CN110364372A - A kind of supercapacitor vanadic acid nickel material, preparation method and application - Google Patents

A kind of supercapacitor vanadic acid nickel material, preparation method and application Download PDF

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CN110364372A
CN110364372A CN201910710672.4A CN201910710672A CN110364372A CN 110364372 A CN110364372 A CN 110364372A CN 201910710672 A CN201910710672 A CN 201910710672A CN 110364372 A CN110364372 A CN 110364372A
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vanadic acid
acid nickel
supercapacitor
nickel material
preparation
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CN110364372B (en
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高云芳
张晏
徐新
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Zhejiang University of Technology ZJUT
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    • C01G31/00Compounds of vanadium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract

The present invention discloses a kind of preparation method of supercapacitor vanadic acid nickel material, step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, obtains reaction mixture;Step 3: reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, is obtained product vanadic acid nickel material.Using one step hydro thermal method, using a variety of alkaline reagents as structure directing agent, and vanadic acid nickel material is obtained by adjusting pH, it is easy to operate and safe, at low cost, product purity is high.A kind of flower-shaped vanadic acid nickel material is also disclosed, and in the flower-like structure that lamella is accumulated, specific surface area is larger, there is good electric conductivity and Surface Permeability, and reactivity site is more.A kind of flower-shaped vanadic acid nickel material is also disclosed as electrode material for super capacitor application, shows high specific capacitance, good capacity retention and high rate performance, electrochemical impedance are low.

Description

A kind of supercapacitor vanadic acid nickel material, preparation method and application
Technical field
The present invention relates to bimetallic oxide electrode material technical fields, and in particular to a kind of supercapacitor vanadic acid nickel Material, preparation method and application.
Background technique
In recent years, there is an urgent need to develop the environmental-friendly energy and energy storage to fill for ever-increasing energy demand and environmental problem It sets.Supercapacitor is as model electrochemical energy storage device, with its superior power density, quick charging and discharging capabilities and excellent The chemical property outstanding such as cyclical stability cause the extensive concern of people.According to energy storage mechnism difference, super capacitor Device is generally divided into two classes, i.e. double layer capacitor (EDLC) and fake capacitance capacitor.The material of EDLC is mostly carbon material, such as activity Charcoal, carbon nanotube, graphene etc. carry out energy storage by forming electric double layer in electrode and solution interface.And fake capacitance capacitor The working principle of device is electric energy to be converted into chemical energy storage, and general fake capacitance material has metal oxide and conducting polymer. Hinder supercapacitor in the widely applied significant challenge of energy storage field first is that its limited energy density.In order to overcome this Obstacle explores height ratio capacity, the new electrode materials of broad potential window are one of hot spots of supercapacitor research.
Transiton metal binary oxides (BTMO) are used as a kind of battery material, due to the multiple oxidation state of its crystal structure With unique electrochemical energy storage mechanism, the extensive concern for causing research field is nearest.It is single by introducing different metal element The mixed-metal oxides formed in one metal oxide, can synergistically improve the reversible capacity of single metal oxides, electricity Chemical stability and high rate performance.Barium oxide is as a kind of important mixed-metal oxides, since composite structure is special The difficulty of barium oxide, is almost forgotten by people.Vanadic acid nickel has significant chemical property, the structures such as nanometer sheet and nanotube Being produced and being verified can be used as high performance lithium ion battery negative material use.
Vaiyapuri Soundharrajan et al. is simple in one kind that Ceramics International is reported Metal organic framework-burning (MOF-C) technology one pot process Ni3V2O8(NVO).Its pattern is irregular rodlike, porous The particle of balsam pear and micro-/ nano hydridization.Using the material as lithium ion battery (LIBS) electrode material, surveyed in cathode of lithium battery In examination, the discharge capacity for the first time of electrode is 1362 mA h g-1, reversible capacity is 822 mA h g-1.In 2000 mA g-1Under, After 5000 circulations, it is still able to maintain 724 mA h g-1Reversible capacity.
Ding Shujiang research team reports in J. Mater. Chem. A using simple hydrothermal method and roasting technique, It is successfully prepared for ordered mesopore carbon (CMK-3) load Ni for the first time3V2O8Novel orderly hybrid nanostructure (Ni3V2O8@CMK- 3).Have benefited from its firm porous structure and excellent conductive characteristic, the stratiform hydridization Ni of preparation3V2O8@CMK-3 composite material Cyclical stability with higher is 500 mA g in current density-1After lower circulation 200 times, reversible capacity is up to 945.9 mA h g-1, when circulating current density is 20 A g-1When, high-speed capacity is 161.5 mA h g-1
The Chinese invention patent application that application publication number is CN108101123A discloses a kind of square prism vanadic acid nickel and receives Rice material and preparation method thereof, can apply in the energy storage fields such as electrode material for super capacitor.
However, square prism vanadic acid nickel is since specific surface area is small, electric conductivity and Surface Permeability are poor, reactivity site It is few, there are specific capacitances when being used for supercapacitor as electrode material it is low, circulation conservation rate is low the problems such as.Therefore, it is necessary to develop A kind of vanadic acid nickel electrode material and preparation method thereof more than high surface area, high conductivity and Surface Permeability, reactivity site, And be applied in supercapacitor as electrode material, and improve the structure and preparation method of vanadic acid nickel material, it realizes high Specific capacitance and good circulation performance.
Summary of the invention
It is an object of the present invention in view of the above shortcomings of the prior art, propose it is a kind of it is easy to operate, at low cost, Material morphology is controllable and prepares the preparation method of the supercapacitor vanadic acid nickel material of resulting materials electrochemical performance.
It is another object of the present invention to propose a kind of high surface area, highly conductive for the above-mentioned deficiency of the prior art Flower-shaped supercapacitor vanadic acid nickel material more than property and Surface Permeability, reactivity site.
It is another object of the present invention to propose a kind of flower-shaped supercapacitor for the above-mentioned deficiency of the prior art Vanadic acid nickel material is used to show high specific capacitance performance and good cycle performance as the application of electrode material for super capacitor.
The present invention solve technical problem the technical solution adopted is that, propose a kind of system of supercapacitor vanadic acid nickel material Preparation Method, comprising the following steps:
Step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Vanadium in the ammonium vanadate Additional amount and the nickel nitrate in nickel element additional amount molar ratio be (1-6): 6;The solvent is ethyl alcohol, one in water Kind is any than mixing;The nickel nitrate includes nickel nitrate hydrate;
Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, it is mixed to obtain reaction Close liquid;The alkaline structure directed agents are one of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine or several any Than mixing;Preferably, the potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine be aqueous solution form or ethanol solutions or (water/ethyl alcohol) mixed solution form;
Step 3: the reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, solid after cooling Liquid separation is dried to obtain product vanadic acid nickel material after solid product washing for several times at 50-100 DEG C.
Preferably, the alkaline structure directed agents are ethanol amine in step 2.
Preferably, in step 1, the solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is (0.1-1): 1.
Preferably, in step 1, in the ammonium vanadate in the additional amount of vanadium and the nickel nitrate nickel element plus The molar ratio for entering amount is (3-5): 6.
Preferably, the condition of nickel nitrate is added described in step 1 are as follows: by nickel nitrate under the conditions of 50-90 DEG C of stirring in water bath It is added in Ammonium Vanadate Solution.
Preferably, the reaction temperature is 150-160 DEG C in step 3.
Preferably, the reaction time is 10-12h in step 3.
Preferably, the method for the separation of solid and liquid is filtering or centrifugation in step 3.
Preferably, dry described in step 3 are as follows: the vacuum drying 12-24h at 60-80 DEG C.
Preferably, the alkaline structure directed agents are ethanol amine in step 2.
Preferably, adjusting pH value to 9 with alkaline structure directed agents in step 2.
Preferably, in step 2, it is described to be uniformly mixed are as follows: to stir 20 min under 80 DEG C of water bath conditions.
Preferably, the reaction time is 10h in step 3.
The present invention also provides the flower-shaped supercapacitor vanadic acid nickel materials that a kind of above-mentioned preparation method is prepared.
The present invention also provides a kind of above-mentioned flower-shaped supercapacitors to use vanadic acid nickel material as electrode of super capacitor material The application of material.
A kind of flower-shaped supercapacitor provided by the invention is had the following beneficial effects: with the preparation method of vanadic acid nickel material
1, using one step hydro thermal method, using a variety of alkaline reagents as structure directing agent, and vanadic acid nickel material is obtained by adjustment process pH Material, it is easy to operate and safe, at low cost, product purity is high.
2, the dissolution of ammonium metavanadate is conducive to as solvent using the aqueous solution of ethyl alcohol.
A kind of flower-shaped supercapacitor provided by the invention is had the following beneficial effects: with vanadic acid nickel material
1, vanadic acid nickel material is in the flower-like structure of lamella accumulation, and specific surface area is larger, there is good electric conductivity and Surface Permeability, For flower-like structure there are a large amount of central hole structure, pore-size distribution is wide, and reactivity site is more.
A kind of flower-shaped supercapacitor provided by the invention uses vanadic acid nickel material as electrode material for super capacitor application When have the following beneficial effects:
1, high specific capacitance is shown when as single electrode material, in 1 A g-1Under current density, specific capacitance reaches 1054 F g-1;Good capacity retention is shown, is had extended cycle life, specific capacitance conservation rate is up to 89 after 10000 charge and discharge cycles %;In addition, flower-shaped vanadic acid nickel material electrochemical impedance is low, high rate performance is good.
2, being assembled into supercapacitor has biggish operating potential, biggish power density and energy density and excellent Cyclical stability.
Detailed description of the invention
Fig. 1 is the XRD diagram of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 3 is the TEM figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 4 is the nitrogen adsorption desorption curve and graph of pore diameter distribution of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 5 is CV and the GCD figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 6 is the long circulating figure of flower-shaped vanadic acid nickel material in the embodiment of the present invention 1.
Fig. 7 is the SEM figure of material 2 in comparative example 2 of the present invention, material 3, material 4, material 5, material 6, material 11.
Fig. 8-13 is that material 2, material 3, material 4, material 5, material 6, material 11 are made in comparative example 2 of the present invention respectively CV figure after electrode.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described, However, the present invention is not limited to these examples.
Embodiment 1
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5: 1;6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O is obtained Reaction precursor liquid.PH value is adjusted to about 9 with alkaline structure directed agents (aqueous ethanolamine), continues 20 min of stirring in water bath, Obtain reaction mixture.Reaction mixture is transferred in the stainless steel autoclave of 100 mL Teflon linings.Heat and After being kept for 10 hours at 150 DEG C, cooled to room temperature.Centrifuge separation, the substance after synthesis is washed with deionized water and ethyl alcohol It washs for several times, dry 16h obtains vanadic acid nickel solid in 60 DEG C of vacuum drying oven.
Above-mentioned vanadic acid nickel material, acetylene black and the PVDF being prepared is weighed by the mass ratio of 8:1:1, is mixed Few drops of N-Methyl pyrrolidone reagents are added after grinding, magnetic agitation handles 12 h, and obtained slurry, which is coated on area, is 1cm2Preparation nickel foam substrate on, then at 80 DEG C dry 24 hours in vacuum drying oven.The quality of active material is negative Lotus is about 2mg cm-1
The vanadic acid nickel material being prepared using the above method is subjected to X-ray diffraction analysis (abbreviation XRD, similarly hereinafter), it is real It tests as shown in Figure 1 using the X ' Pert PRO type X-ray diffraction spectra instrument result of PANalytical company, Holland production.From figure It can be seen that in 1 (122) of the diffraction maximum and vanadic acid nickel at 2 θ=35.84 °, 44.07 °, 58.7 °, 63.9 °, (042), (442) it is corresponded to well with (162) crystal face.
The vanadic acid nickel being prepared using the above method is subjected to morphology characterization using scanning electron microscope (abbreviation SEM, similarly hereinafter), Its microscopic appearance is studied, the Hitachi S4700 type scanning electron microscope of Hitachi company, Japan is used in experiment.Fig. 2 is The SEM characterization result of vanadic acid nickel material, it can be clearly seen that, prepared vanadic acid nickel material shows flower-like structure, lamella Thickness is uniform, and laminated structure has big contact area.
The vanadic acid nickel being prepared using the above method is characterized using transmission electron microscope (abbreviation TEM, similarly hereinafter), is studied Its microscopic appearance feature.It is transmitted in experiment using the Tecnai G2 F30 S-Twin high-resolution of Philips-FEI company, Holland Electron microscope, as a result as shown in Figure 3.Fig. 3 is the TEM characterization result of vanadic acid nickel under different enlargement ratios, it is clearly illustrated Lamella is accumulated to form pore structure and be self-assembled into flower-like structure.
The vanadic acid nickel material being prepared using the above method is subjected to isothermal N2Adsorption desorption (BET) test, experiment use The 2010 type Full-automatic physical chemical adsorption instrument of ASAP of Micromeritics company production carries out BET and pore-size distribution analysis, As a result as shown in Figure 4.Show relative pressure (P/P0) significant hysteresis loop between 0.65-1.0, belong to typical IV Type thermoisopleth shows that there are central hole structures in vanadic acid nickel material.It can be clearly seen that vanadic acid nickel material from graph of pore diameter distribution Material has apparent meso-hole structure.It is calculated according to BET and NLDFT model, the specific surface area of vanadic acid nickel is 50 m2 g-1, pore-size distribution It is concentrated mainly on as 3-6 nm.This high-specific surface area and a high proportion of central hole structure are capable of providing material in enough activity The heart.Flower-like structure can effectively adjust the volume change in continuous charge and discharge process, this is for improving chemical property very It is ideal.
Fig. 5 is the cyclic voltammetry (CV) and constant current charge-discharge test (GCD) figure of vanadic acid nickel material.Experiment uses three Electrode system and CHI760E type electrochemical workstation are tested.The specific capacitance of active material can be calculated according to the following formula by GCD (three-electrode system):
Wherein: C is specific capacitance (Fg-1), I is current density (Ag-1), Δ t is discharge time (s), and Δ V is electric potential scanning Range (V).The specific capacitance value under different scanning rates is calculated accordingly.Electrode is respectively in 1 to 20 Ag-1Current density under Specific capacitance is respectively 1054,966.4,896,780,728 Fg-1.It is obvious that with the increase of current density, specific capacitance subtracts Small, still, under the high current density of 20 A g-1, vanadic acid nickel material electrode still maintains 64.4% high capacitance.10 A·g-1Current density under study vanadic acid nickel material long circulating performance (Fig. 6).In first 300 circulations, due to electrode material Polarized state gradually activation and enhancing, the specific capacitance of electrode material increases.Finally, 10, after 000 circulation, specific capacitance The initial specific capacitance that slightly decays may remain in 89%.Flower-like structure can slow down the volume change of material, keep stable structure It does not collapse.The result shows that flower-shaped vanadic acid nickel material has excellent cyclical stability.
Embodiment 2
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1. 6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With alkalinity PH value is adjusted to about 7 by structure directing agent (aqueous ethanolamine), continues 20 min of stirring in water bath.By finally obtained mixture It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 10 hours at 150 DEG C, natural cooling To room temperature.Be separated by solid-liquid separation, by after synthesis substance deionized water and ethanol washing for several times, it is dry in 70 DEG C of vacuum drying oven 12h obtains vanadic acid nickel solid.Solid powder is tested through SEM, and structure is blocky-shaped particle.
Embodiment 3
By 3 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.3: 1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 50 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property structure directing agent (aqueous ethanolamine) pH value is adjusted to about 8, continue 20 min of stirring in water bath.By finally obtained mixing Object is transferred in the stainless steel autoclave of 100 mL Teflon linings.It is naturally cold after heating and being kept for 10 hours at 150 DEG C But to room temperature.Be separated by solid-liquid separation, by after synthesis substance deionized water and ethanol washing for several times, in 70 DEG C of vacuum drying oven do It is dry to obtain vanadic acid nickel solid for 24 hours.Solid powder is tested through SEM, and structure is evenly dispersed lamellar structure.
Embodiment 4
By 5 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.8: 1;.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 60 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property solution (ethanol amine) pH value is adjusted to about 10, continue 20 min of stirring in water bath.Finally obtained mixture is transferred to 100 In the stainless steel autoclave of mL Teflon lining.After heating and being kept for 10 hours at 150 DEG C, cooled to room temperature.Solid-liquid Separation, by after synthesis substance deionized water and ethanol washing for several times, in 60 DEG C of vacuum drying oven drying obtain vanadic acid for 24 hours Nickel solid.Solid powder is tested through SEM, and lamellar structure is biggish and random.
Embodiment 5
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5: 1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property solution (ethanol amine) pH value is adjusted to about 12, continue 20 min of stirring in water bath.Finally obtained mixture is transferred to 100 In the stainless steel autoclave of mL Teflon lining.After heating and being kept for 12 hours at 160 DEG C, cooled to room temperature.Centrifugation Separation, by after synthesis substance deionized water and ethanol washing for several times, dry 16h obtains vanadic acid in 70 DEG C of vacuum drying oven Nickel solid.Solid powder is tested through SEM, and structure is in biggish bulk.
Embodiment 6
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.5: 1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 90 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property structure directing agent (potassium hydroxide solution) pH value is adjusted to about 9, continue 20 min of stirring in water bath.Remaining step and process are same Embodiment 1.
Embodiment 7
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath 6 mmol Ni(NO are added in liquid3)2·6H2O.PH value is adjusted to about 9 with alkaline structure directed agents (sodium hydroxide solution), after Continuous 20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 8
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath 6 mmol Ni(NO are added in liquid3)2·6H2O.PH value is adjusted to about 9 with alkaline structure directed agents (ammonia aqueous solution), is continued 20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 9
By 4 mmol NH4VO3It is completely dissolved in a solvent.Ultrasonic treatment is after 30 minutes, to above-mentioned molten under 80 DEG C of stirring in water bath 6 mmol Ni(NO are added in liquid3)2·6H2O.With mixed-alkali structure directing agent (sodium hydroxide+potassium hydroxide solution) by pH Value is adjusted to about 9, continues 20 min of stirring in water bath.Remaining step and process are the same as embodiment 1.
Embodiment 10
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1. 6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With mixing PH value is adjusted to about 9 by alkaline structure directed agents (ammonium hydroxide+potassium hydroxide solution), continues 20 min of stirring in water bath.Remaining step And process is the same as embodiment 1.
Embodiment 11
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.1: 1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property structure directing agent (ethanolamine solutions) pH value is adjusted to about 9, continue 20 min of stirring in water bath.By finally obtained mixture It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 12 hours at 155 DEG C, natural cooling To room temperature.Filtering, by after synthesis substance deionized water and ethanol washing for several times, the dry 12h in 80 DEG C of vacuum drying oven Obtain vanadic acid nickel solid.
Embodiment 12
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 1: 1. 6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.With alkalinity PH value is adjusted to about 9 by structure directing agent (ethanolamine solutions), continues 20 min of stirring in water bath.Finally obtained mixture is turned It moves on in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 11 hours at 160 DEG C, naturally cool to Room temperature.Filtering, by after synthesis substance deionized water and ethanol washing for several times, in 70 DEG C of vacuum drying oven it is dry for 24 hours To vanadic acid nickel solid.
Embodiment 13
By 4 mmol NH4VO3It is completely dissolved in a solvent, solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.8: 1.6 mmol Ni(NO are added after 30 minutes in ultrasonic treatment under 80 DEG C of stirring in water bath into above-mentioned solution3)2·6H2O.Use alkali Property structure directing agent (ethanolamine solutions) pH value is adjusted to about 9, continue 20 min of stirring in water bath.By finally obtained mixture It is transferred in the stainless steel autoclave of 100 mL Teflon linings.After heating and being kept for 11 hours at 150 DEG C, natural cooling To room temperature.Centrifugation, by after synthesis substance deionized water and ethanol washing for several times, the dry 16h in 80 DEG C of vacuum drying oven Obtain vanadic acid nickel solid.
Comparative example 1
Flower-shaped vanadic acid nickel (abbreviation material 1) that embodiment 1 is prepared, using quiet superfine in International Periodicals 3295-3302 pages of volume 46 of upper 2017 of DaltonTransactions deliver " high-performance super capacitor is with three-dimensional porous Co3V2O8Nanometer rods and two dimension NiCo2V2O8The easy synthesis of nanometer sheet and its electro-catalysis oxygen evolution reaction performance " method be prepared into The vanadic acid cobalt material (abbreviation material 2) that arrives, using P. Vishnukumar etc. in International Periodicals Materials Letters " the supercapacitor NiO/Ni delivered on 114-118 pages of volume 219 in 20183V2O8The synthesis of nanocomposite and table Sign " the NiO/Ni that is prepared of method3V2O8Material (abbreviation material 3), using K. Thiagarajan etc. in International Periodicals J " the efficient electrode material for super capacitor delivered on 527-536 pages of volume 22 of Solid State Electrochem 2018 Ni3V2O8The synthesis of@stannic oxide/graphene nano composite material " the Ni that is prepared of method3V2O8Material (abbreviation material 4) is adopted With Low Wei Hau etc. in International Periodicals Journal of Alloys and Compounds 995- of volume 768 in 2018 " the symmetrical electrode of super capacitor graphene/Ni of high-performance delivered on page 10053V2O8The solvent thermal design of nanocomposite " The Ni that is prepared of method3V2O8It is material (abbreviation material 5), auspicious etc. in International Periodicals Electrochimica Acta using fourth " the efficient electrode material for super capacitor Ni delivered on 494-502 pages of volume 107 in 20133V2O8@stannic oxide/graphene nano is multiple The synthesis of condensation material " the Ni that is prepared of method3V2O8Material (abbreviation material 6), use application publication number for The square prism vanadic acid nickel nano material that method disclosed in the Chinese invention patent application of CN108101123A is prepared is (referred to as Material 7).Experiment is compared, specific capacitance, the cycle performance of six kinds of materials are compared.
The parameter comparison of 1 different materials of table
Test condition: above-mentioned vanadic acid nickel material, acetylene black and the PVDF being prepared is weighed by the mass ratio of 8:1:1, Few drops of N-Methyl pyrrolidone reagents are added after mixed grinding, magnetic agitation handles 8 h, obtains active material slurry.By one Quantitative slurry is coated uniformly on 1 × 1 cm of area2Nickel foam on.The electrode prepared is done in 80 DEG C of convection ovens Dry 12 h.Using cyclic voltammetry in 2 mV s-1Current potential sweeps the specific capacitance and cycle performance of test material under speed.
The result shows that the specific capacitance for the vanadic acid nickel material that embodiment 1 is prepared is higher, and there is excellent cyclicity Energy.
Comparative example 2
Using control variate method, the experiment condition to prepare vanadic acid nickel material in embodiment 1 is basic experimental conditions (that is, if nothing Specified otherwise, the experiment condition in addition to variable is with the experiment condition for preparing vanadic acid nickel material in embodiment 1), by adjusting alkalinity 11 kinds of vanadic acid nickel materials as shown in table 2 are prepared in structure directing agent type.By comparing experiment, compare different condition Specific capacitance, cycle performance and the high rate performance of lower obtained vanadic acid nickel material, the results are shown in Table 2, test method and specific capacitance, Cycle performance and high rate performance calculation method are the same as embodiment 1.
The parameter comparison of material under the conditions of the different alkaline structure directed agents of table 2
The result shows that different alkaline structure directed agents have apparent influence for the pattern and performance of vanadic acid nickel material.Such as Fig. 7 (a) and (b), (c), (d), (e), (f) are the SEM figure of material 2, material 3, material 4, material 5, material 6, material 11 respectively.Fig. 7 (f) shown in, when, without alkaline structure directing agent, vanadic acid nickel material is the non-uniform large area sheet knot of micron order in reaction system Structure.And pass through the thin slice that the vanadic acid nickel material that structure directing agent precipitates is mostly micro-or nano size, show that alkaline structure is oriented to Agent is the key factor of synthetizing micro-nano structure vanadic acid nickel material.Fig. 7 (a) is prepared by structure directing agent of potassium hydroxide Vanadic acid nickel material be mostly graininess, agglomeration is serious.Fig. 7 (b) is prepared using sodium hydroxide as structure directing agent Vanadic acid nickel material pattern it is similar as the vanadic acid nickel material pattern of structure directing agent with using potassium hydroxide, same agglomeration is tight Weight is in block structure.The vanadic acid nickel material pattern that Fig. 7 (c) is prepared using ammonium hydroxide as structure directing agent is mostly uniform piece Layer.
The Analysis on Mechanism that alkaline structure directed agents influence vanadic acid nickel material pattern: under alkaline condition, vanadic acid nickel can be fast Speed precipitating.Sodium hydroxide and potassium hydroxide show the block structure of aggregation as sample prepared by structure directing agent in the secure execution mode (sem, by Highly basic is belonged in sodium hydroxide and potassium hydroxide, and when they encounter nickel ion and vanadium ion in solution, ionized Hydroxide ion can precipitate to form nucleus rapidly.Since crystallization process is relatively fast, cause the growth of crystal grain not specific The reunion of vanadic acid nickel material easily has occurred in shape.However, since ammonium hydroxide belongs to weak base, hydroxide ion slow release, nucleus First there are the growths of the side of hydroxide ion.Meanwhile the growth of nucleus becomes slowly form evenly dispersed lamella knot Structure.
Fig. 8-13 is respectively the circulation of material 2, material 3, material 4, material 5, material 6, material 11 under different scanning rates Volt-ampere curve figure, different from the rectangular characteristic of double layer capacity, the shape of CV curve clearly illustrates that capacitive property is anti-by faraday It should control.Redox peaks are mainly due to Ni2+ / Ni3+And V4+ / V5+Two kinds of active redox reaction presence.Root Each electrode specific capacitance value calculated according to constant current charge-discharge curve, it is known that material 2, material 3 specific capacitance value be not much different, and material Due to there is the participation of weak base, specific capacitance is big compared with material 2, material 3 for material 4, material 5.Current density is from 1 A g-1 Increase to 20 A g-1, the specific capacitance of six kinds of materials reduces that amplitude is larger, and capacity retention is not high.This is because expose thoroughly rate when, electrolyte Ion has little time to cause effective ratio area to reduce into the mesoporous gap of material, and electric double layer interface is reduced.Comparatively, exist Under same scan speed, the specific capacitance value of the material through structure directing agent precipitating, which is all higher than to precipitate without sour structure directing agent, to be prepared The specific capacitance value of obtained vanadic acid nickel material shows that alkaline structure directed agents are the key that synthetizing micro-nano structure vanadic acid nickel materials Factor.
The specific capacitance for the flower-shaped vanadic acid nickel material that embodiment 1 is prepared is apparently higher than obtained material under the conditions of others Material, and there is good circulation and high rate performance.This is attributed to:
(1) weakly alkaline ethanol amine is as structure directing agent, so that the growth of nucleus becomes slowly form even sheet layer heap Long-pending flower-like structure.
(2) high-specific surface area and a high proportion of central hole structure are capable of providing flower-shaped vanadic acid nickel material in enough activity The heart.
(3) flower-shaped vanadic acid nickel material has loose porous structure, is conducive to the infiltration of electrolyte and quickly moving for ion It moves.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.

Claims (10)

1. a kind of supercapacitor preparation method of vanadic acid nickel material, it is characterised in that the following steps are included:
Step 1: in a solvent by ammonium vanadate dissolution, nickel nitrate is added, obtains reaction precursor liquid;Vanadium in the ammonium vanadate Additional amount and the nickel nitrate in nickel element additional amount molar ratio be (1-6): 6;The solvent is ethyl alcohol, one in water Kind is any than mixing;
Step 2: reaction precursor liquid alkaline structure directed agents are adjusted into pH value to 7-12, is uniformly mixed, it is mixed to obtain reaction Close liquid;The alkaline structure directed agents are one of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ethanol amine or several any Than mixing;
Step 3: the reaction mixture is transferred in autoclave, is reacted 8-15 hours at 100-180 DEG C, solid after cooling Liquid separation is dried to obtain product vanadic acid nickel material after solid product washing for several times at 50-100 DEG C.
2. a kind of preparation method of supercapacitor vanadic acid nickel material as described in claim 1, it is characterised in that:
In step 2, the alkaline structure directed agents are ethanol amine.
3. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 2, it is characterised in that:
In step 1, the solvent is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is (0.1-1): 1.
4. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 3, it is characterised in that:
In step 1, the additional amount of vanadium and the molar ratio of the additional amount of nickel element in the nickel nitrate are in the ammonium vanadate (3-5): 6.
5. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 4, it is characterised in that step 1 The condition that nickel nitrate is added are as follows:
Nickel nitrate is added in Ammonium Vanadate Solution under the conditions of 50-90 DEG C of stirring in water bath.
6. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 5, it is characterised in that:
In step 3, the reaction temperature is 150-160 DEG C.
7. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 6, it is characterised in that:
In step 3, the reaction time is 10-12h.
8. a kind of preparation method of supercapacitor vanadic acid nickel material as claimed in claim 7, it is characterised in that:
In step 3, the method for the separation of solid and liquid is filtering or centrifugation, the drying are as follows: the vacuum drying 12- at 60-80 DEG C 24h。
9. the flower-shaped supercapacitor vanadic acid nickel material that method according to claim 1 to 8 is prepared.
10. flower-shaped supercapacitor according to claim 9 uses vanadic acid nickel material as electrode material for super capacitor Using.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111146018A (en) * 2020-01-08 2020-05-12 贵阳学院 Electrode active material for supercapacitor, preparation method of electrode active material, electrode material for supercapacitor, supercapacitor and electric device
CN111816454A (en) * 2020-07-02 2020-10-23 西安交通大学 Foamed nickel loaded NiCo2V2O8Method for assembling flexible supercapacitor
CN112186168A (en) * 2020-10-10 2021-01-05 宁波大学 Zinc ion battery electrode material and preparation method and application thereof
CN113023793A (en) * 2021-03-24 2021-06-25 浙江工业大学 Cobalt-nickel-vanadium-oxygen electrode material and preparation method thereof
CN113149085A (en) * 2021-02-23 2021-07-23 北京科技大学 Positioning synthesis method and application of mixed metal vanadate with two-dimensional structure
CN113171746A (en) * 2021-04-26 2021-07-27 内江师范学院 Flaky nickel vanadate nano material for adsorbing VB and preparation method thereof
CN115096956A (en) * 2022-06-29 2022-09-23 西北工业大学 Hollow spherical nickel vanadate-nickel oxide heterogeneous material, preparation method and application thereof, and triethylamine gas sensor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101051685A (en) * 2007-04-11 2007-10-10 南开大学 Method for preparing transition metal vanadate one dimension electrode material and its use
CN108101123A (en) * 2017-12-27 2018-06-01 同济大学 Four-prism vanadic acid nickel nano material and preparation method thereof
CN109599271A (en) * 2018-11-26 2019-04-09 新疆大学 A kind of electrode material Ni3V2O8And its synthetic method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101051685A (en) * 2007-04-11 2007-10-10 南开大学 Method for preparing transition metal vanadate one dimension electrode material and its use
CN108101123A (en) * 2017-12-27 2018-06-01 同济大学 Four-prism vanadic acid nickel nano material and preparation method thereof
CN109599271A (en) * 2018-11-26 2019-04-09 新疆大学 A kind of electrode material Ni3V2O8And its synthetic method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DEBABRATA NANDI,ET AL: ""Unique nanopetals of nickel vanadate: crystal structure elucidation and supercapacitive performance"", 《NEW J.CHEM.》 *
YANG LI,ET AL.: ""One-step synthesis of micro/nano flower-like Ni3V2O8 as anode for Li-ion batteries"", 《MATERIALS LETTERS》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111146018A (en) * 2020-01-08 2020-05-12 贵阳学院 Electrode active material for supercapacitor, preparation method of electrode active material, electrode material for supercapacitor, supercapacitor and electric device
CN111146018B (en) * 2020-01-08 2021-07-06 贵阳学院 Electrode active material for supercapacitor, preparation method of electrode active material, electrode material for supercapacitor, supercapacitor and electric device
CN111816454A (en) * 2020-07-02 2020-10-23 西安交通大学 Foamed nickel loaded NiCo2V2O8Method for assembling flexible supercapacitor
CN111816454B (en) * 2020-07-02 2022-04-22 西安交通大学 Foamed nickel loaded NiCo2V2O8Method for assembling flexible supercapacitor
CN112186168A (en) * 2020-10-10 2021-01-05 宁波大学 Zinc ion battery electrode material and preparation method and application thereof
CN112186168B (en) * 2020-10-10 2021-10-19 宁波大学 Zinc ion battery electrode material and preparation method and application thereof
CN113149085A (en) * 2021-02-23 2021-07-23 北京科技大学 Positioning synthesis method and application of mixed metal vanadate with two-dimensional structure
CN113023793A (en) * 2021-03-24 2021-06-25 浙江工业大学 Cobalt-nickel-vanadium-oxygen electrode material and preparation method thereof
CN113023793B (en) * 2021-03-24 2022-09-02 浙江工业大学 Cobalt-nickel-vanadium-oxygen electrode material and preparation method thereof
CN113171746A (en) * 2021-04-26 2021-07-27 内江师范学院 Flaky nickel vanadate nano material for adsorbing VB and preparation method thereof
CN115096956A (en) * 2022-06-29 2022-09-23 西北工业大学 Hollow spherical nickel vanadate-nickel oxide heterogeneous material, preparation method and application thereof, and triethylamine gas sensor
CN115096956B (en) * 2022-06-29 2024-10-01 西北工业大学 Hollow spherical nickel vanadate-nickel oxide heterogeneous material, preparation method and application thereof, and triethylamine gas sensor

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