CN105448535A - Preparation method of metal sulfide/carbon nanotube film super capacitor electrode material - Google Patents
Preparation method of metal sulfide/carbon nanotube film super capacitor electrode material Download PDFInfo
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- CN105448535A CN105448535A CN201510866656.6A CN201510866656A CN105448535A CN 105448535 A CN105448535 A CN 105448535A CN 201510866656 A CN201510866656 A CN 201510866656A CN 105448535 A CN105448535 A CN 105448535A
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- deionized water
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a preparation method of a metal sulfide/carbon nanotube film super capacitor electrode material. The method comprises the following steps: firstly, preparing a diluted ammonia water solution from deionized water and 25% ammonia water at the volume ratio of (18:1) to (10:1), or dissolving urea into the deionized water to prepare 25-75mg/ml of urea solution; adding a metal nitrate or metal chloride solution with the concentration of 0.1M to the diluted ammonia water solution or the urea solution at the volume ratio of (40:1) to (70:1); soaking a carbon nanotube film into the solution, reacting for 6-36 hours, and washing and drying the reacted carbon nanotube film; additionally dissolving a sulphur source into a mixed solution of the deionized water and ethyl alcohol, putting the carbon nanotube film into the solution, and transferring the carbon nanotube film and the solution into a polytetrafluoroethylene reaction kettle for reacting at 120-180 DEG C for 12 hours; and washing and drying the product and then preparing the metal sulfide/carbon nanotube film super capacitor electrode material. The preparation method is simple in process and friendly to environment; no harmful substance is generated; and a relatively uniform compound film is obtained.
Description
Technical field
The invention relates to ultracapacitor, particularly a kind of chemical reaction method prepares the method for metal sulfide/carbon nano-tube film electrode material for super capacitor.
Background technology
Metal sulfide is a kind of important transistion metal compound, and metal sulfide has the advantages such as good conductivity, higher redox active, cheap cost, is a kind of important electrode material with the ultracapacitor of development potentiality.But metal sulfide has two shortcomings: (1) and metal oxide are similar, and metal sulfide also has volumetric expansion in cyclic process, affect the electrical contact between active material; (2) metal sulfide generally presents pulverulence, and being prepared into electrode needs to use binding agent, and the technique of complexity.The method overcome the above problems at present has metal sulfide and material with carbon element compound, as Graphene or carbon nano-tube, or by metal sulfide growth on the conduction bodies such as nickel foam.But these methods all can not overcome above two problems simultaneously, for this reason, researchers consider binder free ground composite reactive electrode material in flexible electrode material.Common are at present and carry out complex sulfide on carbon cloth or carbon fiber, but on carbon cloth or carbon fiber, specific area is large not, and reaction exists and needs acid treatment etc. to have the course of reaction of pollution.
Summary of the invention
Object of the present invention, overcome the shortcoming that prior art can not overcome metal sulfide well, course of reaction exists to be polluted, and has the complex matrix of more bigger serface simultaneously, provides a kind of two step chemical methodes that adopt to prepare metal sulfide/carbon nano-tube film electrode material for super capacitor.
The present invention is achieved by following technical solution.
(1) by deionized water and 25% ammoniacal liquor by volume 18:1 ~ 10:1 be hybridly prepared into dilute ammonia solution, or urea is dissolved in the urea liquid that deionized water compound concentration is 25 ~ 75mg/ml, magnetic agitation is even; In above-mentioned dilute ammonia solution or urea liquid, add metal nitrate or metal chloride solutions that concentration is 0.1M, stir; The volume ratio of dilute ammonia solution or urea liquid and metal nitrate or metal chloride solutions is 40:1 ~ 70:1;
(2) by area 1cm
2carbon nano-tube film is soaked in step (1) solution, in 25 DEG C ~ 140 DEG C reaction 6 ~ 36h;
(3) deionized water step (2) reacted carbon nano-tube film is spent, the dry 24h of normal-temperature vacuum, for subsequent use;
(4) by deionized water with ethanol by volume for 5:1 mixes, add Na
2s or CN
2h
4s is as sulphur source, and being mixed with concentration is 1mg/ml ~ 2mg/ml solution, and magnetic agitation is even;
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move into polytetrafluoroethylene reactor, in 120 DEG C ~ 180 DEG C reaction 12h;
(6) spend deionized water step (5) reacted carbon nano-tube film, the dry 24h of normal-temperature vacuum, namely obtains metal sulfide/carbon nano-tube super-capacitor electrode material.
Beneficial effect of the present invention uses to be compounded with SiO
2carbon nano-tube film make depositing base, avoid acid treatment etc. complicated and there is the pretreatment process of pollution, utilizing two step chemical reactions, provide the method for metal sulfide/carbon nano-tube film electrode material for super capacitor.The method technique is simple, and environmental friendliness, does not produce harmful substance, and can obtain more uniform complex thin film.
Accompanying drawing explanation
Fig. 1 is the Ni obtained in example 1
3si
2o
5(OH)
4the low power scan image of/carbon nano-tube coextruded film material;
Fig. 2 is the Ni obtained in example 1
3si
2o
5(OH)
4the high power scan image of/carbon nano-tube coextruded film material; Wherein white arrow indication is carbon nano-tube, and black tip indication is Ni
3si
2o
5(OH)
4;
Fig. 3 is the Ni obtained in example 1
3si
2o
5(OH)
4the transmission image of/carbon nano-tube coextruded film material;
Fig. 4 is the Ni obtained in example 1
3si
2o
5(OH)
4the X ray diffracting spectrum of/carbon nano-tube coextruded film material;
Fig. 5 is the Ni obtained in example 1
3s
2the low power scan image of/carbon nano-tube coextruded film material;
Fig. 6 is the Ni obtained in example 1
3s
2the high power scan image of/carbon nano-tube coextruded film material;
Fig. 7 is the Ni obtained in example 1
3s
2the transmission image of/carbon nano-tube coextruded film material;
Fig. 8 is the Ni obtained in example 1
3s
2the cyclic voltammetry curve of/carbon nano-tube coextruded film material;
Fig. 9 is the Ni obtained in example 1
3s
2the charging and discharging curve of/carbon nano-tube coextruded film material.
Embodiment
The present invention utilizes rational chemical reaction composition metal sulfide in self-supporting electrode material carbon nano-tube film, described carbon nano-tube film is the material with carbon element (see 2012103349212 patent applications) with Specific surface area of the applicant's one-step synthesis, the crystallinity of this carbon nano-tube film is good, there is unique mechanics, electrical properties and design feature, the superior conductive network of conductivity can be formed in the electrodes.By carbon nano-tube film and metal sulfide bi-material compound, the conductivity between active material can be optimized, alleviate the volumetric expansion problem that metal sulfide causes in redox reaction simultaneously, and prepare electrode process and do not need binding agent, thus substantially increase the utilance of electrode active material, make composite material have higher capacitive property and cycle performance.
The present invention adopts two step chemical methodes to prepare metal sulfide/carbon nano-tube coextruded film electrode material, to be compounded with SiO
2carbon nano-tube film make depositing base, than simple carbon nano-tube, there is better hydrophily, do not need the processes such as acid treatment, with SiO
2as reactivity site, reaction condition is gentle, and experimental implementation is simple, overcomes the problem of the uneven compound that simple chemical deposition exists simultaneously.
The present invention is done more specifically bright below in conjunction with specific embodiment.
Embodiment 1
(1) mixed by the ammoniacal liquor of 6ml deionized water and 0.33ml25%, magnetic agitation 5min to even, then adds 0.158ml0.1MNi (NO
3)
2solution, stirs;
(2) carbon nano-tube film of 1mg is soaked in above-mentioned solution, in 25 DEG C of reaction 24h;
(3) the reacted carbon nano-tube film of deionized water is spent, the dry 24h of normal-temperature vacuum, for subsequent use;
(4) 5ml deionized water is mixed with 1ml ethanol, add 6mgNa
2s is as sulphur source, and concentration is 1.0mg/ml, and magnetic agitation is even;
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move in 20ml polytetrafluoroethylene reactor, in 120 DEG C of reaction 12h;
(6) spend deionized water step (5) reacted carbon nano-tube film, the dry 24h of normal-temperature vacuum, obtains Ni
3s
2/ carbon nano-tube film electrode material for super capacitor.
Fig. 1 to Fig. 3 is the morphology characterization after the first step chemical reaction of embodiment 1, can find out the composite construction of sheet and tubulose; Fig. 4 is that the thing after the first step chemical reaction of embodiment 1 characterizes mutually, and explanation is Ni
3si
2o
5(OH)
4/ carbon nano-tube film composite material; Fig. 5 to Fig. 7 is the morphology characterization of the second step reaction of embodiment 1, can find out the basic pattern maintaining previous step reaction of second step reaction; Fig. 8 to Fig. 9 is the detection data of the electrode material of embodiment 1, comprises cyclic voltammetry curve and time-measuring electric potential curve, illustrates that synthetic can as super capacitor material.
Embodiment 2
(1) be dissolved in 20ml deionized water by 1g urea, magnetic agitation 5min to even, then adds 0.28ml0.1MNi (NO
3)
2, stir.
(2) 1mg carbon nano-tube film is soaked in above-mentioned solution, in 140 DEG C of reaction 12h.
(3) the reacted carbon nano-tube film of deionized water is spent, the dry 24h of normal-temperature vacuum, for subsequent use.
(4) 5ml deionized water is mixed with 1ml ethanol, add 6mgNa
2s, concentration is 1mg/ml, and magnetic agitation is even.
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move in 20ml polytetrafluoroethylene reactor, in 120 DEG C of reaction 12h.
(6) spend deionized water step (5) reacted carbon nano-tube film, the dry 24h of normal-temperature vacuum, obtains Ni
3s
2/ carbon nano-tube film electrode material for super capacitor.
Embodiment 3
(1) mixed by the ammoniacal liquor of 6ml deionized water and 0.6ml25%, magnetic agitation 5min to even, then adds 0.12ml0.1MCo (NO
3)
2, stir.
(2) 1mg carbon nano-tube film is soaked in above-mentioned solution, in 25 DEG C of reaction 24h.
(3) the reacted carbon nano-tube film of deionized water is spent, the dry 24h of normal-temperature vacuum, for subsequent use.
(4) 5ml deionized water is mixed with 1ml ethanol, add 12mgNa
2s, concentration is 2mg/ml, and magnetic agitation is even.
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move in 20ml polytetrafluoroethylene reactor, in 180 DEG C of reaction 12h.
(6) spend deionized water step (5) reacted carbon nano-tube film, the dry 24h of normal-temperature vacuum, obtains Ni
3s
2/ carbon nano-tube film electrode material for super capacitor.
Embodiment 4
(1) be dissolved in 20ml deionized water by 1g urea, magnetic agitation 5min to even, then adds 0.5ml0.1MNi (NO
3)
2with 0.3ml0.1MCo (NO
3)
2, stir.
(2) 1mg carbon nano-tube film is soaked in above-mentioned solution, in 120 DEG C of reaction 12h.
(3) the reacted carbon periosteum of deionized water is spent, the dry 24h of normal-temperature vacuum, for subsequent use.
(4) 5ml deionized water is mixed with 1ml ethanol, add 12mgCN
2h
4s, concentration is that magnetic agitation is even.
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move in 20ml polytetrafluoroethylene reactor, in 140 DEG C of reaction 12h.
(6) spend deionized water step (5) reacted carbon nano-tube film, the dry 24h of normal-temperature vacuum, obtains Ni
3s
2/ carbon nano-tube film electrode material for super capacitor.
The above-mentioned description to embodiment is convenient to those skilled in the art can understand and apply the invention.Person skilled in the art easily makes various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Each raw material cited by the present invention can realize the present invention, and the bound value of raw material, interval value can realize the present invention, then this is not illustrated one by one.
Claims (4)
1. a preparation method for metal sulfide/carbon nano-tube film electrode material for super capacitor, has following steps:
(1) by deionized water and 25% ammoniacal liquor by volume 18:1 ~ 10:1 be hybridly prepared into dilute ammonia solution, or urea is dissolved in the urea liquid that deionized water compound concentration is 25 ~ 75mg/ml, magnetic agitation is even; In above-mentioned dilute ammonia solution or urea liquid, add metal nitrate or metal chloride solutions that concentration is 0.1M, stir; The volume ratio of dilute ammonia solution or urea liquid and metal nitrate or metal chloride solutions is 40:1 ~ 70:1.
(2) by area 1cm
2carbon nano-tube film is soaked in step (1) solution, in 25 DEG C ~ 140 DEG C reaction 6 ~ 36h;
(3) deionized water step (2) reacted carbon nano-tube film is spent, the dry 24h of normal-temperature vacuum, for subsequent use;
(4) by deionized water with ethanol by volume for 5:1 mixes, add Na
2s or CN
2h
4s is as sulphur source, and being mixed with concentration is 1mg/ml ~ 2mg/ml solution, and magnetic agitation is even;
(5) carbon nano-tube film that step (3) obtains is put into step (4) solution, together move into polytetrafluoroethylene reactor, in 120 DEG C ~ 180 DEG C reaction 12h;
(6) spend the reacted carbon nano-tube film of deionized water, the dry 24h of normal-temperature vacuum, namely obtains metal sulfide/carbon nano-tube super-capacitor electrode material.
2. the preparation method of metal sulfide according to claim 1/carbon nano-tube film electrode material for super capacitor, its feature exists, and the metal nitrate in described step (1) is Ni (NO
3)
2, Co (NO
3)
2wherein a kind of or two kinds add simultaneously.
3. the preparation method of metal sulfide according to claim 1/carbon nano-tube film electrode material for super capacitor, its feature exists, and the metal chloride in described step (1) is NiCl
2, CoCl
2wherein a kind of or two kinds add simultaneously.
4. the preparation method of metal sulfide according to claim 1/carbon nano-tube film electrode material for super capacitor, its feature exists, the carbon nano-tube film in described step (2) be adopt the synthesis of floating catalytic chemical vapour deposition technique there is 10% ~ 80%SiO
2the carbon nano-tube film of content.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615620A (en) * | 2018-06-20 | 2018-10-02 | 华南理工大学 | It is a kind of using nickel foam as the carbon nanotube of substrate/metal sulfide combination electrode and preparation method thereof |
| CN108807005A (en) * | 2018-08-07 | 2018-11-13 | 华东师范大学 | A kind of preparation and its application of two selenizings vanadium nanometer sheet/carbon nano tube compound material |
| CN110070993A (en) * | 2018-01-24 | 2019-07-30 | 南京大学 | The preparation method of carbon nano-tube film high load Mn-Co sulfide flexible electrode material |
| CN114974913A (en) * | 2021-02-24 | 2022-08-30 | 北京大学深圳研究院 | Flexible electrode and preparation method and application thereof |
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| WO2010143793A1 (en) * | 2009-06-13 | 2010-12-16 | 경상대학교산학협력단 | Electrode for anode containing additive and metal sulfide, preparation method thereof, and battery using same |
| CN102881872A (en) * | 2012-09-11 | 2013-01-16 | 天津大学 | Method for synthesizing silicon oxide/carbon nanotube membranous lithium ion battery anode material by one step by utilizing chemical vapor deposition method |
| CN103531847A (en) * | 2012-07-06 | 2014-01-22 | 微宏动力系统（湖州）有限公司 | Lithium ion solid battery as well as synthesis method and synthesis device thereof |
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2015
- 2015-11-30 CN CN201510866656.6A patent/CN105448535B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010143793A1 (en) * | 2009-06-13 | 2010-12-16 | 경상대학교산학협력단 | Electrode for anode containing additive and metal sulfide, preparation method thereof, and battery using same |
| CN103531847A (en) * | 2012-07-06 | 2014-01-22 | 微宏动力系统（湖州）有限公司 | Lithium ion solid battery as well as synthesis method and synthesis device thereof |
| CN102881872A (en) * | 2012-09-11 | 2013-01-16 | 天津大学 | Method for synthesizing silicon oxide/carbon nanotube membranous lithium ion battery anode material by one step by utilizing chemical vapor deposition method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110070993A (en) * | 2018-01-24 | 2019-07-30 | 南京大学 | The preparation method of carbon nano-tube film high load Mn-Co sulfide flexible electrode material |
| CN110070993B (en) * | 2018-01-24 | 2021-06-22 | 南京大学 | Preparation method of carbon nanotube film high-load Mn-Co sulfide flexible electrode material |
| CN108615620A (en) * | 2018-06-20 | 2018-10-02 | 华南理工大学 | It is a kind of using nickel foam as the carbon nanotube of substrate/metal sulfide combination electrode and preparation method thereof |
| CN108807005A (en) * | 2018-08-07 | 2018-11-13 | 华东师范大学 | A kind of preparation and its application of two selenizings vanadium nanometer sheet/carbon nano tube compound material |
| CN114974913A (en) * | 2021-02-24 | 2022-08-30 | 北京大学深圳研究院 | Flexible electrode and preparation method and application thereof |
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Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |
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Granted publication date: 20171027 Termination date: 20211130 |