WO2016078509A1 - Electrode applied to electrochemical energy storage apparatus and method for preparing same - Google Patents

Electrode applied to electrochemical energy storage apparatus and method for preparing same Download PDF

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WO2016078509A1
WO2016078509A1 PCT/CN2015/093468 CN2015093468W WO2016078509A1 WO 2016078509 A1 WO2016078509 A1 WO 2016078509A1 CN 2015093468 W CN2015093468 W CN 2015093468W WO 2016078509 A1 WO2016078509 A1 WO 2016078509A1
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electrode
energy storage
electrochemical energy
nickel
storage device
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PCT/CN2015/093468
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French (fr)
Chinese (zh)
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金玉红
王莉
何向明
李建军
尚玉明
张玉峰
赵鹏
刘恒伟
高剑
王要武
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江苏合志锂硫电池技术有限公司
江苏华东锂电技术研究院有限公司
清华大学
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Publication of WO2016078509A1 publication Critical patent/WO2016078509A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Definitions

  • the invention relates to an electrode applied to an electrochemical energy storage device and a preparation method thereof.
  • Supercapacitors are a new type of energy storage device with performance between physical capacitors and secondary batteries. They combine the high specific power of physical capacitors with the high specific energy of the battery. Due to its high power density, long cycle life, rapid charge and discharge of large currents, wide operating temperature range, safety, and no pollution, supercapacitors are widely used in electric vehicles, uninterruptible power supplies, aerospace, military and many other fields. The application prospect has attracted extensive attention from researchers at home and abroad and has become one of the research hotspots in the field of chemical power supply.
  • the transition metal oxide is an electrode active material commonly used for supercapacitor electrodes, wherein nickel cobaltate (NiCo 2 O 4 ) is low in cost, highly available, and environmentally friendly. More importantly, NiCo 2 O 4 has higher conductivity and electrochemical reactivity than NiO and Co 3 O 4 and has received wide attention from researchers.
  • NiCo 2 O 4 nickel cobaltate
  • the electrode is prepared by first preparing NiCo 2 O 4 particles, then forming an electrode slurry, and then coating the electrode slurry on the surface of a current collector such as nickel foam, and then drying to form an electrode.
  • a current collector such as nickel foam
  • An electrode for an electrochemical energy storage device comprising a current collector and an array of nickel cobalt oxide nanosheets disposed on the current collector, the nickel cobalt nanocrystal array comprising a plurality of nickel cobaltate nanosheets.
  • a method for preparing an electrode applied to an electrochemical energy storage device includes the following steps:
  • the nickel salt, the cobalt salt, the precipitating agent and the ammonium fluoride are uniformly mixed in water to form a mixed liquid;
  • the electrode precursor is calcined to obtain the electrode.
  • a NiCo 2 O 4 nanosheet array having a three-dimensional porous network structure can be directly formed on the surface of the current collector by adding ammonium fluoride during the hydrothermal reaction of the nickel salt and the cobalt salt.
  • the structure can greatly reduce the distance of ion transmission and transmission, thereby enhancing the utilization rate of the electrode active material, and the electrochemical energy storage device using the electrode has high power, energy density (capacity), chemical cycle stability and capacity. Retention rate.
  • the preparation method of the electrode is simple, the cost is low, and the method is easy to be repeated, thereby facilitating industrial production.
  • FIG. 1 is a schematic structural diagram of an electrode applied to an electrochemical energy storage device according to an embodiment of the present invention.
  • FIG. 2 is a flow chart of a method for preparing an electrode applied to an electrochemical energy storage device according to an embodiment of the present invention.
  • Example 3 is an X-ray diffraction pattern (XRD) of an electrode active material applied to an electrode of an electrochemical energy storage device prepared in Example 1 of the present invention.
  • XRD X-ray diffraction pattern
  • Example 4 is a field emission scanning electron micrograph (FESEM) of a NiCo 2 O 4 nanosheet array in an electrode prepared in Example 1 of the present invention at different magnifications.
  • FESEM field emission scanning electron micrograph
  • Figure 5 is a cyclic voltammetry curve of a capacitor made of an electrode applied to an electrochemical energy storage device at a scan rate of 5 mV/s prepared in Example 1 of the present invention.
  • Fig. 6 is a charge and discharge curve of a capacitor made of an electrode applied to an electrochemical energy storage device prepared in Example 1 of the present invention at a charge and discharge current density of 2 A/g.
  • an embodiment of the present invention provides an electrode 100 for an electrochemical energy storage device, the electrode 100 including a current collector 10 and nickel cobaltate (NiCo 2 O 4 ) nanometer disposed on the surface of the current collector 10 .
  • the wafer array 20, the NiCo 2 O 4 nanosheet array 20 includes a plurality of NiCo 2 O 4 nanosheets 22.
  • the electrode 100 can be applied to an electrochemical energy storage device.
  • the electrochemical energy storage device can be, but is not limited to, a supercapacitor or a secondary battery.
  • the current collector 10 is used to carry NiCo 2 O 4 as an electrode active material.
  • the current collector 10 may have a dense continuous structure or a porous structure.
  • the current collector 10 is a porous layered or sheet-like structure. More preferably, the current collector 10 is a three-dimensional (3D) mesh structure having a certain thickness. The pores are preferably micropores.
  • the current collector 10 using the 3D network structure can greatly enhance electrolyte permeation to promote ion diffusion.
  • the material of the current collector 10 may be a metal or a non-metal as long as it can conduct electricity and can carry the electrode active material.
  • the metal may be, but not limited to, at least one of aluminum, nickel, and copper.
  • the current collector 10 may be a metal piece or a metal mesh.
  • the non-metal may be a carbon material such as, but not limited to, carbon nanotubes or graphene. Accordingly, the current collector 10 may be at least one of a porous or non-porous carbon nanotube film and a graphene film. In the embodiment of the invention, a nickel mesh is selected as the current collector 10.
  • the NiCo 2 O 4 nanosheet array 20 includes a plurality of NiCo 2 O 4 nanosheets 22 disposed vertically on the surface of the current collector 10.
  • the vertical means that the two-dimensional plane formed by the NiCo 2 O 4 nanosheet 22 in the length and width directions forms an angle ⁇ with the two-dimensional plane of the current collector 10 formed in the length and width directions, Among them, 30 o ⁇ ⁇ ⁇ 90 o .
  • the NiCo 2 O 4 nanosheet 22 is perpendicular to the current collector 10.
  • the plurality of NiCo 2 O 4 nanosheets 22 intersect each other to form a three-dimensional porous network structure, and the plurality of mutually intersecting NiCo 2 O 4 nanosheets 22 are combined with the current collector 10 to form a plurality of transparent layers.
  • the channel facilitates the penetration of the electrolyte solution.
  • the plurality of NiCo 2 O 4 nanosheets 22 are tightly fixed to the surface of the current collector 10 by intermolecular forces.
  • the plurality of NiCo 2 O 4 nanosheets 22 have a uniform thickness.
  • each of the NiCo 2 O 4 nanosheets 22 may have a thickness of 10 nm to 20 nm.
  • the surface size of the NiCo 2 O 4 nanosheet 22 at a vertical thickness is on the order of micrometers.
  • the nanosheet 242 has excellent flexibility and mechanical stability.
  • NiCo 2 O 4 nanosheet array 20 or the NiCo 2 O 4 nanosheet 22 is NiCo 2 O 4 .
  • an embodiment of the present invention further provides a method for preparing an electrode 100 applied to an electrochemical energy storage device, including the following steps:
  • the nickel salt and the cobalt salt are preferably selected from water-soluble salts, and may be, but not limited to, at least one of a nitrate, a sulfate, and an acetate.
  • the precipitating agent is used to react with the nickel salt and the cobalt salt in the hydrothermal reaction to obtain NiCo 2 O 4 .
  • the precipitating agent is soluble in water. More preferably, the precipitating agent is weakly basic.
  • urea is selected as the precipitant.
  • the content of the precipitating agent can be selected according to the amount of the nickel salt or the cobalt salt, as long as the precipitating agent can be completely reacted with the nickel salt or the cobalt salt.
  • the ammonium fluoride can promote the subsequent formation of the nanosheet-shaped NiCo 2 O 4 nanosheet array 20 while promoting the formation of the NiCo 2 O 4 nanosheet array 20 as a monolithic, self-supporting three-dimensional porous network structure.
  • the molar content of the ammonium fluoride is greater than or equal to the total molar content of nickel and cobalt in the nickel salt and the cobalt salt, and the range is more favorable for promoting the uniformity of the NiCo 2 O 4 nanosheet array 20 which is uniform in morphology.
  • the molar content of the ammonium fluoride is equal to the total molar content of the nickel salt and the cobalt salt.
  • the nickel salt, the cobalt salt, the precipitating agent, and the ammonium fluoride are uniformly mixed while continuously stirring the nickel salt, the cobalt salt, the precipitating agent, and the ammonium fluoride in water.
  • the preparation method includes ultrasonically shaking the mixed solution after the formation of the mixed solution to obtain a uniform, transparent mixed solution.
  • step S2 includes:
  • the precipitating agent is first added to the first solution, and then the ammonium fluoride is further added to form the mixed solution, and the subsequently formed nanosheet array is formed by the order of the addition.
  • the shape is more uniform and controllable.
  • the hydrothermal reaction may be carried out in a closed reactor having a temperature of from 80 ° C to 160 ° C.
  • the hydrothermal reaction has a temperature of from 80 °C to 120 °C.
  • the time of the hydrothermal reaction may be as long as the reaction is completed, and preferably, it may be from 3 hours to 18 hours.
  • the reactor may be further cooled to obtain the electrode precursor, and the electrode precursor is further washed with water and an organic solvent to remove unnecessary impurities.
  • step S3 after the hydrothermal reaction, a pink-purple cobalt-nickel precursor material is formed on the surface of the current collector 10, and the cobalt-nickel precursor material has a nano-sheet array.
  • the electrode precursor may be placed in a muffle furnace for calcination.
  • the calcined environment is an aerobic environment.
  • the calcination temperature may be from 250 ° C to 350 ° C.
  • the calcination may be carried out by gradually increasing the temperature to a predetermined temperature and then heating and heating for a certain period of time.
  • the rate of temperature rise is preferably from 1 ° C / min to 5 ° C / min.
  • the calcination time may be from 2 hours to 5 hours.
  • the pink-purple cobalt-nickel precursor gradually turns into a black product, which is the electrode active material NiCo 2 O 4 .
  • the calcined product may be further cooled to room temperature to obtain the electrode 100.
  • the collector is made of foamed nickel, and the foamed nickel is ultrasonically cleaned in a hydrochloric acid solution for 20 minutes to remove the surface oxide of the foamed nickel.
  • XRD analysis of the black product on the foamed nickel shows that the black product is a NiCo 2 O 4 material.
  • NiCo 2 O 4 crosses each other in a nano-sheet form to form a porous network structure.
  • the embodiment of the present invention further applies a NiCo 2 O 4 electrode to a supercapacitor to test its electrochemical performance.
  • the NiCo 2 O 4 nanosheet array has good electrochemical reversibility after testing. Please refer to FIG. 6 again. It can be seen that the NiCo 2 O 4 nanosheet array has a specific capacitance value of about 800 F/g when the charge and discharge current density is 2 A/g.
  • the electrode is formed by directly adding a three-dimensional porous network structure NiCo 2 O 4 nanosheet array on the surface of the current collector by adding ammonium fluoride during the thermal reaction of the nickel salt and the cobalt salt water.
  • the structure can greatly reduce the distance of ion transmission and transmission, thereby enhancing the utilization rate of the electrode active material, and the electrochemical energy storage device using the electrode 100 has high power, energy density (capacity), chemical cycle stability, and Capacity retention rate.
  • the electrode 100 is simple in preparation method, low in cost, and easy to be repeatedly implemented, thereby facilitating industrial production.

Abstract

The present invention relates to an electrode applied to an electrochemical energy storage apparatus. The electrode comprises a current collector and a nickel-cobalt-oxide nano-sheet array disposed on the current collector. The nickel-cobalt-oxide nano-sheet array comprises multiple nickel-cobalt-oxide nano-sheets. The present invention further relates to a method for preparing the electrode. The electrode has desirable electrochemical cycling performance in the application to an electrochemical energy storage apparatus.

Description

应用于电化学储能装置的电极及其制备方法Electrode for electrochemical energy storage device and preparation method thereof 技术领域Technical field
本发明涉及一种应用于电化学储能装置的电极及其制备方法。The invention relates to an electrode applied to an electrochemical energy storage device and a preparation method thereof.
背景技术Background technique
超级电容器是一类性能介于物理电容器和二次电池之间的新型储能器件，兼有物理电容器高比功率和电池高比能量的特点。由于具有功率密度高、循环寿命长、能瞬间大电流快速充放电、工作温度范围宽、安全、无污染等特点，超级电容器在电动汽车、不间断电源、航空航天、军事等诸多领域有广阔的应用前景，引起了国内外研究者的广泛关注，成为当前化学电源领域的研究热点之一。Supercapacitors are a new type of energy storage device with performance between physical capacitors and secondary batteries. They combine the high specific power of physical capacitors with the high specific energy of the battery. Due to its high power density, long cycle life, rapid charge and discharge of large currents, wide operating temperature range, safety, and no pollution, supercapacitors are widely used in electric vehicles, uninterruptible power supplies, aerospace, military and many other fields. The application prospect has attracted extensive attention from researchers at home and abroad and has become one of the research hotspots in the field of chemical power supply.
过渡金属氧化物是一种超级电容器电极常用的电极活性材料，其中，钴酸镍（NiCo2O4）由于具有低成本，高可用性且环境友好。更为重要的是，NiCo2O4相比于NiO和Co3O4具有更高的电导率和电化学反应活性，因此，受到研究者的广泛关注。The transition metal oxide is an electrode active material commonly used for supercapacitor electrodes, wherein nickel cobaltate (NiCo 2 O 4 ) is low in cost, highly available, and environmentally friendly. More importantly, NiCo 2 O 4 has higher conductivity and electrochemical reactivity than NiO and Co 3 O 4 and has received wide attention from researchers.
现有技术中电极的制备方法首先制作NiCo2O4颗粒，然后制成电极浆料，再将电极浆料涂覆在泡沫镍等集电体表面，然后干燥形成电极。然而这种方式制备的电极在电化学循环的过程中电极活性材料的利用率不高，电化学循环性能较差。In the prior art, the electrode is prepared by first preparing NiCo 2 O 4 particles, then forming an electrode slurry, and then coating the electrode slurry on the surface of a current collector such as nickel foam, and then drying to form an electrode. However, in the electrode prepared by this method, the utilization rate of the electrode active material is not high during the electrochemical cycle, and the electrochemical cycle performance is poor.
发明内容Summary of the invention
有鉴于此，确有必要提供一种具有较高活性材料利用率且较好电化学循环性能的应用于电化学储能装置的电极及其制备方法。In view of this, it is indeed necessary to provide an electrode for an electrochemical energy storage device having a higher active material utilization rate and better electrochemical cycle performance and a preparation method thereof.
一种应用于电化学储能装置的电极，其包括集电体以及设置在集电体上的钴酸镍纳米片阵列，所述钴酸镍纳米片阵列包括多个钴酸镍纳米片。An electrode for an electrochemical energy storage device, comprising a current collector and an array of nickel cobalt oxide nanosheets disposed on the current collector, the nickel cobalt nanocrystal array comprising a plurality of nickel cobaltate nanosheets.
一种应用于电化学储能装置的电极的制备方法，包括以下步骤：A method for preparing an electrode applied to an electrochemical energy storage device includes the following steps:
提供镍盐、钴盐、沉淀剂以及氟化铵；Providing a nickel salt, a cobalt salt, a precipitating agent, and ammonium fluoride;
将所述镍盐、钴盐、沉淀剂以及氟化铵在水中均匀混合形成一混合液；The nickel salt, the cobalt salt, the precipitating agent and the ammonium fluoride are uniformly mixed in water to form a mixed liquid;
将一集电体放置在所述混合液中，并进行水热反应获得一电极前驱体；以及Depositing a current collector in the mixed solution and performing a hydrothermal reaction to obtain an electrode precursor;
煅烧该电极前驱体获得所述电极。The electrode precursor is calcined to obtain the electrode.
本发明实施例通过在镍盐、钴盐在水热反应的过程加入氟化铵可在集电体表面直接形成三维多孔网络结构状的NiCo2O4纳米片阵列。该种结构可以大大缩小离子透过和传输的距离，从而可增强电极活性材料的利用率，应用该电极的电化学储能装置具有高的功率、能量密度（容量）、化学循环稳定性以及容量保持率。此外，该电极的制备方法简单，成本较低，易于重复实现，从而利于产业化生产。In the embodiment of the present invention, a NiCo 2 O 4 nanosheet array having a three-dimensional porous network structure can be directly formed on the surface of the current collector by adding ammonium fluoride during the hydrothermal reaction of the nickel salt and the cobalt salt. The structure can greatly reduce the distance of ion transmission and transmission, thereby enhancing the utilization rate of the electrode active material, and the electrochemical energy storage device using the electrode has high power, energy density (capacity), chemical cycle stability and capacity. Retention rate. In addition, the preparation method of the electrode is simple, the cost is low, and the method is easy to be repeated, thereby facilitating industrial production.
附图说明DRAWINGS
图1为本发明实施例提供的应用于电化学储能装置的电极的结构示意图。FIG. 1 is a schematic structural diagram of an electrode applied to an electrochemical energy storage device according to an embodiment of the present invention.
图2为本发明实施例提供的应用于电化学储能装置的电极制备方法的流程图。2 is a flow chart of a method for preparing an electrode applied to an electrochemical energy storage device according to an embodiment of the present invention.
图3为本发明实施例1制备的应用于电化学储能装置的电极中电极活性材料的X射线衍射图谱（XRD）。3 is an X-ray diffraction pattern (XRD) of an electrode active material applied to an electrode of an electrochemical energy storage device prepared in Example 1 of the present invention.
图4为本发明实施例1制备的电极中的NiCo2O4纳米片阵列在不同倍率下的场发射扫描电镜照片（FESEM）。4 is a field emission scanning electron micrograph (FESEM) of a NiCo 2 O 4 nanosheet array in an electrode prepared in Example 1 of the present invention at different magnifications.
图5为本发明实施例1制备的应用于电化学储能装置的电极制成的电容器在5mV/S的扫描速率下的循环伏安曲线。Figure 5 is a cyclic voltammetry curve of a capacitor made of an electrode applied to an electrochemical energy storage device at a scan rate of 5 mV/s prepared in Example 1 of the present invention.
图6为本发明实施例1制备的应用于电化学储能装置的电极制成的电容器在在充放电电流密度是2A/g时的充放电曲线。Fig. 6 is a charge and discharge curve of a capacitor made of an electrode applied to an electrochemical energy storage device prepared in Example 1 of the present invention at a charge and discharge current density of 2 A/g.
主要元件符号说明Main component symbol description
电极electrode 100100
集电体Collector 1010
纳米片阵列Nanosheet array 2020
纳米片Nanosheets 22twenty two
如下具体实施方式将结合上述附图进一步说明本发明。The invention will be further illustrated by the following detailed description in conjunction with the accompanying drawings.
具体实施方式detailed description
下面将结合附图及具体实施例对本发明提供的应用于电化学储能装置的电极及其制备方法作进一步的详细说明。The electrode applied to the electrochemical energy storage device and the preparation method thereof provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
请参阅图1，本发明实施例提供一种应用于电化学储能装置的电极100，该电极100包括集电体10以及设置在集电体10表面的钴酸镍（NiCo2O4）纳米片阵列20，所述NiCo2O4纳米片阵列20包括多个NiCo2O4纳米片22。Referring to FIG. 1 , an embodiment of the present invention provides an electrode 100 for an electrochemical energy storage device, the electrode 100 including a current collector 10 and nickel cobaltate (NiCo 2 O 4 ) nanometer disposed on the surface of the current collector 10 . The wafer array 20, the NiCo 2 O 4 nanosheet array 20 includes a plurality of NiCo 2 O 4 nanosheets 22.
该电极100可应用于电化学储能装置。所述电化学储能装置可以为但不限于超级电容器或二次电池。The electrode 100 can be applied to an electrochemical energy storage device. The electrochemical energy storage device can be, but is not limited to, a supercapacitor or a secondary battery.
所述集电体10用于承载作为电极活性材料的NiCo2O4。该集电体10可以为致密连续的结构也可以多孔结构。优选地，所述集电体10为多孔的层状或片状结构。更为优选地，所述集电体10为具有一定厚度的三维（3D）网状结构。所述孔优选为微孔。采用所述3D网状结构的集电体10可大大地提高电解液渗透，以促进离子扩散。该集电体10的材料可以为金属也可以为非金属，只要能导电且可承载所述电极活性材料即可。所述金属可以为但不限于铝、镍以及铜中的至少一种，对应地，所述集电体10可以为金属片或金属网。所述非金属可以为碳材料，例如但不限于碳纳米管或石墨烯，相应地，所述集电体10可以为多孔或无孔的碳纳米管膜以及石墨烯膜至少一种。本发明实施例中选用镍网作为所述集电体10。The current collector 10 is used to carry NiCo 2 O 4 as an electrode active material. The current collector 10 may have a dense continuous structure or a porous structure. Preferably, the current collector 10 is a porous layered or sheet-like structure. More preferably, the current collector 10 is a three-dimensional (3D) mesh structure having a certain thickness. The pores are preferably micropores. The current collector 10 using the 3D network structure can greatly enhance electrolyte permeation to promote ion diffusion. The material of the current collector 10 may be a metal or a non-metal as long as it can conduct electricity and can carry the electrode active material. The metal may be, but not limited to, at least one of aluminum, nickel, and copper. Correspondingly, the current collector 10 may be a metal piece or a metal mesh. The non-metal may be a carbon material such as, but not limited to, carbon nanotubes or graphene. Accordingly, the current collector 10 may be at least one of a porous or non-porous carbon nanotube film and a graphene film. In the embodiment of the invention, a nickel mesh is selected as the current collector 10.
所述NiCo2O4纳米片阵列20包括多个竖直设置在所述集电体10表面的NiCo2O4纳米片22。所述竖直是指所述NiCo2O4纳米片22在长度和宽度方向形成的二维平面与所述集电体10在长度和宽度方向成成的二维平面之间形成一角度α，其中，30o≤α≤90o。优选地，所述NiCo2O4纳米片22垂直于所述集电体10。该多个NiCo2O4纳米片22之间相互交叉，从成形成一三维多孔网络结构，该多个相互交叉的NiCo2O4纳米片22与所述集电体10组合形成多个通透的通道，利于电解质溶液的渗透。该多个NiCo2O4纳米片22通过分子间作用力紧密固定在所述集电体10的表面。该多个NiCo2O4纳米片22具有均一的厚度。优选地，每个所述NiCo2O4纳米片22的厚度可以为10纳米至20纳米。该NiCo2O4纳米片22在垂直厚度的表面尺寸长度为微米级。该纳米片242具有优良的柔韧性以及机械稳定性。The NiCo 2 O 4 nanosheet array 20 includes a plurality of NiCo 2 O 4 nanosheets 22 disposed vertically on the surface of the current collector 10. The vertical means that the two-dimensional plane formed by the NiCo 2 O 4 nanosheet 22 in the length and width directions forms an angle α with the two-dimensional plane of the current collector 10 formed in the length and width directions, Among them, 30 o ≤ α ≤ 90 o . Preferably, the NiCo 2 O 4 nanosheet 22 is perpendicular to the current collector 10. The plurality of NiCo 2 O 4 nanosheets 22 intersect each other to form a three-dimensional porous network structure, and the plurality of mutually intersecting NiCo 2 O 4 nanosheets 22 are combined with the current collector 10 to form a plurality of transparent layers. The channel facilitates the penetration of the electrolyte solution. The plurality of NiCo 2 O 4 nanosheets 22 are tightly fixed to the surface of the current collector 10 by intermolecular forces. The plurality of NiCo 2 O 4 nanosheets 22 have a uniform thickness. Preferably, each of the NiCo 2 O 4 nanosheets 22 may have a thickness of 10 nm to 20 nm. The surface size of the NiCo 2 O 4 nanosheet 22 at a vertical thickness is on the order of micrometers. The nanosheet 242 has excellent flexibility and mechanical stability.
该NiCo2O4纳米片阵列20或者NiCo2O4纳米片22的材料为NiCo2O4。The material of the NiCo 2 O 4 nanosheet array 20 or the NiCo 2 O 4 nanosheet 22 is NiCo 2 O 4 .
请参阅图2，本发明实施例进一步提供一种应用于电化学储能装置的电极100的制备方法，包括以下步骤：Referring to FIG. 2, an embodiment of the present invention further provides a method for preparing an electrode 100 applied to an electrochemical energy storage device, including the following steps:
S1，提供镍盐、钴盐、沉淀剂以及氟化铵；S1, providing a nickel salt, a cobalt salt, a precipitating agent, and ammonium fluoride;
S2，将所述镍盐、钴盐、沉淀剂以及氟化铵在水中均匀混合形成一混合液；S2, uniformly mixing the nickel salt, the cobalt salt, the precipitating agent and the ammonium fluoride in water to form a mixed liquid;
S3，将所述集电体10放置在所述混合液中，并使该放置有集电体10的混合液进行水热反应得到一电极前驱体；以及S3, placing the current collector 10 in the mixed liquid, and subjecting the mixed liquid in which the current collector 10 is placed to hydrothermal reaction to obtain an electrode precursor;
S4，煅烧该电极前驱体获得所述电极100。S4, calcining the electrode precursor to obtain the electrode 100.
在上述步骤S1中，所述镍盐、钴盐优选地选取可溶于水的盐类物质，可以为但不限于硝酸盐、硫酸盐以及醋酸盐中的至少一种。所述镍盐与钴盐的摩尔比优选为Ni:Co=1:2。In the above step S1, the nickel salt and the cobalt salt are preferably selected from water-soluble salts, and may be, but not limited to, at least one of a nitrate, a sulfate, and an acetate. The molar ratio of the nickel salt to the cobalt salt is preferably Ni:Co=1:2.
所述沉淀剂用于在所述水热反应中与所述镍盐以及钴盐反应来获得NiCo2O4。优选地，该沉淀剂可溶于水中。更为优选地，该沉淀剂呈弱碱性。本发明实施例中选取尿素作为所述沉淀剂。所述沉淀剂的含量可根据所述镍盐、钴盐的量来选择，只要可使所述沉淀剂与镍盐、钴盐反应完全即可。优选地，所述沉淀剂与所述镍盐、钴盐的摩尔比为：沉淀剂：Ni：Co=（1~8）:1:2。The precipitating agent is used to react with the nickel salt and the cobalt salt in the hydrothermal reaction to obtain NiCo 2 O 4 . Preferably, the precipitating agent is soluble in water. More preferably, the precipitating agent is weakly basic. In the embodiment of the invention, urea is selected as the precipitant. The content of the precipitating agent can be selected according to the amount of the nickel salt or the cobalt salt, as long as the precipitating agent can be completely reacted with the nickel salt or the cobalt salt. Preferably, the molar ratio of the precipitating agent to the nickel salt and the cobalt salt is: precipitant: Ni:Co=(1~8): 1:2.
所述氟化铵可促进后续形成纳米片状的NiCo2O4纳米片阵列20，同时可促进形成NiCo2O4纳米片阵列20为一整体地、自支撑的三维多孔网络结构。所述氟化铵的摩尔含量大于等于所述镍盐和钴盐中镍和钴总的摩尔含量，该范围内更利于促成形貌可控均一的所述NiCo2O4纳米片阵列20。优选地，所述氟化铵的摩尔含量等于所述所述镍盐和钴盐总的摩尔含量。The ammonium fluoride can promote the subsequent formation of the nanosheet-shaped NiCo 2 O 4 nanosheet array 20 while promoting the formation of the NiCo 2 O 4 nanosheet array 20 as a monolithic, self-supporting three-dimensional porous network structure. The molar content of the ammonium fluoride is greater than or equal to the total molar content of nickel and cobalt in the nickel salt and the cobalt salt, and the range is more favorable for promoting the uniformity of the NiCo 2 O 4 nanosheet array 20 which is uniform in morphology. Preferably, the molar content of the ammonium fluoride is equal to the total molar content of the nickel salt and the cobalt salt.
在上述步骤S2中，在将所述镍盐、钴盐、沉淀剂以及氟化铵加入到水中的过程中可持续充分搅拌使所述镍盐、钴盐、沉淀剂以及氟化铵均匀混合。In the above step S2, the nickel salt, the cobalt salt, the precipitating agent, and the ammonium fluoride are uniformly mixed while continuously stirring the nickel salt, the cobalt salt, the precipitating agent, and the ammonium fluoride in water.
进一步地，所述制备方法包括在形成所述混合液后，超声振荡所述混合液，以获得一均一、透明的混合溶液。Further, the preparation method includes ultrasonically shaking the mixed solution after the formation of the mixed solution to obtain a uniform, transparent mixed solution.
进一步优选地，上述步骤S2包括：Further preferably, the above step S2 includes:
S21，将所述镍盐以及钴盐在水混合形成一第一溶液；以及S21, mixing the nickel salt and the cobalt salt in water to form a first solution;
S22，将所述沉淀剂以及氟化铵加入到所述第一溶液中均匀混合形成所述混合液。S22, adding the precipitating agent and ammonium fluoride to the first solution to uniformly mix to form the mixed liquid.
在上述步骤S22中，优选地，先将所述沉淀剂加入到所述第一溶液中，然后再加入所述氟化铵形成所述混合液，通过该种加入顺序，后续形成的纳米片阵列形貌更均一可控。In the above step S22, preferably, the precipitating agent is first added to the first solution, and then the ammonium fluoride is further added to form the mixed solution, and the subsequently formed nanosheet array is formed by the order of the addition. The shape is more uniform and controllable.
在所述步骤S3中，所述水热反应可在一密闭反应釜中进行，所述水热反应的温度为80℃至160℃。优选地，所述水热反应的温度为80℃至120℃。所述水热反应的时间只要保证反应完全即可，优选地，可为3小时至18小时。In the step S3, the hydrothermal reaction may be carried out in a closed reactor having a temperature of from 80 ° C to 160 ° C. Preferably, the hydrothermal reaction has a temperature of from 80 °C to 120 °C. The time of the hydrothermal reaction may be as long as the reaction is completed, and preferably, it may be from 3 hours to 18 hours.
在反应完毕后，可进一步冷却所述反应釜获得所述电极前驱体，并进一步采用水和有机溶剂洗涤该电极前驱体以去除不需要的杂质。After the reaction is completed, the reactor may be further cooled to obtain the electrode precursor, and the electrode precursor is further washed with water and an organic solvent to remove unnecessary impurities.
上述步骤S3中，在所述水热反应后，在所述集电体10的表面形成粉紫色的钴镍前驱体材料，该钴镍前驱体材料呈纳米片状阵列。In the above step S3, after the hydrothermal reaction, a pink-purple cobalt-nickel precursor material is formed on the surface of the current collector 10, and the cobalt-nickel precursor material has a nano-sheet array.
在上述步骤S4中，可将所述电极前驱体放置在马弗炉中进行煅烧。所述煅烧的环境为有氧环境。所述煅烧的温度可以为250℃至350℃。所述煅烧的方式可以为逐步升温到预定温度，然后保温加热一定时间。所述升温的速率优选为1℃/分钟至5℃/分钟。所述煅烧的时间可以为2小时至5小时。煅烧的过程中，所述粉紫色的钴镍前驱体逐步变成黑色产物，该黑色产物即为所述电极活性材料NiCo2O4。在上述方法中，可进一步将煅烧后的产物冷却至室温，得到所述电极100。In the above step S4, the electrode precursor may be placed in a muffle furnace for calcination. The calcined environment is an aerobic environment. The calcination temperature may be from 250 ° C to 350 ° C. The calcination may be carried out by gradually increasing the temperature to a predetermined temperature and then heating and heating for a certain period of time. The rate of temperature rise is preferably from 1 ° C / min to 5 ° C / min. The calcination time may be from 2 hours to 5 hours. During the calcination, the pink-purple cobalt-nickel precursor gradually turns into a black product, which is the electrode active material NiCo 2 O 4 . In the above method, the calcined product may be further cooled to room temperature to obtain the electrode 100.
实施例1Example 1
NiCo2O4电极的制备Preparation of NiCo 2 O 4 electrode
（1）集电体选取泡沫镍，将泡沫镍在盐酸溶液中超声清洗20分钟，去除泡沫镍表面氧化物。(1) The collector is made of foamed nickel, and the foamed nickel is ultrasonically cleaned in a hydrochloric acid solution for 20 minutes to remove the surface oxide of the foamed nickel.
（2）将Ni(NO3)2·6H2O、Co(NO3)2·6H2O按摩尔比1:2溶解在去离子水中，然后加入0.015mol的尿素和0.006mol的氟化铵，搅拌30分钟，放入处理过的泡沫镍，在80℃-160℃进行水热反应3小时-18小时，冷却至室温，取出，用去离子水超声去除泡沫镍上负载的松散的产物，直至超声液为无色，然后用乙醇超声，在60℃真空干燥箱中干燥12小时，干燥完成后，明显发现在泡沫镍上负载有粉紫色钴镍前驱体。(2) Dissolving Ni(NO 3 ) 2 ·6H 2 O, Co(NO 3 ) 2 ·6H 2 O in a molar ratio of 1:2 in deionized water, then adding 0.015 mol of urea and 0.006 mol of ammonium fluoride. Stir for 30 minutes, put the treated nickel foam, carry out hydrothermal reaction at 80 ° C - 160 ° C for 3 hours - 18 hours, cool to room temperature, take out, ultrasonically remove the loose product supported on the foamed nickel with deionized water. Until the ultrasonic liquid was colorless, it was then dried with ethanol and dried in a vacuum oven at 60 ° C for 12 hours. After the drying was completed, it was apparent that the powdery nickel cobalt nickel precursor was supported on the foamed nickel.
（3）将负载有钴镍前驱体的泡沫镍放置马弗炉中，在250℃-350℃，以1℃/分钟，煅烧2小时，冷却至室温，发现粉紫色钴镍前驱体变成黑色产物，即获得负载在泡沫镍上的NiCo2O4纳米片阵列。(3) The foamed nickel loaded with the cobalt-nickel precursor was placed in a muffle furnace, calcined at 250 ° C - 350 ° C at 1 ° C / min for 2 hours, cooled to room temperature, and the pink-purple cobalt nickel precursor was found to be black. The product, i.e., an array of NiCo 2 O 4 nanosheets supported on nickel foam.
请参阅图3，对所述泡沫镍上的黑色产物进行XRD分析可知，该黑色产物为NiCo2O4材料。请参阅图4，从图中可以看出，NiCo2O4以纳米片状形态相互交叉形成多孔网络状结构。本发明实施例进一步将NiCo2O4电极应用到超级电容器中来测试其电化学性能。请参阅图5，经测试可知，该NiCo2O4纳米片阵列具有很好的电化学可逆性。请进一步参阅图6，经测试可知，该NiCo2O4纳米片阵列在充放电电流密度是2A/g时，该材料的比电容值可达800F/g左右。Referring to FIG. 3, XRD analysis of the black product on the foamed nickel shows that the black product is a NiCo 2 O 4 material. Referring to FIG. 4, it can be seen from the figure that NiCo 2 O 4 crosses each other in a nano-sheet form to form a porous network structure. The embodiment of the present invention further applies a NiCo 2 O 4 electrode to a supercapacitor to test its electrochemical performance. Referring to FIG. 5, the NiCo 2 O 4 nanosheet array has good electrochemical reversibility after testing. Please refer to FIG. 6 again. It can be seen that the NiCo 2 O 4 nanosheet array has a specific capacitance value of about 800 F/g when the charge and discharge current density is 2 A/g.
本发明实施例通过在镍盐、钴盐水热反应的过程加入氟化铵可在集电体表面直接形成三维多孔网络结构状的NiCo2O4纳米片阵列来形成所述电极。该种结构可以大大缩小离子透过和传输的距离，从而可增强电极活性材料的利用率，应用该电极100的电化学储能装置具有高的功率、能量密度（容量）、化学循环稳定性以及容量保持率。此外，该电极100的制备方法简单，成本较低，易于重复实现，从而利于产业化生产。In the embodiment of the present invention, the electrode is formed by directly adding a three-dimensional porous network structure NiCo 2 O 4 nanosheet array on the surface of the current collector by adding ammonium fluoride during the thermal reaction of the nickel salt and the cobalt salt water. The structure can greatly reduce the distance of ion transmission and transmission, thereby enhancing the utilization rate of the electrode active material, and the electrochemical energy storage device using the electrode 100 has high power, energy density (capacity), chemical cycle stability, and Capacity retention rate. In addition, the electrode 100 is simple in preparation method, low in cost, and easy to be repeatedly implemented, thereby facilitating industrial production.
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。In addition, those skilled in the art can make other changes in the spirit of the present invention. Of course, the changes made in accordance with the spirit of the present invention should be included in the scope of the present invention.

Claims (11)

  1. 一种应用于电化学储能装置的电极，其特征在于，包括集电体以及设置在集电体上的钴酸镍纳米片阵列，所述钴酸镍纳米片阵列包括多个钴酸镍纳米片。 An electrode applied to an electrochemical energy storage device, comprising: a current collector and an array of nickel cobaltate nanosheets disposed on the current collector, the nickel cobalt nanocrystal array comprising a plurality of nickel cobaltate nanometers sheet.
  2. 如权利要求1所述的应用于电化学储能装置的电极，其特征在于，所述多个纳米片垂直设置在所述集电体表面。 The electrode for use in an electrochemical energy storage device according to claim 1, wherein the plurality of nanosheets are vertically disposed on a surface of the current collector.
  3. 如权利要求1所述的应用于电化学储能装置的电极，其特征在于，所述多个纳米片相互交叉形成一三维多孔网络结构。 The electrode for use in an electrochemical energy storage device according to claim 1, wherein said plurality of nanosheets cross each other to form a three-dimensional porous network structure.
  4. 如权利要求1所述的应用于电化学储能装置的电极，其特征在于，所述电极仅由所述集电体以及所述钴酸镍纳米片阵列组成。 The electrode for use in an electrochemical energy storage device according to claim 1, wherein said electrode is composed only of said current collector and said nickel cobalt oxide nanosheet array.
  5. 一种应用于电化学储能装置的电极的制备方法，包括以下步骤： A method for preparing an electrode applied to an electrochemical energy storage device includes the following steps:
    提供镍盐、钴盐、沉淀剂以及氟化铵；Providing a nickel salt, a cobalt salt, a precipitating agent, and ammonium fluoride;
    将所述镍盐、钴盐、沉淀剂以及氟化铵在水中均匀混合形成一混合液；The nickel salt, the cobalt salt, the precipitating agent and the ammonium fluoride are uniformly mixed in water to form a mixed liquid;
    将一集电体放置在所述混合液中，并进行水热反应获得一电极前驱体；以及Depositing a current collector in the mixed solution and performing a hydrothermal reaction to obtain an electrode precursor;
    煅烧该电极前驱体获得所述电极。The electrode precursor is calcined to obtain the electrode.
  6. 如权利要求5所述的应用于电化学储能装置的电极的制备方法，其特征在于，所述沉淀剂为尿素。 A method of preparing an electrode for use in an electrochemical energy storage device according to claim 5, wherein the precipitating agent is urea.
  7. 如权利要求5所述的应用于电化学储能装置的电极的制备方法，其特征在于，所述氟化铵的的摩尔含量大于等于所述钴盐和镍盐中钴和镍总的摩尔含量。 The method for preparing an electrode for an electrochemical energy storage device according to claim 5, wherein the molar content of the ammonium fluoride is greater than or equal to the total molar content of cobalt and nickel in the cobalt salt and the nickel salt. .
  8. 如权利要求5所述的应用于电化学储能装置的电极的制备方法，其特征在于，所述混合液形成的过程具体包括以下步骤： The method for preparing an electrode for an electrochemical energy storage device according to claim 5, wherein the process of forming the mixed liquid specifically comprises the following steps:
    将所述镍盐以及钴盐在水混合形成一第一溶液；以及Mixing the nickel salt and the cobalt salt in water to form a first solution;
    将所述沉淀剂以及氟化铵加入到所述第一溶液中均匀混合形成所述混合液。The precipitating agent and ammonium fluoride are added to the first solution to be uniformly mixed to form the mixed solution.
  9. 如权利要求8所述的应用于电化学储能装置的电极的制备方法，其特征在于，先将所述沉淀剂加入到所述第一溶液中，然后再加入所述氟化铵形成所述混合液。 A method of preparing an electrode for use in an electrochemical energy storage device according to claim 8, wherein said precipitating agent is first added to said first solution, and then said ammonium fluoride is further added to form said Mixture.
  10. 如权利要求5所述的应用于电化学储能装置的电极的制备方法，其特征在于，所述煅烧的温度为250℃至350℃。 A method of producing an electrode for use in an electrochemical energy storage device according to claim 5, wherein the calcination temperature is from 250 ° C to 350 ° C.
  11. 如权利要求5所述的应用于电化学储能装置的电极的制备方法，其特征在于，所述镍盐、钴盐以及沉淀剂的摩尔比为1：2：1~8。 The method for preparing an electrode for use in an electrochemical energy storage device according to claim 5, wherein the molar ratio of the nickel salt, the cobalt salt and the precipitant is 1:2:1-8.
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CN114705737A (en) * 2021-11-29 2022-07-05 苏州科技大学 Carbon cloth surface modified metal organic framework derived nickel cobaltate nanosheet array composite material and preparation and application thereof
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