镍钴硫化物电极材料。
步骤（1）中，按质量比计，氯化锰：柠檬酸钠=1:1。
步骤（3）中，所述超声的工艺参数为：超声功率为200W，超声温度为25℃，超声时间为1h。
步骤（4）中，按摩尔比计，硝酸镍：硝酸钴=1:（0.5~2）；硝酸镍溶液和硝酸钴溶液的浓度均为10g/L。
步骤（4）中，所述六次甲基四胺溶液的浓度为10g/L，添加量为20~40mL。
步骤（7）中，按质量比计，镍钴硫化物：导电极乙炔黑：粘结剂PVDF=16:3:1。
步骤（7）中，泡沫镍的预处理过程为：将厚度为0.5mm的石墨毡剪成1 cm×1 cm的L形状长条，随后依次用稀盐酸、丙酮、乙醇洗涤，去除表面的氧化物和其他污染物，最后用大量的去离子水超声洗涤，最后在60℃真空条件下干燥24小时。
（1）
[0005] 本发明所制备的电极材料使用了二次水热反应，第一次水热反应合成了硫化锰前驱体，然后通过第二次水热反应在硫化锰前驱体上生长出镍钴硫化物，同时锰粒子和镍钴粒子发生柯肯达尔效应得到多孔结构，从而制备出三维花瓣纳米球结构的镍钴硫化物；
（2）本发明制备过程中无需高温煅烧，且水热反应的温度比较温和，在相对较低的温度下合成的电极材料具有较高的比表面积，恰当的孔径分布，比容量高，优异的循环稳定性能，对能源消耗低；
（3）本发明制备过程中使用水溶剂，使用的化学试剂污染小，对环境较友好。
图1为本发明中实施例1所制备材料的XRD图谱；
图2为本发明中实施例1所制备材料的扫描电镜图片；
图3为本发明中实施例1所制备三维花瓣状镍钴硫化物电极材料的循环伏安特性曲线图；
图4为本发明中所制备的镍钴硫化物电极材料的充放电曲线图。
[0007] 以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。
实施例
1
一种三维花瓣状镍钴硫化物电极材料的制备方法，具体过程如下：
（1）硫化锰的合成
将0.3g氯化锰和0.3g柠檬酸钠溶解在40mL去离子水中；随后，在磁力搅拌下将30mL
0.1mol/L 的硫化钠水溶液滴加到混合溶液中，20分钟后将混合溶液转移到100mL特氟隆内衬的不锈钢高压反应釜中，在120℃下保温12小时；
取出高压反应釜并自然冷却至室温后，将得到的粉红色沉淀，用乙醇和去离子水洗涤数次后，超声分散在40mL去离子水中，超声功率为200W，超声温度为25℃，超声时间为1h，得到硫化锰分散液。
（2）三维花瓣状镍钴硫化物的合成
将20mL浓度为10g/ L的硝酸镍溶液和10mL浓度为10g /L的硝酸钴溶液混合均匀，并逐滴加入到硫化锰分散液中，磁力搅拌20分钟后，再将30mL浓度为10g/L的六次甲基四胺溶液逐滴加入溶液中；
将混合液转移到100mL特氟龙内衬的不锈钢高压反应釜中，在120℃下保温24小时；取出高压反应釜并自然冷却至室温后，将所得产物用去离子水和乙醇洗涤数次后，在冻干机中干燥一夜，得到镍钴硫化物（Ni
2CoS
4）。
（3）制备测试电极
将3.2mg的镍钴硫化物与0.6mg的导电极乙炔黑和0.2mg的粘结剂PVDF按16:3:1的比例混合均匀，然后滴加适量的N-甲基吡咯烷酮 ( NMP) 溶剂，配制成均匀的粘稠浆料，将其均匀地涂覆在预预处理好的泡沫镍集流体上，真空干燥并压制成片，即可得到用于测试的工作电极；所述的泡沫镍的预处理过程为：将厚度为0.5mm的石墨毡剪成1 cm×1 cm的L形状长条，随后依次用稀盐酸、丙酮、乙醇洗涤，去除表面的氧化物和其他污染物，最后用大量的去离子水超声洗涤，最后在60℃真空条件下干燥24小时。
实施例
2
一种三维花瓣状镍钴硫化物电极材料的制备方法，具体过程如下：
（1）硫化锰的合成
将0.3g氯化锰和0.3g柠檬酸钠溶解在30mL去离子水中；随后，在磁力搅拌下将20mL
0.1mol/L 的硫化钠水溶液滴加到混合溶液中，20分钟后将混合溶液转移到100mL特氟隆内衬的不锈钢高压反应釜中，在120℃下保温12小时；
取出高压反应釜并自然冷却至室温后，将得到的粉红色沉淀，用乙醇和去离子水洗涤数次后，超声分散在30mL去离子水中，超声功率为200W，超声温度为25℃，超声时间为1h，得到硫化锰分散液。
（2）三维花瓣状镍钴硫化物的合成
将15mL浓度为10g/ L的硝酸镍溶液和15mL浓度为10g /L的硝酸钴溶液混合均匀，并逐滴加入到硫化锰分散液中，磁力搅拌20分钟后，再将20mL浓度为10g/L的六次甲基四胺溶液逐滴加入溶液中；
将混合液转移到100mL特氟龙内衬的不锈钢高压反应釜中，在120℃下保温24小时；取出高压反应釜并自然冷却至室温后，将所得产物用去离子水和乙醇洗涤数次后，在冻干机中干燥一夜，得到镍钴硫化物（NiCoS
4）。
（3）制备测试电极
将3.2mg的镍钴硫化物与0.6mg的导电极乙炔黑和0.2mg的粘结剂PVDF按16:3:1的比例混合均匀，然后滴加适量的N-甲基吡咯烷酮 ( NMP) 溶剂，配制成均匀的粘稠浆料，将其均匀地涂覆在预预处理好的泡沫镍集流体上，真空干燥并压制成片，即可得到用于测试的工作电极；所述的泡沫镍的预处理过程为：将厚度为0.5mm的石墨毡剪成1 cm×1 cm的L形状长条，随后依次用稀盐酸、丙酮、乙醇洗涤，去除表面的氧化物和其他污染物，最后用大量的去离子水超声洗涤，最后在60℃真空条件下干燥24小时。
实施例
3
一种三维花瓣状镍钴硫化物电极材料的制备方法，具体过程如下：
（1）硫化锰的合成
将0.3g氯化锰和0.3g柠檬酸钠溶解在50mL去离子水中；随后，在磁力搅拌下将40mL
0.1mol/L 的硫化钠水溶液滴加到混合溶液中，20分钟后将混合溶液转移到100mL特氟隆内衬的不锈钢高压反应釜中，在120℃下保温12小时；
取出高压反应釜并自然冷却至室温后，将得到的粉红色沉淀，用乙醇和去离子水洗涤数次后，超声分散在50mL去离子水中，超声功率为200W，超声温度为25℃，超声时间为1h，得到硫化锰分散液。
（2）三维花瓣状镍钴硫化物的合成
将10mL浓度为10g/ L的硝酸镍溶液和20mL浓度为10g /L的硝酸钴溶液混合均匀，并逐滴加入到硫化锰分散液中，磁力搅拌20分钟后，再将40mL浓度为10g/L的六次甲基四胺溶液逐滴加入溶液中；
将混合液转移到100mL特氟龙内衬的不锈钢高压反应釜中，在120℃下保温24小时；取出高压反应釜并自然冷却至室温后，将所得产物用去离子水和乙醇洗涤数次后，在冻干机中干燥一夜，得到镍钴硫化物（NiCo
2S
4）。
（3）制备测试电极
将3.2mg的镍钴硫化物与0.6mg的导电极乙炔黑和0.2mg的粘结剂PVDF按16:3:1的比例混合均匀，然后滴加适量的N-甲基吡咯烷酮 ( NMP) 溶剂，配制成均匀的粘稠浆料，将其均匀地涂覆在预预处理好的泡沫镍集流体上，真空干燥并压制成片，即可得到用于测试的工作电极；所述的泡沫镍的预处理过程为：将厚度为0.5mm的石墨毡剪成1 cm×1 cm的L形状长条，随后依次用稀盐酸、丙酮、乙醇洗涤，去除表面的氧化物和其他污染物，最后用大量的去离子水超声洗涤，最后在60℃真空条件下干燥24小时。
图1为实施例1所制备材料的XRD图谱；经与标准PDF卡片对比，证明制备的材料确为镍钴硫化物电极材料。
图2为实施例1所制备材料的扫描电镜图片；由图2可知所制备的镍钴硫化物电极材料呈三维花瓣状结构。
图3为实施例1所制备三维花瓣状镍钴硫化物电极材料的循环伏安特性曲线图；由图3可知所合成的电极材料在充放电过程中有明显的法拉第反应，呈现赝电容特性。
图4为实施例1~3所制备的镍钴硫化物电极材料的充放电曲线图；由图4可知Ni
2GoS
4电极材料放电时间最长，比电容更好。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (8)
- 一种三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：包括以下步骤：（1）将氯化锰和柠檬酸钠溶解在30~50L去离子水中；随后，在磁力搅拌下将20~40mL的0.1mol/L 的硫化钠水溶液滴加到混合溶液中；（2）将步骤（1）得到的混合物转移到100mL特氟隆内衬的不锈钢高压反应釜中，在120℃下保温12小时；（3）取出高压反应釜并自然冷却至室温后，离心得到粉红色沉淀，将所得沉淀用去离子水洗涤数次后，超声分散在30~50mL去离子水中；（4）将硝酸镍溶液和硝酸钴溶液混合均匀，并逐滴加入到步骤（3）的溶液中，磁力搅拌20分钟后，再将配置好的六次甲基四胺溶液逐滴加入溶液中；（5）将步骤（4）得到的混合物转移到100mL特氟龙内衬的不锈钢高压反应釜中，在120℃下保温24小时；（6）取出高压反应釜并自然冷却至室温后，将得到的产物离心、洗涤、真空干燥后得到镍钴硫化物；（7）将步骤（6）的镍钴硫化物与导电极乙炔黑和粘结剂PVDF混合均匀，然后滴加N-甲基吡咯烷酮溶剂，配制成均匀的粘稠浆料，将其均匀地涂覆在预处理好的泡沫镍集流体上，真空干燥并压制成片，即制得所述三维花瓣状镍钴硫化物电极材料。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（1）中，按质量比计，氯化锰：柠檬酸钠=1:1。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（3）中，所述超声的工艺参数为：超声功率为200W，超声温度为25℃，超声时间为1h。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（4）中，按摩尔比计，硝酸镍：硝酸钴=1:（0.5~2）；硝酸镍溶液和硝酸钴溶液的浓度均为10g/L。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（4）中，所述六次甲基四胺溶液的浓度为10g/L，添加量为20~40mL。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（7）中，按质量比计，镍钴硫化物：导电极乙炔黑：粘结剂PVDF=16:3:1。
- 根据权利要求1所述的三维花瓣状镍钴硫化物电极材料的制备方法，其特征在于：步骤（7）中，泡沫镍的预处理过程为：将厚度为0.5mm的石墨毡剪成1 cm×1 cm的L形状长条，随后依次用稀盐酸、丙酮、乙醇洗涤，去除表面的氧化物和其他污染物，最后用去离子水超声洗涤，最后在60℃真空条件下干燥24小时。
- 一种如权利要求1所述的制备方法制得的三维花瓣状镍钴硫化物电极材料的应用，其特征在于：所述电极材料作为超级电容器电极材料。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776940A (zh) * | 2004-11-15 | 2006-05-24 | 天津大学 | 镍氢电池负极表面处理方法 |
| CN104599853A (zh) * | 2015-02-09 | 2015-05-06 | 中国工程物理研究院材料研究所 | 一种超级电容器用镍钴硫代尖晶石及制备方法 |
| CN104795245A (zh) * | 2015-05-14 | 2015-07-22 | 安徽师范大学 | 一种线状镍钴氧化物@镍钴硫化物异质结构复合材料，其制备方法以及用途 |
Family Cites Families (2)
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| CN104201010B (zh) * | 2014-09-18 | 2017-02-22 | 同济大学 | 一种溶剂热法合成海胆状NiCo2S4电极材料的方法 |
| CN106683892B (zh) * | 2016-11-23 | 2019-01-15 | 广东工业大学 | 一种三维异质结构的硫化钴镍电极材料及其制备方法和应用 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776940A (zh) * | 2004-11-15 | 2006-05-24 | 天津大学 | 镍氢电池负极表面处理方法 |
| CN104599853A (zh) * | 2015-02-09 | 2015-05-06 | 中国工程物理研究院材料研究所 | 一种超级电容器用镍钴硫代尖晶石及制备方法 |
| CN104795245A (zh) * | 2015-05-14 | 2015-07-22 | 安徽师范大学 | 一种线状镍钴氧化物@镍钴硫化物异质结构复合材料，其制备方法以及用途 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111063550A (zh) * | 2019-12-23 | 2020-04-24 | 江苏大学 | 空心核-壳Fe-Co基硫化物@氢氧化镍纳米管阵列的制备方法及其应用 |
| CN113755887A (zh) * | 2021-09-30 | 2021-12-07 | 广州发展新能源股份有限公司 | 一种Ni2S3-Co9S8复合材料析氢催化剂和制备方法及应用 |
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