CN109830380A - A kind of electrode material for super capacitor, preparation method and application - Google Patents

A kind of electrode material for super capacitor, preparation method and application Download PDF

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Publication number
CN109830380A
CN109830380A CN201910123441.3A CN201910123441A CN109830380A CN 109830380 A CN109830380 A CN 109830380A CN 201910123441 A CN201910123441 A CN 201910123441A CN 109830380 A CN109830380 A CN 109830380A
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electrode material
preparation
super capacitor
metal
foam
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CN109830380B (en
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田进军
薛艳
付卫云
田腾飞
余新平
李翛
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Nanyang Institute of Technology
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Nanyang Institute of Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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Abstract

The invention belongs to field of nanometer material technology, specifically a kind of electrode material for super capacitor, preparation method and application.Preparation principle is: by the coordination using triethanolamine and metal ion, generating complex, triethanolamine has certain alkalinity in aqueous solution, and electrolysis can produce OH, complex and OHEffect generates metal hydroxides hydrogel.Preparation method is: the metal hydroxides hydrogel of generation is obtained metal hydroxide thin film after suction filtration, washing, drying, metal hydroxide thin film is cut into the size of needs, foam-metal current collector body is clipped among two panels foamed nickel current collector, it is pushed integrally in 5-20MPa pressure, the working electrode for supercapacitor has been made.The present invention provides a kind of electrode material for super capacitor, preparation method and application, this electrode material can be realized as the function of conventional Super capacitor without conductive agent and adhesive.

Description

A kind of electrode material for super capacitor, preparation method and application
Technical field
The invention belongs to the preparation field of electrode material for super capacitor, it is related to a kind of electrode material for super capacitor, system Preparation Method and application.
Background technique
Supercapacitor is a kind of energy storage device between battery and capacitor.Since supercapacitor has Efficiency for charge-discharge is high, power density is big, the features such as having extended cycle life, is environmental-friendly, be widely used in traffic, mobile communication, The fields such as information technology, aerospace and science and techniques of defence.
Transition metal hydroxide is often chosen as excellent capacitor because it is with high specific capacitance and energy density Material.Traditional supercapacitor is in preparation work electrode process, other than needing transition metal hydroxide, also needs to add Enter conductive agent and adhesive, and the addition of adhesive can cause the increase of internal resistance to inhibit electron-transport, conductive agent and gluing It is added that not only to will increase the weight of working electrode portable to cause capacitor heaviness to be not easy while agent, but also can be with super The long-time service of capacitor be easy to cause falling off for conductive agent and adhesive, to influence the performance of capacitor.
Therefore need to develop a kind of electrode material for super capacitor that conductive agent and adhesive is not added.
Summary of the invention
For above-mentioned technical deficiency, the present invention provides a kind of electrode material for super capacitor, preparation method and Using this electrode material can be realized conventional Super capacitor by conductive agent, adhesive and cross plating metal oxyhydroxide Comprehensive performance.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
The first purpose of the invention is to provide a kind of preparation methods of electrode material for super capacitor, specifically include as follows Step:
(1) by the metal salt concentration soluble in water that is made into for the salting liquid of 0.01-0.1mol/L;The metal salt is chlorination The mixture of one or more of nickel, nickel nitrate, copper chloride or copper nitrate;
(2) triethanolamine is added in the salting liquid that step (1) is prepared and obtains mixed solution, wherein triethanolamine and gold The molar ratio for belonging to ion is 3-24:1;
(3) mixed solution obtained by step (2) is fitted into reaction kettle, the crystallization 6-24h at 120~220 DEG C;
(4) metal hydroxide thin film will be obtained after the washing of crystallization product obtained by step (3), suction filtration, drying;
(5) preparation of foam-metal current collector body: successively using dilute hydrochloric acid, water, EtOH Sonicate washing foam metal, dry in vacuum It is dry, obtain foam-metal current collector body;The foam metal is nickel foam or foam copper;
(6) metal hydroxide thin film in step (4) is clipped among two panels foam-metal current collector body, with tablet press machine plus It is depressed into 5-20MPa, obtains electrode material for super capacitor.
Preferably, when preparing electrode material for super capacitor, the metal salt and the foam metal use same metal.
Preferably, the dry condition of step (4) are as follows: dry 6-8 hours at 40-60 DEG C
Preferably, the vacuum drying condition in step (5) are as follows: 3-5 hours dry at 50-80 DEG C of vacuum.
Preferably, foam-metal current collector type is cut into 2 × 2 × 0.4cm in step (5)3, then wash again.
Preferably, metal hydroxide thin film obtained by step (4) is cut into 1 × 1 × 0.1cm3Size, by step (5) gained foam-metal current collector body is cut into 1 × 1 × 0.2cm3Size;Then the operation of step (6) is carried out again.
Preferably, application of the electrode material for super capacitor in preparation supercapacitor.
Compared with prior art, the beneficial effects of the present invention are:
(1) the present invention provides a kind of electrode material for super capacitor, preparation method and application, triethanolamine is utilized (TEOA) and the coordination of metal ion generates complex, and triethanolamine has certain alkalinity in aqueous solution, and electrolysis can Generate OH-, as temperature increases, coordination weakens, metal ion and OH-Effect generates metal hydroxides hydrogel, passes through Reaction condition is controlled, metal hydroxide thin film material can be prepared.
(2) electrode material for super capacitor provided by the invention is easy to operate in preparation work electrode process, and material can It is arbitrarily cut into required size, conductive agent and adhesive is not added, is directly sandwiched in two panels foam-metal current collector body made of the present invention Centre is used after tablet press machine or roll squeezer direct tablet compressing in supercapacitor as the application of electrode material.
(3) working electrode obtained by metal hydroxides provided by the invention has good electricity in KOH electrolyte Chemical property realizes excellent specific capacitance in three-electrode system, and under the conditions of 0.5A/g, specific capacitance reaches 2268F/g.It is one Kind has the supercapacitor composite material of good capacitive property, has long-range meaning in terms of practical application.
Detailed description of the invention
Fig. 1 is the curling figure of metal hydroxide thin film material of the invention;
Fig. 2 is the stretching, extension figure of metal hydroxide thin film material of the invention;
Fig. 3 is that the SEM of metal hydroxide thin film material of the invention schemes;
Fig. 4 is the XRD diagram of metal hydroxide thin film material of the invention;
Fig. 5 is a kind of working electrode structure figure of electrode material for super capacitor preparation method of the invention;
Fig. 6 is a kind of cyclic voltammetry curve figure of electrode material for super capacitor of the invention under different scanning rates.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, to preferred embodiment and attached drawing 1-5 cooperation detailed description.
Embodiment 1
The preparation method of 1 metal hydroxide thin film material of the present embodiment, comprising the following steps:
The NiCl of precise 1mmol2·6H2O is added water 25mL, is put into magneton and 10min is stirred at room temperature, to NiCl2·6H2All after dissolution, 9mmol triethanolamine is added dropwise in O, and after stirring 20min, obtained mixture is transferred to 50mL not Hydro-thermal reaction is carried out in rust steel reaction kettle, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 12h.It takes out after reaction and cooling To room temperature, centrifuge washing, 60 DEG C of vacuum drying 12h are to get metal hydroxide thin film material.
Embodiment 2
The preparation method of 2 metal hydroxide thin film material of the present embodiment, comprising the following steps:
The NiCl of precise 1mmol2·6H2O is added water 25mL, is put into magneton and 10min is stirred at room temperature, to NiCl2·6H2All after dissolution, 12mmol triethanolamine is added dropwise in O, and after stirring 20min, obtained mixture is transferred to 50mL's Hydro-thermal reaction is carried out in stainless steel cauldron, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 12h.It takes out after reaction and cold But to room temperature, centrifuge washing, 60 DEG C of vacuum drying 12h are to get metal hydroxide thin film material.
Embodiment 3
The preparation method of 3 metal hydroxide thin film material of the present embodiment, comprising the following steps:
The NiCl of precise 1mmol2·6H2O is added water 25mL, is put into magneton and 10min is stirred at room temperature, to NiCl2·6H2All after dissolution, 9mmol triethanolamine is added dropwise in O, and after stirring 20min, obtained mixture is transferred to 50mL not Hydro-thermal reaction is carried out in rust steel reaction kettle, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 8h.It takes out and is cooled to after reaction Room temperature, centrifuge washing, 60 DEG C of vacuum drying 12h are to get metal hydroxide thin film material.
Embodiment 4
The preparation method of 4 metal hydroxide thin film material of the present embodiment, comprising the following steps:
Precise 0.9mmol NiCl2·6H2O and 0.1mmol Cu (NO3)2·6H2O is added water 25mL, is put into magneton 10min is stirred at room temperature, to 0.9mmol NiCl2·6H2O and 0.1mmol Cu (NO3)2·6H2O all after dissolution, is added dropwise After stirring 20min, it is anti-to be transferred to progress hydro-thermal in the stainless steel cauldron of 50mL by 12mmol triethanolamine for obtained mixture It answers, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 12h.It takes out and is cooled to room temperature after reaction, centrifuge washing, 60 DEG C of vacuum Dry 12h is to get metal hydroxide mixture thin-film material.
We carry out performance detection to it by taking metal hydroxide thin film material prepared by embodiment 1 as an example below, In:
Fig. 1 and Fig. 2 is the photo of a kind of embodiment of metal hydroxide thin film, and as seen from Figure 1, embodiment 1 is made Standby material has certain flexibility;As seen from Figure 1, through suction filtration, washing, it is dry after obtain it is more uniform, have it is certain thoroughly Lightness and successional thin-film material.
Fig. 3 is the SEM figure of the metal hydroxide thin film in embodiment 1, as seen from Figure 2, prepared metallic hydrogen Oxide film material has the nanometer chip architecture of ultra-thin 2D, is formed by countless small nano-particles self assembles.
Fig. 4 is the XRD diagram of the metal hydroxide thin film in the embodiment of the present invention 1, as seen from Figure 3 prepared film Sample has β-Ni (OH)2The characteristic absorption peak of (JCPDS 00-014-0117), in 2 θ=33.3 °, 35.59 °, 38.6 °, 43.6 °, 51.8 °, 59.4 °, 62.5 °, 69.5 ° and 72.8 ° have characteristic absorption peak, show that thin-film material is β-Ni (OH)2
Fig. 5 prepares photo for the working electrode that the embodiment of the present invention 1 is electrode material for super capacitor.Working electrode preparation It is relatively simple, only material need to can be cut into 1 × 1 × 0.2cm3Size, is not added conductive agent and adhesive is directly sandwiched in two panels foam Among nickel, use after tablet press machine or roll squeezer direct tablet compressing in supercapacitor as the application of electrode material.
We are also tested embodiment 3-5, they also have with the similar surface micro-structure feature of embodiment 1, Ultra-thin 2D surface micro-structure feature possessed by the electrode material for super capacitor as prepared by embodiment 1-4, they can make For the working electrode material in supercapacitor come using.
We are just with a kind of preparation of the working electrode of electrode material for super capacitor prepared by embodiment 1-4 below, It is tested using performance of the cyclic voltammetry to supercapacitor.
Specific test condition are as follows: use platinum electrode as to electrode, mercuric oxide electrode is reference electrode and above-mentioned work electricity Pole, electrolyte are 6mol KOH solution, voltage window 0-0.5V, sweep speed 5mV/S-100 mV/S.Embodiment 1- is implemented Test result is as follows shown in table 1 as working electrode specific for the electrode material for super capacitor of example 4:
A kind of the performance test results for electrode material for super capacitor that 1 embodiment 1-4 of table is provided
As can be seen from Table 1, the electrode material for super capacitor of embodiment 1-4 preparation has in 6mol KOH electrolyte There is excellent capacitive property.As can be seen that when current density is that 0.5A/g carries out charge and discharge, the embodiment of the present invention 1-4's Specific capacitance can respectively reach 2025F/g, 1956F/g, 1525F/g and 1716 F/g.
Through detecting, in the prior art, when current density is that 1A/g carries out charge and discharge, porous Ni (OH)2Specific capacitance It can reach 1842F/g, the Ni (OH) synthesized with hydro-thermal method2/ rGO is under the current density of 2A/g, specific capacitance 1224F/g, and one In 6mol KOH electrolyte solution, specific capacitance exists the electrode material for super capacitor of the 2D or 3D structure of a little other method preparations It can reach 1747F/g under the current density of 1A/g, from the point of view of 1 testing result of table is compared with the prior art, supercapacitor of the present invention The current density needed is small, but the specific capacitance and the prior art that generate are very nearly the same, and the present invention is not necessarily to conductive agent and gluing Agent.
In addition, we also further determine it and sweep in difference for the electrode material for super capacitor that embodiment 1 provides Retouch the cyclic voltammetry curve figure under rate, Fig. 6 is the metal hydroxide thin film material that provides of embodiment 1 in different scanning rates Under cyclic voltammetry curve figure (sweep speed is followed successively by 5mV/s, 10 mV/s, 20mV/s, 30mV/s, 50mV/ in the direction of the arrow S, 80mV/s, 100mV/s.As seen from Figure 5, metal hydroxide thin film material exists a pair of symmetrical in the case where difference sweeps speed Redox peaks, show that sample all has fake capacitance property.The position of oxidation peak and reduction peak becomes with the increase for sweeping speed Change, with fast increase is swept, the area of redox peaks increases, and shows there is bigger capacitor in the case where height sweeps speed.
In conclusion the present invention provides not only a kind of preparation method of electrode material for super capacitor, and by inspection It surveys, supercapacitor of the invention is fully able to substitute on practicability the traditional capacitor containing conductive agent and adhesive, because This, has long-range meaning in terms of practical application.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.Embodiment described above is only to absolutely prove the present invention And the preferred embodiment lifted, protection scope are without being limited thereto.Those skilled in the art institute on the basis of the present invention The equivalent substitute or transformation of work, within the scope of the present invention, protection scope of the present invention is subject to claims.

Claims (9)

1. a kind of preparation method of electrode material for super capacitor, which is characterized in that specifically comprise the following steps:
(1) by the metal salt concentration soluble in water that is made into for the salting liquid of 0.01-0.1mol/L;The metal salt is nickel chloride, nitre The mixture of one or more of sour nickel, copper chloride or copper nitrate;
(2) triethanolamine is added in the salting liquid that step (1) is prepared and obtains mixed solution, wherein triethanolamine and metal from The molar ratio of son is 3-24:1;
(3) mixed solution obtained by step (2) is fitted into reaction kettle, the crystallization 6-24h at 120~220 DEG C;
(4) metal hydroxide thin film will be obtained after the washing of crystallization product obtained by step (3), suction filtration, drying;
(5) preparation of foam-metal current collector body: successively using dilute hydrochloric acid, water, EtOH Sonicate washing foam metal, be dried in vacuo, Obtain foam-metal current collector body;The foam metal is nickel foam or foam copper;
(6) metal hydroxide thin film in step (4) is clipped among two panels foam-metal current collector body, is forced into tablet press machine 5-20MPa obtains electrode material for super capacitor.
2. a kind of preparation method of electrode material for super capacitor according to claim 1, which is characterized in that prepare super When capacitor electrode material, the metal salt and the foam metal use same metal.
3. a kind of preparation method of electrode material for super capacitor according to claim 1, which is characterized in that step (4) Dry condition are as follows: 6-8 hours dry at 40-60 DEG C.
4. a kind of preparation method of electrode material for super capacitor according to claim 1, which is characterized in that step (5) In vacuum drying condition are as follows: dry 3-5 hours at 50-80 DEG C of vacuum.
5. a kind of preparation method of electrode material for super capacitor according to claim 1, which is characterized in that step (5) The concentration of middle dilute hydrochloric acid is 0.1-1mol/L.
6. a kind of preparation method of electrode material for super capacitor according to claim 1, which is characterized in that step (5) It is middle that foam-metal current collector type is cut into 2 × 2 × 0.4cm3, then wash again.
7. a kind of preparation method of electrode material for super capacitor according to claim 6, which is characterized in that by step (4) gained metal hydroxide thin film is cut into 1 × 1 × 0.1cm3Size, foam-metal current collector body obtained by step (5) is cut At 1 × 1 × 0.2cm3Size;Then the operation of step (6) is carried out again.
8. super capacitor made of a kind of any one of -7 preparation methods of electrode material for super capacitor according to claim 1 Device electrode material.
9. application of the electrode material for super capacitor in preparation supercapacitor according to claim 8.
CN201910123441.3A 2019-02-18 2019-02-18 Super capacitor electrode material, preparation method and application Expired - Fee Related CN109830380B (en)

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