CN104577059A - Method for directly growing carbon nanotube on foamed nickel substrate so as to prepare battery electrodes - Google Patents
Method for directly growing carbon nanotube on foamed nickel substrate so as to prepare battery electrodes Download PDFInfo
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- CN104577059A CN104577059A CN201410763931.7A CN201410763931A CN104577059A CN 104577059 A CN104577059 A CN 104577059A CN 201410763931 A CN201410763931 A CN 201410763931A CN 104577059 A CN104577059 A CN 104577059A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for directly growing a carbon nanotube on a foamed nickel substrate so as to prepare battery electrodes. The method comprises the following steps: (1) performing chemical and ultrasonic cleaning by taking foamed nickel as a catalysis and substrate material for chemical vapor deposition reaction of the carbon nanotube; and (2) setting a CVD reaction device, directly performing the chemical vapor deposition growth of the carbon nanotube on the foamed nickel substrate in the CVD reaction device, the flow ratio between a hydrocarbon gas and a carrier gas is (10-40sccm):(100-400sccm) when the growth temperature is at 600-900DEG C, the growth pressure is at 1-760Torr, and the growth time lasts for 1-30min. The method has the advantages that the significant role in enhancing the performance of a battery device can be achieved, the specific surface area and the electrochemical activity of the CNT-foamed nickel substrate can be obviously improved, and the cycle life of the CNT-foamed nickel substrate nickel-hydrogen battery can be obviously prolonged.
Description
Technical field
The invention belongs to carbon nano-tube application, specifically refer to that in foam nickel base, direct growth carbon nano-tube is to prepare the method for nickel foam battery electrode.
Background technology
Nickel foam has excellent catalytic activity, in loose structure, surface area is large, and in the multiple battery such as Ni-MH battery, ultracapacitor energy device, nickel foam prepares the important materials of battery electrode.Improve the catalytic activity, porousness, conductivity etc. of nickel foam, significant for the performance strengthening battery device.
Carbon nano-tube (CNTs) has typical stratiform hollow structure feature, higher draw ratio, high mechanical properties, stable chemical property, makes it obtain extensive concern and research in the application of battery power devices field.Therefore, being combined with nickel foam by CNTs, is the effective way improving associated batteries energy device performance.
At present, in prior art, the application of CNTs in the battery device relevant to nickel foam mainly contains two kinds of approach: the first is by CNTs and battery active material mixing dry-pressing or makes slurry and be coated in nickel foam, the second is at nickel foam superficial growth CNTs, and main purpose comprises the conductivity improving active material, the specific area increasing nickel foam and activity etc.In the application of nickel foam superficial growth CNTs, the high-quality CNT-underlying structure that preparation binding ability is excellent is the key of application, directly affects the machinery of device, electrical and thermal conductivity performance and life-span.
In the prior art, nickel foam grows in the technique of CNTs, conventional means first deposit one deck catalyst, then carry out CNTs growth through CVD.By the restriction of CNTs growth mechanism, thus there are some inherent shortcomings in this method, comprising:
1) in structural behaviour, be difficult between CNT-catalytic metal film-substrate form strong organically combination, under different application conditions impacts, carbon nanotube thin film easily comes off, and directly affects performance and the life-span of device;
2) electric conductivity of CNT-catalytic metal film-substrate structure is not good, affects the performance of the device such as electronics, the energy;
3) not intimately associated of CNT-catalytic metal film-substrate structure can cause larger heat dissipation, not only can directly affect the characteristics such as the efficiency of energy device, also can accelerate the aging of device.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and to provide in a kind of foam nickel base direct growth carbon nano-tube to prepare the method for nickel foam battery electrode.Grown in foam nickel base evenly by the method carbon nano-tube, crystallographic be good, strong and processing step is simply efficient with substrate caking power, thus improve its performance as nickel foam battery electrode.
For achieving the above object, technical scheme of the present invention comprises the following steps:
(1) select nickel foam to do catalysis and the base material of carbon nanotube chemical vapor deposition reaction, chemistry and ultrasonic clean are carried out to foam nickel base;
(2) CVD reaction unit is set, and foam nickel base is directly carried out to the chemical vapor deposition growth of carbon nano-tube in CVD reaction unit, described CVD reaction unit comprises tube furnace, be arranged at the inlet channel of tube furnace side, and be arranged at the vacuum air pump of the tube furnace other end, the high temperature resistant pallet of foam nickel base is carried, be placed in the middle of tube furnace, with vacuum air pump, tube furnace is evacuated to the vacuum state of pressure <1 Torr, tube furnace is heated simultaneously, and carrier gas is passed in quartzy stove, when diamond heating temperature reaches 600-900 DEG C, the hydrocarbon gas of suitable flow-rate ratio is passed in stove, the flow-rate ratio of this hydrocarbon gas and carrier gas is (10-40sccm): (100-400sccm), and the pressure controlled in reacting furnace is at 1-760Torr, start the carbon nano tube growth of 1-30min, after growth terminates, stop heating, close hydrocarbon source of the gas, maintenance carrier gas passes into, reacting furnace is allowed to be cooled to room temperature, take out sample.
Further setting is the anodization being also provided with foam nickel base between described step (1) and (2), select acid solution, take foam nickel base as positive pole, corrosion-resistant conductor is selected to make negative pole, at the fixed voltage of two interpolars 1-100V in addition, continue 0.1-10 minute, after anodization, chemistry, ultrasonic cleaning are carried out to foam nickel base.
This anodized principle and advantage is: anodic passivity reaction occurs on the surface of metal base and electrolyte contacts, metallic substrates is as anode, betatopic oxidation reaction is there is after energising, under extra electric field impact, metal ion is vagus escape in metal lattice, and crosses metal oxide interface and enter oxide-film, to external migration or diffusion, form hole, chemical equation is:
Form oxonium ion at electrolyte and metal surface, chemical equation is:
Oxonium ion is expanded in the opposite direction, defines metal oxide film when meeting with metal ion.The process generating oxide-film due to anode belongs to exothermic process, and the electric current passed through in the column hole of film can run into larger resistance, and then generation heat energy makes the constant temperature of liquid in groove raise, and cause oxide-film generation chemolysis, its chemical equation is:
When the speed that metal surface forms oxide is less than the speed of its chemolysis, this oxide-film just can disappear under a certain suitable electrolytic parameter.
Therefore regulate electrolytic parameter that metal can be made when surface not modification, only change surface topography.Metal ion can form nano level male and fomale(M&F) after escaping from surface, is conducive to the homoepitaxial of CNTs, and realizes the strong combination of carbon nano-tube and substrate.The innovation of this technology be to after metallic substrates anodization, with the uniformity of the CNT of CVD direct growth and and the tack of substrate significantly improve.The key of technique is to control anodisation conditions, reaches and only changes metal substrate surface pattern, increase metal specific area, and do not make its surface modification.
Further setting is described hydrocarbon gas is acetylene, methane, ethene etc.
Further setting is that in described step (2), the growth temperature of carbon nano-tube is 625 DEG C, and growth pressure is 30Torr, growth time 10min.
General principle of the present invention is the nickel catalysis utilizing nickel foam itself, makes hydrocarbon gas direct catalytic decomposition in foam nickel base go out carbon atom and growth formation carbon nano-tube.By technological parameter of the present invention, control the factor such as type, gas flow, growth pressure, reaction temperature of hydrocarbon gas, the CNT-nickel foam structure of preparation and substrate binding ability excellence.
The beneficial effect of method of the present invention has: 1) CNTs and foam nickel base excellent bonding performance.Under suitable process conditions, CNTs can grow from nickel foam inside, organic with substrate and be combined very consumingly, and mechanical performance is excellent, is conducive to performance and the life-span of improving device;
2) the CNT-nickel foam structural conductive excellent performance of preparation of the present invention, heat dissipation are low, improve the performances such as the electricity of device, calorifics;
3) CNTs can be grown at nickel foam loose structure inner homogeneous, effectively improve specific area and the catalytic activity of foam nickel base;
4) concise in technology, eliminates metal deposition step, is convenient to industrial applications.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
The carbon nano-tube prepared described in Fig. 1 specific embodiment of the invention SEM 50 times in foam nickel base amplifies shape appearance figure;
The carbon nano-tube prepared described in Fig. 2 specific embodiment of the invention SEM 1000 times in foam nickel base amplifies shape appearance figure;
The carbon nano-tube prepared described in Fig. 3 specific embodiment of the invention SEM 20000 times in foam nickel base amplifies shape appearance figure;
Fig. 4 schemes based on the Ni-MH battery negative electrode section S EM of the CNT-nickel foam prepared by the present invention;
The Cyclic voltamogram comparison diagram of the CNT-foam nickel material of Fig. 5 pure foam nickel and preparation of the present invention;
The discharge curve of Fig. 6 (a) CNT-nickel foam battery and pure foam nickel-based battery;
The charge and discharge circulation life figure of Fig. 6 (b) CNT-nickel foam battery and pure foam nickel-based battery two kinds of batteries;
Fig. 7 is based on the Ni-MH battery EIS curve chart of different foam nickel substrate.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
Embodiment
In this CVD reaction unit, carry out direct growth carbon nano-tube in nickeliferous metallic substrates and prepare the method for nickel-hydrogen battery electrode, comprising the following steps:
(1) carry out chemistry, ultrasonic cleaning to nickeliferous metallic substrates, this nickeliferous metallic substrates of the present embodiment is nickel foam;
(2) CVD reaction unit is set, and nickeliferous metallic substrates is carried out to the chemical gas phase reaction growth of carbon nano-tube in CVD reaction unit, described CVD reaction unit comprises quartz heating furnace, be arranged at the inlet channel of quartz heating furnace side, and be arranged at the vacuum air pump of the quartz heating furnace other end, the quartzy pallet of nickeliferous metallic substrates is carried, be placed in the middle of quartz heating furnace, with vacuum air pump, quartz heating furnace is evacuated to the vacuum state of pressure <1 Torr, quartz heating furnace is heated simultaneously, and carrier gas is passed in quartzy stove, when quartz heating furnace heating-up temperature reaches 625 DEG C, the hydrocarbon gas of suitable flow-rate ratio is passed in stove, the flow-rate ratio of this hydrocarbon gas and carrier gas is 20sccm:200sccm, and the pressure controlled in reacting furnace is at 0.5Torr, start the carbon nano tube growth of 10min, after growth terminates, stop heating, close hydrocarbon source of the gas, maintenance carrier gas passes into, reacting furnace is allowed to be cooled to room temperature, take out sample.
To the CNT-nickel foam prepared by above-mentioned condition for the preparation of nickel-hydrogen battery electrode.
(1) cutting CNT-nickel foam is to required size.
(2) AB5 type hydrogen storage alloy powder is used as battery cathode active substance, selects nickel powder as conductive agent; Nickel hydroxide is used as positive active material, selects cobalt protoxide as conductive agent.Add polytetrafluoroethylene (PTFE) micro mist adhesive in both positive and negative polarity active material respectively, and in mortar, carry out hand lapping respectively, mix with electroconductive binder to make active material.
(3) use Manual tablet pressing machine to carry out compressing tablet to a certain amount of active mixture powder, be about 0.6mm at 30MPa lower sheeting to sheet thickness, then clamp this active mixture sheet and compacting under 30MPa by two panels CNT-nickel foam.Or a certain amount of active mixture powder is filled in nickel foam, after press to 0.6mm thickness by tablet press machine at 30MPa.
(4) two panels negative pole is adopted, the structure of a slice positive pole, respectively electric welding lug.
(5) 6M potassium hydroxide aqueous solution is configured, assembling simulation Ni-MH battery test block.
test example
ESEM JEOL6700 is utilized to have studied the pattern of CNTs on nickel foam surface.Fig. 1-3 is at pressure 30torr, 625 DEG C, the SEM shape appearance figure of the CNTs of nickel foam growth under 10min condition.As can be seen from the figure, carbon nano-tube is at surface distributed even compact, and orientation disorder, tangles mutually, and caliber is about about 50nm.
Be studied the application of CNT-nickel foam in battery device prepared by above-mentioned condition, application dry powder rolling techniques, prepared nickel-hydrogen battery electrode, Fig. 4 is the SEM sectional view of negative electrode.As shown in Figure 4, elongated CNTs interts between active material, with the form of limb effectively enhance active material polymerism, enhance bonding force between active material and substrate, serve and slow down the effect that in circulating battery process, active material comes off, and increase the conductivity of material, thus increase battery discharge specific capacity, extend battery cycle life.
By electrochemistry circulation CV characteristic test (Fig. 5) to CNT-nickel foam and pure foam nickel, we find, nickel foam grows after CNTs through CVD, and surface area increases greatly, and electro-chemical activity increases greatly.
Present inventor have studied Ni-MH battery discharge capability based on CNT-foam nickel material and cycle life (not being prepared into sealed cell), and compares with the battery performance based on pure foam nickel.Fig. 6 (a) shows, and battery is after discharge and recharge activation, and under 0.2C charging, 0.4C discharge into cut-ff voltage 0.1V condition, the Ni-MH battery specific discharge capacity based on CNT-nickel foam reaches 360.9mAh/g, and in electric discharge, pressure is 1.26V.And the specific discharge capacity of pure foam nickel-based battery only reaches 303.9mAh/g, in electric discharge, press 1.23V.Under identical discharge and recharge condition, press and be all improved in battery discharge specific capacity and electric discharge, wherein specific discharge capacity improves nearly 20%.Fig. 6 (b) shows, and the nickel-hydrogen cell charging and discharging performance based on CNT-nickel foam is highly stable, and after about 225 charge and discharge cycles, specific discharge capacity only have dropped 9.5%; And pure foam nickel-based battery specific discharge capacity after about 90 circulations declines fast.The polymerization highly significant of CNTs to active material is described, effectively improves the life performance of battery.
Present inventor has also carried out EIS test to Different electrodes, as shown in Figure 7.Compared with pure foam nickel electrode, in nickel foam, direct growth CNTs can reduce the charge transfer resistance in battery greatly, and then improves battery performance.
The application is by CVD direct growth technology, and direct growth CNTs in foam nickel base, serve significant effect to the performance strengthening battery device, specific area and the electro-chemical activity of CNT-foam nickel base are significantly improved.Ni-MH battery application in, the CNTs interted between active material effectively enhance active material polymerism, enhance bonding force between active material and substrate, effectively extend the cycle life of battery; Meanwhile, CNTs is directly connected with substrate, increases the conductivity of electrode active material, reduces the internal resistance of cell, increases battery discharge specific capacity.
Claims (4)
1. in foam nickel base, direct growth carbon nano-tube prepares a method for battery electrode, it is characterized in that comprising the following steps:
(1) select nickel foam to do catalysis and the base material of carbon nanotube chemical vapor deposition reaction, chemistry and ultrasonic clean are carried out to foam nickel base;
(2) CVD reaction unit is set, and foam nickel base is directly carried out to the chemical vapor deposition growth of carbon nano-tube in CVD reaction unit, described CVD reaction unit comprises tube furnace, be arranged at the inlet channel of tube furnace side, and be arranged at the vacuum air pump of the tube furnace other end, the high temperature resistant pallet of foam nickel base is carried, be placed in the middle of tube furnace, with vacuum air pump, tube furnace is evacuated to the vacuum state of pressure <1 Torr, tube furnace is heated simultaneously, and carrier gas is passed in quartzy stove, when diamond heating temperature reaches 600-900 DEG C, the hydrocarbon gas of suitable flow-rate ratio is passed in stove, the flow-rate ratio of this hydrocarbon gas and carrier gas is (10-40sccm): (100-400sccm), and the pressure controlled in reacting furnace is at 1-760Torr, start the carbon nano tube growth of 1-30min, after growth terminates, stop heating, close hydrocarbon source of the gas, maintenance carrier gas passes into, reacting furnace is allowed to be cooled to room temperature, take out sample.
2. in a kind of foam nickel base according to claim 1, direct growth carbon nano-tube prepares the method for nickel foam battery electrode, it is characterized in that: the anodization being also provided with foam nickel base between described step (1) and (2), select acid solution, take foam nickel base as positive pole, corrosion-resistant conductor is selected to make negative pole, at the fixed voltage of two interpolars in addition 1-100V, continue 0.1-10 minute, after anodization, chemistry, ultrasonic cleaning are carried out to foam nickel base.
3. in a kind of foam nickel base according to claim 1, direct growth carbon nano-tube prepares the method for nickel foam battery electrode, it is characterized in that: described hydrocarbon gas is acetylene, methane, ethene.
4. in a kind of foam nickel base according to claim 1, direct growth carbon nano-tube prepares the method for nickel foam battery electrode, it is characterized in that: in described step (2), the growth temperature of carbon nano-tube is 625 DEG C, growth pressure is 30Torr, growth time 10min.
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Cited By (8)
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CN105552382A (en) * | 2016-01-19 | 2016-05-04 | 中国科学院化学研究所 | Current collector for metal secondary battery negative electrode and preparation method and application for current collector |
WO2017124659A1 (en) * | 2016-01-19 | 2017-07-27 | Institute Of Chemistry, Chinese Academy Of Sciences | A modified 3d current collector, its application in lithium metal batteries and method for preparing said composite material |
CN107887177A (en) * | 2017-10-23 | 2018-04-06 | 温州大学 | A kind of preparation method of manganese dioxide CNT foam nickel composite material electrode for capacitors |
CN110040718A (en) * | 2019-04-03 | 2019-07-23 | 温州大学 | A kind of preparation method of multi-walled carbon nanotube derived from 16 core molecule cluster of Thiacalixarene base |
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WO2020224573A1 (en) * | 2019-05-08 | 2020-11-12 | 广州理文科技有限公司 | Manufacturing methods for porous nano-nickel network structure based on crown ether supermolecule bound silver ions, supercapacitor electrode and supercapacitor |
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CN115340084A (en) * | 2022-08-11 | 2022-11-15 | 中国计量大学 | Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101661840A (en) * | 2009-07-23 | 2010-03-03 | 武汉大学 | Preparation method of super capacitor |
CN103700811A (en) * | 2014-01-06 | 2014-04-02 | 中国科学院福建物质结构研究所 | Preparation method for carbon nano tube lithium-air positive electrode material |
-
2014
- 2014-12-11 CN CN201410763931.7A patent/CN104577059B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101661840A (en) * | 2009-07-23 | 2010-03-03 | 武汉大学 | Preparation method of super capacitor |
CN103700811A (en) * | 2014-01-06 | 2014-04-02 | 中国科学院福建物质结构研究所 | Preparation method for carbon nano tube lithium-air positive electrode material |
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CN105552382A (en) * | 2016-01-19 | 2016-05-04 | 中国科学院化学研究所 | Current collector for metal secondary battery negative electrode and preparation method and application for current collector |
WO2017124659A1 (en) * | 2016-01-19 | 2017-07-27 | Institute Of Chemistry, Chinese Academy Of Sciences | A modified 3d current collector, its application in lithium metal batteries and method for preparing said composite material |
CN105552382B (en) * | 2016-01-19 | 2019-03-08 | 中国科学院化学研究所 | A kind of metal secondary batteries cathode collector and its preparation method and application |
US10847804B2 (en) | 2016-01-19 | 2020-11-24 | Institute Of Chemistry, Chinese Academy Of Sciences | Carbon nanosphere modified current collector for lithium metal battery and method for preparing the same |
CN107887177A (en) * | 2017-10-23 | 2018-04-06 | 温州大学 | A kind of preparation method of manganese dioxide CNT foam nickel composite material electrode for capacitors |
CN110040718A (en) * | 2019-04-03 | 2019-07-23 | 温州大学 | A kind of preparation method of multi-walled carbon nanotube derived from 16 core molecule cluster of Thiacalixarene base |
WO2020224573A1 (en) * | 2019-05-08 | 2020-11-12 | 广州理文科技有限公司 | Manufacturing methods for porous nano-nickel network structure based on crown ether supermolecule bound silver ions, supercapacitor electrode and supercapacitor |
CN110585905A (en) * | 2019-08-30 | 2019-12-20 | 辽宁建筑职业学院 | Fuel cell device for photocatalytic degradation of oil smoke and working method thereof |
CN110585905B (en) * | 2019-08-30 | 2021-12-24 | 辽宁建筑职业学院 | Fuel cell device for photocatalytic degradation of oil smoke and working method thereof |
CN113102755A (en) * | 2021-04-25 | 2021-07-13 | 中国海洋大学 | Intermetallic compound-carbon nanotube porous composite material and preparation method thereof |
CN113102755B (en) * | 2021-04-25 | 2022-04-05 | 中国海洋大学 | Intermetallic compound-carbon nanotube porous composite material and preparation method thereof |
CN115340084A (en) * | 2022-08-11 | 2022-11-15 | 中国计量大学 | Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition |
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