CN110299516A - The preparation method of carbon nano pipe array load lithium titanate flexible electrode material - Google Patents
The preparation method of carbon nano pipe array load lithium titanate flexible electrode material Download PDFInfo
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- CN110299516A CN110299516A CN201910498127.3A CN201910498127A CN110299516A CN 110299516 A CN110299516 A CN 110299516A CN 201910498127 A CN201910498127 A CN 201910498127A CN 110299516 A CN110299516 A CN 110299516A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of carbon nano pipe array load lithium titanate flexible electrode material, carbon nano pipe array is grown on the carbon cloth of supported catalyst with chemical vapour deposition technique, and as flexible substrates, carbon nano pipe array is prepared by sol-gal process and high-temperature calcination technique and loads lithium titanate flexible electrode material, is comprised the following steps that and is loaded carbon nano-tube catalyst on carbon cloth using infusion process；Utilize chemical vapour deposition technique original position vertical-growth carbon nano pipe array；Using sol-gal process and high-temperature calcination, carbon nano pipe array is made and loads lithium titanate flexible electrode material.
Description
Technical field
The present invention relates to a kind of preparation methods of carbon nano pipe array load lithium titanate flexible electrode material, specifically
A kind of flexible electrode material for electrochemical energy storage, belongs to electrochemical energy storage field.
Background technique
With a large amount of consumption of the non-renewable energy resources such as fossil fuel, global ecological problems become increasingly conspicuous, while various countries' energy
Source crisis aggravation, therefore it is particularly important to develop novel green clean energy resource.Lithium ion battery exactly meets current energy development shape
Formula and a kind of novel power supply risen.Lithium ion battery is high with energy density, operating voltage is high, have extended cycle life, charge speed
The features such as spending fast, memory-less effect and non-environmental-pollution, therefore rapidly in energy storage such as electric car, portable electronic device power supplys
It is widely used in field.
Negative electrode material is the important component of lithium ion battery, is had extremely to the performance and cost of lithium ion battery
Important influence.The lithium ion battery negative material being commercialized at present mostly uses greatly various embedding lithium carbon materials.However, such carbon materials
Material but exist the precipitation of Li dendrite, easily have an effect with electrolyte, apparent voltage delay phenomenon the disadvantages of.And spinel-type titanium
Sour lithium (Li4Ti5O2) as a kind of " zero strain material " there is stable charging/discharging voltage platform (~1.55V), suitable theoretical
Capacity (~175mAh/g), high coulombic efficiency (> 96%), can effectively avoid Li dendrite and SEI in charge and discharge process
The advantages such as the formation of film (solidelectrolyte interface, solid electrolyte interface film).With commercialized graphitic carbon
Negative electrode material is compared, Li4Ti5O2With superior chemical property and safety in utilization, thus be considered as ideal lithium from
Sub- insertion-host electrode materials.But the electronic conductivity (10 almost to insulate-13S/m it is negative as lithium ion battery) to limit it
The performance of pole material property, it is therefore desirable to which high conductive material carries out compound improving electric conductivity.
Carbon nanotube has the characteristics that bigger serface, excellent electric conductivity and mechanical performance, can be used as conductive agent material
Improve Li4Ti5O2Electric conductivity.For example, CN108878845A report a kind of lithium titanate microballoon carbon nano tube compound material and its
Carbon nanotube is carried out acidification first by preparation method, then using butyl titanate as titanium source, lithium hydroxide as lithium source, second
Glycol obtains lithium titanate precursor by hydro-thermal method as solvent with water, then calcines hydrothermal product in air atmosphere, obtains
Lithium titanate microballoon obtains most finally by finely dispersed carbon nanotube and lithium titanate microballoon ultrasonic disperse obtained by suction filtration
Final product lithium titanate microballoon carbon nano tube compound material discharges under the multiplying power of 1C when being used as lithium ion battery negative material
Specific capacity reaches 172mAh/g, and 100C capacity still has 121mAh/g when charge-discharge magnification is up to.However biggish Li4Ti5O2?
Particle size (> 2 microns) is easy in charge and discharge process the phenomenon that reuniting from recurring structure, and is unfavorable for infiltration and the lithium of electrolyte
The transmission of ion, electronics.CN105591082A report a kind of nano-sheet lithium titanate and multi-wall carbon nano-tube composite material and
Preparation method, using isopropyl titanate as titanium source, lithium hydroxide is lithium source, and diethylenetriamine is surfactant, isopropanol with
Water is solvent, is reacted by surface in situ and carbon nanotube lithium titanate nanometer sheet composite negative pole material is made, and is used as lithium-ion electric
When the negative electrode material of pond, its specific capacity is about 172mAh/g after circulation 100 times.However, the winding arrangement of carbon nanotube is easy to cause
The serious agglomeration traits of carbon nanotube, and the lower specific surface area of multi-walled carbon nanotube also limits it as electrode material
Performance plays.Therefore, carbon nanotube is prepared into array structure by researcher, improves the orientation of carbon nanotube, to optimize electronics
Transmission path improves the chemical property of material.And replace copper foil that good conduction not only can be improved as collector using carbon cloth
Property, also make electrode that there is flexible flex capability, can be applied to the fields such as wearable device and foldable electronic, have
Vast potential for future development.CN106784692A reports graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material
Preparation method for material and application, first with microwave plasma enhanced chemical vapour deposition technique on carbon cloth vertical-growth graphite
Secondly alkene array prepares vertical graphene-supported titanium dioxide combination electrode material using technique for atomic layer deposition, then with hydrogen
Lithia is that lithium source solution carries out hydro-thermal reaction, is then washed, dried and is calcined, and graphene array load lithium titanate is obtained
Composite array electrode.Finally, using chemical vapour deposition technique, it is raw on graphene array load lithium titanate composite array electrode
Long carbon nanotube, obtained graphene array load lithium titanate/carbon/carbon nano tube composite array electrode material have flexible support, height
High rate performance (10000 circulations still have 89.5% initial capacity).Although above-mentioned patent improves to a certain extent
Li4Ti5O2The reversible capacity and cycle life of negative electrode material, but carbon nano pipe array orientation is not high, carbon nanotube is big
It is easy to happen winding during current charging and discharging to reunite, and preparation process very complicated, processing step more difficult to control, affects it
In the application of lithium ion battery.Therefore, Li is refined4Ti5O2Nanoparticle size size, the orientation for improving carbon nanotube, with excellent
Change electron-transport path, the electric conductivity for improving material is to improve Li4Ti5O2The key of negative electrode material chemical property.
Summary of the invention
The object of the present invention is to provide a kind of carbon nano pipe array load lithium titanate flexible electrode material preparation method, with
Refine Li4Ti5O2Nanoparticle size size, the orientation for improving carbon nanotube.Carbon nano pipe array obtained by the present invention is negative
Carrying lithium titanate flexible electrode material also has self-supporting characteristic, is not necessarily to binder, conductive agent, improves the effective use of material
Rate provides new approaches to develop flexible electronic device.The present invention solves technical solution used by the technical problem:
A kind of preparation method of carbon nano pipe array load lithium titanate flexible electrode material, with chemical vapour deposition technique negative
Carbon nano pipe array is grown on the carbon cloth of carried catalyst, and as flexible substrates, passes through sol-gal process and high-temperature calcination work
Skill prepares carbon nano pipe array load lithium titanate flexible electrode material, comprises the following steps that
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process
Choose the metal complex of the first suitable acetylacetone,2,4-pentanedione, metal complex, the 1,2- of second acetylacetone,2,4-pentanedione
Hexadecane diol, oleic acid and oleyl amine are dissolved in suitable dibenzyl ethereal solution, prepare carbon nano-tube catalyst using circumfluence method, wherein
Reflux temperature is 120~300 DEG C, and carbon nano-tube catalyst is made；Then carbon cloth is immersed in carbon nano-tube catalyst solution,
Drying is taken out, obtains the carbon cloth of load carbon nano-tube catalyst, wherein the metal complex of the first acetylacetone,2,4-pentanedione is
Iron, cobalt, nickel, molybdenum, tungsten acetylacetone,2,4-pentanedione complex compound one kind；The metal complex-of second of acetylacetone,2,4-pentanedione be aluminium,
One kind of the complex compound of the acetylacetone,2,4-pentanedione of magnesium.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, in vacuum condition
Under, tube furnace is heated to 400~1200 DEG C under the protection of inert gas atmosphere, hydrogen, carbon-source gas is then passed to, carries out carbon and receive
Growth in situ of the mitron array on carbon cloth, after growth, is cooled to room temperature under inert gas protection, obtains on carbon cloth
The vertical carbon nanotube array of growth in situ.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material
By the lithium source of certain mass, titanium source according to certain mol proportion 4:(1~10), it is dissolved in organic solvent, obtains uniformly
Clear lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in titanium
Sour lithium precursor solution takes out drying；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace,
Under inert atmosphere protection, 300~900 DEG C are heated to, is cooled to room temperature after keeping the temperature a period of time, carbon nano pipe array is finally made
Load lithium titanate flexible electrode material.
Preferably, in step (1), according to 1:(0.1-10): (0.5-8): (0.1-5): the quality proportioning of (0.1-5) weighs
Metal complex, 1,2- hexadecane diol, oleic acid and the oil of the metal complex of the first acetylacetone,2,4-pentanedione, second acetylacetone,2,4-pentanedione
Amine.
Inert gas is nitrogen, argon gas.
Hydrogen flow rate is 50~1000mL/min, carbon-source gas flow velocity is 2~50mL/min.
The carbon-source gas is that one or more of acetylene, methane, natural gas, water-gas arbitrarily mix.
The lithium source is one of lithium hydroxide, lithium acetate, lithium chloride, lithium nitrate.
The titanium source is titanium tetrachloride, in iso-butyl titanate, four fourth rouge of metatitanic acid, isopropyl titanate, titanium acetylacetone
It is a kind of；
Organic solvent is one of methanol, ethyl alcohol, ether.
The organic solvent is one of methanol, ethyl alcohol, ether.
Obtained carbon nano pipe array load lithium titanate flexible electrode material is used as lithium ion battery negative material.
The beneficial effects of the present invention are: compared with prior art, the method for the present invention has substantive distinguishing features outstanding such as
Under:
(1) in design process of the invention, it is believed that influence carbon nano pipe array load lithium titanate flexible electrode material electricity
The principal element of chemical property has the conductive features of lithium titanate, the partial size of lithium titanate particle and carbon nano pipe array supported titanium
The microstructure of sour lithium.Wherein, electric conductivity has influence outstanding to the chemical property of lithium titanate electrode material.Of the invention
In design process, influence of the lithium titanate electric conductivity to negative electrode material chemical property has been fully considered, innovatively use and change
Vapour deposition process is learned, in compliant conductive collector --- growth in situ has high orientation, high conductivity, Large ratio surface on carbon cloth
Long-pending carbon nano pipe array, and in this, as conductive agent, it prepared by the technique combined using sol-gal process with high-temperature calcination
Carbon nano pipe array loads lithium titanate flexible electrode material out.This carbon nano pipe array load lithium titanate flexible electrode material was both
The electric conductivity of lithium titanate nano particle can be greatly improved, and because of the interspersed of carbon nanotube so that material has good structure
Stability；Meanwhile lithium titanate nano particle diameter made from the technique that is combined with high-temperature calcination of sol-gal process only 20~
Between 200nm, the diffusion path while lithium titanate nano particle that can be obviously shortened lithium ion are uniformly carried on vertical orientation
Carbon nano pipe array on, and carbon nano pipe array is as on conductive network growth in situ and flexible current-collecting body, therefore can have
The electric conductivity of the raising lithium titanate anode material of effect, the contact resistance for reducing electrode material and current collector material, are more advantageous to electricity
The quick transmission of chemical reaction process intermediate ion, electronics.Therefore, metatitanic acid is loaded using the carbon nano pipe array of preparation of the invention
The electrochemical performance of lithium flexibility negative electrode material.
(2) in design process of the invention, fully considered that carbon nano pipe array loads lithium titanate flexible electrode material
Preparation process, the period key issues of, it is innovative to use technique that sol-gal process is combined with high-temperature calcination in carbon
Lithium titanate nano particle is loaded on nano-tube array.So that using the final carbon nano pipe array obtained of process of the invention
Load lithium titanate flexible electrode material not only has a good chemical property, also has that preparation process is simple, process cycle is short
The high advantage with preparation efficiency.
Compared with prior art, marked improvement possessed by the method for the present invention is as follows:
(1) compared with prior art CN1O3594694A, the present invention overcomes above-mentioned lithium titanate materials in the prior art
The electric conductivity for expecting itself is poor, electronic conductivity is low, and the reversible capacity reacted in electrochemical reaction process is caused to reduce too fast, shadow
The problems such as ringing its high rate performance and cycle performance.
(2) compared with prior art CN108878845A, the present invention overcomes metatitanic acids made from the above-mentioned prior art
Lithium grain diameter is big, causes not to be in electrical contact effectively inside lithium titanate particle, limits the performance of lithium titanate chemical property, most
The problems such as affecting the lithium storage content and stability of its electrode material eventually,
(3) compared with the prior art is with CN105591082A and CN106784692A, the present invention overcomes above-mentioned existing
There are the low orientated property of carbon nanotube, winding arrangement in lithium titanate made from technology and carbon nano tube compound material, is easy to cause carbon
The serious agglomeration of nanotube, therefore the problems such as it is played as the performance of electrode material is limited, and prepare lithium titanate
With the problems such as complicated the step of carbon nano tube compound material, time-consuming.
(4) carbon nano pipe array prepared by the present invention loads lithium titanate flexible electrode material, passes through the control of synthesis technology
System, in 0.1mA/cm2After recycling 100 weeks, the specific discharge capacity of battery is up to 0.420~0.120mAh/cm2, through circulation 500 weeks
Afterwards, the specific discharge capacity of battery is still up to 0.402~0.108mAh/cm2, there is high reversible capacity and excellent cyclicity
Energy.
In short, carbon nano pipe array prepared by the present invention loads lithium titanate flexible electrode material, overcome in the prior art
The partial size of lithium titanate obtained is larger, the low orientated property of carbon nanotube, winding arrangement in lithium titanate and carbon nano tube compound material,
The lithium ion battery negative material chemical property prepared with it is bad, preparation process complexity and the defect that time-consuming.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 (a) is original carbon cloth electron scanning micrograph, and Fig. 1 (b) is carbon cloth obtained by the embodiment of the present invention 1
The vertical carbon nanotube array scanning electron micrograph of upper growth in situ.
Fig. 2 is that the scanning electron of the load lithium titanate composite material of carbon nano pipe array obtained by the embodiment of the present invention 1 is aobvious
Micro mirror photo.
Fig. 3 is the XRD spectrum that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material.
Fig. 4 is that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material as negative electrode material
When charging and discharging curve.
Fig. 5 is that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material as negative electrode material
When cycle performance curve.
Specific embodiment
Embodiment 1
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process；
By the ferric acetyl acetonade of 3.00g and 1.14g aluminium acetylacetonate, 1.61g 1,2- hexadecane diol, 0.9g oleic acid,
0.9g oleyl amine is dissolved in the mixed solution of 50mL benzyl ether, prepares carbon nano-tube catalyst using circumfluence method, wherein reflux temperature
For 200 DEG C, return time 60min, carbon nano-tube catalyst is made.Then carbon cloth is immersed in carbon nano-tube catalyst solution
In, drying is taken out, the carbon cloth of load carbon nano-tube catalyst is obtained.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized；
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, in vacuum condition
Under, tube furnace is heated to 850 DEG C under the protection of argon gas atmosphere, then passes to hydrogen (flow velocity 500mL/min), acetylene gas
Body (flow velocity 8mL/min) carries out carbon nano-pipe array and is listed in the growth in situ 10min on carbon cloth, after growth, in argon gas gas
It is cooled to room temperature under body protection, obtains the vertical carbon nanotube array of the growth in situ on carbon cloth.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material；
It is dissolved in 0.44g lithium acetate, 2.1g isopropyl titanate (molar ratio 4:5) in 50mL dehydrated alcohol, obtains uniformly
Clear lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in titanium
Sour lithium precursor solution takes out drying；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace,
700 DEG C are heated under argon atmosphere protection, is cooled to room temperature after keeping the temperature 12h, carbon nano pipe array is finally made and loads lithium titanate
Flexible electrode material.
Fig. 1 (a) is original carbon cloth electron scanning micrograph, and Fig. 1 (b) is carbon cloth obtained by the embodiment of the present invention 1
The vertical carbon nanotube array scanning electron micrograph of upper growth in situ.It can be seen from figure 1 that high orientation, highdensity carbon
Nano-tube array growth uniform and vertical on carbon cloth matrix, while remaining the original microscopic appearance of carbon cloth.
Fig. 2 is that the scanning electron of the load lithium titanate composite material of carbon nano pipe array obtained by the embodiment of the present invention 1 is aobvious
Micro mirror photo.It may be seen that lithium titanate nano particle is uniformly distributed between carbon nano pipe array and size is smaller, particle size
Size is about 200nm, and lithium titanate nano particle is connected by carbon nanotube, does not obviously bond agglomeration.
Fig. 3 is the XRD spectrum that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material.By
In synthesized carbon nano pipe array load lithium titanate composite material tool, there are carbon nanotubes, so observing carbon at 26.4o
Diffraction maximum；By comparing, the diffraction maximum in the figure matches with the mark pdf card of lithium titanate, shows that composite material contains
Lithium titanate object phase.
Cut the load of carbon nano pipe array obtained by the embodiment of the present invention 1 lithium titanate flexible electrode material into pieces conduct
Lithium ion battery negative material, i.e. working electrode, metal lithium sheet are auxiliary electrode, use concentration for the lithium hexafluoro phosphate of 1mol/L
(LiPF6) solution (being dissolved in the mixture that volume ratio is the ethylene carbonate of 1:1:1, dimethyl carbonate and diethyl carbonate) conduct
Electrolyte makees diaphragm using microporous polypropylene membrane.Battery assembly carries out in being full of the glove box of argon gas, humidity less than 1%, will
Working electrode, the diaphragm for being saturated with electrolyte, auxiliary electrode are assembled into button CR2025 half-cell.The lithium ion battery that will be assembled
Progress constant current charge-discharge test in 12 hours is placed, charging/discharging voltage is 1.0~3.0V, and lithium-ion electric is measured in room temperature environment
Capacity, multiplying power property and the charge-discharge performance of pond cathode.
Fig. 4 is that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material as negative electrode material
When charging and discharging curve.It may be seen that the head of the load lithium titanate composite material of carbon nano pipe array obtained by the present embodiment
Secondary charging capacity, discharge capacity are respectively 0.205mAh/cm2And 0.198mAh/cm2, irreversible capacity accounts for discharge capacity for the first time
3.41%.
Fig. 5 is that carbon nano pipe array obtained by the embodiment of the present invention 1 loads lithium titanate composite material as negative electrode material
When cycle performance curve.It may be seen that the load lithium titanate composite material warp of carbon nano pipe array obtained by the present embodiment
It crosses 100 weeks circulating and reversible capacity and reaches 0.162mAh/cm2, and its coulombic efficiency is up to 101.2%, the reversible appearance of electrode material
Amount is greatly improved and stable cycle performance.
Embodiment 2
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process；
By the ferric acetyl acetonade of 3.00g and 0.57g aluminium acetylacetonate, 3.22g 1,2- hexadecane diol, 0.30g oleic acid,
2.25g oleyl amine, is dissolved in the mixed solution of 50mL benzyl ether, prepares carbon nano-tube catalyst using circumfluence method, wherein reflux temperature
Degree is 220 DEG C, return time 240min, and carbon nano-tube catalyst is made.Then carbon cloth is immersed in carbon nano-tube catalyst
In solution, drying is taken out, obtains the carbon cloth of load carbon nano-tube catalyst.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized；
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, in vacuum condition
Under, tube furnace is heated to 700 DEG C under the protection of argon gas atmosphere, then passes to hydrogen (flow velocity 200mL/min), acetylene gas
Body (flow velocity 20mL/min) carries out carbon nano-pipe array and is listed in the growth in situ 120min on carbon cloth, after growth, in argon gas
It is cooled to room temperature under gas shield, obtains the vertical carbon nanotube array of the growth in situ on carbon cloth.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material；
It is dissolved in 2.2g lithium acetate, 5.25g isopropyl titanate (molar ratio 4:2.5) in 50mL dehydrated alcohol, obtains
Even clear lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in
Lithium titanate precursor solution takes out and dry；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace
In, 500 DEG C are heated under argon atmosphere protection, is cooled to room temperature after keeping the temperature 4h, carbon nano pipe array supported titanium is finally made
Sour lithium flexible electrode material.
Cut the load of carbon nano pipe array obtained by the embodiment of the present invention 2 lithium titanate flexible electrode material into pieces conduct
Lithium ion battery negative material, i.e. working electrode, metal lithium sheet are auxiliary electrode, use concentration for the lithium hexafluoro phosphate of 1mol/L
(LiPF6) solution (being dissolved in the mixture that volume ratio is the ethylene carbonate of 1:1:1, dimethyl carbonate and diethyl carbonate) conduct
Electrolyte makees diaphragm using microporous polypropylene membrane.Battery assembly carries out in being full of the glove box of argon gas, humidity less than 1%, will
Working electrode, the diaphragm for being saturated with electrolyte, auxiliary electrode are assembled into button CR2025 half-cell.The lithium ion battery that will be assembled
Progress constant current charge-discharge test in 12 hours is placed, charging/discharging voltage is 1.0~3.0V, and lithium-ion electric is measured in room temperature environment
Capacity, multiplying power property and the charge-discharge performance of pond cathode.
Embodiment 3
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process；
By the ferric acetyl acetonade of 0.6g and 0.57g aluminium acetylacetonate, 4.385g 1,2- hexadecane diol, 1.8g oleic acid,
0.2g oleyl amine, is dissolved in the mixed solution of 200mL benzyl ether, prepares carbon nano-tube catalyst using circumfluence method, wherein reflux temperature
Degree is 300 DEG C, return time 1min, and carbon nano-tube catalyst is made.Then it is molten carbon cloth to be immersed in carbon nano-tube catalyst
In liquid, drying is taken out, obtains the carbon cloth of load carbon nano-tube catalyst.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized；
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, in vacuum condition
Under, tube furnace is heated to 1200 DEG C under the protection of argon gas atmosphere, then passes to hydrogen (flow velocity 1000mL/min), acetylene
Gas (flow velocity 50mL/min) carries out carbon nano-pipe array and is listed in the growth in situ 720min on carbon cloth, after growth, in argon
It is cooled to room temperature under gas gas shield, obtains the vertical carbon nanotube array of the growth in situ on carbon cloth.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material；
It is dissolved in 5.0g lithium acetate, 4.76g isopropyl titanate (molar ratio 4:1) in 100mL dehydrated alcohol, obtains
Even clear lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in
Lithium titanate precursor solution takes out drying；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace,
900 DEG C are heated under argon atmosphere protection, is cooled to room temperature after keeping the temperature 1h, carbon nano pipe array is finally made and loads lithium titanate
Flexible electrode material.
Cut the load of carbon nano pipe array obtained by the embodiment of the present invention 3 lithium titanate flexible electrode material into pieces conduct
Lithium ion battery negative material, i.e. working electrode, metal lithium sheet are auxiliary electrode, use concentration for the lithium hexafluoro phosphate of 1mol/L
(LiPF6) solution (being dissolved in the mixture that volume ratio is the ethylene carbonate of 1:1:1, dimethyl carbonate and diethyl carbonate) conduct
Electrolyte makees diaphragm using microporous polypropylene membrane.Battery assembly carries out in being full of the glove box of argon gas, humidity less than 1%, will
Working electrode, the diaphragm for being saturated with electrolyte, auxiliary electrode are assembled into button CR2025 half-cell.The lithium ion battery that will be assembled
Progress constant current charge-discharge test in 12 hours is placed, charging/discharging voltage is 1.0~3.0V, and lithium-ion electric is measured in room temperature environment
Capacity, multiplying power property and the charge-discharge performance of pond cathode.
Embodiment 4
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process；
By the ferric acetyl acetonade of 0.15g and 1.40g aluminium acetylacetonate, 0.1g 1,2- hexadecane diol, 0.75g oleic acid,
0.75g oleyl amine is dissolved in 10mL benzyl ether, prepares carbon nano-tube catalyst using circumfluence method, wherein reflux temperature be 120 DEG C,
Return time is 720min, and carbon nano-tube catalyst is made.Then carbon cloth is immersed in carbon nano-tube catalyst solution, is taken out
It is dry, obtain the carbon cloth of load carbon nano-tube catalyst.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized；
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, in vacuum condition
Under, tube furnace is heated to 400 DEG C under the protection of argon gas atmosphere, then passes to hydrogen (flow velocity 50mL/min), acetylene gas
Body (flow velocity 2mL/min) carries out carbon nano-pipe array and is listed in the growth in situ 1min on carbon cloth, after growth, in argon gas gas
It is cooled to room temperature under body protection, obtains the vertical carbon nanotube array of the growth in situ on carbon cloth.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material；
It is dissolved in 0.1g lithium acetate, 4.8g isopropyl titanate (molar ratio 4:10) in 1mL dehydrated alcohol, obtains uniformly
Clear lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in titanium
Sour lithium precursor solution takes out drying；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace,
300 DEG C are heated under argon atmosphere protection, is cooled to room temperature after keeping the temperature 48h, carbon nano pipe array is finally made and loads lithium titanate
Flexible electrode material.
Cut the load of carbon nano pipe array obtained by the embodiment of the present invention 4 lithium titanate flexible electrode material into pieces conduct
Lithium ion battery negative material, i.e. working electrode, metal lithium sheet are auxiliary electrode, use concentration for the lithium hexafluoro phosphate of 1mol/L
(LiPF6) solution (being dissolved in the mixture that volume ratio is the ethylene carbonate of 1:1:1, dimethyl carbonate and diethyl carbonate) conduct
Electrolyte makees diaphragm using microporous polypropylene membrane.Battery assembly carries out in being full of the glove box of argon gas, humidity less than 1%, will
Working electrode, the diaphragm for being saturated with electrolyte, auxiliary electrode are assembled into button CR2025 half-cell.The lithium ion battery that will be assembled
Progress constant current charge-discharge test in 12 hours is placed, charging/discharging voltage is 1.0~3.0V, and lithium-ion electric is measured in room temperature environment
Capacity, multiplying power property and the charge-discharge performance of pond cathode.
Raw material involved in above-described embodiment are commercially available, and equipment used and technique are this technology necks
Known to the technical staff in domain.
Claims (9)
1. a kind of preparation method of carbon nano pipe array load lithium titanate flexible electrode material, is being loaded with chemical vapour deposition technique
Carbon nano pipe array is grown on the carbon cloth of catalyst, and as flexible substrates, passes through sol-gal process and high-temperature calcination technique
Carbon nano pipe array load lithium titanate flexible electrode material is prepared, is comprised the following steps that
(1) carbon nano-tube catalyst is loaded on carbon cloth using infusion process
Choose the metal complex of the first suitable acetylacetone,2,4-pentanedione, metal complex, the 1,2- 16 of second acetylacetone,2,4-pentanedione
Alkane glycol, oleic acid and oleyl amine are dissolved in suitable dibenzyl ethereal solution, prepare carbon nano-tube catalyst using circumfluence method, wherein flowing back
Temperature is 120~300 DEG C, and carbon nano-tube catalyst is made；Then carbon cloth is immersed in carbon nano-tube catalyst solution, is taken out
It is dry, obtain the carbon cloth of load carbon nano-tube catalyst, wherein the metal complex of the first acetylacetone,2,4-pentanedione be iron,
Cobalt, nickel, molybdenum, tungsten acetylacetone,2,4-pentanedione complex compound one kind；The metal complex-of second of acetylacetone,2,4-pentanedione is aluminium, magnesium
Acetylacetone,2,4-pentanedione complex compound one kind.
(2) chemical vapour deposition technique original position vertical-growth carbon nano pipe array is utilized
The carbon cloth that carbon nano-tube catalyst is loaded prepared by step (1) is placed in tube furnace flat-temperature zone, it under vacuum conditions, will
Tube furnace is heated to 400~1200 DEG C under the protection of inert gas atmosphere, then passes to hydrogen, carbon-source gas, carries out carbon nanotube
Growth in situ of the array on carbon cloth, after growth, is cooled to room temperature under inert gas protection, obtains in situ on carbon cloth
The vertical carbon nanotube array of growth.
(3) sol-gal process and high-temperature calcination are utilized, carbon nano pipe array is made and loads lithium titanate flexible electrode material
By the lithium source of certain mass, titanium source according to certain mol proportion 4:(1~10), it is dissolved in organic solvent, is uniformly clarified
Lithium titanate precursor solution；The vertical carbon nanotube array of growth in situ on carbon cloth obtained by step (2) is impregnated in lithium titanate
Precursor solution takes out drying；Carbon nano pipe array load lithium titanate precursor after drying is placed in tube furnace, in inertia
Under atmosphere protection, 300~900 DEG C are heated to, is cooled to room temperature after keeping the temperature a period of time, carbon nano pipe array load is finally made
Lithium titanate flexible electrode material.
2. the method according to claim 1, wherein in step (1), according to 1:(0.1-10): (0.5-8):
(0.1-5): the quality proportioning of (0.1-5) weighs the metal of the metal complex of the first acetylacetone,2,4-pentanedione, second acetylacetone,2,4-pentanedione
Complex compound, 1,2- hexadecane diol, oleic acid and oleyl amine.
3. the method according to claim 1, wherein inert gas is nitrogen, argon gas.
4. the method according to claim 1, wherein in step (2), hydrogen flow rate be 50~1000mL/min,
Carbon-source gas flow velocity is 2~50mL/min.
5. the method according to claim 1, wherein carbon-source gas described in step (2) is acetylene, methane, day
Any mixing of one or more of right gas and water coal gas.
6. the method according to claim 1, wherein lithium source described in step (3) be lithium hydroxide, lithium acetate,
One of lithium chloride, lithium nitrate.
7. the method according to claim 1, wherein titanium source described in step (3) is titanium tetrachloride, metatitanic acid isobutyl
One of ester, four fourth rouge of metatitanic acid, isopropyl titanate, titanium acetylacetone；Organic solvent is one of methanol, ethyl alcohol, ether.
8. the method according to claim 1, wherein organic solvent described in step (3) is methanol, ethyl alcohol, second
One of ether.
9. the method according to claim 1, wherein obtained carbon nano pipe array load lithium titanate is flexible
Electrode material is used as lithium ion battery negative material.
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