CN107808956A - 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 PDF

Info

Publication number
CN107808956A
CN107808956A CN201711030898.7A CN201711030898A CN107808956A CN 107808956 A CN107808956 A CN 107808956A CN 201711030898 A CN201711030898 A CN 201711030898A CN 107808956 A CN107808956 A CN 107808956A
Authority
CN
China
Prior art keywords
temperature
nanometer rods
warming
carbon nanofiber
20min
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.)
Granted
Application number
CN201711030898.7A
Other languages
Chinese (zh)
Other versions
CN107808956B (en
Inventor
陈明华
亓美丽
陈庆国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin North Joule New Energy Technology Co., Ltd
Original Assignee
Harbin University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Harbin University of Science and Technology filed Critical Harbin University of Science and Technology
Priority to CN201711030898.7A priority Critical patent/CN107808956B/en
Publication of CN107808956A publication Critical patent/CN107808956A/en
Application granted granted Critical
Publication of CN107808956B publication Critical patent/CN107808956B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

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 conductance is low, and capacity can be greatly reduced during output power.Method：First, polyimide acid is prepared；2nd, polyimide nano-fiber is prepared；3rd, hot imidization is handled；4th, charing process；5th, mixed solution A is prepared；6th, mixed solution B is prepared；7th, hydro-thermal reaction, substrate and the powder dried are obtained；8th, anneal, obtain Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode and Ti2Nb10O29Nano particle.The present invention can obtain a kind of Ti2Nb10O29The preparation method of nanometer rods/carbon nanofiber arrays electrode.

Description

A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode
Technical field
The present invention relates to a kind of preparation method of electrode.
Background technology
Because people are to the demand rapid growth of portable electric appts, the rapid hair of lithium ion battery industry have stimulated Exhibition.Lithium ion battery has higher energy density and longer service life, and it has been widely used for people's daily life Among.Graphite is the most wide negative material of current business application, but its limited theoretical energy can not meet growing energy Amount demand.However, because the decomposition of organic electrolyte during primary charging forms passivation solid electrolyte on graphite electrode Film (SEI), substantial amounts of lithium metal can be consumed in this course, and its process is irreversible.In addition, graphite have it is relatively low Li+Potential is stored, safety problem can be produced.When such as with Dicharged at High Current Desity or charging, have lithium metal and separate out to form lithium Crystalline substance is knitted, causes the short circuit of battery；Meanwhile the lithium metal of precipitation be able to may also react with electrolyte, can produce during the course of the reaction Substantial amounts 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 separates out, and there is high safety performance and excellent cyclical stability.But LTO storage lithium ability is less than stone Ink, LTO theoretical capacity are only 175mAh/g, the development of this limiting lithium ion cell.And Ti2Nb10O29Theoretical capacity be 247mAh/g material, there is higher stable circulation performance, original wide variety of LTO electrodes can be replaced, but, Ti2Nb10O29The problem of conductance is low, and capacity can be greatly reduced when output power be present.
The content of the invention
The invention aims to solve existing Ti2Nb10O29Conductance is low, and capacity can be greatly reduced during 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 according to the following steps：
First, polyimide acid is prepared：
4,4 '-diaminodiphenyl ether is dissolved into DMA, then divides 3 times~5 times and adds equal benzene tetramethyl 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 mol ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
2nd, polyimide nano-fiber is prepared：
Electrostatic spinning is carried out to polyamic acid using electrospinning device, obtains the polyimide nano of surface portion solidification Fiber；
3rd, hot imidization is handled：
By surface portion solidify polyimide nano-fiber be 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 Spend to keep 20min~40min 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, hot imidization is completed, obtains polyimide nano-fiber film；
4th, 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~8 DEG C/min heating rate, 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；
5th, tetraisopropyl titanate is added in absolute ethyl alcohol, obtains mixed solution A；
The amount of the material of tetraisopropyl titanate described in step 5 and the volume ratio of absolute ethyl alcohol for (0.001mol~ 0.003mol):50mL；
6th, NbCl is added into mixed solution A first5, absolute ethyl alcohol is added, then in ultrasonic power be 160W~200W Lower ultrasonic disperse 15min~20min, obtains mixed solution B；
NbCl described in step 65Material amount and mixed solution A volume ratio for (0.005mol~ 0.02mol):50mL；
The volume ratio of absolute ethyl alcohol and mixed solution A described in step 6 is (10~15):50；
7th, the polyimide nano-fiber film of charing is immersed in equipped with mixed solution B's as substrate, then by substrate In PVDF reactor inner bags, then PVDF reactor inner bags are put into reactor, then by reactor be placed in temperature for 180 DEG C~ In 210 DEG C of baking oven, then 6h~8h is reacted at being 180 DEG C~210 DEG C in temperature, then the powder of substrate and reactor bottom is divided Do not take out, substrate and the powder taken out are respectively washed 3 times~5 times using deionized water, then dried respectively, obtain substrate With dry powder；
8th, the powder of the 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 the present invention：
First, the present invention is first by the partially cured polyimide nano-fiber of the method synthetic surface of electrostatic spinning, so Hot imidization is carried out by thermal aging oven afterwards, obtains polyimide nano-fiber film；Polyimide nano-fiber film is led to Cross tube furnace to be carbonized, the polyimide nano-fiber film carbonized；By the polyimide nano-fiber film of charing As substrate, then by hydro-thermal method and the method for annealing, prepare Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode, this Kind Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is directly connected with collector, it is not necessary to any conductive additive, improves The energy density of battery；Importantly, in subsequent cycle performance test, so that under 10C current density, the present invention makes Standby Ti2Nb10O29Capacity retention can be very good after the circle of discharge and recharge 1000 for nanometer rods/carbon nanofiber arrays electrode；
2nd, under 10C current density, the Ti of the invention prepared2Nb10O29Nanometer rods/carbon nanofiber arrays electrode Charging, which is held, is up to 282mAh g-1, under 20C current density, the Ti of the invention prepared2Nb10O29Nanometer rods/carbon nano-fiber The charging capacity of array electrode is equally up to 206mAh g-1；
3rd, in 10C (2820mA g-1) current density under, the Ti for preparing of 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 obtain a kind of Ti2Nb10O29The preparation method of nanometer rods/carbon nanofiber arrays electrode.
Brief description of the drawings
Fig. 1 is the Ti prepared in embodiment one2Nb10O29The schematic diagram of nanometer rods/carbon nanofiber arrays electrode, 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 the step 4 of embodiment one amplifies 40000 times of SEM Figure；
Fig. 3 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 20000 SEM figures again；
Fig. 4 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 40000 SEM figures again；
Fig. 5 is the Ti obtained in the step 8 of embodiment one2Nb10O29Member is carried out on nanometer rods/carbon nanofiber arrays electrode The TEM figures of element analysis；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the O elemental maps analyzed in Fig. 5；
Fig. 8 is the N element figure analyzed in Fig. 5；
Fig. 9 is the C element figure analyzed in Fig. 5；
Figure 10 is the Nb elemental maps analyzed in Fig. 5；
Figure 11 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100,000 TEM figures again；
Figure 12 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100 Ten thousand times of HRTEM figures；
Figure 13 is XRD spectra, and 1 is the Ti obtained in the step 8 of embodiment one in Figure 132Nb10O29Nanometer rods/carbon Nanowire The XRD curves of array electrode are tieed up, 2 be the Ti obtained in the step 8 of embodiment one2Nb10O29The XRD curves of nano particle；
Figure 14 is the Ti obtained in the step 8 of embodiment one2Nb10O29The Raman of nanometer rods/carbon nanofiber arrays electrode is bent Line；
Figure 15 is the Ti obtained in the step 8 of embodiment one2Nb10O29The circulation of nanometer rods/carbon nanofiber arrays electrode 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.
Embodiment
Embodiment one：Present embodiment is a kind of preparation of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode Method, complete according to the following steps：
First, polyimide acid is prepared：
4,4 '-diaminodiphenyl ether is dissolved into DMA, then divides 3 times~5 times and adds equal benzene tetramethyl 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 mol ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
2nd, polyimide nano-fiber is prepared：
Electrostatic spinning is carried out to polyamic acid using electrospinning device, obtains the polyimide nano of surface portion solidification Fiber；
3rd, hot imidization is handled：
By surface portion solidify polyimide nano-fiber be 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 Spend to keep 20min~40min 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, hot imidization is completed, obtains polyimide nano-fiber film；
4th, 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~8 DEG C/min heating rate, 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；
5th, tetraisopropyl titanate is added in absolute ethyl alcohol, obtains mixed solution A；
The amount of the material of tetraisopropyl titanate described in step 5 and the volume ratio of absolute ethyl alcohol for (0.001mol~ 0.003mol):50mL；
6th, NbCl is added into mixed solution A first5, absolute ethyl alcohol is added, then in ultrasonic power be 160W~200W Lower ultrasonic disperse 15min~20min, obtains mixed solution B；
NbCl described in step 65Material amount and mixed solution A volume ratio for (0.005mol~ 0.02mol):50mL；
The volume ratio of absolute ethyl alcohol and mixed solution A described in step 6 is (10~15):50；
7th, the polyimide nano-fiber film of charing is immersed in equipped with mixed solution B's as substrate, then by substrate In PVDF reactor inner bags, then PVDF reactor inner bags are put into reactor, then by reactor be placed in temperature for 180 DEG C~ In 210 DEG C of baking oven, then 6h~8h is reacted at being 180 DEG C~210 DEG C in temperature, then the powder of substrate and reactor bottom is divided Do not take out, substrate and the powder taken out are respectively washed 3 times~5 times using deionized water, then dried respectively, obtain substrate With dry powder；
8th, the powder of the 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：
First, present embodiment is fine by the partially cured polyimide nano of the method synthetic surface of electrostatic spinning first Dimension, hot imidization is then carried out 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 prepares Ti as substrate, then by hydro-thermal method and the method for annealing2Nb10O29Nanometer rods/carbon nanofiber arrays electricity Pole, this Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is directly connected with collector, it is not necessary to any conductive addition Agent, improve the energy density of battery；Importantly, in subsequent cycle performance test, with 10C current density, Ti prepared by present embodiment2Nb10O29Nanometer rods/carbon nanofiber arrays electrode capacity retention after the circle of discharge and recharge 1000 Can be very good；
2nd, under 10C current density, 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 20C current density, the Ti of present embodiment preparation2Nb10O29Nanometer rods/carbon The charging capacity of nanofiber array electrode is equally up to 206mAh g-1；
3rd, in 10C (2820mA g-1) current density under, present embodiment prepare Ti2Nb10O29Nanometer rods/carbon is received Rice fiber array electrode remains greater than 256mAh g after 1000 cycle periods-1Capacity, this shows good circulation Performance, it is remained above 90.7% capacity.
Present embodiment can obtain a kind of Ti2Nb10O29The preparation method of nanometer rods/carbon nanofiber arrays electrode.
Embodiment two：Present embodiment is with the difference of embodiment one：Polyamides described in step 1 The solid content of amino acid is 14%~15%.Other steps are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：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；It is 200kr/min to collect roller rotating speed, and transverse axis translational speed is 20cm/min.Other steps are identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Will in step 3 The polyimide nano-fiber of surface portion solidification is put into thermal aging oven, and thermal aging oven is warming up into 70 DEG C~80 DEG C, then Temperature is that 20min~30min is kept at 70 DEG C~80 DEG C, then thermal aging oven is warming up into 130 DEG C~140 DEG C, then is in temperature 130 DEG C~140 times holding 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 protected 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 embodiment one It is identical to three.
Embodiment five：Present embodiment is with one of embodiment one to four difference：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's 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, then in temperature be 480 again 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.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Will in step 7 The polyimide nano-fiber film of charing is immersed in the PVDF reactors equipped with mixed solution B as substrate, then by substrate In courage, then PVDF reactor inner bags are put into reactor, then reactor is placed in the baking oven that temperature is 180 DEG C~200 DEG C In, then 6h~7h is reacted at being 180 DEG C~200 DEG C in temperature, then the powder of substrate and reactor bottom is taken out respectively, use Deionized water is respectively washed 3 times~5 times to substrate and the powder taken out, then is dried respectively, obtains substrate and the powder dried End.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Will in step 8 The substrate that is obtained in step 7 and the powder dried 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, obtain Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode.Other steps and the phase of embodiment one to six Together.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：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 with embodiment one to seven.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：Institute in step 5 The amount of the material for the tetraisopropyl titanate stated and the volume ratio of absolute ethyl alcohol are (0.001mol~0.002mol):50mL.It is other Step is identical with embodiment one to eight.
Embodiment ten：Present embodiment is with one of embodiment one to nine difference：Institute in step 6 The NbCl stated5The amount of material and the volume ratio of mixed solution A 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 Into：
First, polyimide acid is prepared：
By 3g 4,4 '-diaminodiphenyl ether is dissolved into 40mL DMAs, then is divided 4 times and added equal benzene four Formic acid dianhydride, then reaction 2h is stirred at room temperature, obtain polyamic acid；
The mol ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:1.05；
2nd, polyimide nano-fiber is prepared：
Electrostatic spinning is carried out to polyamic acid using electrospinning device, obtains the polyimide nano of surface portion solidification 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；It is 200kr/min to collect roller rotating speed, and transverse axis translational speed is 20cm/min；
3rd, hot imidization is handled：
The polyimide nano-fiber that the surface portion obtained in step 2 solidifies 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 into 140 DEG C, then in temperature is 140 Keep 30min at DEG C, then thermal aging oven is warming up to 200 DEG C, then 30min is kept at being 200 DEG C in temperature, then by thermal aging oven It 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 in temperature is 320 30min is kept at DEG C, hot imidization is completed, obtains polyimide nano-fiber film；
4th, charing process：
The 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 5 DEG C/min heating rate under atmosphere, then 25min is kept at being 300 DEG C in temperature, then with 5 DEG C/min heating rate 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；
5th, 0.5689g tetraisopropyl titanates are added in 50mL absolute ethyl alcohols, obtain mixed solution A；
6th, 2.7g NbCl are added in the mixed solution A obtained first into step 55, 10mL absolute ethyl alcohols are added, The ultrasonic disperse 20min in the case where ultrasonic power is 160W again, obtains mixed solution B；
7th, the polyimide nano-fiber film of the charing obtained in step 4 is immersed in as substrate, then by substrate In PVDF reactor inner bags equipped with mixed solution B, then PVDF reactor inner bags are put into reactor, then reactor is put In the baking oven that temperature is 200 DEG C, then 7h is reacted at being 200 DEG C in temperature, then the powder of substrate and reactor bottom is distinguished Take out, substrate and the powder taken out are respectively washed 5 times using deionized water, then dried respectively, obtain substrate and drying Powder；
8th, the powder of the 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 5 DEG C/min heating rate under atmosphere, then 2h is kept 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 one2Nb10O29The schematic diagram of nanometer rods/carbon nanofiber arrays electrode, 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 the step 4 of embodiment one amplifies 40000 times of SEM Figure；
As can be seen from Figure 2, the polyimide nano-fiber carbonized in the polyimide nano-fiber film of charing it is a diameter of 200nm~300nm.
Fig. 3 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 20000 SEM figures again；
As can be seen from Figure 3, the polyimide nano-fiber in charing is grown completely by Ti2Nb10O29Nanometer rods cover, Ti2Nb10O29Nanometer rods/carbon nanofiber arrays after water-heat process by still keeping array structure.
Fig. 4 is the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 40000 SEM figures again；
As can be seen from Figure 4, Ti2Nb10O29The diameter of nanometer rods/carbon nano-fiber is about 400nm~500nm.
Fig. 5 is the Ti obtained in the step 8 of embodiment one2Nb10O29Member is carried out on nanometer rods/carbon nanofiber arrays electrode The TEM figures of element analysis；
Fig. 6 is the C element figure analyzed in Fig. 5；
Fig. 7 is the O elemental maps analyzed in Fig. 5；
Fig. 8 is the N element figure analyzed in Fig. 5；
Fig. 9 is the C element figure analyzed in Fig. 5；
Figure 10 is the Nb elemental maps analyzed in Fig. 5；
It was found from Fig. 5~Figure 10, to Ti2Nb10O29The elementary 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 Elementary analysis can be seen that this several element uniformity be distributed in Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electricity In the structure of pole.Wherein C, N element are present in the polyimide nano-fiber of charing, and O, Ti, Nb element have Ti2Nb10O29In, Ti can be clearly demonstrated that from these elementary 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 the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100,000 TEM figures again；
As can be seen from Figure 11, the polyimide nano-fiber of charing is by Ti2Nb10O29Nanometer rods are wrapped up, and surface after parcel 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 the Ti obtained in the step 8 of embodiment one2Nb10O29Nanometer rods/carbon nanofiber arrays electrode amplification 100 Ten thousand times of HRTEM figures；
As can be seen from Figure 12, it is 0.18nm, 0.25nm, 0.35nm and 0.37nm corresponding respectively to analyze interplanar distance by lattice In (200), (206), the Ti in (111) and (011) face2Nb10O29Nano stick crystal chain structure, it is Ti according to the brilliant card of standard2Nb10O29 (JCPDS 72-0159).
Figure 13 is XRD spectra, and 1 is the Ti obtained in the step 8 of embodiment one in Figure 132Nb10O29Nanometer rods/carbon Nanowire The XRD curves of array electrode are tieed up, 2 be the Ti obtained in the step 8 of embodiment one2Nb10O29The XRD curves of nano particle；
As can be seen from Figure 13, all there is the Ti of very high peak intensity in two collection of illustrative plates2Nb10O29Diffraction maximum, it can prove out Ti2Nb10O29Presence.Simultaneously from Ti2Nb10O29XRD curves 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), the crystal face of (21-1), (11-3), (21-5), (41-1), (51-5), (31-10), (700) and (020), reference standard It is Ti that spectrogram (JCPDS No.72-0159), which is understood,2Nb10O29Crystal.From Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode XRD diffracting spectrums in, it is observed that Ti2Nb10O29Diffraction maximum presence, it was demonstrated that Ti2Nb10O29The presence of nanometer rods. But the diffraction maximum of the polyimide nano-fiber of charing is can't see in this diffracting spectrum, in many previous studies all Show can not all to detect the diffraction maximum of the polyimide nano-fiber of charing in the XRD diffracting spectrums of wide-angle, therefore to carbon The detection of material will measure Raman collection of illustrative plates, and the presence of carbon material is can see from following Raman collection of illustrative plates.Contrast Raman and XRD Diffracting spectrum result shows, Ti2Nb10O29The polyimide nano that charing in nanometer rods/carbon nanofiber arrays electrode be present is fine The core and Ti of dimension2Nb10O29The shell of nanometer rods.
Figure 14 is the Ti obtained in the step 8 of embodiment one2Nb10O29The Raman of nanometer rods/carbon nanofiber arrays electrode is bent Line；
Ti after hydro-thermal and annealing2Nb10O29Can in the Raman spectrum of nanometer rods/carbon nanofiber arrays electrode To find out, typical 545cm in this sample be present-1, 638cm-1, 884cm-1And 998cm-1Peak position, be Ti2Nb10O29 The Raman peaks of nanometer rods, two strong peak are located at 1352cm-1D peaks and 1596cm-1G peaks, for the polyimides that typically carbonizes The Raman peaks of nanofiber.
Figure 15 is the Ti obtained in the step 8 of embodiment one2Nb10O29The circulation of nanometer rods/carbon nanofiber arrays electrode 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 10C current density, Ti2Nb10O29Nanometer rods/carbon nanofiber arrays electrode is in charge and discharge Capacity retention can be very good after the circle of electricity 1000.Meanwhile under 10C current density, Ti2Nb10O29Nanometer rods/carbon Nanowire Up to 282mAhg is held in the charging for tieing up array electrode-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 Ti2Nb10O29The structure of nanometer rods/carbon nanofiber arrays electrode has larger 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 Changes caused by electrochemical reaction process are reduced, deposited so as to improve the lithium of the electrode Energy storage power.

Claims (10)

  1. A kind of a kind of 1. preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode, it is characterised in that titanium niobium oxygen nanometer The preparation method of rod/carbon nanofiber arrays electrode is completed according to the following steps：
    First, polyimide acid is prepared：
    4,4 '-diaminodiphenyl ether is dissolved into DMA, then divides 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 for (2g~ 5g):40mL；
    The mol ratio of 4,4 '-diaminodiphenyl ether and pyromellitic acid anhydride described in step 1 is 1:(1~1.05)；
    2nd, polyimide nano-fiber is prepared：
    Electrostatic spinning is carried out to polyamic acid using electrospinning device, the polyimide nano for obtaining surface portion solidification is fine Dimension；
    3rd, hot imidization is handled：
    The polyimide nano-fiber that surface portion solidifies 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 that 20min~40min is kept at 130 DEG C~150 DEG C, then thermal aging oven is warming up into 190 DEG C~210 DEG C, then in temperature To keep 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, hot imidization is completed, obtains polyimide nano-fiber film；
    4th, 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 min heating rate ~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 Spend to keep 20min~30min, the polyimide nano-fiber film carbonized at 480 DEG C~520 DEG C；
    5th, tetraisopropyl titanate is added in absolute ethyl alcohol, obtains mixed solution A；
    The amount of the material of tetraisopropyl titanate described in step 5 and the volume ratio of absolute ethyl alcohol for (0.001mol~ 0.003mol):50mL；
    6th, NbCl is added into mixed solution A first5, absolute ethyl 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 65The amount of material and the volume ratio of mixed solution A be (0.005mol~0.02mol): 50mL；
    The volume ratio of absolute ethyl alcohol and mixed solution A described in step 6 is (10~15):50；
    7th, the polyimide nano-fiber film of charing is immersed in the PVDF equipped with mixed solution B as substrate, then by substrate In reactor inner bag, then PVDF reactor inner bags are put into reactor, then reactor is placed in temperature as 180 DEG C~210 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, substrate and the powder taken out be respectively washed 3 times~5 times using deionized water, then dried respectively, obtain substrate and Dry powder；
    8th, the powder of the substrate obtained in step 7 and drying is put into the tube furnace for being passed through argon gas, then in argon gas 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. 2. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature The solid content for being the polyamic acid described in step 1 is 14%~15%.
  3. 3. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature The voltage for being the electrostatic spinning described in step 2 is 15kV~20kV, and spinneret speed is 0.3mL/h~0.5mL/h, spinning The distance of spinning head and aluminium foil is 15cm~20cm；The electrostatic spinning time is 8h~10h；It is 200kr/min to collect roller rotating speed, Transverse axis translational speed is 20cm/min.
  4. 4. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature The polyimide nano-fiber that surface portion solidifies is being put into thermal aging oven in step 3, 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, then in temperature be to keep 20min~30min 130 DEG C~140 time, then thermal aging oven is warming up to 190 DEG C~200 DEG C, then Temperature is that 20min~30min is kept at 190 DEG C~200 DEG C, then thermal aging oven is warming up into 250 DEG C~260 DEG C, then in temperature To keep 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. 5. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature Polyimide nano-fiber film is being put into the tube furnace for being passed through argon gas in step 4, 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. 6. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature The polyimide nano-fiber film of charing is being immersed in equipped with mixed solution B as substrate, then by substrate in step 7 PVDF reactor inner bags in, then PVDF reactor inner bags are put into reactor, then reactor is placed in temperature as 180 DEG C In~200 DEG C of baking oven, then 6h~7h, then the powder by substrate and reactor bottom are reacted at being 180 DEG C~200 DEG C in temperature Take out, substrate and the powder taken out are respectively washed 3 times~5 times respectively using deionized water, then dried respectively, obtain base Piece and the powder dried.
  7. 7. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature The substrate obtained in step 7 and the powder dried are being 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. 8. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature Be 4,4 '-diaminodiphenyl ether described in step 1 quality and DMAC N,N' dimethyl acetamide volume ratio for (2g~ 3g):40mL。
  9. 9. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, its feature Be the material of the tetraisopropyl titanate described in step 5 amount and absolute ethyl alcohol volume ratio for (0.001mol~ 0.002mol):50mL。
  10. 10. a kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode according to claim 1, it is special Sign is the NbCl described in step 65The amount of material and the volume ratio of mixed solution A be (0.01mol~0.02mol): 50mL。
CN201711030898.7A 2017-10-27 2017-10-27 A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode Active CN107808956B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711030898.7A CN107808956B (en) 2017-10-27 2017-10-27 A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711030898.7A CN107808956B (en) 2017-10-27 2017-10-27 A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode

Publications (2)

Publication Number Publication Date
CN107808956A true CN107808956A (en) 2018-03-16
CN107808956B CN107808956B (en) 2019-09-24

Family

ID=61582932

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711030898.7A Active CN107808956B (en) 2017-10-27 2017-10-27 A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode

Country Status (1)

Country Link
CN (1) CN107808956B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111403718A (en) * 2020-03-31 2020-07-10 浙江大学 Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111403718A (en) * 2020-03-31 2020-07-10 浙江大学 Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof
CN111403718B (en) * 2020-03-31 2021-06-15 浙江大学 Titanium niobium oxide/vertical graphene/titanium carbide-carbon composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN107808956B (en) 2019-09-24

Similar Documents

Publication Publication Date Title
Reddy et al. Preparation and electrochemical studies of electrospun TiO2 nanofibers and molten salt method nanoparticles
Wu et al. Core–shell CeO 2@ C nanospheres as enhanced anode materials for lithium ion batteries
Senthilkumar et al. Studies on electrochemical properties of hetarolite (ZnMn2O4) nanostructure for supercapacitor application
CN106006715B (en) The method for preparing nano zine oxide using liquid phase barrier film discharge plasma
Wang et al. Hydrothermal synthesis of α-MoO3 and the influence of later heat treatment on its electrochemical properties
CN102074683A (en) Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof
Sanad et al. Robust and facile strategy for tailoring CoMn2O4 and MnCo2O4 structures as high capacity anodes for Li-ions batteries
CN101488584A (en) Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole
Xu et al. Biotemplate synthesis of mesoporous α-Fe2O3 hierarchical structure with assisted pseudocapacitive as an anode for long-life lithium ion batteries
CN108807915B (en) CoFe2O4Preparation method and application of/graphene composite nanofiber
CN107994216B (en) A kind of preparation method of ultra-high magnifications, long-life flexible nano fiber array electrode
CN107634206A (en) A kind of lithium ion battery flexibility negative material and preparation method thereof
CN106229544A (en) A kind of high performance lithium ionic cell cathode material Ni/C composite nano fiber and preparation method thereof
CN105489863A (en) C/Ti4O7 composite nanofiber based lithium-sulfur battery positive electrode material and preparation method therefor
CN102936048B (en) Leaf-type NH4V3O8 microcrystalline preparation method
Liu et al. The effects of Li 2 CO 3 particle size on the properties of lithium titanate as anode material for lithium-ion batteries
CN103632856A (en) Production method and application of cobaltous oxide/carbon nanostructure array
CN107808956B (en) A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode
Wei et al. Research on the electrochemical performance of rutile and anatase composite TiO2 nanotube arrays in lithium-ion batteries
CN104157856B (en) Core-shell type LaFeO3@C lithium battery anode material and preparation method thereof
CN110289399A (en) Negative electrode material and preparation method thereof, lithium ion battery
CN109755528A (en) A kind of preparation method and applications of manganese selenide/carbon fiber energy storage material
CN106784722B (en) A kind of lithium titanate/titanium dioxide combination electrode material and preparation method thereof
CN111540887A (en) Carbon-coated cobaltosic oxide and tin dioxide composite lithium battery material and preparation method thereof
Wang et al. Boosting lithium storage performance of Co-Sn double hydroxide nanocubes in-situ grown in mesoporous hollow carbon nanospheres

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: 20200604

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