CN112071662A - Preparation of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor positive electrode material - Google Patents

Preparation of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor positive electrode material Download PDF

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Publication number
CN112071662A
CN112071662A CN202010870304.9A CN202010870304A CN112071662A CN 112071662 A CN112071662 A CN 112071662A CN 202010870304 A CN202010870304 A CN 202010870304A CN 112071662 A CN112071662 A CN 112071662A
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cobalt
nickel
oxygen
phosphorus
tube furnace
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Inventor
马丽颖
刘佳楠
赵乃勤
师春生
何春年
何芳
刘恩佐
沙军威
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Tianjin University
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Tianjin University
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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
    • H01G11/84—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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01G11/24—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 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
    • H01G11/30—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

Abstract

The invention relates to a preparation method of oxygen-doped nickel-cobalt-phosphorus nanoneedle for a super capacitor anode material, which comprises the following steps: 1) preparing a nickel-cobalt double metal hydroxide (NiCo-OH) precursor: dissolving nickel nitrate, cobalt nitrate and urea in water to prepare a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, putting a carbon cloth into the reaction kettle, preserving the heat at the temperature of 110-130 ℃ for a period of time, cleaning the carbon cloth after the reaction kettle is cooled, drying, and collecting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor for later use. 2) Preparing oxygen-doped nickel-cobalt-phosphorus (O-NiCoP) nanoneedles: will be provided withPutting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor into a tube furnace, and adding NaH2PO2·H2And O is placed at the upstream end of the tube furnace, the tube furnace is heated to 280-320 ℃ under the protection of inert atmosphere, the temperature is kept for a period of time, and the tube furnace is taken out after being cooled to the room temperature.

Description

Preparation of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor positive electrode material
Technical Field
The invention belongs to the technical field of preparation of a super capacitor anode material, and particularly relates to a preparation method for growing oxygen-doped nickel-cobalt-phosphorus nanoneedles on carbon cloth and application of the oxygen-doped nickel-cobalt-phosphorus nanoneedles in a super capacitor.
Background
Rapid development of sustainable economy and consumption of conventional fossil fuels make energy exhaustion and environmental pollution problems more and more serious, and thus, development of renewable energy sources such as solar energy, wind energy, tidal energy, etc. is urgently required. The intermittent nature of renewable energy sources has created a greater demand for advanced energy storage systems with high power and high energy density. The super capacitor benefits from the conversion from the traditional electrode to the nanometer electrode, the performance of the super capacitor is greatly improved, and the super capacitor has the characteristics of high power density, high safety performance, low cost, quick charge and discharge, long cycle life and the like, and has attracted extensive attention in recent years. However, since supercapacitors have a lower energy density than lithium ion batteries, research on supercapacitors has focused on increasing their energy density. The electrode material is used as a main component of a super capacitor, plays an important role in improving energy density, and is particularly a battery type material represented by a transition metal compound.
The cell type material mainly includes transition metal oxides, hydroxides, sulfides, selenides, phosphides, and the like. Among these materials, transition metal oxides and hydroxides have high internal resistance due to slow ion adsorption and desorption rates and electron transfer rates, and thus have low practical capacity and rate capability. Transition metal sulfides, selenides and phosphides have smaller band gaps than oxides and hydroxides and have higher conductivity, and particularly, Transition Metal Phosphides (TMPs) have multi-electron-orbit characteristics, show metalloid behaviors and ultrahigh conductivity, have excellent redox activity, are rich in resources, are environment-friendly and the like. In recent years, transition metal phosphides have been widely used in the field of electrocatalysis, however, their use in supercapacitors has been very limited due to their poor cycling stability during long-term charging and discharging.
Among the common phosphides, nickel-based and cobalt-based phosphides are the most potential electrode material candidates due to their n-type semiconductor properties, high theoretical energy storage capacity and redox activity. A large number of researches show that the nickel-cobalt double-metal phosphide has higher charge storage capacity and cycle performance than single-metal phosphide, and the double-metal phosphide combines the characteristics of high theoretical capacity of a nickel-based material and high cycle stability and rate capability of a cobalt-based material, thereby showing excellent energy storage property. However, limited reactivity and conductivity of phosphide still cannot meet the requirements of high-performance devices, and therefore, researchers have proposed various modification methods, in which heterogeneous element doping is one of the most effective methods for improving the performance of phosphide, foreign atoms with different atomic radii and electronegativity are introduced into the crystal lattice of phosphide to induce fine lattice distortion, resulting in redistribution of electron density, thereby adjusting the electronic structure of phosphide and improving its intrinsic activity. The TMPs can be doped with metal atoms such as Mn, Zn and the like, and can also be doped with nonmetal atoms such as S, O and the like, and theoretical and experimental calculations show that the introduction of oxygen can adjust the electronic structure of the material and increase the conductivity of the material, but the research on the application of the oxygen-doped transition metal phosphide in the field of supercapacitors is very few.
Disclosure of Invention
The invention provides a preparation method of oxygen-doped nickel-cobalt-phosphorus nanoneedles for improving the capacity of a super capacitor anode material, the method grows the oxygen-doped nickel-cobalt-phosphorus nanoneedles on carbon cloth, combines the advantages of a hydrothermal method and a Chemical Vapor Deposition (CVD) method, and has the characteristics of simple and convenient operation, low cost and the like. In addition, by regulating and controlling the CVD reaction time, the uniform and controllable oxygen-doped nickel-cobalt-phosphorus nanoneedle active material can be obtained. The invention is realized by the following technical scheme:
a preparation method of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor anode material comprises the following steps:
1) preparation of Nickel cobalt double hydroxide (NiCo-OH) precursor
Dissolving nickel nitrate, cobalt nitrate and urea in water to prepare a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, putting a carbon cloth into the reaction kettle, preserving the heat at the temperature of 110-130 ℃ for a period of time, cleaning the carbon cloth after the reaction kettle is cooled, drying, and collecting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor for later use.
2) Preparation of oxygen-doped nickel-cobalt-phosphorus (O-NiCoP) nanoneedle
Putting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor into a tube furnace, and adding NaH2PO2·H2And O is placed at the upstream end of the tube furnace, the tube furnace is heated to 280-320 ℃ under the protection of inert atmosphere, the temperature is kept for a period of time, and the tube furnace is taken out after being cooled to the room temperature.
Preferably, the nickel nitrate, the cobalt nitrate and the urea are prepared into a mixed solution in a mass ratio of 1 (1.8-2.2) to (5-7).
According to the invention, the oxygen-doped nickel-cobalt-phosphorus active material is synthesized in situ on the carbon cloth by using a hydrothermal method and a subsequent CVD method, the operation method is simple and efficient, and the appearance of the sample is controllable. The energy storage property of the NiCoP nano needle in the alkaline electrolyte is improved by using an O doping strategy. The excellent conductivity of the transition metal phosphide reduces the impedance of the electrode material and improves the rate capability of the electrode material; the nano needle structure promotes the penetration of electrolyte and shortens the ion diffusion distance; the synergistic effect of Co and Ni provides more redox reaction, and the energy storage property of the electrode material is improved. The invention provides a high-efficiency anode material for the super capacitor.
Drawings
Fig. 1 is an SEM image of a nickel cobalt double hydroxide precursor prepared according to the present invention. It can be seen from the figure that the precursor exhibited the morphology of nanoneedles.
Fig. 2 is an SEM image of oxygen-doped nickel cobalt phosphorus prepared by the present invention. From the figure, it can be observed that the phosphorized sample well retains the nanoneedle morphology of the precursor.
Fig. 3 is an XRD spectrum of the nickel-cobalt double metal hydroxide precursor prepared by the present invention. Except diffraction peaks of the carbon cloth substrate, other diffraction peaks correspond to PDF card 48-0083, which indicates that the nickel-cobalt hydroxide is successfully prepared.
Fig. 4 is an XRD pattern of oxygen-doped nickel cobalt phosphorus prepared by the invention. Except diffraction peaks of the carbon cloth substrate, other diffraction peaks of the map correspond to PDF card 71-2336, and the successful preparation of nickel, cobalt and phosphorus is shown.
Fig. 5 is an XPS spectrum of an oxygen-doped nickel-cobalt-phosphorus O1s orbital prepared by the present invention. The presence of oxygen-metal bonds further demonstrates successful doping of oxygen.
FIG. 6 is a chart of a charge-discharge curve of oxygen-doped nickel cobalt phosphorus prepared by the present invention. The map shows that the prepared material has high specific capacity, high coulombic efficiency and good rate capability.
Nothing in this specification is said to apply to the prior art.
Specific examples of the production method of the present invention are given below. The examples are intended only to further illustrate the preparation process of the present invention and do not limit the scope of the claims of the present application.
Example 1
0.582g of nickel nitrate hexahydrate, 1.164g of cobalt nitrate hexahydrate and 0.72g of urea were weighed respectively, dissolved in 40mL of deionized water, and sufficiently stirred to obtain a uniform solution. The solution was poured into a 50mL stainless steel autoclave, and then a carbon cloth (1X 2 cm) washed with acetone, concentrated nitric acid, deionized water and ethanol in this order was placed2) Vertically placing the mixture into a high-pressure reaction kettle for sealed storage, and preserving the heat for 8 hours at the temperature of 120 ℃. And after the high-pressure reaction kettle is cooled to room temperature, taking out the carbon cloth, washing the carbon cloth by deionized water and alcohol, and drying the carbon cloth for 12 hours at the temperature of 60 ℃ to finally obtain the nickel-cobalt hydroxide precursor. Followed byAnd then, under the protection of argon atmosphere, placing the nickel-cobalt hydroxide precursor in the center of the tube furnace, placing sodium hypophosphite in the upstream section of the tube furnace, heating the tube furnace to 300 ℃ at the heating rate of 2 ℃/min, and preserving heat for 30 min. When the temperature of the tube furnace rises to a certain temperature, the sodium hypophosphite is decomposed to release PH3And reacting the gas with the hydroxide precursor to finally obtain the oxygen-doped nickel-cobalt-phosphorus active material grown in situ on the carbon cloth. And taking out the sample after the tube furnace is cooled to the room temperature. Meanwhile, the oxygen content in the sample was calculated to be 5.10% based on the ratio of the metal-oxygen bond in the XPS spectrum of the O1s orbital.
Example 2
Considering the effect of oxygen doping amount on the energy storage property of nickel cobalt phosphide, with reference to example 1, nickel cobalt phosphide with higher oxygen doping amount and lower oxygen doping amount was prepared. The preparation of the nickel cobalt double metal hydroxide precursor was the same as in example 1, and the degree of phosphating of the sample was reduced by reducing the phosphating time during the subsequent phosphating treatment, thereby obtaining a higher oxygen doping amount of nickel cobalt phosphorus. The phosphating time in this example was 10min and the other operations were the same as in example 1. Finally, the amount of oxygen doped was calculated to be 9.01%.
Example 3
The procedure for preparing the nickel cobalt double metal hydroxide precursor was the same as in example 1, and then during the CVD phosphating treatment, the degree of phosphating was increased by increasing the phosphating time, thereby reducing the amount of oxygen doped in nickel cobalt phosphorus. The phosphating time in this example was 60min and the other steps were the same as in example 1. Finally, the amount of oxygen doped was calculated to be 2.73% from the XPS spectrum of the O1s orbital.

Claims (2)

1. A preparation method of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor anode material comprises the following steps:
1) preparation of Nickel cobalt double hydroxide (NiCo-OH) precursor
Dissolving nickel nitrate, cobalt nitrate and urea in water to prepare a mixed solution, pouring the mixed solution into a high-pressure reaction kettle, putting a carbon cloth into the reaction kettle, preserving the heat at the temperature of 110-130 ℃ for a period of time, cleaning the carbon cloth after the reaction kettle is cooled, drying, and collecting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor for later use.
2) Preparation of oxygen-doped nickel-cobalt-phosphorus (O-NiCoP) nanoneedle
Putting a nickel-cobalt double metal hydroxide (NiCo-OH) precursor into a tube furnace, and adding NaH2PO2·H2And O is placed at the upstream end of the tube furnace, the tube furnace is heated to 280-320 ℃ under the protection of inert atmosphere, the temperature is kept for a period of time, and the tube furnace is taken out after being cooled to the room temperature.
2. The production method according to claim 1, wherein the nickel nitrate, the cobalt nitrate and the urea are prepared as a mixed solution in a mass ratio of 1 (1.8-2.2) to (5-7).
CN202010870304.9A 2020-08-26 2020-08-26 Preparation of oxygen-doped nickel-cobalt-phosphorus nanoneedle for super capacitor positive electrode material Pending CN112071662A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115246659A (en) * 2021-10-18 2022-10-28 齐齐哈尔大学 Preparation method of defective hollow nickel cobaltate nanocube

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN109585177A (en) * 2018-11-28 2019-04-05 浙江大学 A kind of preparation method of the nickel cobalt phosphorus integral electrodes material of core-shell structure
CN110323073A (en) * 2019-06-28 2019-10-11 中国地质大学（北京） A kind of oxygen doping phosphatization cobalt nickel-redox graphene composite material and its application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109585177A (en) * 2018-11-28 2019-04-05 浙江大学 A kind of preparation method of the nickel cobalt phosphorus integral electrodes material of core-shell structure
CN110323073A (en) * 2019-06-28 2019-10-11 中国地质大学（北京） A kind of oxygen doping phosphatization cobalt nickel-redox graphene composite material and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUBO SHAO等: "Three-Dimensional Hierarchical NixCo1−xO/NiyCo2−yP@C Hybrids on Nickel Foam for Excellent Supercapacitors", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115246659A (en) * 2021-10-18 2022-10-28 齐齐哈尔大学 Preparation method of defective hollow nickel cobaltate nanocube
CN115246659B (en) * 2021-10-18 2024-05-03 齐齐哈尔大学 Preparation method of defect type hollow nickel cobalt oxide nanocube

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Application publication date: 20201211