CN110137461A - Lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material and preparation method thereof derived from MOF - Google Patents
Lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material and preparation method thereof derived from MOF Download PDFInfo
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Abstract
The present invention provides cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from a kind of lithium ion battery MOF and preparation method thereof, using the mixed liquor of polyacrylonitrile and metal-organic framework material ZIF-67 as the precursor solution of electrostatic spinning, the carbon nano-fiber containing ZIF-67 is obtained by the method for electrostatic spinning, then electrospun fibers pre-oxidized, be carbonized and oxidizing thermal treatment, synthesized Co3O4Carbon nano-fiber flexible electrode material.Flexible electrode material prepared by the present invention not only has the good electric conductivity of carbon material and cyclical stability (in 200mA g‑1Current density it is lower 100 times circulation after 900mAh g‑1), and it also has good high rate performance 5000mA g‑1Current density under be still able to maintain 550mA g‑1Capacity) and Co3O4The characteristics of high specific capacity.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to lithium ion battery cobalt derived from MOF
Oxide carbon nano-fiber flexible electrode material and preparation method thereof.
Background technique
The Green Chemistry power supply that lithium ion battery is electrochemically transformed and stores as New World, since it is with outstanding electricity
Chemical property is widely used in every field, becomes the emphasis of countries in the world development and research.Currently, commercialized lithium ion
Cell negative electrode material is mainly graphite, but its lower capacity is not able to satisfy the demand of future development, so seeking capacity height
And novel anode material at low cost is one of the emphasis of current research Study on Li-ion batteries.
Metal organic frame is synthesized by metal center ion and organic ligand, synthesizes different holes by changing reaction condition
The frame structure of diameter feature.MOF synthetic method is simple, large specific surface area and the features such as structure-controllable urge it in gas storage
The fields such as change, molecular recognition, drug delivery cause extensive concern.MOF derived material is one kind of latest developments and research
Negative electrode material, the material key dimension derived reach some transition metal oxides of Nano grade.The transition of nano-scale
Its capacity of metal oxide is high, can lower the bulk effect of electrode material significantly.But the nanoparticle that MOF is derived holds
Electric conductivity easy to reunite and poor limits the application in electrochemical field；Currently used method include [Zheng,
Honghe,Liu,et al.Graphene oxides-guided growth of ultrafine
Co3O4nanocrystallites from MOFs as high-performance anode of Li-ion batteries
[J].Carbon:An International Journal Sponsored by the American Carbon Society,
2015,92119-125.], [Li Qiuzhong, Wei Fen, He little Ying wait lithium ion battery Co3O4The preparation of/C composite negative pole material and
Chemical property [J] Ningde college of education's journal (natural science edition), 2018,30 (3): 286-292.].But it is all
Co3O4When/carbon composite is as negative electrode of lithium ion battery, prepares electrode and still use the method for traditional slurrying by electrode material
On a current collector, this method causes electrode material insecure in conjunction with collector for coating, is easy to fall off in reaction process, and makes
Standby electrode process is cumbersome.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides cobalt/cobalt oxide derived from a kind of lithium ion battery MOF
Carbon nano-fiber flexible electrode material and preparation method thereof, Co in the material of preparation3O4Not easy to reunite, electrode material remains good
Good ground is flexible, prepares electrode and is easy, and is not easily to fall off.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF, packet
Include following steps:
(1) metal organic frame ZIF-67 nano particle is prepared；
(2) polyacrylonitrile is dispersed in n,N-Dimethylformamide, adding the metal obtained in step (1) has
Machine frame ZIF-67 nano particle is dispersed with stirring uniformly, obtains electrostatic spinning precursor liquid, then carry out electrostatic spinning, by turning
Axial receivers are collected, and obtain just spinning carbon fiber；
(3) it will just spin carbon fiber to be pre-oxidized, be carbonized and oxidation processes, and obtain Co derived from ZIF-673O4Carbon Nanowire
Tie up flexible electrode material.
Preferably, in step (1), the preparation process of metal organic frame ZIF-67 nano particle includes the following steps:
Cabaltous nitrate hexahydrate is dissolved in alcohol solvent, solution A is obtained；2-methylimidazole is dissolved in methanol solvate,
Obtain solution B；Solution A and solution B are mixed, stirred evenly, is centrifugated, obtains metal organic frame ZIF-67 nanometers
Grain.
Preferably, in step (2), the quality volume solubility of polyacrylonitrile is 0.08~0.1g/ in electrostatic spinning precursor liquid
ML, the quality volume solubility of metal organic frame ZIF-67 nano particle are 0.02~0.10g/mL.
4. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode derived from MOF
The preparation method of material, which is characterized in that in step (2), stirring carries out at 60~80 DEG C.
Preferably, in step (2), electrospinning parameters are provided that voltage is 14~16kV, the revolving speed of shaft receiver
For 300~500r/min, receiving distance is 15~18cm, and syringe fltting speed is 2~4mm/h.
Preferably, in step (3), pre-oxidation carries out under air atmosphere in Muffle furnace, and temperature is 220~280 DEG C, heating
0.5~2 DEG C/min of rate, time are 1~2h.
Preferably, in step (3), carbonization carries out under tube furnace argon atmosphere, and temperature is 500~800 DEG C, heating rate
5~10 DEG C/min, the time is 1~2h.
Preferably, in step (3), oxidation carries out under air atmosphere in Muffle furnace, and temperature is 250~350 DEG C, heating speed
5~10 DEG C/min of rate, time are 20~40min.
The lithium ion battery that the preparation method is prepared cobalt/cobalt oxide carbon nano-fiber flexible electrical derived from MOF
Pole material.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention by using the mixed liquor of polyacrylonitrile and metal-organic framework material ZIF-67 as electrostatic spinning before
Liquid solution is driven, the carbon nano-fiber containing ZIF-67 is obtained by the method for electrostatic spinning, then pass through pre-oxidation, carbonization and oxidation
Obtain cobalt/cobalt oxide carbon nano-fiber combination electrode material derived from MOF.On the one hand, the Co obtained3O4Carbon nano-fiber is compound
Electrode material is fiber membrane, remains good flexibility, which can be directly sandwiched on electrode, convenient separation,
Flexible electrode directly can be made in the material of acquisition, avoid the binding force between generally existing electrode matrix and material coating
Bad problem improves electrode cycle stability；On the other hand, the Co that the method obtains3O4Particle is present in carbon nano-fiber
There is good binding force in portion with carbon nano-fiber, effectively reduces Co3O4Particle falling off during the reaction, thus whole
Its chemical property is improved on body；In another aspect, Co derived from MOF3O4Particle is evenly dispersed in carbon nano-fiber composition
In three-dimensional structure, reduce Co3O4Reunion between nano particle, improves Co3O4The electric conductivity of cell negative electrode material.This is soft
Battery made of property electrode not only has the good electric conductivity of carbon material and cyclical stability (in 200mA g-1Current density under
900mAh g after 100 circulations-1), and it also has good high rate performance (5000mA g-1Current density under remain to protect
Hold 550mA g-1Capacity) and high specific capacity, to improve its chemical property on the whole.The present invention is in preparation side
Have many advantages, such as that easy to operate, at low cost, environmentally protective, preparation Product size is uniform in method.
Cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF prepared by the present invention, good conductivity, by the flexibility
Electrode battery made of electrode material has higher specific capacity and good circulation, high rate performance.
Detailed description of the invention
Fig. 1 is by Co prepared by the present invention3O4The X-ray diffracting spectrum of carbon nano-fiber flexible electrode material；
Fig. 2 is by Co prepared by the present invention3O4Carbon nano-fiber flexible electrode material high rate performance under same current density
Figure.
Fig. 3 is by Co of the present invention3O4Carbon nano-fiber flexible electrode material is in 200mA g-1When cycle performance figure.
Fig. 4 is by Co of the present invention3O4The SEM photograph of carbon nano-fiber flexible electrode material.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The preparation side of the lithium ion battery of the invention cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Method includes the following steps:
(1) use is stirred at room temperature method and prepares metal organic frame ZIF-67 nano particle of uniform size；
(2) polyacrylonitrile is dispersed in n,N-Dimethylformamide, then the ZIF- obtained in step (1) will be added
67 nano particles are dispersed with stirring uniformly, obtain the precursor liquid of electrostatic spinning, then contain polyacrylonitrile by electrostatic spinning preparation
With the first spinning carbon fiber of ZIF-67 particle, collected by shaft receiver.
(3) the first spinning carbon fiber that step (2) obtain pre-oxidized, be carbonized and oxidation processes, it is derivative to obtain ZIF-67
Co3O4Carbon nano-fiber flexible electrode material.
In step (1), the preparation process of metal organic frame ZIF-67 nano particle includes the following steps:
Cabaltous nitrate hexahydrate is dissolved in alcohol solvent, 2-methylimidazole is dissolved in methanol solvate, and the two is blended in
Magnetic agitation 1-3h at room temperature, centrifuge separation, obtains metal organic frame ZIF-67 nano particle.In reaction process, magnetic force is stirred
The revolving speed mixed is 400-600r/min.The mass ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is (1.75~8.75): (0.92~
9.60)。
In step (2), polyacrylonitrile quality volume solubility is 0.08g/mL in the precursor liquid of electrostatic spinning, magnetic agitation
Temperature is 60~80 DEG C, and the quality volume solubility of ZIF-67 nano particle is 0.02~0.10g/mL.
In step (2), the setting parameter of electrostatic spinning is as follows:
Voltage is 14~16kV, and the revolving speed of shaft receiver is 300~500r/min, and receiving distance is 15~18cm, note
Emitter fltting speed is 2~4mm/h, and gained fibre diameter is 100~300nm.
In step (3), pre-oxidation carries out under air atmosphere in Muffle furnace, and temperature is 220~280 DEG C, heating rate
0.5-2 DEG C/min, the time is 1~2h.
In step (3), carbonization carries out under tube furnace argon atmosphere, and temperature is 500~800 DEG C, and 5-10 DEG C of heating rate/
Min, time are 1~2h.
In step (3), oxidation carries out under air atmosphere in Muffle furnace, and temperature is 250~350 DEG C, heating rate 5-10
DEG C/min, the time is 20~40min.
Embodiment 1:
Step 1: taking 1.75g cabaltous nitrate hexahydrate to be dissolved in 20mL alcohol solvent, 1.92g methylimidazole is separately taken to be dissolved in
In 20mL methanol solvate, after above two solution is stirred well to and is completely dissolved, methylimidazole solution is poured into nitre rapidly
In acidic cobalt solution, it is vigorously stirred at room temperature.After the reaction was completed, it is separated using supercentrifuge, obtains ZIF-67 material.
Step 2: 0.8g polyacrylonitrile being dissolved in 10mL n,N-Dimethylformamide, magnetic agitation 6h, is stirred at 60 DEG C
Mixing to solution is glassy yellow, obtains PAN solution.
Step 3: the 0.2g ZIF-67 material that step 1 obtains being added in PAN solution, stirring and dissolving is uniform, obtains quiet
Electrospun precursor liquid.
Step 4: the parameter of electrostatic spinning: voltage 14kV is set, the revolving speed of shaft receiver is 300r/min, receive away from
From for 15cm, syringe fltting speed is 2mm/h.Fiber membrane can be obtained after electrostatic spinning 8h.
Step 5: obtained fiber membrane is subjected to pre-oxidation 2h for 280 DEG C in air atmosphere, heating rate is 2 DEG C/
min。
Step 6: the obtained fiber membrane of pre-oxidation is subjected to carbonization 1h at 800 DEG C of argon atmosphere, heating rate is 10 DEG C/
min。
Step 7；The fiber membrane obtained after carbonization is aoxidized in Muffle furnace, oxidizing temperature is 350 DEG C, and the time is
40min, heating rate are 10 DEG C/min, and Co can be obtained3O4Carbon nano-fiber flexible electrode material.
Embodiment 2:
Step 1: taking 1.75g cabaltous nitrate hexahydrate to be dissolved in 20mL alcohol solvent, 1.92g methylimidazole is separately taken to be dissolved in
In 20mL methanol solvate, after above two solution is stirred well to and is completely dissolved, methylimidazole solution is poured into nitre rapidly
In acidic cobalt solution, it is vigorously stirred at room temperature.After the reaction was completed, it is separated using supercentrifuge, obtains ZIF-67 material.
Step 2: 1g polyacrylonitrile being dissolved in 10mL n,N-Dimethylformamide, magnetic agitation 6h at 80 DEG C, stirred
It is glassy yellow to solution, obtains PAN solution.
Step 3: the 0.5g ZIF-67 material that step 1 obtains being added in PAN solution, stirring and dissolving is uniform, obtains quiet
Electrospun precursor liquid.
Step 4: the parameter of electrostatic spinning: voltage 15kV is set, the revolving speed of shaft receiver is 500r/min, receive away from
From for 18cm, syringe fltting speed is 4mm/h.Fiber membrane can be obtained after electrostatic spinning 8h.
Step 5: obtained fiber membrane is subjected to pre-oxidation 1h, heating rate 0.5 for 220 DEG C in air atmosphere
℃/min。
Step 6: the fiber membrane that pre-oxidation obtains is subjected to carbonization 1.5h, heating rate 8 for 500 DEG C under an argon atmosphere
℃/min。
Step 7；The fiber membrane obtained after carbonization is aoxidized in Muffle furnace, oxidizing temperature is 250 DEG C, and the time is
20min, heating rate are 5 DEG C/min, and Co can be obtained3O4Carbon nano-fiber flexible electrode material.
Embodiment 3:
Step 1: taking 1.75g cabaltous nitrate hexahydrate to be dissolved in 20mL alcohol solvent, 1.92g methylimidazole is separately taken to be dissolved in
In 20mL methanol solvate, after above two solution is stirred well to and is completely dissolved, methylimidazole solution is poured into nitre rapidly
In acidic cobalt solution, it is vigorously stirred 2h at room temperature.After the reaction was completed, it is separated using supercentrifuge, obtains ZIF-67 material.
Step 2: 0.9g polyacrylonitrile being dissolved in 10mL n,N-Dimethylformamide, magnetic agitation 6h, is stirred at 70 DEG C
Mixing to solution is glassy yellow, obtains PAN solution.
Step 3: the 0.3g ZIF-67 material that step 1 obtains being added in PAN solution, stirring and dissolving is uniform, obtains quiet
Electrospun precursor liquid.
Step 4: the parameter of electrostatic spinning: voltage 15kV is set, the revolving speed of shaft receiver is 400r/min, receive away from
From for 16cm, syringe fltting speed is 3mm/h.Fiber membrane can be obtained after electrostatic spinning 8h.
Step 5: obtained fiber membrane is subjected to pre-oxidation 1.5h, heating rate 1 for 260 DEG C in air atmosphere
℃/min。
Step 6: the fiber membrane that pre-oxidation obtains is subjected to carbonization 2h, heating rate 5 for 600 DEG C under an argon atmosphere
℃/min。
Step 7；The fiber membrane obtained after carbonization is aoxidized in Muffle furnace, oxidizing temperature is 300 DEG C, and the time is
30min, heating rate are 8 DEG C/min, and Co can be obtained3O4Carbon nano-fiber flexible electrode material.
Embodiment 4:
Step 1: taking 1.75g cabaltous nitrate hexahydrate to be dissolved in 20mL alcohol solvent, 1.92g methylimidazole is separately taken to be dissolved in
In 20mL methanol solvate, after above two solution is stirred well to and is completely dissolved, methylimidazole solution is poured into nitre rapidly
In acidic cobalt solution, it is vigorously stirred 2h at room temperature.After the reaction was completed, it is separated using supercentrifuge, obtains ZIF-67 material.
Step 2: 0.8g polyacrylonitrile being dissolved in 10mL n,N-Dimethylformamide, magnetic agitation 6h, is stirred at 75 DEG C
Mixing to solution is glassy yellow, obtains PAN solution.
Step 3: the 0.8g ZIF-67 material that step 1 obtains being added in PAN solution, stirring and dissolving is uniform, obtains quiet
Electrospun precursor liquid.
Step 4: the parameter of electrostatic spinning: voltage 16kV is set, the revolving speed of shaft receiver is 350r/min, receive away from
From for 16cm, syringe fltting speed is 3mm/h.Fiber membrane can be obtained after electrostatic spinning 8h.
Step 5: obtained fiber membrane is subjected to pre-oxidation 1h, heating rate 0.5 for 240 DEG C in air atmosphere
℃/min。
Step 6: the fiber membrane that pre-oxidation obtains is subjected to carbonization 2h, heating rate 8 for 700 DEG C under an argon atmosphere
℃/min。
Step 7；The fiber membrane obtained after carbonization is aoxidized in Muffle furnace, oxidizing temperature is 280 DEG C, and the time is
35min, heating rate are 8 DEG C/min, and Co can be obtained3O4Carbon nano-fiber flexible electrode material.
Fig. 1 is Co prepared by the embodiment of the present invention 23O4Carbon nano-fiber composite material XRD diagram, as can be seen from the figure
Prepared sample respectively corresponds corresponding to standard card PFD42-1467 (cobaltosic oxide), and main peak is clear, and object is compared pure.Figure
2 be the high rate performance figure of 2 combination electrode material of embodiment performance, and as can be seen from the figure electrode material is under different current densities
Charge and discharge are carried out, by maximum current density 5A g-1Afterwards, 100mA g is returned to-1Original performance can also be maintained, is shown good
High rate performance.Fig. 3 is Co prepared by embodiment 23O4Carbon nano-fiber flexible electrode material is 200mA g in current density-1
When cycle performance figure, as seen from the figure battery have good cycle performance.Fig. 4 is Co prepared by the embodiment of the present invention 23O4Carbon
The SEM photograph of nanofiber flexible electrode material, as can be seen from Figure Co3O4It is particle studded inside carbon nano-fiber, and
It is even to be dispersed in inside carbon nano-fiber.
The present invention is by mixing ZIF-67 and PAN, electrostatic spinning, then obtains MOF by pre-oxidation, carbonization and oxidation
Derivative cobalt/cobalt oxide carbon nano-fiber flexible electrode material, the Co of preparation3O4Carbon nano-fiber composite material electrode remains good
Good ground is flexible, Co derived from MOF3O4Particle is evenly dispersed in the three-dimensional structure of carbon nanometer composition, reduces nano particle
Reunite on ground.The material granule that the method obtains is present in fibrous inside, has good binding force with carbon fiber, efficiently reduces
Electrode material during the reaction falls off.Battery made of the flexible electrode not only have the good electric conductivity of carbon material and
Cyclical stability, and it also has good high rate performance and Co3O4The characteristics of high specific capacity, to improve on the whole
Its chemical property.
Claims (9)
1. a kind of preparation method of lithium ion battery cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF, special
Sign is, includes the following steps:
(1) metal organic frame ZIF-67 nano particle is prepared；
(2) polyacrylonitrile is dispersed in n,N-Dimethylformamide, adding the metal obtained in step (1) has machine frame
Frame ZIF-67 nano particle is dispersed with stirring uniformly, obtains electrostatic spinning precursor liquid, then carry out electrostatic spinning, connect by shaft
It receives device to collect, obtains just spinning carbon fiber；
(3) it will just spin carbon fiber to be pre-oxidized, be carbonized and oxidation processes, and obtain Co derived from ZIF-673O4Carbon nano-fiber is soft
Property electrode material.
2. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (1), the preparation process of metal organic frame ZIF-67 nano particle includes as follows
Step:
Cabaltous nitrate hexahydrate is dissolved in alcohol solvent, solution A is obtained；2-methylimidazole is dissolved in methanol solvate, is obtained
Solution B；Solution A and solution B are mixed, stirred evenly, is centrifugated, obtains metal organic frame ZIF-67 nano particle.
3. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (2), in electrostatic spinning precursor liquid the quality volume solubility of polyacrylonitrile be 0.08
~0.1g/mL, the quality volume solubility of metal organic frame ZIF-67 nano particle are 0.02~0.10g/mL.
4. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (2), stirring carried out at 60~80 DEG C.
5. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (2), electrospinning parameters be provided that voltage be 14~16kV, shaft receive
The revolving speed of device is 300~500r/min, and receiving distance is 15~18cm, and syringe fltting speed is 2~4mm/h.
6. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (3), pre-oxidation carried out under air atmosphere in Muffle furnace, temperature be 220~280
DEG C, 0.5~2 DEG C/min of heating rate, the time is 1~2h.
7. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (3), carbonization carried out under tube furnace argon atmosphere, temperature be 500~800 DEG C,
5~10 DEG C/min of heating rate, time are 1~2h.
8. lithium ion battery according to claim 1 cobalt/cobalt oxide carbon nano-fiber flexible electrode material derived from MOF
Preparation method, which is characterized in that in step (3), oxidation carried out under air atmosphere in Muffle furnace, temperature be 250~350
DEG C, 5~10 DEG C/min of heating rate, the time is 20~40min.
9. lithium ion battery cobalt/cobalt oxide derived from MOF that the described in any item preparation methods of claim 1-8 are prepared
Carbon nano-fiber flexible electrode material.
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