CN108346787A - Hollow carbon nano-fiber lithium cell cathode material of a kind of high power capacity TiO2-VO2 doping and preparation method thereof - Google Patents
Hollow carbon nano-fiber lithium cell cathode material of a kind of high power capacity TiO2-VO2 doping and preparation method thereof Download PDFInfo
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- CN108346787A CN108346787A CN201810070075.5A CN201810070075A CN108346787A CN 108346787 A CN108346787 A CN 108346787A CN 201810070075 A CN201810070075 A CN 201810070075A CN 108346787 A CN108346787 A CN 108346787A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of high power capacity TiO2 VO2 to adulterate hollow carbon nano-fiber lithium cell cathode material, including hollow carbon nano-fiber and TiO2 the and VO2 nano particles for being coated on the hollow carbon nano-fiber outer surface；The content of the TiO2 nano particles is 10~80.0wt%, and the content of the VO2 nano particles is 0.1~20.0wt%, and surplus is hollow carbon nano-fiber；The invention also discloses the preparation methods of the negative material, the high power capacity TiO2 VO2 of the present invention adulterate hollow carbon nano-fiber lithium cell cathode material, with hierarchical porous structure and high load amount, is conducive to electrolyte permeability and enters negative material, while being conducive to the insertion of lithium ion and the transmission of electronics；The conductivity, specific capacity and stability for improving negative material make it have excellent high rate performance and cycle performance.
Description
Technical field
The present invention relates to lithium cell cathode material fields more particularly to a kind of high power capacity TiO2-VO2 to adulterate hollow carbon nanometer
Fiber lithium cell cathode material and preparation method thereof.
Background technology
Lithium ion battery is a kind of novel Green Chemistry power supply, is had compared with traditional nickel-cadmium cell, Ni-MH battery
The big advantage of voltage height, long lifespan, energy density.From after nineteen ninety Sony Corporation of Japan's release first generation lithium ion battery, it
Various portable devices have been rapidly developed and be widely used in, the necks such as 3C Product, power plant, energy storage device are related to
Domain.Due to new-energy automobile flourish, the demand to power battery is increasing, the basis of power battery be have it is excellent
The negative material of charge-discharge performance.
Currently, negative material then in carbon-based material, lithium titanate, silica, silicon nanoparticle and Nanoalloy one
Kind or several, commercialized mainly graphite, but graphite electrode is due to there are the growth question of lithium dendrite arm, cell safety hidden danger compared with
Greatly, and the lattice dilatation during the total embedding and removal lithium embedded of solvent is easy to cause graphite flake layer stripping and falls off, and leads to cyclic process
In capacity attenuation, to limit its service life.Therefore, numerous researchers is dedicated to developing novel cathode material
The drawbacks of material, solution lithium dendrite growth and capacity attenuation.Titanium base material, as monoclinic system TiO2 and it is sharp admire mine type TiO2,
Theoretical capacity up to 335mAh/g, volume expansion it is small (<3%), there is unique fast charging and discharging performance and environment friendly.
The maximum advantage of TiO2 type negative materials is that voltage platform is higher, and higher than the blanking voltage for generating Li dendrite, institute W is negative with TiO2 types
Pole material can fundamentally solve the problems, such as the generation of lithium dendrite arm.But low (the 10-13 of electronic conductivity of TiO2 type negative materials
~10-17S/cm) cause practical removal lithium embedded process high rate performance and embedded dynamics relatively low.In addition, single nano material ratio
Surface area is big, but the unsaturated key such as surface dangling bond is more, causes surface energy larger.Nano particle during repeated charge,
It is easy mutually to reunite between nano particle, causes the dispersion of TiO2 and conductive drug uneven, cut off effective delivering path of electronics.
Therefore, existing TiO2 types negative material also has many defects, it is necessary to provide one kind and can increase material and compare table
The TiO2 type negative materials and preparation method thereof of area and specific capacity.
Invention content
The drawbacks of in order to overcome TiO2 type negative materials, the present invention adulterate by the regulation and control of nanostructure and active material
Increase material specific surface area and specific capacity.
It is the effective way for solving TiO2 type negative material drawbacks to prepare TiO2/ carbon composite constructions.The present invention is using coaxial
Method of electrostatic spinning, i.e., by surface modification or surface-functionalized, by TiO2 particles or the modification of TiO2 nano coatings in Porous hollow
The surface of carbon nano-fiber, is the high-throughput important method for preparing porous carbon base material, and load capacity controlled range is wider.It is heavier
That wants is coaxial electrostatic spinning method by Coaxial nozzle that inside and outside two channels form, (stratum nucleare solution is perfused in internal channel, outside by it
Shell solution is perfused in channel, and two strands of solution are generally immiscible), by controlling the operating parameter of device for spinning, can further spin
Make the nanofiber with nucleocapsid structure.
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of high power capacity TiO2-VO2 to adulterate hollow carbon nanometer
Fiber lithium cell cathode material and preparation method thereof.
The present invention is achieved by the following technical solutions：
The invention discloses a kind of hollow carbon nano-fiber lithium cell cathode materials of high power capacity TiO2-VO2 doping, including in
Empty carbon nano-fiber and TiO2 the and VO2 nano particles for being coated on the hollow carbon nano-fiber outer surface；The TiO2 receives
The content of rice grain is 10~80.0wt%, and the content of the VO2 nano particles is 0.1~20.0wt%, and surplus is hollow carbon
Nanofiber.
Preferably, the content of the TiO2 nano particles is 50~70.0wt%, and the content of the VO2 nano particles is
1.0~10.0wt%, surplus are hollow carbon nano-fiber.
Preferably, the grain size of the TiO2 nano particles is 1~90nm, the grain sizes of the VO2 nano particles is 1~
100nm。
Preferably, the grain size of the TiO2 nano particles is 10~25nm, and the grain size of the VO2 nano particles is 10-
30nm。
Preferably, the hollow carbon nanofiber diameter is 50-400nm, the length of the single hollow carbon nano-fiber
It it is 1~300 μm, the hollow carbon nano-fiber wall thickness is 10-120nm.
Preferably, the hollow carbon nanofiber diameter is 100-230nm, the length of the single hollow carbon nano-fiber
It it is 1~100 μm, the hollow carbon nano-fiber wall thickness is 30-80nm.
Preferably, the mesoporous pore size size on the hollow carbon nano-fiber shell is 1-30nm.
Preferably, the mesoporous pore size size on the hollow carbon nano-fiber shell is 5-10nm.
The invention also discloses the systems that a kind of high power capacity TiO2-VO2 adulterates hollow carbon nano-fiber lithium cell cathode material
Preparation Method includes the following steps：
S1. organic precursor, titanium source, hydrolysis inhibitor, organic solvent and vanadium powder are used, shell layer spinning solution is prepared；
S2. coaxial electrostatic spinning method is used, the shell layer spinning solution and stratum nucleare spinning solution are subjected to electrostatic spinning, prepared
Obtain non-woven fibre film；
S3. the non-woven fibre film is heat-treated, you can the hollow carbon nano-fiber for obtaining TiO2-VO2 doping is negative
Pole material.
Preferably, the step S1 is specifically included：
S101. organic precursor is added in organic solvent, stirs to get solution A, by titanium source, hydrolysis inhibitor and organic
Solvent mixes, and stirs to get solution B；The mass ratio of the organic precursor and the organic solvent is (1-2.5)：(12-65)；
The titanium source, hydrolysis inhibitor, organic solvent volume ratio be：2-6:1-5:0.5-2.
S102. solution B is slowly added in solution A, after charging, stirring 10-30min obtains the mixed liquor of the two；
S103. after liquid cooled to room temperature to be mixed, vanadium source is added thereto, ultrasonic disperse to powder is thoroughly mixed,
Obtain shell layer spinning solution.
Preferably, further include after the step S2：The non-woven fibre film is soaked in the organic solvent, is removed
Then the non-woven fibre film is stood and is air-dried, obtains dry non-woven fibre film by remaining stratum nucleare spinning solution at normal temperatures.
Preferably, the setting condition of coaxial electrostatic spinning is in the step S2：Electric field strength is 1~2.5kV/cm, institute
It is respectively 0.01~0.2mL/h and 0.1~1.5mL/h, reception device to state stratum nucleare spinning solution and the flow of the shell layer spinning solution
To load the rotating cylinder of aluminium foil, the rotating speed of rotating cylinder is 500~2000rpm, the acquisition time of every non-woven fibre film is 15~
90min。
Preferably, the step S3 is specifically included：The non-woven fibre film is put into quartz ampoule, indifferent gas in pipe is kept
Body atmosphere is warming up to 800~1300 DEG C with the heating rate of 1~10 DEG C/min；Then pass to argon hydrogen gaseous mixture, wherein hydrogen with
The volume ratio of argon gas is 1：9；After keeping the temperature 4~48h, cooled to room temperature, you can the hollow carbon for obtaining TiO2-VO2 doping is received
Rice fiber negative material.
Preferably, the organic precursor be polyvinylpyrrolidone, dimethylformamide, polymethyl methacrylate,
It is one or more in polytetrafluoroethylene (PTFE), polyacrylonitrile, polyethylene oxide.
Preferably, the organic solvent is ethyl alcohol, acetic acid, methylacetamide ether, acetone, methyl methacrylate, third
One or more in olefin(e) acid, isopropanol, butyl glycol ether, tetrahydrofuran, the organic solvent is that analysis is pure.
Preferably, the stratum nucleare spinning solution is atoleine, paraffin oil or glycerine.
Preferably, the titanium source is isopropyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanium tetrachloride.
Preferably, the vanadium source is vanadyl oxalate, vanadyl acetylacetonate, tartaric acid vanadyl, malonic acid azanol vanadium, levulinic
Ketone vanadium or ammonium metavanadate.
Preferably, the hydrolysis inhibitor is glacial acetic acid, acetylacetone,2,4-pentanedione or hydrochloric acid.
Preferably, the content of TiO2 nano particles is 10~80.0wt% in the negative material, and VO2 nano particles contain
Amount is 0.1~20.0wt%.
Preferably, the grain size of the TiO2 nano particles is 1~90nm, the grain sizes of the VO2 nano particles is 1~
100nm。
Preferably, the hollow carbon nanofiber diameter is 100-230nm, the length of the single hollow carbon nano-fiber
It it is 1~100 μm, the hollow carbon nano-fiber wall thickness is 30-80nm.
Preferably, the mesoporous pore size size on the hollow carbon nano-fiber shell is 1-30nm.
Preferably, the mesoporous pore size size on the hollow carbon nano-fiber shell is 5-10nm.
Inert gas in the step S3 is one or more in nitrogen, helium, neon, argon gas, Krypton and xenon.
The advantage of TiO2 types negative material is that voltage platform is higher in the present invention, is higher than the blanking voltage for generating Li dendrite,
TiO2 types negative material can fundamentally solve the problems, such as the generation of lithium dendrite arm.
And for V (+3/+4), since its ionization energy is low, therefore the electrode potential generated is relatively low, and for example VO2 has stratiform knot
Structure can allow lithium ion deintercalation, theoretical capacity 313.6mAh/g, along with its higher density (is 2 times of graphite electrode
It is more), there is high volume energy density, the performance of material can be advanced optimized by being applied in negative material.But vanadium oxygen
Former circles that expansion of the compound cathode in volume causes cycle charge-discharge have the generation of irreversible capacity, negative so as to cause vanadium
Pole reversibility of electrode is poor；It is whole that the material that TiO2, VO2 and carbon nano-fiber are combined can be effectively improved material by the present invention
The electric conductivity and stability of body, and then improve the invertibity of electrode reaction.
The TiO2-VO2 composite nano-fiber membranes of the present invention have hierarchical porous structure：It is empty that cavity is formed between fiber and fiber
It is mesoporous that there is hollow cavity, single fiber shell to be distributed with for gap, single fiber, and it is saturating, lithium ion embedding to be conducive to electrolyte Seepage
Enter the transmission with electronics, improves the conductivity and lithium ion deintercalation ability of negative material.
The beneficial effects of the invention are as follows：
(1) high power capacity TiO2-VO2 of the invention adulterates the preparation method of hollow carbon nano-fiber lithium cell cathode material,
By loading the nano particle of TiO2 and VO2 on carbon nano-fiber, solves the security risk that cathode lithium dendrite growth is brought
And capacity fade problem caused by lattice dilatation in charge and discharge process, wherein TiO2 and VO2 play mutual synergistic effect, improve
The specific capacity of material；
(2) high power capacity TiO2-VO2 prepared by method of the invention adulterates hollow carbon nano-fiber lithium cell cathode material,
The load capacity of wherein active material has been more than 60wt%；
(3) high power capacity TiO2-VO2 of the invention adulterates hollow carbon nano-fiber lithium cell cathode material, has multi-stage porous
Structure and high load amount are conducive to electrolyte permeability and enter negative material, while being conducive to the insertion of lithium ion and the transmission of electronics；
The conductivity, specific capacity and stability for improving negative material make it have excellent high rate performance and cycle performance；
(4) load capacity of the negative material that the present invention is prepared using coaxial electrostatic spinning method, active material is high, breaches table
The bottleneck that active material load capacity is low in negative material prepared by method is modified in face.
Description of the drawings
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme of the present invention
The attached drawing used is briefly described, it should be apparent that, the accompanying drawings in the following description is only the embodiment of the present invention, for this
For the those of ordinary skill of field, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the low range that the TiO2-VO2 of the embodiment of the present invention 1 adulterates hollow carbon nano-fiber lithium cell cathode material
Scanning electron microscope diagram；
Fig. 2 is the high magnification that the TiO2-VO2 of the embodiment of the present invention 1 adulterates hollow carbon nano-fiber lithium cell cathode material
Scanning electron microscope diagram；
Fig. 3 is the EDS that the TiO2-VO2 of the embodiment of the present invention 1 adulterates Ti in hollow carbon nano-fiber lithium cell cathode material
Collection of illustrative plates；
Fig. 4 is the EDS that the TiO2-VO2 of the embodiment of the present invention 1 adulterates V in hollow carbon nano-fiber lithium cell cathode material
Collection of illustrative plates；
Fig. 5 is that the hollow carbon nano-fiber lithium cell cathode material of TiO2-VO2 doping of the embodiment of the present invention 1 is assembled into button
The multiplying power property curve of formula battery.
Specific implementation mode
Below in conjunction with the attached drawing in the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on this hair
Embodiment in bright, the every other reality that those of ordinary skill in the art are obtained under the premise of not making creative work
Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
The invention discloses the preparations that a kind of high power capacity TiO2-VO2 adulterates hollow carbon nano-fiber lithium cell cathode material
Method includes the following steps：
S1. 0.32g polyvinylpyrrolidonepowder powders are added in 5mL ethyl alcohol, stir to get solution A；Using liquid-transfering gun standard
4mL isopropyl titanates are really measured, 2mL glacial acetic acid and 1mL ethyl alcohol is then added, mixing obtains solution B；Solution B is slow
It is added in solution A, after charging, stirring 10min obtains the mixed liquor of the two；After liquid cooled to room temperature to be mixed, to
0.3g vanadyl acetylacetonate powder is wherein added, ultrasonic disperse to powder is thoroughly mixed, and obtains shell layer spinning solution；
The shell layer spinning solution is filled into outer tunnel, atoleine is filled into internal channel, keeps electric field strength
Flow for 2kV/cm, interior foreign minister is respectively 0.1mL/h and 0.6mL/h, and reception device is to load the rotating cylinder of aluminium foil, and rotating cylinder turns
Speed is 1000rpm, and the acquisition time of every non-woven fibre film is 30min；
S2. the non-woven fibre film weaved is immersed in isopropanol, removes interior phase organic solution；The nonwoven washed is fine
Film natural drying is tieed up to stay overnight；
S3. the non-woven fibre film of drying is put into quartz ampoule, keeps nitrogen atmosphere in pipe, with the heating speed of 2 DEG C/min
Rate is warming up to 800 DEG C；Argon hydrogen gaseous mixture is then passed to, the wherein volume ratio of hydrogen and argon gas is 1：9；It is naturally cold after heat preservation for 24 hours
But to room temperature, you can obtain the hollow carbon nanofiber anode material of TiO2-VO2 doping.
The content of the TiO2 nano particles is 55.1wt%, and the content of the VO2 nano particles is 4.9wt%, surplus
For hollow carbon nano-fiber；As shown in Figs. 1-2, the grain size of the TiO2 nano particles is 10-25nm, the VO2 nano particles
Grain size be 5-20nm；The hollow carbon nanofiber diameter is about 160nm, and the length of the single hollow carbon nano-fiber is about
It it is 150 μm, the hollow carbon nano-fiber wall thickness is 50nm；Mesoporous pore size size on the hollow carbon nano-fiber shell is about
For 10nm.As shown in Figure 3-4, EDS energy spectrum diagrams are shown, Ti elements and V element are contained in composite material.
The TiO2-VO2 composite nano-fiber membranes of the present embodiment have hierarchical porous structure：Cavity is formed between fiber and fiber
It is mesoporous that there is hollow cavity, single fiber shell to be distributed with for gap, single fiber, and it is saturating, lithium ion to be conducive to electrolyte Seepage
Embedded and electronics transmission, improves the conductivity and lithium ion deintercalation ability of negative material.
To examine the performance for utilizing lithium ion battery negative material manufactured in the present embodiment, by the composite fibre of the present embodiment
Negative material is as negative electrode of lithium ion battery, using lithium piece as anode, using LiPF6-EC/DEC (1:1) it is used as electrolyte, every
Film is 2400 type polypropylene screens of Celgard companies production, assembles CR2016 type button cells, and charging/discharging voltage is limited in 0-
3.0V, 0.05~10C of electric current carry out cyclic voltammetry and charge-discharge magnification test.As shown in figure 5, close in charging and discharging currents
Degree is that reversible capacity reaches 559mAh/g under 0.3C, and especially under the conditions of 20C high current density charge and discharge, composite material passes through
After 1000 cycles, capacity retention ratio 94%.
Embodiment 2
The invention discloses the preparations that a kind of high power capacity TiO2-VO2 adulterates hollow carbon nano-fiber lithium cell cathode material
Method includes the following steps：
S1. 0.4g polyvinylpyrrolidonepowder powders are dissolved in 10mL ethyl alcohol, stirs to get solution A；Using liquid-transfering gun standard
6mL isopropyl titanates are really measured, the agent of 4mL glacial acetic acid and 2mL ethyl alcohol is then added, mixing obtains solution B；Solution B is delayed
Slow to be added in solution A, after charging, stirring 10min obtains the mixed liquor of the two；After liquid cooled to room temperature to be mixed,
0.3g vanadyl acetylacetonate powder is added thereto, ultrasonic disperse to powder is thoroughly mixed, and obtains shell layer spinning solution.
The shell layer spinning solution is filled into outer tunnel, paraffin oil is filled into internal channel, holding electric field strength is
The flow of 2kV/cm, interior foreign minister are respectively 0.1mL/h and 0.6mL/h, and reception device is to load the rotating cylinder of aluminium foil, the rotating speed of rotating cylinder
Acquisition time for 1000rpm, every non-woven fibre film is 30min；
S2. the non-woven fibre film weaved is immersed in isopropanol, removes interior phase organic solution；The nonwoven washed is fine
Film natural drying is tieed up to stay overnight；
S3. the non-woven fibre film of drying is put into quartz ampoule, inert gas atmosphere in pipe is kept, with the liter of 2 DEG C/min
Warm rate is warming up to 800 DEG C；Argon hydrogen gaseous mixture is then passed to, the wherein volume ratio of hydrogen and argon gas is 1：9；Keep the temperature 4~48h
Afterwards, cooled to room temperature, you can obtain the hollow carbon nanofiber anode material of TiO2-VO2 doping.
The TiO2-VO2 composite nano-fiber membranes of the present embodiment have hierarchical porous structure：Cavity is formed between fiber and fiber
It is mesoporous that there is hollow cavity, single fiber shell to be distributed with for gap, single fiber, and it is saturating, lithium ion to be conducive to electrolyte Seepage
Embedded and electronics transmission, improves the conductivity and lithium ion deintercalation ability of negative material.
To examine the performance for utilizing lithium ion battery negative material manufactured in the present embodiment, by the composite fibre of the present embodiment
Negative material is as negative electrode of lithium ion battery, using lithium piece as anode, using LiPF6-EC/DEC (1:1) it is used as electrolyte, every
Film is 2400 type polypropylene screens of Celgard companies production, assembles CR2016 type button cells, and charging/discharging voltage is limited in 0-
3.0V, 0.05~10C of electric current carry out cyclic voltammetry and charge-discharge magnification test.In the case where charging and discharging currents density is 0.3C
Reversible capacity is 539mAh/g, and under the conditions of 20C high current density charge and discharge, composite material is after 1000 cycles, capacity
Conservation rate is 91%.
Embodiment 3
The invention discloses the preparations that a kind of high power capacity TiO2-VO2 adulterates hollow carbon nano-fiber lithium cell cathode material
Method includes the following steps：
S1. 0.50g polymethylmethacrylate powders are dissolved in 5mL acrylic acid, stirs to get solution A；Using liquid relief
Rifle accurately measures 4mL tetrabutyl titanates, and 2mL acetylacetone,2,4-pentanediones and 1mL ethyl alcohol is then added, and mixing obtains solution B；By solution
B is slowly added in solution A, and after charging, stirring 30min obtains the mixed liquor of the two；Liquid cooled to room temperature to be mixed
Afterwards, 0.3g vanadyl oxalate powder is added thereto, ultrasonic disperse to powder is thoroughly mixed, and obtains shell layer spinning solution.
The shell layer spinning solution is filled into outer tunnel, paraffin oil is filled into internal channel, holding electric field strength is
The flow of 2.5kV/cm, interior foreign minister are respectively 0.6mL/h and 0.9mL/h, and reception device is to load the rotating cylinder of aluminium foil, and rotating cylinder turns
Speed is 1000rpm, and the acquisition time of every non-woven fibre film is 30min；
S2. the non-woven fibre film weaved is immersed in isopropanol, removes interior phase organic solution；The nonwoven washed is fine
Film natural drying is tieed up to stay overnight；
S3. the non-woven fibre film of drying is put into quartz ampoule, inert gas atmosphere in pipe is kept, with the liter of 10 DEG C/min
Warm rate is warming up to 1300 DEG C；Argon hydrogen gaseous mixture is then passed to, the wherein volume ratio of hydrogen and argon gas is 1：9；After keeping the temperature 36h,
Cooled to room temperature, you can obtain the hollow carbon nanofiber anode material of TiO2-VO2 doping.
The TiO2-VO2 composite nano-fiber membranes of the present embodiment have hierarchical porous structure：Cavity is formed between fiber and fiber
It is mesoporous that there is hollow cavity, single fiber shell to be distributed with for gap, single fiber, and it is saturating, lithium ion to be conducive to electrolyte Seepage
Embedded and electronics transmission, improves the conductivity and lithium ion deintercalation ability of negative material.
To examine the performance for utilizing lithium ion battery negative material manufactured in the present embodiment, by the composite fibre of the present embodiment
Negative material is as negative electrode of lithium ion battery, using lithium piece as anode, using LiPF6-EC/DEC (1:1) it is used as electrolyte, every
Film is 2400 type polypropylene screens of Celgard companies production, assembles CR2016 type button cells, and charging/discharging voltage is limited in 0-
3.0V, 0.05~10C of electric current carry out cyclic voltammetry and charge-discharge magnification test.In the case where charging and discharging currents density is 0.3C
Reversible capacity is 517mAh/g, and under the conditions of 20C high current density charge and discharge, composite material is after 1000 cycles, capacity
Conservation rate is 91%.
Comparative example 1
S1. 0.32g polyvinylpyrrolidonepowder powders are added in 5mL ethyl alcohol, stir to get solution A；Using liquid-transfering gun standard
4mL isopropyl titanates are really measured, 2mL glacial acetic acid and 1mL ethyl alcohol is then added, mixing obtains solution B；Solution B is slow
It is added in solution A, after charging, stirring 10min obtains the mixed liquor of the two；After liquid cooled to room temperature to be mixed, to
0.3g vanadyl acetylacetonate powder is wherein added, ultrasonic disperse to powder is thoroughly mixed, and obtains shell layer spinning solution.
The shell layer spinning solution is filled into internal channel, holding electric field strength is 2kV/cm, and the flow of interior foreign minister is distinguished
For 0.6mL/h and 0mL/h, reception device is to load the rotating cylinder of aluminium foil, and the rotating speed of rotating cylinder is 1000rpm, every non-woven fibre film
Acquisition time be 30min；
S2. the non-woven fibre film weaved is immersed in isopropanol, removes interior phase organic solution；The nonwoven washed is fine
Film natural drying is tieed up to stay overnight；
S3. the non-woven fibre film of drying is put into quartz ampoule, keeps nitrogen atmosphere in pipe, with the heating speed of 2 DEG C/min
Rate is warming up to 800 DEG C；Argon hydrogen gaseous mixture is then passed to, the wherein volume ratio of hydrogen and argon gas is 1：9；It is naturally cold after heat preservation for 24 hours
But to room temperature, you can obtain the hollow carbon nanofiber anode material of TiO2-VO2 doping.
To examine the performance for utilizing lithium ion battery negative material manufactured in the present embodiment, by the composite fibre of the present embodiment
Negative material is as negative electrode of lithium ion battery, using lithium piece as anode, using LiPF6-EC/DEC (1:1) it is used as electrolyte, every
Film is 2400 type polypropylene screens of Celgard companies production, assembles CR2016 type button cells, and charging/discharging voltage is limited in 0-
3.0V, 0.05~10C of electric current carry out cyclic voltammetry and charge-discharge magnification test.In the case where charging and discharging currents density is 0.3C
Reversible capacity is 455mAh/g, and under the conditions of 20C high current density charge and discharge, composite material is after 1000 cycles, capacity
Conservation rate is 85%.
Comparative example 2
0.32g polyvinylpyrrolidonepowder powders are added in 5mL ethyl alcohol, solution A is stirred to get；Using liquid-transfering gun correct amount
4mL isopropyl titanates are taken, 2mL glacial acetic acid and 1mL ethyl alcohol is then added, mixing obtains solution B；Solution B is slowly added to
In solution A, after charging, stirring 10min obtains the mixed liquor of the two；After liquid cooled to room temperature to be mixed, thereto
0.3g vanadyl acetylacetonate powder is added, ultrasonic disperse to powder is thoroughly mixed；
The mixed solution is lighted, dry powder body is obtained after burning fully, then solid-phase grinding is uniform；Above-mentioned powder is put into stone
Ying Guanzhong keeps nitrogen atmosphere in pipe, 800 DEG C is warming up to the heating rate of 2 DEG C/min；Argon hydrogen gaseous mixture is then passed to,
The volume ratio of middle hydrogen and argon gas is 1：9；After heat preservation for 24 hours, cooled to room temperature, you can obtain the hollow of TiO2-VO2 doping
Carbon nano-fiber negative material.
To examine the performance for utilizing lithium ion battery negative material manufactured in the present embodiment, by the composite fibre of the present embodiment
Negative material is as negative electrode of lithium ion battery, using lithium piece as anode, using LiPF6-EC/DEC (1:1) it is used as electrolyte, every
Film is 2400 type polypropylene screens of Celgard companies production, assembles CR2016 type button cells, and charging/discharging voltage is limited in 0-
3.0V, 0.05~10C of electric current carry out cyclic voltammetry and charge-discharge magnification test.In the case where charging and discharging currents density is 0.3C
Reversible capacity is 324mAh/g, and under the conditions of 20C high current density charge and discharge, composite material is after 1000 cycles, capacity
Conservation rate is 68%.
The beneficial effects of the invention are as follows：
(1) high power capacity TiO2-VO2 of the invention adulterates the preparation method of hollow carbon nano-fiber lithium cell cathode material,
By loading the nano particle of TiO2 and VO2 on carbon nano-fiber, solves the security risk that cathode lithium dendrite growth is brought
And capacity fade problem caused by lattice dilatation in charge and discharge process, wherein TiO2 and VO2 play mutual synergistic effect, improve
The specific capacity of material；
(2) high power capacity TiO2-VO2 prepared by method of the invention adulterates hollow carbon nano-fiber lithium cell cathode material,
The load capacity of wherein active material has been more than 60wt%；
(3) high power capacity TiO2-VO2 of the invention adulterates hollow carbon nano-fiber lithium cell cathode material, has multi-stage porous
Structure and high load amount are conducive to electrolyte permeability and enter negative material, while being conducive to the insertion of lithium ion and the transmission of electronics；
The conductivity, specific capacity and stability for improving negative material make it have excellent high rate performance and cycle performance；
(4) load capacity of the negative material that the present invention is prepared using coaxial electrostatic spinning method, active material is high, breaches table
The bottleneck that active material load capacity is low in negative material prepared by method is modified in face.
The above is the preferred embodiment of the present invention, it should be noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (10)
1. a kind of TiO2-VO2 adulterates hollow carbon nano-fiber lithium cell cathode material, which is characterized in that including hollow carbon nanometer
Fiber and TiO2 the and VO2 nano particles for being coated on the hollow carbon nano-fiber outer surface；The TiO2 nano particles
Content is 10~80.0wt%, and the content of the VO2 nano particles is 0.1~20.0wt%, and surplus is hollow carbon nano-fiber.
2. a kind of TiO2-VO2 according to claim 1 adulterates hollow carbon nano-fiber lithium cell cathode material, feature
It is, the grain size of the TiO2 nano particles is 1~90nm, and the grain size of the VO2 nano particles is 1~100nm.
3. a kind of TiO2-VO2 according to claim 1 or 2 adulterates hollow carbon nano-fiber lithium cell cathode material, special
Sign is that the hollow carbon nanofiber diameter is 50-400nm, and the length of the single hollow carbon nano-fiber is 1~300 μ
M, the hollow carbon nano-fiber wall thickness are 10-120nm.
4. a kind of TiO2-VO2 adulterates the preparation method of hollow carbon nano-fiber lithium cell cathode material, which is characterized in that including
Following steps：
S1. organic precursor, titanium source, hydrolysis inhibitor, organic solvent and vanadium source are used, shell layer spinning solution is prepared；
S2. coaxial electrostatic spinning method is used, the shell layer spinning solution and stratum nucleare spinning solution are subjected to electrostatic spinning, are prepared
Non-woven fibre film；
S3. the non-woven fibre film is heat-treated, you can obtain the hollow carbon nano-fiber cathode material of TiO2-VO2 doping
Material.
5. a kind of TiO2-VO2 according to claim 4 adulterates the preparation side of hollow carbon nano-fiber lithium cell cathode material
Method, which is characterized in that the step S1 is specifically included：
S101. organic precursor is added in organic solvent, solution A is stirred to get, by titanium source, hydrolysis inhibitor and organic solvent
Mixing, stirs to get solution B；
S102. solution B is added in solution A, after charging, stirring 10-30min obtains the mixed liquor of the two；
S103. after liquid cooled to room temperature to be mixed, vanadium source is added thereto, ultrasonic disperse to powder is thoroughly mixed, obtains
Shell layer spinning solution.
6. a kind of TiO2-VO2 according to claim 4 or 5 adulterates the system of hollow carbon nano-fiber lithium cell cathode material
Preparation Method, which is characterized in that further include after the step S2：The non-woven fibre film is soaked in the organic solvent,
Remaining stratum nucleare spinning solution is removed, then the non-woven fibre film is stood at normal temperatures and is air-dried, dry non-woven fibre is obtained
Film.
7. a kind of TiO2-VO2 according to claim 6 adulterates the preparation side of hollow carbon nano-fiber lithium cell cathode material
Method, which is characterized in that the setting condition of coaxial electrostatic spinning is in the step S2：Electric field strength is 1~2.5kV/cm, described
Stratum nucleare spinning solution and the flow of the shell layer spinning solution are respectively 0.01~0.2mL/h and 0.1~1.5mL/h, and reception device is
The rotating cylinder of aluminium foil is loaded, the rotating speed of rotating cylinder is 500~2000rpm, and the acquisition time of every non-woven fibre film is 15~90min.
8. a kind of TiO2-VO2 according to claim 7 adulterates the preparation side of hollow carbon nano-fiber lithium cell cathode material
Method, which is characterized in that the step S3 is specifically included：The non-woven fibre film is put into quartz ampoule, indifferent gas in pipe is kept
Body atmosphere is warming up to 800~1300 DEG C with the heating rate of 1~10 DEG C/min；Then pass to argon hydrogen gaseous mixture, wherein hydrogen with
The volume ratio of argon gas is 1：9；After keeping the temperature 4~48h, cooled to room temperature, you can the hollow carbon for obtaining TiO2-VO2 doping is received
Rice fiber negative material.
9. a kind of TiO2-VO2 according to claim 8 adulterates the preparation side of hollow carbon nano-fiber lithium cell cathode material
Method, which is characterized in that the organic precursor is polyvinylpyrrolidone, dimethylformamide, polymethyl methacrylate, gathers
It is one or more in tetrafluoroethene, polyacrylonitrile, polyethylene oxide；The stratum nucleare spinning solution be atoleine, paraffin oil or
Glycerine；The titanium source is isopropyl titanate, tetrabutyl titanate, tetraisopropyl titanate or titanium tetrachloride；The vanadium source is oxalic acid oxygen
Vanadium, vanadyl acetylacetonate, tartaric acid vanadyl, malonic acid azanol vanadium, vanadium acetylacetonate or ammonium metavanadate；The hydrolysis inhibitor is
Glacial acetic acid, acetylacetone,2,4-pentanedione or hydrochloric acid.
10. a kind of TiO2-VO2 according to claim 9 adulterates the preparation of hollow carbon nano-fiber lithium cell cathode material
Method, which is characterized in that the content of TiO2 nano particles is 10~80.0wt% in the negative material, VO2 nano particles
Content is 0.1~20.0wt%；Hollow carbon nanofiber diameter is 100-230nm, the length of the single hollow carbon nano-fiber
Degree is 1~100 μm, and the hollow carbon nano-fiber wall thickness is 30-80nm.
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| CN112978713A (en) * | 2021-02-01 | 2021-06-18 | 武汉大学 | Nano-micron carbon tube, preparation method thereof, electrode and lithium ion battery |
| CN114635200A (en) * | 2022-03-11 | 2022-06-17 | 宁德新能源科技有限公司 | Tubular nanofiber material, negative electrode plate and lithium metal battery |
| CN114883567A (en) * | 2022-06-30 | 2022-08-09 | 河南科隆新能源股份有限公司 | Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof |
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