CN107808956B - A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode - Google Patents
A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode Download PDFInfo
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Abstract
A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode, it is related to a kind of preparation method of electrode.The invention aims to solve existing Ti2Nb10O29The problem of conductivity is low, and capacity can be greatly reduced when 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, hydro-thermal reaction obtains substrate and dry powder；Eight, it anneals, obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nano particle.The present invention can get a kind of Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode preparation method.
Description
Technical field
The present invention relates to a kind of preparation methods of electrode.
Background technique
Demand rapid growth due to people to portable electronic device have stimulated the rapid hair of lithium ion battery industry
Exhibition.Lithium ion battery energy density with higher and longer service life, have been widely used for people's daily life
Among.Graphite is the most wide negative electrode material of current business application, but its limited theoretical energy is unable to satisfy growing energy
Amount demand.However, since the decomposition of organic electrolyte during primary charging forms passivation solid electrolyte on graphite electrode
Film (SEI) can consume a large amount of lithium metal in this course, and its process is irreversible.In addition, graphite is with lower
Li+Potential is stored, safety problem can be generated.When such as with Dicharged at High Current Desity or charging, has lithium metal and be precipitated to form lithium
Crystalline substance is knitted, the short circuit of battery is caused；Meanwhile the lithium metal of precipitation may also can be reacted with electrolyte, can be generated during the reaction
A large amount of heat, causes the generation of peril.To solve the above problems, Li4Ti5O12(LTO) it is widely used in lithium ion battery
Electrode material, because it is for Li+Redox reaction current potential with a 1~2V, this is eliminated in electrochemical reaction process
The possibility that middle lithium metal is precipitated, and there is high safety performance and excellent cyclical stability.But the storage lithium ability of LTO is lower than stone
Ink, the theoretical capacity of LTO are only 175mAh/g, the development of this limiting lithium ion cell.And Ti2Nb10O29Theoretical capacity be
The material of 247mAh/g, stable circulation performance with higher can replace original widely applied LTO electrode, but,
Ti2Nb10O29Conductivity is low, there are problems that capacity can be greatly reduced when output power.
Summary of the invention
The invention aims to solve existing Ti2Nb10O29Conductivity is low, and capacity can be greatly reduced when output power
Problem, and a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode is provided.
A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode is completed 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 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, 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 (0.001mol~
0.003mol):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 (0.005mol~
0.02mol):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 750 DEG C~850 DEG C with 3 DEG C/min~8 DEG C/min heating rate under atmosphere, then in temperature is 750 DEG C
1.5h~3h is kept at~850 DEG C, obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nanometer
Grain.
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, prepares Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode, this
Kind Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is directly connected with collector, does not need any conductive additive, improves
The energy density of battery；Importantly, in subsequent cycle performance test, under the current density of 10C, system of the present invention
Standby Ti2Nb10O29Capacity retention can be very good after the circle of charge and discharge 1000 for nanometer rods/carbon nanofiber arrays electrode；
Two, under the current density of 10C, Ti prepared by the present invention2Nb10O29Nanometer rods/carbon nanofiber arrays electrode
Charging, which is held, is up to 282mAh g-1, under the current density of 20C, Ti prepared by the present invention2Nb10O29Nanometer rods/carbon nano-fiber
The charging capacity of array electrode is equally up to 206mAh g-1；
Three, in 10C (2820mA g-1) current density under, Ti prepared by the present invention2Nb10O29Nanometer rods/carbon Nanowire
Dimension array electrode remains greater than 256mAh g after 1000 cycle periods-1Capacity, this shows good cycle performance,
It is remained above 90.7% capacity.
The present invention can get a kind of Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode preparation method.
Detailed description of the invention
Fig. 1 is the Ti prepared in embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode schematic diagram, 1 in Fig. 1
It is Ti for the polyimide nano-fiber film of charing, 22Nb10O29Nanometer rods/carbon nanofiber arrays electrode；
Fig. 2 is that the polyimide nano-fiber film of the charing obtained in step 4 of embodiment one amplifies 40000 times of SEM
Figure；
Fig. 3 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 20000
SEM figure again；
Fig. 4 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 40000
SEM figure again；
Fig. 5 is Ti obtained in one step 8 of embodiment2Nb10O29Member is carried out on nanometer rods/carbon nanofiber arrays electrode
The TEM figure of element analysis；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the O elemental map analyzed in Fig. 5；
Fig. 8 is the N element figure analyzed in Fig. 5；
Fig. 9 is the Ti elemental map analyzed in Fig. 5；
Figure 10 is the Nb elemental map analyzed in Fig. 5；
Figure 11 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100,000
TEM figure again；
Figure 12 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100
Ten thousand times of HRTEM figure；
Figure 13 is XRD spectra, and 1 is Ti obtained in one step 8 of embodiment in Figure 132Nb10O29Nanometer rods/carbon Nanowire
The XRD curve of array electrode is tieed up, 2 be Ti obtained in one step 8 of embodiment2Nb10O29The XRD curve of nano particle；
Figure 14 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode Raman is bent
Line；
Figure 15 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode circulation times
Rate curve, the current density in region 1 is 10C in Figure 15, and the current density in region 2 is 20C, and " ■ " is discharge curve, and " " is
Charging curve.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of preparation of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode
Method is completed 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 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, 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 (0.001mol~
0.003mol):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 (0.005mol~
0.02mol):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 750 DEG C~850 DEG C with 3 DEG C/min~8 DEG C/min heating rate under atmosphere, then in temperature is 750 DEG C
1.5h~3h is kept at~850 DEG C, obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nanometer
Grain.
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, prepares Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electricity
Pole, this Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is directly connected with collector, does not need any conductive addition
Agent improves the energy density of battery；Importantly, in subsequent cycle performance test, under the current density of 10C,
The Ti of present embodiment preparation2Nb10O29Nanometer rods/carbon nanofiber arrays electrode capacity retention after the circle of charge and discharge 1000
It can be very good；
Two, under the current density of 10C, the Ti of present embodiment preparation2Nb10O29Nanometer rods/carbon nanofiber arrays electricity
The charging of pole, which is held, is up to 282mAh g-1, under the current density of 20C, the Ti of present embodiment preparation2Nb10O29Nanometer rods/carbon
The charging capacity of nanofiber array electrode is equally up to 206mAh g-1；
Three, in 10C (2820mA g-1) current density under, present embodiment preparation Ti2Nb10O29Nanometer rods/carbon is received
Rice fiber array electrode remains greater than 256mAh g after 1000 cycle periods-1Capacity, this shows good circulation
Performance is remained above 90.7% capacity.
Present embodiment can get a kind of Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode preparation method.
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: institute in step 2
The voltage for the electrostatic spinning stated is 15kV~20kV, and spinneret speed is 0.3mL/h~0.5mL/h, spinning nozzle and aluminium foil
Distance is 15cm~20cm；The electrostatic spinning time is 8h~10h；Collection idler wheel revolving speed is 200kr/min, and horizontal axis movement speed is
20cm/min.Other steps are 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 70 DEG C~80 DEG C, then
Temperature is 20min~30min to be kept at 70 DEG C~80 DEG C, then thermal aging oven is warming up to 130 DEG C~140 DEG C, then be in temperature
130 DEG C~140 it is lower keep 20min~30min, then thermal aging oven is warming up to 190 DEG C~200 DEG C, then temperature be 190 DEG C~
20min~30min is kept at 200 DEG C, then thermal aging oven is warming up to 250 DEG C~260 DEG C, then in temperature is 250 DEG C~260 DEG C
Lower holding 20min~30min, then thermal aging oven is warming up to 310 DEG C~320 DEG C, then protect at being 310 DEG C~320 DEG C in temperature
20min~30min is held, hot imidization is completed, obtains polyimide nano-fiber film.Other steps and specific embodiment one
It is identical to three.
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 3 DEG C/min~5 DEG C/min
Tube furnace is warming up to 290 DEG C~300 DEG C by heating rate, then keeps 20min~30min at being 290 DEG C~300 DEG C in temperature,
480 DEG C~500 DEG C are warming up to from 290 DEG C~300 DEG C with 3 DEG C/min~5 DEG C/min heating rate again, then in temperature are 480
DEG C~500 DEG C at keep 20min~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: 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~200 DEG C
In, then at being 180 DEG C~200 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 3 times~5 times, then is dried respectively, and substrate and dry powder are obtained
End.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six 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 750 DEG C~800 DEG C by min~5 DEG C/min heating rate, then is kept at being 750 DEG C~800 DEG C in temperature
1.5h~2h obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode.Other steps and one to six phase of specific embodiment
Together.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: institute in step 1
The quality of 4,4 ' stated-diaminodiphenyl ether and the volume ratio of DMAC N,N' dimethyl acetamide are (2g~3g): 40mL.Other steps
It is identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: institute in step 5
The amount of the substance for the tetraisopropyl titanate stated and the volume ratio of dehydrated alcohol are (0.001mol~0.002mol): 50mL.It is other
Step is identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: institute in step 6
The NbCl stated5Substance amount and mixed solution A volume ratio be (0.01mol~0.02mol): 50mL.Other steps and tool
Body embodiment one to nine is identical.
Embodiment one: a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode, is complete according to the following steps
At:
One, polyimide acid is prepared:
4,4 '-diaminodiphenyl ether of 3g is dissolved into 40mL n,N-dimethylacetamide, then divides 4 times and equal benzene four is added
Formic acid dianhydride, then reaction 2h 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 is carried out to polyamic acid using electrospinning device, obtains the cured polyimide nano of surface portion
Fiber；
The voltage of electrostatic spinning described in step 2 is 18kV, and spinneret speed is 0.4mL/h, spinning nozzle and aluminium foil
Distance be 18cm；The electrostatic spinning time is 9h；Collection idler wheel revolving speed is 200kr/min, and horizontal axis movement speed is 20cm/min；
Three, hot imidization is handled:
The cured polyimide nano-fiber of surface portion obtained in step 2 is put into thermal aging oven, by heat ageing
Case is warming up to 80 DEG C, then 30min is kept at being 80 DEG C in temperature, then thermal aging oven is warming up to 140 DEG C, then in temperature is 140
It keeps 30min at DEG C, then thermal aging oven is warming up to 200 DEG C, then keep 30min at being 200 DEG C in temperature, then by thermal aging oven
It is warming up to 260 DEG C, then keeps 30min at being 260 DEG C in temperature, then thermal aging oven is warming up to 320 DEG C, then in temperature be 320
30min is kept at DEG C, is completed hot imidization, is obtained polyimide nano-fiber film；
Four, charing process:
Polyimide nano-fiber film obtained in step 3 is put into the tube furnace for being passed through argon gas, then in argon gas gas
Tube furnace is warming up to 300 DEG C with the heating rate of 5 DEG C/min under atmosphere, then keeps 25min at being 300 DEG C in temperature, then with 5
DEG C/heating rate of min is warming up to 500 DEG C from 300 DEG C, then keeps 25min at being 500 DEG C in temperature, the polyamides carbonized
Imine nanometer fiber membrane；
Five, 0.5689g tetraisopropyl titanate is added in 50mL dehydrated alcohol, obtains mixed solution A；
Six, 2.7g 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 160W again, obtains mixed solution B；
Seven, the polyimide nano-fiber film of charing obtained in step 4 is immersed in as substrate, then by substrate
In PVDF reaction kettle liner equipped with mixed solution B, then PVDF reaction kettle liner is put into reaction kettle, then reaction kettle is set
7h is reacted in the baking oven that temperature is 200 DEG C, then at being 200 DEG C in temperature, then the powder of substrate and reactor bottom is distinguished
It takes out, is respectively washed 5 times using powder of the deionized water to substrate and taking-up, then dried respectively, obtains substrate and drying
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 800 DEG C with the heating rate of 5 DEG C/min under atmosphere, then keeps 2h at being 800 DEG C in temperature, is obtained
Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nano particle.
Fig. 1 is the Ti prepared in embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode schematic diagram, 1 in Fig. 1
It is Ti for the polyimide nano-fiber film of charing, 22Nb10O29Nanometer rods/carbon nanofiber arrays electrode；
Fig. 2 is that the polyimide nano-fiber film of the charing obtained in step 4 of embodiment one amplifies 40000 times of SEM
Figure；
As can be seen from Figure 2, the diameter of the polyimide nano-fiber carbonized in the polyimide nano-fiber film of charing is
200nm~300nm.
Fig. 3 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 20000
SEM figure again；
As can be seen from Figure 3, the polyimide nano-fiber in charing is grown completely by Ti2Nb10O29Nanometer rods covering,
Ti2Nb10O29Nanometer rods/carbon nanofiber arrays are by still keeping array structure after water-heat process.
Fig. 4 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 40000
SEM figure again；
As can be seen from Figure 4, Ti2Nb10O29Nanometer rods/carbon nano-fiber diameter is about 400nm~500nm.
Fig. 5 is Ti obtained in one step 8 of embodiment2Nb10O29Member is carried out on nanometer rods/carbon nanofiber arrays electrode
The TEM figure of element analysis；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the O elemental map analyzed in Fig. 5；
Fig. 8 is the N element figure analyzed in Fig. 5；
Fig. 9 is the Ti elemental map analyzed in Fig. 5；
Figure 10 is the Nb elemental map analyzed in Fig. 5；
From Fig. 5~Figure 10 it is found that Ti2Nb10O29The elemental analysis of nanometer rods/carbon nanofiber arrays electrode confirms
Ti2Nb10O29Ti in nanometer rods/carbon nanofiber arrays electrode2Nb10O29With the presence of carbon fiber.To C, O, N, Ti, Nb element
Elemental analysis can be seen that these types of element uniformity be distributed in Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electricity
In the structure of pole.Wherein C, N element exist in the polyimide nano-fiber of charing, and there are Ti for O, Ti, Nb element2Nb10O29In,
Ti can be clearly demonstrated that from these elemental analyses2Nb10O29The presence of nanometer rods/carbon nano-fiber, it is sub- comprising charing polyamides
The core and Ti of amine nanofiber2Nb10O29The shell of nanometer rods.
Figure 11 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100,000
TEM figure again；
As can be seen from Figure 11, the polyimide nano-fiber of charing is by Ti2Nb10O29Nanometer rods package, and wrap up rear surface
Become coarse, the structure of the polyimide nano-fiber of charing is by complete in store, Ti2Nb10O29Nanometer rods/carbon nano-fiber
Diameter be about 400nm.
Figure 12 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100
Ten thousand times of HRTEM figure；
As can be seen from Figure 12, analyzing interplanar distance by lattice is 0.18nm, 0.25nm, 0.35nm and 0.37nm corresponding respectively
In (200), (206), the Ti in (111) and (011) face2Nb10O29Nano stick crystal chain structure is Ti according to standard crystalline substance card2Nb10O29
(JCPDS 72-0159).
Figure 13 is XRD spectra, and 1 is Ti obtained in one step 8 of embodiment in Figure 132Nb10O29Nanometer rods/carbon Nanowire
The XRD curve of array electrode is tieed up, 2 be Ti obtained in one step 8 of embodiment2Nb10O29The XRD curve of nano particle；
As can be seen from Figure 13, all with the Ti of very high peak intensity in two maps2Nb10O29Diffraction maximum can prove out
Ti2Nb10O29Presence.Simultaneously from Ti2Nb10O29XRD curve obtain Ti2Nb10O29Diffraction maximum respectively appear in 22.5 °,
24.1 °, 25.8 °, 28.6 °, 32.5 °, 36.8 °, 39.1 °, 44.3 °, 46.4 ° and 47.8 ° of position, can correspond to (001),
(400), (21-1), (11-3), (21-5), (41-1), (51-5), (31-10), (700) and (020) crystal face, reference standard
It is Ti known to spectrogram (JCPDS No.72-0159)2Nb10O29Crystal.From Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode
XRD diffracting spectrum in, it can be observed that Ti2Nb10O29Diffraction maximum presence, it was demonstrated that Ti2Nb10O29The presence of nanometer rods.
But can't see the diffraction maximum of the polyimide nano-fiber of charing in this diffracting spectrum, many previous studies all
Show the diffraction maximum that the polyimide nano-fiber of charing can not be all detected in the XRD diffracting spectrum of wide-angle, therefore to carbon
The detection of material will measure Raman map, can see the presence of carbon material from following Raman map.Compare Raman and XRD
Diffracting spectrum the result shows that, Ti2Nb10O29The polyimide nano that there is charing in nanometer rods/carbon nanofiber arrays electrode is fine
The core and Ti of dimension2Nb10O29The shell of nanometer rods.
Figure 14 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode Raman is bent
Line；
Ti after hydro-thermal and annealing2Nb10O29It can in nanometer rods/carbon nanofiber arrays electrode Raman spectrum
To find out, there are typical 545cm in this sample-1, 638cm-1, 884cm-1And 998cm-1Peak position, be Ti2Nb10O29
The Raman peaks of nanometer rods, two strong peak are located at 1352cm-1The peak D and 1596cm-1The peak G, for the polyimides that typically carbonizes
The Raman peaks of nanofiber.
Figure 15 is Ti obtained in one step 8 of embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode circulation times
Rate curve, the current density in region 1 is 10C in Figure 15, and the current density in region 2 is 20C, and " ■ " is discharge curve, and " " is
Charging curve.
From figure 15, it can be known that under the current density of 10C, Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is in charge and discharge
Capacity retention can be very good after 1000 circle of electricity.Meanwhile under the current density of 10C, Ti2Nb10O29Nanometer rods/carbon Nanowire
The charging for tieing up array electrode, which is held, is up to 282mAhg-1, and Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is at 1000
256mAhg is remained greater than after cycle period-1Capacity, this shows good cycle performance, is remained above 90.7% appearance
Amount.In 20C (5640mAg-1) current density under, Ti2Nb10O29The charging of nanometer rods/carbon nanofiber arrays electrode is held same
Up to 206mAh g-1Capacity.
Ti prepared by embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode has excellent circulating ratio
Can, it is due to Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode structure has biggish specific surface area, bigger serface
The polyimide nano-fiber structure of charing increase electrolyte and Ti2Nb10O29The contact area of nanometer rods, shorten lithium from
The transmission path of son, and volume change caused by reducing in electrochemical reaction process, so that the lithium for improving the electrode is deposited
Energy storage power.
Claims (10)
1. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode, it is characterised in that a kind of titanium niobium oxygen nanometer
Stick/carbon nanofiber arrays electrode preparation method is completed 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 is carried out to polyamic acid using electrospinning device, it is fine to obtain the cured polyimide nano of surface portion
Dimension；
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, 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~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 (0.001mol~
0.003mol):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 (0.005mol~0.02mol):
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 750 DEG C~850 DEG C, then in temperature be 750 DEG C~850
1.5h~3h is kept at DEG C, obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nano particle.
2. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
The solid content for being polyamic acid described in step 1 is 14%~15%.
3. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
The voltage for being electrostatic spinning described in step 2 is 15kV~20kV, and spinneret speed is 0.3mL/h~0.5mL/h, spinning
Spinning head is 15cm~20cm at a distance from aluminium foil；The electrostatic spinning time is 8h~10h；Collection idler wheel revolving speed is 200kr/min,
Horizontal axis movement speed is 20cm/min.
4. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
It is in step 3 for the cured polyimide nano-fiber of surface portion to be put into thermal aging oven, thermal aging oven is warming up to 70
DEG C~80 DEG C, then 20min~30min is kept at being 70 DEG C~80 DEG C in temperature, then thermal aging oven is warming up to 130 DEG C~140
DEG C, it then in temperature is 130 DEG C~140 lower holding 20min~30min, then thermal aging oven is warming up to 190 DEG C~200 DEG C, then
Temperature is 20min~30min to be kept at 190 DEG C~200 DEG C, then thermal aging oven is warming up to 250 DEG C~260 DEG C, then in temperature
It is holding 20min~30min at 250 DEG C~260 DEG C, then thermal aging oven is warming up to 310 DEG C~320 DEG C, then in temperature is 310
DEG C~320 DEG C at keep 20min~30min, complete hot imidization, obtain polyimide nano-fiber film.
5. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
Be in step 4 for polyimide nano-fiber film to be 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 290 DEG C~300 DEG C by min~5 DEG C/min heating rate, then is kept at being 290 DEG C~300 DEG C in temperature
20min~30min, then 480 DEG C~500 DEG C are warming up to from 290 DEG C~300 DEG C with 3 DEG C/min~5 DEG C/min heating rate,
20min~30min, the polyimide nano-fiber film carbonized are kept at being again 480 DEG C~500 DEG C in temperature.
6. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
It is to be immersed in the polyimide nano-fiber film of charing equipped with mixed solution B as substrate, then by substrate in step 7
PVDF reaction kettle liner in, then PVDF reaction kettle liner is put into reaction kettle, then it is 180 DEG C that reaction kettle, which is placed in temperature,
6h~7h is reacted in~200 DEG C of baking oven, then at being 180 DEG C~200 DEG C in temperature, then by the powder of substrate and reactor bottom
It takes out respectively, is respectively washed 3 times~5 times using powder of the deionized water to substrate and taking-up, then dried respectively, obtains base
Piece and dry powder.
7. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
It is 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 in argon gas
Tube furnace is warming up to 750 DEG C~800 DEG C with 3 DEG C/min~5 DEG C/min heating rate under atmosphere, then in temperature is 750 DEG C
1.5h~2h is kept at~800 DEG C, obtains Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode.
8. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
Be 4,4 '-diaminodiphenyl ether described in step 1 quality and DMAC N,N' dimethyl acetamide volume ratio be (2g~
3g):40mL。
9. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, feature
Be the substance of tetraisopropyl titanate described in step 5 amount and dehydrated alcohol volume ratio be (0.001mol~
0.002mol):50mL。
10. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, special
Sign is NbCl described in step 65Substance amount and mixed solution A volume ratio be (0.01mol~0.02mol):
50mL。
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| CN101172654A (en) * | 2007-10-16 | 2008-05-07 | 中国科学院上海硅酸盐研究所 | Method of producing nano-titanium niobium oxynitride powder body |
| CN105575675A (en) * | 2015-12-30 | 2016-05-11 | 哈尔滨工业大学 | Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor |
| CN105712316A (en) * | 2015-09-23 | 2016-06-29 | 哈尔滨理工大学 | Preparation method of zinc oxide nanowire array/carbon nanofiber composite material |
| CN105970483A (en) * | 2016-05-23 | 2016-09-28 | 苏州纳赛博丝新材料科技有限公司 | Electrostatic spinning directional nanofiber membrane and preparation method and application thereof |
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| CN101172654A (en) * | 2007-10-16 | 2008-05-07 | 中国科学院上海硅酸盐研究所 | Method of producing nano-titanium niobium oxynitride powder body |
| CN105712316A (en) * | 2015-09-23 | 2016-06-29 | 哈尔滨理工大学 | Preparation method of zinc oxide nanowire array/carbon nanofiber composite material |
| CN105575675A (en) * | 2015-12-30 | 2016-05-11 | 哈尔滨工业大学 | Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor |
| CN105970483A (en) * | 2016-05-23 | 2016-09-28 | 苏州纳赛博丝新材料科技有限公司 | Electrostatic spinning directional nanofiber membrane and preparation method and application thereof |
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