CN105448535B - The preparation method of metal sulfide/carbon nano-tube film electrode material for super capacitor - Google Patents
The preparation method of metal sulfide/carbon nano-tube film electrode material for super capacitor Download PDFInfo
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- CN105448535B CN105448535B CN201510866656.6A CN201510866656A CN105448535B CN 105448535 B CN105448535 B CN 105448535B CN 201510866656 A CN201510866656 A CN 201510866656A CN 105448535 B CN105448535 B CN 105448535B
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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 kind of preparation method of metal sulfide/carbon nano-tube film electrode material for super capacitor, first by deionized water with 25% ammoniacal liquor by volume 18:1~10:1 is configured to dilute ammonia solution, or urea is dissolved in into the urea liquid that deionized water compound concentration is 25~75mg/ml；Again in above-mentioned dilute ammonia solution or urea liquid by volume 40:1~70:1 adds the metal nitrate or metal chloride solutions that concentration is 0.1M；Carbon nano-tube film is soaked in above-mentioned solution again, 6~36h is reacted, after reacted carbon nano-tube film is washed, dried；It is another that sulphur source is dissolved in deionized water with alcohol mixed solution, carbon nano-tube film being put into this solution, is transferred along to ptfe autoclave, react 12h in 120 DEG C~180 DEG C；Metal sulfide/carbon nano-tube film electrode material for super capacitor is made after washing, drying.Present invention process is simple, environment-friendly, does not produce harmful substance, has obtained than more uniform complex thin film.
Description
Technical field
The present invention is that, on ultracapacitor, more particularly to one kind prepares metal sulfide/carbon with chemical reaction method
The method of nanotube films electrode material for super capacitor.
Background technology
Metal sulfide is a kind of important transistion metal compound, and metal sulfide has good electric conductivity, higher
The advantage such as redox active, cheap cost, be a kind of important electrode material of the ultracapacitor with development potentiality.
But metal sulfide has two shortcomings：(1) similar with metal oxide, metal sulfide also has body in cyclic process
Electrical contact between product expansion, influence active material；(2) pulverulence is typically presented in metal sulfide, is prepared into electrode needs
Using binding agent, and complicated technique.The method of solution problem above, which has, at present is combined metal sulfide with carbon material, such as
Graphene or CNT, or metal sulfide is grown on the conductive body such as nickel foam.But these methods all can not be same
When overcome two above problem, therefore, researchers consider the binder free ground composite reactive electrode material in flexible electrode material
Material.It common are at present and complex sulfide carried out on carbon cloth or carbon fiber, but specific surface area is inadequate on carbon cloth or carbon fiber
Greatly, and react in the presence of the course of reaction that needs acid treatment etc. to have pollution.
The content of the invention
The purpose of the present invention, is to overcome prior art to overcome the shortcoming of metal sulfide well, course of reaction is deposited
In pollution, at the same have the complex matrix of more bigger serface there is provided it is a kind of using two step chemical methodes 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 mass percent for 25% ammoniacal liquor by volume 18:1~10:1 is hybridly prepared into dilute ammonia
The aqueous solution, or urea is dissolved in the urea liquid that deionized water compound concentration is 25~75mg/ml, magnetic agitation is uniform；
Metal nitrate or metal chloride solutions that concentration is 0.1M are added in above-mentioned dilute ammonia solution or urea liquid, stirring is equal
It is even；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 1cm2It is compounded with SiO2Carbon nano-tube film be soaked in step (1) solution, it is anti-in 25 DEG C~140 DEG C
Answer 6~36h；
(3) it is washed with deionized that step (2) is reacted to be compounded with SiO2Carbon nano-tube film, normal-temperature vacuum dry
24h, it is standby；
(4) it is 5 by volume by deionized water and ethanol:1 mixing, adds Na2S or CN2H4S is configured to dense as sulphur source
Spend for 1mg/ml~2mg/ml solution, magnetic agitation is uniform；
(5) SiO will be compounded with obtained by step (3)2Carbon nano-tube film be put into step (4) solution, together move into
Ptfe autoclave, 12h is reacted in 120 DEG C~180 DEG C；
(6) it is washed with deionized that step (5) is reacted to be compounded with SiO2Carbon nano-tube film, normal-temperature vacuum dry
24h, that is, obtain metal sulfide/carbon nano-tube super-capacitor electrode material.
Beneficial effects of the present invention, are to use to be compounded with SiO2Carbon nano-tube film make depositing base, it is to avoid acid treatment etc.
Pretreatment process that is complicated and having pollution, using two steps chemical reaction, there is provided the super electricity of metal sulfide/carbon nano-tube film
The method of container electrode material.This method technique is simple, environment-friendly, does not produce harmful substance, and it is equal to obtain comparison
Even complex thin film.
Brief description of the drawings
Fig. 1 be in example 1 obtained by Ni3Si2O5(OH)4The low power scan image of/carbon nano-tube coextruded film material；
Fig. 2 be in example 1 obtained by Ni3Si2O5(OH)4The high power scan image of/carbon nano-tube coextruded film material；
Wherein white arrow meaning is CNT, and black tip meaning is Ni3Si2O5(OH)4；
Fig. 3 be in example 1 obtained by Ni3Si2O5(OH)4The transmission image of/carbon nano-tube coextruded film material；
Fig. 4 be in example 1 obtained by Ni3Si2O5(OH)4The X ray diffracting spectrum of/carbon nano-tube coextruded film material；
Fig. 5 be in example 1 obtained by Ni3S2The low power scan image of/carbon nano-tube coextruded film material；
Fig. 6 be in example 1 obtained by Ni3S2The high power scan image of/carbon nano-tube coextruded film material；
Fig. 7 be in example 1 obtained by Ni3S2The transmission image of/carbon nano-tube coextruded film material；
Fig. 8 be in example 1 obtained by Ni3S2The cyclic voltammetry curve of/carbon nano-tube coextruded film material；
Fig. 9 be in example 1 obtained by Ni3S2The charging and discharging curve of/carbon nano-tube coextruded film material.
Embodiment
The present invention utilizes the composition metal sulfide, institute in self-supporting electrode material carbon nano-tube film that reasonably chemically reacts
It is the carbon material with Specific surface area of the applicant's one-step synthesis (see 2012103349212 patents to state carbon nano-tube film
Application), the crystallinity of the carbon nano-tube film is good, with unique mechanics, electrical properties and design feature, can shape in the electrodes
Into the superior conductive network of electric conductivity.By carbon nano-tube film and two kinds of Material claddings of metal sulfide, active matter can be optimized
Electric conductivity between matter, while alleviating metal sulfide volumetric expansion problem caused by redox reaction, and is prepared
Electrode process does not need binding agent, so as to substantially increase the utilization rate of electrode active material so that composite has higher
Capacitive property and cycle performance.
The present invention prepares metal sulfide/carbon nano-tube coextruded film electrode material using two step chemical methodes, with compound
There is SiO2Carbon nano-tube film make depositing base, there is more preferable hydrophily than simple CNT, it is not necessary to acid treatment etc.
Process, with SiO2As reactivity site, reaction condition is gentle, and experimental implementation is simple, while overcoming simple chemical deposition
Exist it is uneven compound the problem of.
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
(1) 6ml deionized waters and 0.33ml 25% ammoniacal liquor are mixed, magnetic agitation 5min is added to uniform
0.158ml 0.1M Ni(NO3)2Solution, stirs；
(2) 1mg carbon nano-tube film is soaked in above-mentioned solution, 24h is reacted in 25 DEG C；
(3) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, standby；
(4) 5ml deionized waters are mixed with 1ml ethanol, adds 6mg Na2S is as sulphur source, and concentration is 1.0mg/ml, magnetic
Power stirs；
(5) carbon nano-tube film obtained by step (3) is put into step (4) solution, together moves into 20ml polytetrafluoroethyl-nes
In alkene reaction kettle, 12h is reacted in 120 DEG C；
(6) step (5) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, produces Ni3S2/
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, it can be seen that sheet and tubulose are answered
Close structure；Fig. 4 is that the thing after the first step chemical reaction of embodiment 1 is mutually characterized, and explanation is Ni3Si2O5(OH)4/ carbon nano-tube film
Composite；Fig. 5 to Fig. 7 is the morphology characterization of the second step reaction of embodiment 1, it can be seen that second step reaction is basic to be maintained
The pattern of single step reaction；Fig. 8 to Fig. 9 is the detection data of the electrode material of embodiment 1, including cyclic voltammetry curve and timing electricity
Position curve, illustrates that synthetic can be as super capacitor material.
Embodiment 2
(1) 1g urea is dissolved in 20ml deionized waters, magnetic agitation 5min adds 0.28ml 0.1M Ni to uniform
(NO3)2, stir.
(2) 1mg carbon nano-tube films are soaked in above-mentioned solution, 12h is reacted in 140 DEG C.
(3) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, standby.
(4) 5ml deionized waters are mixed with 1ml ethanol, adds 6mg Na2S, concentration is 1mg/ml, and magnetic agitation is uniform.
(5) carbon nano-tube film obtained by step (3) is put into step (4) solution, together moves into 20ml polytetrafluoroethyl-nes
In alkene reaction kettle, 12h is reacted in 120 DEG C.
(6) step (5) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, produces Ni3S2/
Carbon nano-tube film electrode material for super capacitor.
Embodiment 3
(1) 6ml deionized waters and 0.6ml 25% ammoniacal liquor are mixed, magnetic agitation 5min is added to uniform
0.12ml0.1M Co(NO3)2, stir.
(2) 1mg carbon nano-tube films are soaked in above-mentioned solution, 24h is reacted in 25 DEG C.
(3) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, standby.
(4) 5ml deionized waters are mixed with 1ml ethanol, adds 12mg Na2S, concentration is 2mg/ml, and magnetic agitation is equal
It is even.
(5) carbon nano-tube film obtained by step (3) is put into step (4) solution, together moves into 20ml polytetrafluoroethyl-nes
In alkene reaction kettle, 12h is reacted in 180 DEG C.
(6) step (5) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, produces Ni3S2/
Carbon nano-tube film electrode material for super capacitor.
Embodiment 4
(1) 1g urea is dissolved in 20ml deionized waters, magnetic agitation 5min adds 0.5ml 0.1M Ni to uniform
(NO3)2With 0.3ml 0.1M Co (NO3)2, stir.
(2) 1mg carbon nano-tube films are soaked in above-mentioned solution, 12h is reacted in 120 DEG C.
(3) reacted carbon periosteum is washed with deionized, normal-temperature vacuum dries 24h, standby.
(4) 5ml deionized waters are mixed with 1ml ethanol, adds 12mg CN2H4S, concentration is that magnetic agitation is uniform.
(5) carbon nano-tube film obtained by step (3) is put into step (4) solution, together moves into 20ml polytetrafluoroethyl-nes
In alkene reaction kettle, 12h is reacted in 140 DEG C.
(6) step (5) reacted carbon nano-tube film is washed with deionized, normal-temperature vacuum dries 24h, produces Ni3S2/
Carbon nano-tube film electrode material for super capacitor.
The above-mentioned description to embodiment is easy for those skilled in the art and is understood that and using the present invention.It is ripe
The personnel for knowing art technology easily make various modifications to these embodiments, and General Principle described herein is applied to
Without passing through performing creative labour in other embodiment.Therefore, the invention is not restricted to embodiment here, people in the art
Member is according to the announcement of the present invention, and the improvement made for the present invention and modification all should be 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 be real
Show the present invention, then this is not illustrated one by one.
Claims (4)
1. the preparation method of a kind of metal sulfide/carbon nano-tube film electrode material for super capacitor, with following steps：
(1) by deionized water and mass percent for 25% ammoniacal liquor by volume 18:1~10:1 to be hybridly prepared into weak aqua ammonia molten
Liquid, or urea is dissolved in the urea liquid that deionized water compound concentration is 25~75mg/ml, magnetic agitation is uniform；Above-mentioned
Metal nitrate or metal chloride solutions that concentration is 0.1M are added in dilute ammonia solution or urea liquid, is stirred；
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 1cm2It is compounded with SiO2Carbon nano-tube film be soaked in step (1) solution, in 25 DEG C~140 DEG C react 6
~36h；
(3) it is washed with deionized that step (2) is reacted to be compounded with SiO2Carbon nano-tube film, normal-temperature vacuum dry 24h, it is standby
With；
(4) it is 5 by volume by deionized water and ethanol:1 mixing, adds Na2S or CN2H4S is as sulphur source, and being configured to concentration is
1mg/ml~2mg/ml solution, magnetic agitation is uniform；
(5) SiO will be compounded with obtained by step (3)2Carbon nano-tube film be put into step (4) solution, together move into polytetrafluoro
Ethylene reaction kettle, 12h is reacted in 120 DEG C~180 DEG C；
(6) it is washed with deionized and reacted is compounded with SiO2Carbon nano-tube film, normal-temperature vacuum dry 24h, that is, obtain 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 the step (1) is Ni (NO3)2、Co(NO3)2One of which or two kinds of additions 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 the step (1) is NiCl2、CoCl2One of which or two kinds of additions 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 the step (2) be using floating catalytic chemical vapour deposition technique synthesize have 10%~
80%SiO2The carbon nano-tube film of content.
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| 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 |
| CN108615620B (en) * | 2018-06-20 | 2020-09-22 | 华南理工大学 | Carbon nano tube/metal sulfide composite electrode with foamed nickel as substrate and preparation method thereof |
| CN108807005B (en) * | 2018-08-07 | 2019-11-01 | 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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| 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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| WO2010143793A1 (en) * | 2009-06-13 | 2010-12-16 | 경상대학교산학협력단 | Electrode for anode containing additive and metal sulfide, preparation method thereof, and battery using same |
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| 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 |
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