CN107994216B - A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode - Google Patents
A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode Download PDFInfo
- Publication number
- CN107994216B CN107994216B CN201711177605.8A CN201711177605A CN107994216B CN 107994216 B CN107994216 B CN 107994216B CN 201711177605 A CN201711177605 A CN 201711177605A CN 107994216 B CN107994216 B CN 107994216B
- Authority
- CN
- China
- Prior art keywords
- temperature
- array electrode
- warming
- tinb
- ultra
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
Abstract
The preparation method of a kind of ultra-high magnifications, long-life flexible nano fiber array electrode, it is related to a kind of preparation method of array electrode.The invention aims to solve existing TiNb2O7Capacity can be greatly reduced when the ion transmission efficiency of electrode material is poor, conductivity is lower and there are problems that output power.Method: one, polyimide acid is prepared；Two, polyimide nano-fiber is prepared；Three, hot imidization is handled；Four, charing process；Five, mixed solution A is prepared；Six, mixed solution B is prepared；Seven, it anneals, obtains ultra-high magnifications, long-life flexible nano fiber array electrode.Under the current density of 10C, area load prepared by the present invention has TiNb2O7The carbon nanofibers array electrode of nanometer stick array remains greater than 230mAh g after 1000 cycle periods‑1Capacity.The present invention can get a kind of ultra-high magnifications, long-life flexible nano fiber array electrode.
Description
Technical field
The present invention relates to a kind of preparation methods of array electrode.
Background technique
Currently, lithium ion battery has become the indispensable equipment of our daily lifes.With the hair of science and technology
The promotion of exhibition and people to life requirement, the property such as fast charging and discharging, long-life, safety and stability and bent flexibility of battery
It can become more and more important.Li4Ti5O12(LTO) for Li+Redox reaction current potential with a 1~2V this eliminate
The possibility that lithium metal is precipitated in electrochemical reaction process, and there is high safety performance and excellent cyclical stability.Therefore LTO quilt
It being widely used in lithium ion battery electrode material, but the theoretical capacity of LTO is only 175mAh/g, its storage lithium ability is lower than graphite,
The development of this limiting lithium ion cell.It is used to substitute the TiNb of traditional LTO electrode material2O7, it is a kind of with monocline stratiform knot
The electrode material of structure is with a wide range of applications in field of lithium ion secondary.And TiNb2O7Theoretical capacity be
387.6mAh/g, its theoretical capacity are similar to graphite (372mAh/g), in addition, it operating voltage with higher is (super simultaneously
Cross 1.5V), make it have higher multiplying power；The brilliant decomposition with electrolyte is knitted since lithium metal can be prevented to be precipitated, and is had higher
Security performance.It can replace original widely applied LTO electrode, but, TiNb2O7Ion transmission efficiency it is poor and itself
Conductivity it is lower, there are problems that capacity can be greatly reduced when output power.
Summary of the invention
The invention aims to solve existing TiNb2O7The ion transmission efficiency of electrode material is poor, conductivity is lower and
There are problems that capacity can be greatly reduced when output power, and a kind of ultra-high magnifications, long-life flexible nano fiber array are provided
The preparation method of column electrode.
A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode, it is specifically complete according to the following steps
At:
One, polyimide acid is prepared:
4,4 '-diaminodiphenyl ethers are dissolved into n,N-dimethylacetamide, then divides 3 times~5 times and equal benzene tetramethyl is added
Acid dianhydride, then reaction 2h~3h is stirred at room temperature, obtain polyamic acid；
The quality of 4,4 '-diaminodiphenyl ether described in step 1 and the volume ratio of DMAC N,N' dimethyl acetamide are (2g
~5g): 40mL；
The molar ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
Two, polyimide nano-fiber is prepared:
Electrostatic spinning voltage is 15kV~20kV, spinneret speed is 0.3mL/h~0.5mL/h, spinning nozzle and aluminium
Under conditions of it is 200kr/min that the distance of foil, which is 15cm~20cm, collects idler wheel revolving speed and horizontal axis movement speed is 20cm/min
Electrostatic spinning 8h~10h is carried out to polyamic acid using electrospinning device, obtains the cured polyimide nano of surface portion
Fiber；
Three, hot imidization is handled:
The cured polyimide nano-fiber of surface portion is put into thermal aging oven, by thermal aging oven be warming up to 70 DEG C~
90 DEG C, then 20min~40min is kept at being 70 DEG C~90 DEG C in temperature, then thermal aging oven is warming up to 130 DEG C~150 DEG C, then
20min~40min is kept at being 130 DEG C~150 DEG C in temperature, then thermal aging oven is warming up to 190 DEG C~210 DEG C, then in temperature
Degree is 20min~40min to be kept at 190 DEG C~210 DEG C, then thermal aging oven is warming up to 250 DEG C~270 DEG C, then be in temperature
20min~40min is kept at 250 DEG C~270 DEG C, then thermal aging oven is warming up to 310 DEG C~330 DEG C, then in temperature is 310 DEG C
20min~40min is kept at~330 DEG C, then thermal aging oven is warming up to 340 DEG C~360 DEG C, then in temperature is 340 DEG C~360
20min~40min is kept at DEG C, is completed hot imidization, is obtained polyimide nano-fiber film；
Four, charing process:
Polyimide nano-fiber film is put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 3 DEG C/min
Tube furnace is warming up to 290 DEG C~310 DEG C by the heating rate of~8 DEG C/min, then is kept at being 290 DEG C~310 DEG C in temperature
20min~30min, then 480 DEG C~520 DEG C are warming up to from 290 DEG C~310 DEG C with 3 DEG C/min~8 DEG C/min heating rate,
20min~30min, the polyimide nano-fiber film carbonized are kept at being again 480 DEG C~520 DEG C in temperature；
Five, tetraisopropyl titanate is added in dehydrated alcohol, obtains mixed solution A；
The amount of the substance of tetraisopropyl titanate described in step 5 and the volume ratio of dehydrated alcohol be (0.0003mol~
0.0007mol):50mL；
Six, NbCl is added into mixed solution A first5, add dehydrated alcohol, then in ultrasonic power be 160W~200W
Lower ultrasonic disperse 15min~20min, obtains mixed solution B；
NbCl described in step 65Substance amount and mixed solution A volume ratio be (0.0008mol~
0.004mol):50mL；
The volume ratio of dehydrated alcohol described in step 6 and mixed solution A is (10~15): 50；
Seven, the polyimide nano-fiber film of charing is immersed in as substrate, then by substrate equipped with mixed solution B's
In PVDF reaction kettle liner, then PVDF reaction kettle liner is put into reaction kettle, then by reaction kettle be placed in temperature be 180 DEG C~
6h~8h is reacted in 210 DEG C of baking oven, then at being 180 DEG C~210 DEG C in temperature, then the powder of substrate and reactor bottom is divided
It does not take out, is respectively washed 3 times~5 times using powder of the deionized water to substrate and taking-up, then dried respectively, obtains substrate
With dry powder；
Eight, the powder of substrate obtained in step 7 and drying is put into the tube furnace for being passed through argon gas, then in argon gas
Tube furnace is warming up to 650 DEG C~720 DEG C with 3 DEG C/min~8 DEG C/min heating rate under atmosphere, then in temperature is 650 DEG C
1.5h~3h is kept at~720 DEG C, obtaining area load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array and
TiNb2O7Nano particle, area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, length
Flexible service life nanofiber array electrode.
The principle of the present invention and advantage:
One, present invention polyimide nano-fiber partially cured by the method synthetic surface of electrostatic spinning first, so
Hot imidization is carried out by thermal aging oven afterwards, obtains polyimide nano-fiber film；Polyimide nano-fiber film is led to
It crosses tube furnace to be carbonized, the polyimide nano-fiber film carbonized；By the polyimide nano-fiber film of charing
As substrate, then pass through the method for hydro-thermal method and annealing, preparing area load has TiNb2O7The charcoal Nanowire of nanometer stick array
Array electrode is tieed up, this area load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array is connected with collector, no
Any conductive additive is needed, the energy density of battery is improved, it is often more important that, in subsequent cycle performance test, with
Under the current density of 10C, area load prepared by the present invention has TiNb2O7The carbon nanofibers array electrode of nanometer stick array exists
Capacity retention can be very good after charge and discharge 1000 are enclosed；
Two, under the current density of 10C, area load prepared by the present invention has TiNb2O7The charcoal Nanowire of nanometer stick array
The charging for tieing up array electrode, which is held, is up to 262mAh g-1, under the current density of 20C, area load prepared by the present invention has
TiNb2O7Equally up to 198mAh g is held in the charging of the carbon nanofibers array electrode of nanometer stick array-1；
Three, under the current density of 10C, area load prepared by the present invention has TiNb2O7The charcoal Nanowire of nanometer stick array
Dimension array electrode remains greater than 230mAh g after 1000 cycle periods-1Capacity, this shows good cycle performance,
It is remained above 87.7% capacity.
The present invention can get a kind of ultra-high magnifications, long-life flexible nano fiber array electrode.
Detailed description of the invention
Fig. 1 is that area load prepared by embodiment one has TiNb2O7The carbon nanofibers array electrode of nanometer stick array shows
It is intended to, 1 polyimide nano-fiber handled for superficial charring in Fig. 1,2 have TiNb for area load2O7The charcoal of nanometer stick array
Nanofiber array electrode；
Fig. 2 is the polyimide nano-fiber array electrode amplification of the processing of superficial charring obtained in one step 3 of embodiment
5000 times of SEM figure；
Fig. 3 is that area load obtained in one step 8 of embodiment has TiNb2O7The carbon nanofibers array of nanometer stick array
Electrode amplifies 60000 times of SEM figure；
Fig. 4 is that area load obtained in one step 8 of embodiment has TiNb2O7The carbon nanofibers array of nanometer stick array
Electrode amplifies 20000 times of SEM figure；
Fig. 5 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber battle array of nanometer stick array
The TEM figure of the enterprising row element analysis of column electrode；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the N element figure analyzed in Fig. 5；
Fig. 8 is the Nb elemental map analyzed in Fig. 5；
Fig. 9 is the Ti elemental map analyzed in Fig. 5；
Figure 10 is the O elemental map analyzed in Fig. 5；
Figure 11 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 100,000 times of TEM figure；
Figure 12 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 200,000 times of TEM figure；
Figure 13 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 1,000,000 times of HRTEM figure；
Figure 14 is XRD spectra, and 1 is TiNb obtained in one step 8 of embodiment in Figure 142O7XRD curve, 2 for implement
Area load obtained in one step 8 of example has TiNb2O7The XRD curve of the charing nanofiber array electrode of nanometer stick array；
Figure 15 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
The Raman spectrogram of array electrode；
Figure 16 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
The curve of double curvature of array electrode, " " is charging in Figure 16, and " ■ " is electric discharge, and the current density of region A is 10C, the electricity of region B
Current density is 20C.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of ultra-high magnifications, long-life flexible nano fiber array electrode
Preparation method is specifically realized by the following steps:
One, polyimide acid is prepared:
4,4 '-diaminodiphenyl ethers are dissolved into n,N-dimethylacetamide, then divides 3 times~5 times and equal benzene tetramethyl is added
Acid dianhydride, then reaction 2h~3h is stirred at room temperature, obtain polyamic acid；
The quality of 4,4 '-diaminodiphenyl ether described in step 1 and the volume ratio of DMAC N,N' dimethyl acetamide are (2g
~5g): 40mL；
The molar ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
Two, polyimide nano-fiber is prepared:
Electrostatic spinning voltage is 15kV~20kV, spinneret speed is 0.3mL/h~0.5mL/h, spinning nozzle and aluminium
Under conditions of it is 200kr/min that the distance of foil, which is 15cm~20cm, collects idler wheel revolving speed and horizontal axis movement speed is 20cm/min
Electrostatic spinning 8h~10h is carried out to polyamic acid using electrospinning device, obtains the cured polyimide nano of surface portion
Fiber；
Three, hot imidization is handled:
The cured polyimide nano-fiber of surface portion is put into thermal aging oven, by thermal aging oven be warming up to 70 DEG C~
90 DEG C, then 20min~40min is kept at being 70 DEG C~90 DEG C in temperature, then thermal aging oven is warming up to 130 DEG C~150 DEG C, then
20min~40min is kept at being 130 DEG C~150 DEG C in temperature, then thermal aging oven is warming up to 190 DEG C~210 DEG C, then in temperature
Degree is 20min~40min to be kept at 190 DEG C~210 DEG C, then thermal aging oven is warming up to 250 DEG C~270 DEG C, then be in temperature
20min~40min is kept at 250 DEG C~270 DEG C, then thermal aging oven is warming up to 310 DEG C~330 DEG C, then in temperature is 310 DEG C
20min~40min is kept at~330 DEG C, then thermal aging oven is warming up to 340 DEG C~360 DEG C, then in temperature is 340 DEG C~360
20min~40min is kept at DEG C, is completed hot imidization, is obtained polyimide nano-fiber film；
Four, charing process:
Polyimide nano-fiber film is put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 3 DEG C/min
Tube furnace is warming up to 290 DEG C~310 DEG C by the heating rate of~8 DEG C/min, then is kept at being 290 DEG C~310 DEG C in temperature
20min~30min, then 480 DEG C~520 DEG C are warming up to from 290 DEG C~310 DEG C with 3 DEG C/min~8 DEG C/min heating rate,
20min~30min, the polyimide nano-fiber film carbonized are kept at being again 480 DEG C~520 DEG C in temperature；
Five, tetraisopropyl titanate is added in dehydrated alcohol, obtains mixed solution A；
The amount of the substance of tetraisopropyl titanate described in step 5 and the volume ratio of dehydrated alcohol be (0.0003mol~
0.0007mol):50mL；
Six, NbCl is added into mixed solution A first5, add dehydrated alcohol, then in ultrasonic power be 160W~200W
Lower ultrasonic disperse 15min~20min, obtains mixed solution B；
NbCl described in step 65Substance amount and mixed solution A volume ratio be (0.0008mol~
0.004mol):50mL；
The volume ratio of dehydrated alcohol described in step 6 and mixed solution A is (10~15): 50；
Seven, the polyimide nano-fiber film of charing is immersed in as substrate, then by substrate equipped with mixed solution B's
In PVDF reaction kettle liner, then PVDF reaction kettle liner is put into reaction kettle, then by reaction kettle be placed in temperature be 180 DEG C~
6h~8h is reacted in 210 DEG C of baking oven, then at being 180 DEG C~210 DEG C in temperature, then the powder of substrate and reactor bottom is divided
It does not take out, is respectively washed 3 times~5 times using powder of the deionized water to substrate and taking-up, then dried respectively, obtains substrate
With dry powder；
Eight, the powder of substrate obtained in step 7 and drying is put into the tube furnace for being passed through argon gas, then in argon gas
Tube furnace is warming up to 650 DEG C~720 DEG C with 3 DEG C/min~8 DEG C/min heating rate under atmosphere, then in temperature is 650 DEG C
1.5h~3h is kept at~720 DEG C, obtaining area load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array and
TiNb2O7Nano particle, area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, length
Flexible service life nanofiber array electrode.
The principle and advantage of present embodiment:
One, present embodiment pass through first electrostatic spinning the partially cured polyimide nano of method synthetic surface it is fine
Then dimension carries out hot imidization by thermal aging oven, obtains polyimide nano-fiber film；Polyimide nano-fiber is thin
Film is carbonized by tube furnace, the polyimide nano-fiber film carbonized；By the polyimide nano-fiber of charing
Film is as substrate, then passes through the method for hydro-thermal method and annealing, and preparing area load has TiNb2O7The charcoal of nanometer stick array is received
Rice fiber array electrode, this area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array and collector phase
Even, any conductive additive is not needed, the energy density of battery is improved, it is often more important that, it is tested in subsequent cycle performance
In, under the current density of 10C, the area load of present embodiment preparation has TiNb2O7The carbon nanofibers battle array of nanometer stick array
Capacity retention can be very good after the circle of charge and discharge 1000 for column electrode；
Two, under the current density of 10C, the area load of present embodiment preparation has TiNb2O7The charcoal of nanometer stick array is received
The charging of rice fiber array electrode, which is held, is up to 262mAh g-1, under the current density of 20C, the surface of present embodiment preparation is negative
It is loaded with TiNb2O7Equally up to 198mAh g is held in the charging of the carbon nanofibers array electrode of nanometer stick array-1；
Three, under the current density of 10C, the area load of present embodiment preparation has TiNb2O7The charcoal of nanometer stick array is received
Rice fiber array electrode remains greater than 230mAh g after 1000 cycle periods-1Capacity, this shows good circulation
Performance is remained above 87.7% capacity.
Present embodiment can get a kind of ultra-high magnifications, long-life flexible nano fiber array electrode.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: polyamides described in step 1
The solid content of amino acid is 14%~15%.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: in step 2
Electrostatic spinning voltage is 15kV~18kV, spinneret speed is 0.3mL/h~0.4mL/h, spinning nozzle is at a distance from aluminium foil
15cm~18cm, collect idler wheel revolving speed be 200kr/min and horizontal axis movement speed be 20cm/min under conditions of utilize Static Spinning
Silk equipment carries out electrostatic spinning 8h~9h to polyamic acid, obtains the cured polyimide nano-fiber of surface portion.Other steps
It is rapid the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: will in step 3
The cured polyimide nano-fiber of surface portion is put into thermal aging oven, and thermal aging oven is warming up to 80 DEG C~90 DEG C, then
Temperature is 30min~40min to be kept at 80 DEG C~90 DEG C, then thermal aging oven is warming up to 140 DEG C~150 DEG C, then be in temperature
30min~40min is kept at 140 DEG C~150 DEG C, then thermal aging oven is warming up to 200 DEG C~210 DEG C, then in temperature is 200 DEG C
30min~40min is kept at~210 DEG C, then thermal aging oven is warming up to 260 DEG C~270 DEG C, then in temperature is 260 DEG C~270
30min~40min is kept at DEG C, then thermal aging oven is warming up to 320 DEG C~330 DEG C, then in the case where temperature is 320 DEG C~330 DEG C
30min~40min is kept, then thermal aging oven is warming up to 350 DEG C~360 DEG C, then keep at being 350 DEG C~360 DEG C in temperature
30min~40min completes hot imidization, obtains polyimide nano-fiber film.Other steps and specific embodiment one to
Three is identical.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: will in step 4
Polyimide nano-fiber film is put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 5 DEG C/min~8 DEG C/min
Tube furnace is warming up to 300 DEG C~310 DEG C by heating rate, then keeps 20min~25min at being 300 DEG C~310 DEG C in temperature,
500 DEG C~520 DEG C are warming up to from 300 DEG C~310 DEG C with 5 DEG C/min~8 DEG C/min heating rate again, then in temperature are 500
DEG C~520 DEG C at keep 25min~30min, the polyimide nano-fiber film carbonized.Other steps and specific implementation
Mode one to four is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 5
The amount of the substance for the tetraisopropyl titanate stated and the volume ratio of dehydrated alcohol are (0.0003mol~0.0005mol): 50mL.Its
Its step is identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 6
The NbCl stated5Substance amount and mixed solution A volume ratio be (0.0008mol~0.002mol): 50mL.Other steps with
Specific embodiment one to six is identical.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: will in step 7
The polyimide nano-fiber film of charing is immersed in the PVDF reaction kettle equipped with mixed solution B as substrate, then by substrate
In gallbladder, then PVDF reaction kettle liner is put into reaction kettle, then reaction kettle is placed in the baking oven that temperature is 180 DEG C~210 DEG C
In, then at being 180 DEG C~210 DEG C in temperature 6h~7h is reacted, then the powder of substrate and reactor bottom taken out respectively, it uses
Deionized water is respectively washed the powder of substrate and taking-up 4 times~5 times, then is dried respectively, and substrate and dry powder are obtained
End.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: will in step 8
Substrate obtained in step 7 and dry powder are put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 5 DEG C/
Tube furnace is warming up to 650 DEG C~700 DEG C by min~8 DEG C/min heating rate, then is kept at being 650 DEG C~700 DEG C in temperature
2h~3h, obtaining area load has TiNb2O7The carbon nanofibers array electrode and TiNb of nanometer stick array2O7Nano particle, table
Face load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, long-life flexible nano fiber array
Column electrode.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: will in step 8
Substrate obtained in step 7 and dry powder are put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 3 DEG C/
Tube furnace is warming up to 700 DEG C~720 DEG C by min~5 DEG C/min heating rate, then is kept at being 700 DEG C~720 DEG C in temperature
2h~3h, obtaining area load has TiNb2O7The carbon nanofibers array electrode and TiNb of nanometer stick array2O7Nano particle, table
Face load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, long-life flexible nano fiber array
Column electrode.Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: the preparation method of a kind of ultra-high magnifications, long-life flexible nano fiber array electrode, specifically by with
Lower step is completed:
One, polyimide acid is prepared:
4,4 '-diaminodiphenyl ether of 3g is dissolved into 40mL n,N-dimethylacetamide, then divides 5 times and equal benzene four is added
Formic acid dianhydride, then reaction 2.5h is stirred at room temperature, obtain polyamic acid；
The molar ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:1.05；
Two, polyimide nano-fiber is prepared:
Electrostatic spinning voltage is 15kV, spinneret speed is 0.4mL/h, spinning nozzle be at a distance from aluminium foil 15cm,
Collect idler wheel revolving speed be 200kr/min and horizontal axis movement speed be 20cm/min under conditions of using electrospinning device to polyamides
Amino acid carries out electrostatic spinning 10h, obtains the cured polyimide nano-fiber of surface portion；
Three, hot imidization is handled:
The cured polyimide nano-fiber of surface portion is put into thermal aging oven, thermal aging oven is warming up to 80 DEG C,
30min is kept at being again 80 DEG C in temperature, then thermal aging oven is warming up to 140 DEG C, then keep 30min at being 140 DEG C in temperature,
Thermal aging oven is warming up to 200 DEG C again, then keeps 30min at being 200 DEG C in temperature, then thermal aging oven is warming up to 260 DEG C, then
30min is kept at being 260 DEG C in temperature, then thermal aging oven is warming up to 320 DEG C, then keep 30min at being 320 DEG C in temperature,
Thermal aging oven is warming up to 350 DEG C again, then keeps 30min at being 350 DEG C in temperature, hot imidization is completed, obtains polyimides
Nano-fiber film；
Four, charing process:
Polyimide nano-fiber film is put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 5 DEG C/min
Heating rate tube furnace is warming up to 300 DEG C, then 30min is kept at being 300 DEG C in temperature, then with the heating speed of 5 DEG C/min
Rate is warming up to 500 DEG C from 300 DEG C, then keeps 30min at being 500 DEG C in temperature, and the polyimide nano-fiber carbonized is thin
Film；
Five, 0.27g tetraisopropyl titanate is added in 50mL dehydrated alcohol, obtains mixed solution A；
Six, 0.54g NbCl is added first into mixed solution A obtained in step 55, 10mL dehydrated alcohol is added,
The ultrasonic disperse 20min in the case where ultrasonic power is 200W again, obtains mixed solution B；
Seven, the polyimide nano-fiber film of charing is immersed in as substrate, then by substrate equipped with mixed solution B's
In PVDF reaction kettle liner, then PVDF reaction kettle liner is put into reaction kettle, then it is 180 DEG C that reaction kettle, which is placed in temperature,
8h is reacted in baking oven, then at being 180 DEG C in temperature, then the powder of substrate and reactor bottom is taken out respectively, uses deionization
Water is respectively washed the powder of substrate and taking-up 5 times, then is dried respectively, and substrate and dry powder are obtained；
Eight, the powder of substrate obtained in step 7 and drying is put into the tube furnace for being passed through argon gas, then in argon gas
Tube furnace is warming up to 700 DEG C with the heating rate of 5 DEG C/min under atmosphere, then keeps 3h at being 700 DEG C in temperature, obtains surface
Load has TiNb2O7The carbon nanofibers array electrode and TiNb of nanometer stick array2O7Nano particle, area load have TiNb2O7
The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, long-life flexible nano fiber array electrode.
Fig. 1 is that area load prepared by embodiment one has TiNb2O7The carbon nanofibers array electrode of nanometer stick array shows
It is intended to, 1 polyimide nano-fiber handled for superficial charring in Fig. 1,2 have TiNb for area load2O7The charcoal of nanometer stick array
Nanofiber array electrode.
Fig. 2 is the polyimide nano-fiber array electrode amplification of the processing of superficial charring obtained in one step 3 of embodiment
5000 times of SEM figure；
As can be seen from Figure 2, the polyimide nano-fiber array electricity of the processing of superficial charring obtained in one step 3 of embodiment
The diameter of the polyimide nano-fiber carbonized in extremely is 100~200nm.
Fig. 3 is that area load obtained in one step 8 of embodiment has TiNb2O7The carbon nanofibers array of nanometer stick array
Electrode amplifies 60000 times of SEM figure；
As can be seen from Figure 3, area load obtained in one step 8 of embodiment has TiNb2O7The charcoal Nanowire of nanometer stick array
The polyimide nano-fiber carbonized in dimension array electrode is completely by TiNb2O7Nanometer covering, each area load have
TiNb2O7The carbon nanofibers of nanometer stick array still keep the structure of array by water-heat process later.
Fig. 4 is that area load obtained in one step 8 of embodiment has TiNb2O7The carbon nanofibers array of nanometer stick array
Electrode amplifies 20000 times of SEM figure；
As can be seen from Figure 4, area load obtained in one step 8 of embodiment has TiNb2O7The charcoal Nanowire of nanometer stick array
Area load has TiNb in dimension array electrode2O7The diameter of the carbon nanofibers of nanometer stick array is about 300nm~400nm.
Fig. 5 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber battle array of nanometer stick array
The TEM figure of the enterprising row element analysis of column electrode；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the N element figure analyzed in Fig. 5；
Fig. 8 is the Nb elemental map analyzed in Fig. 5；
Fig. 9 is the Ti elemental map analyzed in Fig. 5；
Figure 10 is the O elemental map analyzed in Fig. 5；
From Fig. 5~Figure 10 it is found that having TiNb to area load obtained in one step 8 of embodiment2O7Nanometer stick array
The elemental analysis of charing nanofiber array electrode confirms TiNb in sample2O7With the presence of carbon fiber.To C, O, N, Ti, Nb
The area load that is distributed in that the elemental analysis of element can be seen that these types of element uniformity has TiNb2O7Nanometer stick array
In the structure for carbonizing nanofiber.Wherein C, N element exist in the polyimide nano-fiber of charing, and O, Ti, Nb element exist
TiNb2O7In nanometer rods, it can clearly demonstrate that area load has TiNb from these elemental analyses2O7The charcoal of nanometer stick array
Change the presence of nanofiber, the core and TiNb of the polyimide nano-fiber comprising charing2O7The shell of nanometer rods.
Figure 11 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 100,000 times of TEM figure；
As can be seen from Figure 11, the polyimide nano-fiber of charing is by TiNb2O7Nanometer rods are fully wrapped around, and table after package
Face becomes coarse, and the structure of the polyimide nano-fiber of charing is by complete in store, obtained in one step 8 of embodiment
Area load has TiNb2O7The diameter of the charing nanofiber of nanometer stick array is about 300nm.
Figure 12 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 200,000 times of TEM figure；
Figure 13 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
Array electrode amplifies 1,000,000 times of HRTEM figure；
From Figure 12 and Figure 13 it is found that analyzing spacing of lattice by lattice is 0.27nm, 0.31nm and 0.37nm corresponding respectively
In (312), the TiNb in (303) and (103) face2O7Nano stick crystal chain structure is TiNb according to standard crystalline substance card2O7(JCPDS 39-
1407)。
Figure 14 is XRD spectra, and 1 is TiNb obtained in one step 8 of embodiment in Figure 142O7XRD curve, 2 for implement
Area load obtained in one step 8 of example has TiNb2O7The XRD curve of the charing nanofiber array electrode of nanometer stick array；
Figure 15 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
The Raman spectrogram of array electrode；
As can be seen from Figure 14, all with the TiNb of very high peak intensity in two maps2O7Diffraction maximum can prove out TiNb2O7's
In the presence of.Simultaneously from TiNb2O7XRD spectrum obtain TiNb2O7Diffraction maximum respectively appear in 23.6 °, 25.1 °, 32.2 °,
39.8 °, 44.4 °, 47.7 °, 51.8 °, 55.4 ° and 59.6 ° of position, can correspond to (- 110), (- 303), (312), (-
611), the crystal face of (703), (020), (1000), (813) and (217), reference standard spectrogram (JCPDS No.39-1407) are known
For TiNb2O7Crystal.The area load obtained in one step 8 of embodiment has TiNb2O7The charing Nanowire of nanometer stick array
In the XRD diffracting spectrum for tieing up array electrode, it can be observed that TiNb2O7Diffraction maximum presence, it was demonstrated that TiNb2O7Nanometer rods
Presence.But can't see the diffraction maximum of the polyimide nano-fiber of charing in this diffracting spectrum, many pervious
Research all surfaces can not all detect the diffraction maximum of the polyimide nano-fiber of charing in the XRD diffracting spectrum of wide-angle, because
This will measure Raman map to the detection of carbon material, can see the presence of carbon material from the Raman map of Figure 15.Comparison diagram
XRD diffracting spectrum in Raman spectrogram and Figure 14 in 15 the result shows that, area load obtained in one step 8 of embodiment
There is TiNb2O7Nanometer stick array charing nanofiber array electrode in exist charing polyimide nano-fiber core and
TiNb2O7The shell of nanometer rods.
From figure 15, it can be known that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanometer of nanometer stick array
There are typical 535cm in fiber array electrode-1, 648cm-1, 886cm-1And 996cm-1Peak position, be TiNb2O7Nanometer rods
Raman peaks, two strong peak are located at 1342cm-1The peak D and 1596cm-1The peak G, for the polyimide nano-fiber that typically carbonizes
Raman peaks.
Figure 16 is that area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber of nanometer stick array
The curve of double curvature of array electrode, " " is charging in Figure 16, and " ■ " is electric discharge, and the current density of region A is 10C, the electricity of region B
Current density is 20C.
As can be seen from Figure 16, under the current density of 10C, area load obtained in one step 8 of embodiment has TiNb2O7It receives
Capacity retention can be very good after the circle of charge and discharge 1000 for the charing nanofiber array electrode of rice stick array.Meanwhile in 10C
Current density under, area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber battle array of nanometer stick array
The charging of column electrode, which is held, is up to 262mAh g-1, and area load obtained in one step 8 of embodiment has TiNb2O7Nanometer rods
The charing nanofiber array electrode of array remains greater than 230mAh g after 1000 cycle periods-1Capacity, this display
Good cycle performance out is remained above 87.7% capacity.Under the current density of 20C, obtained in one step 8 of embodiment
Area load have TiNb2O7Equally up to 198mAh g is held in the charging of the charing nanofiber array electrode of nanometer stick array-1
Capacity.
Area load obtained in one step 8 of embodiment has TiNb2O7The charing nanofiber array electricity of nanometer stick array
It is great to have excellent circulating ratio performance, it is since the electrode has biggish specific surface area, large-specific surface area nano fiber knot
Structure increases electrolyte and TiNb2O7The contact area of nanometer rods, shortens the transmission path of lithium ion, and reduces in electrification
Volume change caused by reaction process is learned, to improve the lithium storage capacity of the electrode.
Claims (10)
1. the preparation method of a kind of ultra-high magnifications, long-life flexible nano fiber array electrode, it is characterised in that a kind of super-high power
Rate, the preparation method of long-life flexible nano fiber array electrode are specifically realized by the following steps:
One, polyimide acid is prepared:
4,4 '-diaminodiphenyl ethers are dissolved into n,N-dimethylacetamide, then divide 3 times~5 times addition Pyromellitic Acids two
Acid anhydride, then reaction 2h~3h is stirred at room temperature, obtain polyamic acid；
The quality of 4,4 '-diaminodiphenyl ether described in step 1 and the volume ratio of DMAC N,N' dimethyl acetamide be (2g~
5g):40mL；
The molar ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
Two, polyimide nano-fiber is prepared:
Electrostatic spinning voltage is 15kV~20kV, spinneret speed is 0.3mL/h~0.5mL/h, spinning nozzle and aluminium foil
Distance be 15cm~20cm, collection idler wheel revolving speed be 200kr/min and horizontal axis movement speed be 20cm/min under conditions of utilize
Electrospinning device carries out electrostatic spinning 8h~10h to polyamic acid, obtains the cured polyimide nano-fiber of surface portion；
Three, hot imidization is handled:
The cured polyimide nano-fiber of surface portion is put into thermal aging oven, thermal aging oven is warming up to 70 DEG C~90
DEG C, then 20min~40min is kept at being 70 DEG C~90 DEG C in temperature, then thermal aging oven is warming up to 130 DEG C~150 DEG C, then
Temperature is 20min~40min to be kept at 130 DEG C~150 DEG C, then thermal aging oven is warming up to 190 DEG C~210 DEG C, then in temperature
It is holding 20min~40min at 190 DEG C~210 DEG C, then thermal aging oven is warming up to 250 DEG C~270 DEG C, then in temperature is 250
DEG C~270 DEG C at keep 20min~40min, then thermal aging oven is warming up to 310 DEG C~330 DEG C, then temperature be 310 DEG C~
20min~40min is kept at 330 DEG C, then thermal aging oven is warming up to 340 DEG C~360 DEG C, then in temperature is 340 DEG C~360 DEG C
Lower holding 20min~40min completes hot imidization, obtains polyimide nano-fiber film；
Four, charing process:
Polyimide nano-fiber film is put into the tube furnace for being passed through argon gas, then under an argon atmosphere with 3 DEG C/min~8
DEG C/tube furnace is warming up to 290 DEG C~310 DEG C, then keeps 20min at being 290 DEG C~310 DEG C in temperature by the heating rate of min
~30min, then 480 DEG C~520 DEG C are warming up to from 290 DEG C~310 DEG C with 3 DEG C/min~8 DEG C/min heating rate, then in temperature
Degree is that 20min~30min, the polyimide nano-fiber film carbonized are kept at 480 DEG C~520 DEG C；
Five, tetraisopropyl titanate is added in dehydrated alcohol, obtains mixed solution A；
The amount of the substance of tetraisopropyl titanate described in step 5 and the volume ratio of dehydrated alcohol be (0.0003mol~
0.0007mol):50mL；
Six, NbCl is added into mixed solution A first5, dehydrated alcohol is added, then surpass in the case where ultrasonic power is 160W~200W
Sound disperses 15min~20min, obtains mixed solution B；
NbCl described in step 65Substance amount and mixed solution A volume ratio be (0.0008mol~0.004mol):
50mL；
The volume ratio of dehydrated alcohol described in step 6 and mixed solution A is (10~15): 50；
Seven, the polyimide nano-fiber film of charing is immersed in the PVDF equipped with mixed solution B as substrate, then by substrate
In reaction kettle liner, then PVDF reaction kettle liner is put into reaction kettle, then it is 180 DEG C~210 that reaction kettle, which is placed in temperature,
DEG C baking oven in, then temperature be 180 DEG C~210 DEG C at react 6h~8h, then by the powder of substrate and reactor bottom distinguish
Take out, be respectively washed 3 times~5 times using powder of the deionized water to substrate and taking-up, then dried respectively, obtain substrate and
Dry powder；
Eight, the powder of substrate obtained in step 7 and drying is put into the tube furnace for being passed through argon gas, then in argon atmosphere
Under with 3 DEG C/min~8 DEG C/min heating rate tube furnace is warming up to 650 DEG C~720 DEG C, then in temperature be 650 DEG C~720
1.5h~3h is kept at DEG C, obtaining area load has TiNb2O7The carbon nanofibers array electrode and TiNb of nanometer stick array2O7
Nano particle, area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array be ultra-high magnifications, long-life it is soft
Property nanofiber array electrode.
2. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
The solid content for being characterized in that polyamic acid described in step 1 is 14%~15%.
3. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
Be characterized in that in step 2 electrostatic spinning voltage is 15kV~18kV, spinneret speed is 0.3mL/h~0.4mL/h, spinning spray
Silk head is 15cm~18cm at a distance from aluminium foil, collection idler wheel revolving speed is 200kr/min and horizontal axis movement speed is 20cm/min
Under conditions of using electrospinning device electrostatic spinning 8h~9h is carried out to polyamic acid, it is sub- to obtain the cured polyamides of surface portion
Amine nanofiber.
4. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
It is characterized in that in step 3 for the cured polyimide nano-fiber of surface portion being put into thermal aging oven, thermal aging oven is heated up
To 80 DEG C~90 DEG C, then temperature be 80 DEG C~90 DEG C at keep 30min~40min, then by thermal aging oven be warming up to 140 DEG C~
150 DEG C, then 30min~40min is kept at being 140 DEG C~150 DEG C in temperature, then thermal aging oven is warming up to 200 DEG C~210
DEG C, then 30min~40min is kept at being 200 DEG C~210 DEG C in temperature, then thermal aging oven is warming up to 260 DEG C~270 DEG C, then
30min~40min is kept at being 260 DEG C~270 DEG C in temperature, then thermal aging oven is warming up to 320 DEG C~330 DEG C, then in temperature
Degree is 30min~40min to be kept at 320 DEG C~330 DEG C, then thermal aging oven is warming up to 350 DEG C~360 DEG C, then be in temperature
30min~40min is kept at 350 DEG C~360 DEG C, is completed hot imidization, is obtained polyimide nano-fiber film.
5. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
Be characterized in that in step 4 for polyimide nano-fiber film being put into the tube furnace for being passed through argon gas, then under an argon atmosphere with
Tube furnace is warming up to 300 DEG C~310 DEG C by the heating rate of 5 DEG C/min~8 DEG C/min, then in the case where temperature is 300 DEG C~310 DEG C
20min~25min is kept, then is warming up to 500 DEG C~520 from 300 DEG C~310 DEG C with 5 DEG C/min~8 DEG C/min heating rate
DEG C, then 25min~30min, the polyimide nano-fiber film carbonized are kept at being 500 DEG C~520 DEG C in temperature.
6. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
Be characterized in that the substance of tetraisopropyl titanate described in step 5 amount and dehydrated alcohol volume ratio be (0.0003mol~
0.0005mol):50mL。
7. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
It is characterized in that NbCl described in step 65Substance amount and mixed solution A volume ratio be (0.0008mol~
0.002mol):50mL。
8. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
Be characterized in that using the polyimide nano-fiber film of charing as substrate in step 7, then by substrate be immersed in equipped with mix it is molten
In the PVDF reaction kettle liner of liquid B, then PVDF reaction kettle liner is put into reaction kettle, then reaction kettle is placed in temperature and is
6h~7h is reacted in 180 DEG C~210 DEG C of baking oven, then at being 180 DEG C~210 DEG C in temperature, then by substrate and reactor bottom
Powder take out respectively, be respectively washed 4 times~5 times using powder of the deionized water to substrate and taking-up, then dried respectively,
Obtain substrate and dry powder.
9. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
It is characterized in that substrate obtained in step 7 and dry powder being put into the tube furnace for being passed through argon gas in step 8, then
Tube furnace is warming up to 650 DEG C~700 DEG C with 5 DEG C/min~8 DEG C/min heating rate under argon atmosphere, then is in temperature
2h~3h is kept at 650 DEG C~700 DEG C, obtaining area load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array and
TiNb2O7Nano particle, area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, length
Flexible service life nanofiber array electrode.
10. the preparation method of a kind of ultra-high magnifications according to claim 1, long-life flexible nano fiber array electrode,
It is characterized in that substrate obtained in step 7 and dry powder are put into the tube furnace for being passed through argon gas in step 8, then
Tube furnace is warming up to 700 DEG C~720 DEG C with 3 DEG C/min~5 DEG C/min heating rate under an argon atmosphere, then is in temperature
2h~3h is kept at 700 DEG C~720 DEG C, obtaining area load has TiNb2O7The carbon nanofibers array electrode of nanometer stick array and
TiNb2O7Nano particle, area load have TiNb2O7The carbon nanofibers array electrode of nanometer stick array is ultra-high magnifications, length
Flexible service life nanofiber array electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177605.8A CN107994216B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711177605.8A CN107994216B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107994216A CN107994216A (en) | 2018-05-04 |
| CN107994216B true CN107994216B (en) | 2019-09-24 |
Family
ID=62032710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711177605.8A Active CN107994216B (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107994216B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301210B (en) * | 2018-09-28 | 2021-01-29 | 哈尔滨理工大学 | Carbon fiber/boron nitride flexible composite electrode and preparation method and application thereof |
| CN110112405B (en) * | 2019-05-29 | 2021-05-18 | 哈尔滨理工大学 | Core-shell structure silicon/carbon fiber flexible composite electrode material and preparation method and application thereof |
| CN115478341A (en) * | 2022-09-15 | 2022-12-16 | 江西赣锋锂电科技股份有限公司 | Preparation method of lithium ion negative electrode composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606689A (en) * | 2013-11-14 | 2014-02-26 | 清华大学 | Method for preparing carbon nanofiber based non-noble-metal catalyst through oxidation improved electrostatic spinning |
| CN106835342A (en) * | 2015-12-04 | 2017-06-13 | 南京林业大学 | The polymer nanofiber of high intensity is prepared using BPDA/PDA series polyimides |
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
-
2017
- 2017-11-22 CN CN201711177605.8A patent/CN107994216B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103606689A (en) * | 2013-11-14 | 2014-02-26 | 清华大学 | Method for preparing carbon nanofiber based non-noble-metal catalyst through oxidation improved electrostatic spinning |
| CN106835342A (en) * | 2015-12-04 | 2017-06-13 | 南京林业大学 | The polymer nanofiber of high intensity is prepared using BPDA/PDA series polyimides |
| CN107201645A (en) * | 2017-04-28 | 2017-09-26 | 东华大学 | A kind of metal organic frame/carbon nano-fiber composite film material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107994216A (en) | 2018-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Electrospun nanofiber-based anodes, cathodes, and separators for advanced lithium-ion batteries | |
| CN105591079B (en) | A kind of preparation method of carbon coating nano-micrometer grade lithium titanate composite anode material | |
| Zhao et al. | A 3D porous architecture composed of TiO 2 nanotubes connected with a carbon nanofiber matrix for fast energy storage | |
| CN106340395A (en) | Fibrous composite electrode material and preparation method thereof | |
| CN106601490A (en) | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof | |
| CN104332640B (en) | Thermal reduction graphene oxide/carbon nano-fiber method for preparing composite electrode used for all-vanadium redox flow battery | |
| CN107994216B (en) | A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode | |
| CN102074683A (en) | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof | |
| Xu et al. | Biotemplate synthesis of mesoporous α-Fe2O3 hierarchical structure with assisted pseudocapacitive as an anode for long-life lithium ion batteries | |
| CN105489863B (en) | One kind is based on C/Ti4O7Lithium sulfur battery anode material of composite nano fiber and preparation method thereof | |
| CN108149343A (en) | The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation | |
| CN108807915B (en) | CoFe2O4Preparation method and application of/graphene composite nanofiber | |
| CN109545578A (en) | The derivative one-dimensional nitrogen-doped nanometer carbon electrode material of acylamide polymer and preparation method | |
| Yan et al. | Green H2O2 activation of electrospun polyimide-based carbon nanofibers towards high-performance free-standing electrodes for supercapacitors | |
| Qiu et al. | Electrospun carboxymethyl cellulose acetate butyrate (CMCAB) nanofiber for high rate lithium-ion battery | |
| Li et al. | Porous carbons from Sargassum muticum prepared by H 3 PO 4 and KOH activation for supercapacitors | |
| CN113224292A (en) | High-performance lithium ion battery polyacrylonitrile carbon fiber negative electrode material and preparation method thereof | |
| CN110331469A (en) | The preparation method and applications of CuO/Cu nitrogen-doped carbon nano-fiber material | |
| CN109888220A (en) | A method of lithium cell cathode material is prepared to be pyrolyzed large biological molecule | |
| CN113097469A (en) | Preparation method of Si/SiC/C nanofiber membrane, battery cathode and lithium ion battery | |
| Li et al. | Tailoring the phase evolution of molybdenum-based nanocrystals in carbon nanofibers for enhanced performance of lithium-ion batteries | |
| Wang et al. | Facile synthesis and electrochemical properties of alicyclic polyimides based carbon microflowers for electrode materials of supercapacitors | |
| CN103632856A (en) | Production method and application of cobaltous oxide/carbon nanostructure array | |
| Xia et al. | Structures and properties of SnO 2 nanofibers derived from two different polymer intermediates | |
| CN107475815B (en) | A kind of Sb2S3The electrostatic spinning preparation method of C nano fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200609 Address after: 309-41, service center, Chentang technology business district, No. 20, Dongting Road, chentangzhuang street, Hexi District, Tianjin 300000 Patentee after: Tianjin North Joule New Energy Technology Co., Ltd Address before: 150080 Harbin, Heilongjiang, Nangang District Road, No. 52 Patentee before: HARBIN University OF SCIENCE AND TECHNOLOGY |