CN108630921A - The preparation method of ferriferous oxide/carbon fiber composite lithium ion battery cathode material - Google Patents
The preparation method of ferriferous oxide/carbon fiber composite lithium ion battery cathode material Download PDFInfo
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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Abstract
The invention discloses a kind of preparation methods of ferriferous oxide/carbon fiber composite lithium ion battery cathode material：It using ferrous metals organic backbone as presoma, is mixed with PAN solution, obtains metal organic framework/PAN fiber through electrostatic spinning, metal organic framework/PAN fiber is heat-treated under an inert atmosphere, prepares ferriferous oxide/carbon fibre composite.Ferriferous oxide/carbon fibre composite prepared by the present invention has good flexibility, electric conductivity, orderly pore passage structure and big specific surface area, as lithium ion battery negative material, with higher first discharge specific capacity, charge specific capacity, initial coulomb efficiency and cyclical stability and high rate performance.
Description
Technical field
The invention belongs to the preparation fields of electrode material, and in particular to a kind of ferriferous oxide/carbon fiber compound lithium ion electricity
The preparation method of pond cathode (material).
Background technology
Negative material is the chief component of lithium ion battery, directly affects the performance of lithium ion battery.Quotient at present
Industry lithium ion battery negative material is mainly graphite, but its theoretical specific capacity only has 372mA h/g, it is difficult to meet dynamic field
If New-energy electric vehicle is for the demand of large capacity, high power electrochmical power source.Therefore, exploitation is with height ratio capacity, high safety
Property, low cost negative material have become one of the hot spot of theoretical research and application study.
Metal organic framework (MOFs) material is made of metal ion and organic ligand, the porous knot for having rule controllable
Structure, super large specific surface area and purity it is high the features such as, while its as electrode material, have can for the metal ion in charge and discharge process
It can occur redox reaction, and the duct of its three-dimensional structure is conducive to lithium ion storing and transmitting wherein, therefore, gold
It may be a kind of potential new type lithium ion battery electrode material to belong to organic framework material.However, at present about the organic bone of metal
Frame material is also fewer directly as the research of lithium ion battery electrode material, is primarily due to MOFs materials in charge and discharge process
The problems such as there are structure collapses, chemical composition changes, causes material reversible capacity low, and coulombic efficiency is low, cyclical stability and again
Rate poor performance.Contain a large amount of metal center ion and abundant organic ligand in MOFs materials, under certain atmospheric condition
High-temperature calcination is carried out using MOFs as presoma, can prepare novel metal oxide, they can retain to a certain extent
The morphological structure of MOFs presomas.Thus, using MOFs as presoma template, prepare novel cathode material for lithium ion battery
The interest of domestic and international researcher is also resulted in recent years.But MOFs or carbon fiber either by calcining, it is obtained
Cell negative electrode material can not be used directly as electrode, but need to be coated in metal collector by conductive agent, binder
On, not only Fabrication Technology of Electrode is complicated, but also chemical property is also to be improved.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of ferriferous oxide/carbon fiber composite lithium ion battery cathode material
Method, this method select MIL series as presoma, have better pattern adjustability, and easy to operate, process stabilizing, repeat
The features such as property is good, and product purity is high.It can be directly as flexible electrical through ferriferous oxide/carbon fibre composite made from this method
Pole avoids the use of conductive agent, binder and metal collector in traditional technology for preparing electrode, shows excellent electricity
Chemical property.
In order to achieve the above objectives, present invention employs following technical schemes：
1) preparation of ferrous metals organic backbone/polyacrylonitrile fibre：0.03~0.5g ferrous metals organic backbones are added
Enter in 3~5mL dimethylformamides, 20~30min of ultrasonic disperse obtains suspension, by 0.32~0.52g polyacrylonitrile (PAN)
It is added in suspension, obtains mixed liquor, mixed liquor is placed in 50~65 DEG C of stirred in water bath 18~take out afterwards for 24 hours, in 25~40 DEG C
4~6h is stood, solution is obtained, by solution electrostatic spinning, drying (drying temperature is 60~80 DEG C), obtains the organic bone of ferrous metals
Frame/polyacrylonitrile fibre；
2) preparation of ferriferous oxide/carbon fibre composite：By ferrous metals organic backbone/polyacrylonitrile fibre in 200
~250 DEG C of 2~4h of pre-oxidation, are then heat-treated 3~6h in 400~600 DEG C under an inert atmosphere, obtain ferriferous oxide/carbon fiber
Tie up composite material.
Preferably, the ferrous metals organic backbone is selected from MIL-88A, MIL-88B, MIL-53, MIL-100 or MIL-
101。
Preferably, the ferrous metals organic backbone is rodlike or spherical, and size is 20~500nm.
Preferably, the addition of the ferrous metals organic backbone is ferrous metals organic backbone and polyacrylonitrile gross mass
10%~60%.
Preferably, the ferriferous oxide/carbon fibre composite is flexible foldable tunica fibrosa.
Preferably, in the ferriferous oxide/carbon fibre composite, carbon fiber diameter is 0.8~10 μm；Ferriferous oxide is
Rodlike or spherical morphology feature Fe2O3, it is distributed in the carbon fibers (for example, iron is distributed in carbon fiber surface in experimental observation
Oxide), rodlike Fe2O3A length of 1~2 μm, a diameter of 15~500nm, spherical Fe2O3Size be 15~500nm.
Preferably, the condition of the electrostatic spinning is：Voltage is 10~15kV, and it is 10~16cm, solution stream to receive distance
Speed is 150~300 μ L/min.
Preferably, the preparation method of the ferrous metals organic backbone includes the following steps：By the anti-fourths of 0.351~1.053g
Enedioic acid, terephthalic acid (TPA) or trimesic acid and 0.81~2.43g FeCl3·6H2O is packed into reaction kettle after being mixed in water,
Then reaction kettle is put into 10~12h of reaction in 100~150 DEG C of baking oven, precipitation obtained by the reaction is cleaned through deionized water
After dry, obtain ferrous metals organic backbone.
Beneficial effects of the present invention are embodied in：
The present invention prepares ferrous metals organic backbone/polyacrylonitrile fibre by method of electrostatic spinning, and then is heat-treated and obtains
Ferriferous oxide/carbon fibre composite, this method is easy to operate, process stabilizing, reproducible, and product purity is high, iron obtained
Oxide/carbon fibrous composite have big specific surface area, orderly pore passage structure and a large amount of active sites, morphology controllable,
Sufficient space and reaction site can be provided for the insertion and abjection of lithium ion, can be used as lithium ion battery negative material.
Ferriferous oxide/carbon fibre composite produced by the present invention be flexible foldable tunica fibrosa, can directly as lithium from
Sub- battery cathode (flexible electrode), this not only avoids conductive agent, binder and metal collection in traditional technology for preparing electrode
The use of fluid so that technology for preparing electrode is simplified, and significantly improves the energy density of battery, shows excellent electricity
Chemical property.
The first discharge specific capacity of ferriferous oxide produced by the present invention/carbon fiber composite lithium ion battery cathode is reachable
902.9mAh/g, charge specific capacity is up to 562mAh/g, and initial coulomb efficiency is up to 66%.After cycle 50 times, discharge specific volume
Amount is still up to 375mAh/g.
Description of the drawings
Fig. 1 is the XRD curves of ferriferous oxide/carbon fibre composite prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM photograph of ferriferous oxide/carbon fibre composite prepared by the embodiment of the present invention 1.
Fig. 3 is ferriferous oxide/carbon fibre composite filling as negative electrode of lithium ion battery prepared by the embodiment of the present invention 1
Discharge curve.
Fig. 4 is the SEM photograph of ferriferous oxide/carbon fibre composite prepared by the embodiment of the present invention 2.
Fig. 5 is ferriferous oxide/carbon fibre composite filling as negative electrode of lithium ion battery prepared by the embodiment of the present invention 2
Discharge curve.
Fig. 6 is the SEM photograph of ferriferous oxide/carbon fibre composite prepared by the embodiment of the present invention 3.
Fig. 7 is ferriferous oxide/carbon fibre composite filling as negative electrode of lithium ion battery prepared by the embodiment of the present invention 3
Discharge curve.
Fig. 8 is the SEM photograph of ferriferous oxide/carbon fibre composite prepared by the embodiment of the present invention 4.
Fig. 9 is ferriferous oxide/carbon fibre composite filling as negative electrode of lithium ion battery prepared by the embodiment of the present invention 4
Discharge curve.
Figure 10 be independent MOFs calcining after as lithium ion battery negative material charging and discharging curve (conductive agent, binder,
In collector is considered in).
Specific implementation mode
The present invention is described in further details with reference to the accompanying drawings and examples.
First, bibliography prepares predecessor MIL-88A：0.702g fumaric acid is dissolved in deionized water, is stirred
1.62g FeCl are added after mixing uniformly3·6H2O is packed into autoclave after so that it is sufficiently mixed, and puts into anti-in 100 DEG C of baking oven
12h, reactant (reddish-brown precipitation) is answered to obtain MIL-88A russet in the drying after deionized water cleaning repeatedly.
Fumaric acid is replaced using terephthalic acid (TPA) or trimesic acid, MIL-53 or MIL-100 can be made.It is such
MOFs can be converted into porous ferriferous oxide after high temperature pyrolysis.
Embodiment 1
(1) preparation of MIL-88A/PAN composite fibres
0.480g MIL-88A are dissolved in 3mL dimethylformamides (DMF) (i.e. MIL-88A contents are 60wt%),
Ultrasonic disperse 20min, obtains suspension.It weighs 0.32g PAN to be dissolved in above-mentioned suspension, mixed liquor is then placed in 65 DEG C of water
18h is stirred in bath, is taken out, and is stored at room temperature solution electrostatic spinning after 4h, the process conditions setting of electrostatic spinning is as follows：Voltage
For 15kV, it is 16cm to receive distance, and solution flow rate is 200 μ L/min, is dried in 80 DEG C of drying box, prepares MIL-88A/
PAN fiber.
(2) preparation of ferriferous oxide/carbon fiber
MIL-88A/PAN fibers are placed in tube furnace, first 250 DEG C of heat preservation 2h are pre-oxidized under air conditions, then
It is passed through nitrogen (N2>99.99%), at 400 DEG C keep the temperature 3h be heat-treated, be naturally cooling to room temperature later, obtain ferriferous oxide/
Carbon fibre composite.The XRD diagram of composite material is as shown in Figure 1, the position of diffraction maximum passes through and standard card (JCPDF 33-
0664) it compares, illustrates that prepared sample is Fe2O3/ carbon fiber (Fe2O3/ CF) composite material, and purity is high.It can be with from Fig. 2
Find out that carbon fiber surface is evenly distributed with ferriferous oxide, carbon fiber diameter is about 4 μm, Fe2O3It has been effectively retained the stick of MIL-88A
Shape shape characteristic, about 1.2 μm long, diameter is about 300nm.
(3) lithium ion battery assembles
By ferriferous oxide/carbon fibre composite of preparation directly as working electrode (ferriferous oxide/carbon fiber complex lithium
Ion battery cathode), without using conductive agent and binder, lithium piece is to electrode and reference electrode, 1mol/L LiPF6Carbon
Diethyl phthalate and ethylene carbonate mixed liquor (volume ratio 1:1) it is electrolyte.All assemblings are in the glove box full of argon gas
It carries out.
Ferriferous oxide/carbon fiber composite lithium ion battery cathode is can be seen that from charging and discharging curve shown in Fig. 3 for the first time
Specific discharge capacity reaches 850mAh/g, and charge specific capacity reaches 562mAh/g, and initial coulomb efficiency is up to 66%, after recycling 50 times,
Specific discharge capacity is still up to 375mAh/g.
Embodiment 2
0.0355g MIL-88A are dissolved in 3mL dimethylformamides (i.e. MIL-88A contents are 10wt%), ultrasound
Disperse 20min, obtains suspension.It weighs 0.32g PAN to be dissolved in above-mentioned suspension, mixed liquor is then placed in 65 DEG C of water-baths
Middle stirring 18h takes out, and is stored at room temperature solution electrostatic spinning after 4h, the process conditions setting of electrostatic spinning is as follows：Voltage is
10kV, it is 12cm to receive distance, and solution flow rate is 200 μ L/min, is dried in 80 DEG C of drying box, prepares MIL-88A/
PAN fiber.
MIL-88A/PAN fibers are placed in tube furnace, first 250 DEG C of heat preservation 2h are pre-oxidized under air conditions, then
It is passed through nitrogen (N2>99.99%), at 400 DEG C keep the temperature 3h be heat-treated, be naturally cooling to room temperature later, obtain ferriferous oxide/
Carbon fiber (Fe2O3/ CF) composite material.As can be seen from Figure 4 rodlike ferriferous oxide is distributed in carbon fiber surface.
By ferriferous oxide/carbon fibre composite of preparation directly as working electrode (ferriferous oxide/carbon fiber complex lithium
Ion battery cathode), without using conductive agent and binder.From charging and discharging curve shown in fig. 5 can be seen that ferriferous oxide/
The first discharge specific capacity of carbon fiber composite lithium ion battery cathode reaches 582.1mAh/g, and charge specific capacity reaches 300.2mAh/g,
Initial coulomb efficiency is up to 52%, and after recycling 50 times, specific discharge capacity is still up to 204.3mAh/g.
Embodiment 3
0.080g MIL-88A are dissolved in 3mL dimethylformamides (i.e. MIL-88A contents are 20wt%), ultrasound point
20min is dissipated, suspension is obtained.It weighs 0.32g PAN to be dissolved in above-mentioned suspension, then mixed liquor is placed in 65 DEG C of water-baths
18h is stirred, is taken out, is stored at room temperature solution electrostatic spinning after 4h, the process conditions setting of electrostatic spinning is as follows：Voltage is
13kV, it is 10cm to receive distance, and solution flow rate is 200 μ L/min, is dried in 80 DEG C of drying box, prepares MIL-88A/
PAN fiber.
MIL-88A/PAN fibers are placed in tube furnace, first 250 DEG C of heat preservation 2h are pre-oxidized under air conditions, then
It is passed through nitrogen (N2>99.99%), at 400 DEG C keep the temperature 3h be heat-treated, be naturally cooling to room temperature later, obtain ferriferous oxide/
Carbon fiber (Fe2O3/ CF) composite material.As can be seen from Figure 6 rodlike ferriferous oxide is distributed in carbon fiber surface.
By ferriferous oxide/carbon fibre composite of preparation directly as working electrode (ferriferous oxide/carbon fiber complex lithium
Ion battery cathode), without using conductive agent and binder.Charging and discharging curve shown in Fig. 7 can be seen that ferriferous oxide/
The first discharge specific capacity of carbon fiber composite lithium ion battery cathode reaches 902.9mAh/g, and charge specific capacity reaches 426.9mAh/g,
Initial coulomb efficiency is up to 47%, and after recycling 50 times, specific discharge capacity is still up to 238.5mAh/g.
Embodiment 4
0.215g MIL-88A are dissolved in 3mL dimethylformamides (i.e. MIL-88A contents are 40wt%), ultrasound point
20min is dissipated, suspension is obtained.It weighs 0.32g PAN to be dissolved in above-mentioned suspension, then mixed liquor is placed in 65 DEG C of water-baths
18h is stirred, is taken out, is stored at room temperature solution electrostatic spinning after 4h, the process conditions setting of electrostatic spinning is as follows：Voltage is
13kV, it is 15cm to receive distance, and solution flow rate is 200 μ L/min, is dried in 80 DEG C of drying box, prepares MIL-88A/
PAN fiber.
MIL-88A/PAN fibers are placed in tube furnace, first 250 DEG C of heat preservation 2h are pre-oxidized under air conditions, then
It is passed through nitrogen (N2>99.99%), at 400 DEG C keep the temperature 3h be heat-treated, be naturally cooling to room temperature later, obtain ferriferous oxide/
Carbon fiber (Fe2O3/ CF) composite material.As can be seen from Figure 8 rodlike ferriferous oxide is distributed in carbon fiber surface, and rodlike
Ferriferous oxide is perpendicular to carbon fiber surface.
By ferriferous oxide/carbon fibre composite of preparation directly as working electrode (ferriferous oxide/carbon fiber complex lithium
Ion battery cathode), without using conductive agent and binder.From charging and discharging curve shown in Fig. 9 can be seen that ferriferous oxide/
The first discharge specific capacity of carbon fiber composite lithium ion battery cathode reaches 813.5mAh/g, and charge specific capacity reaches 506.1mAh/g,
Initial coulomb efficiency is up to 62%, and after recycling 50 times, specific discharge capacity is still up to 297.7mAh/g.
In order to further embody meaning of the present invention, the material after independent MOFs (MIL-88A) is calcined is as work electricity
Pole (ferriferous oxide negative electrode of lithium ion battery), using carbon black as conductive agent, PVDF is binder, and lithium piece is to electrode and reference electricity
Pole, 1mol/L LiPF6Diethyl carbonate and ethylene carbonate mixed liquor (volume ratio 1:1) it is that electrolyte is assembled into button electricity
Its chemical property is tested in pond.
It can be seen that from charging and discharging curve shown in Fig. 10 and take into account the factors such as conductive agent, binder and collector
The first discharge specific capacity of ferriferous oxide negative electrode of lithium ion battery reach 116.6mAh/g, charge specific capacity reaches 89.5mAh/g, first
Secondary coulombic efficiency is up to 77%, and after recycling 50 times, specific discharge capacity is still 87.3mAh/g.After being calcined compared to independent MOFs
Material, the chemical property of ferriferous oxide/carbon fibre composite, which has, to be obviously improved, and it is certain to show that the present invention has
Progress meaning.
Claims (10)
1. a kind of preparation method of ferriferous oxide/carbon fibre composite, it is characterised in that：Include the following steps：
1) preparation of ferrous metals organic backbone/polyacrylonitrile fibre：By 0.03~0.5g ferrous metals organic backbones be added 3~
In 5mL dimethylformamides, 20~30min of ultrasonic disperse obtains suspension, and suspension is added in 0.32~0.52g polyacrylonitrile
In, mixed liquor is obtained, mixed liquor is placed in 50~65 DEG C of stirred in water bath 18~for 24 hours to be taken out and stands 4~6h in 25~40 DEG C afterwards,
It obtains solution and the solution electrostatic spinning is obtained into ferrous metals organic backbone/polyacrylonitrile fibre；
2) preparation of ferriferous oxide/carbon fibre composite：By ferrous metals organic backbone/polyacrylonitrile fibre in 200~250
DEG C pre-oxidation 2~4h, then under an inert atmosphere in 400~600 DEG C be heat-treated 3~6h, it is compound to obtain ferriferous oxide/carbon fiber
Material.
2. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
Ferrous metals organic backbone is selected from MIL-88A, MIL-88B, MIL-53, MIL-100 or MIL-101.
3. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
Ferrous metals organic backbone is rodlike or spherical.
4. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
The addition of ferrous metals organic backbone is the 10%~60% of ferrous metals organic backbone and polyacrylonitrile gross mass.
5. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
Ferriferous oxide/carbon fibre composite is flexible foldable tunica fibrosa.
6. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
In ferriferous oxide/carbon fibre composite, ferriferous oxide is distributed in carbon fiber surface.
7. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
The condition of electrostatic spinning is：Voltage is 10~15kV, and it is 10~16cm to receive distance, and solution flow rate is 150~300 μ L/min.
8. a kind of preparation method of ferriferous oxide/carbon fibre composite according to claim 1, it is characterised in that：It is described
The preparation method of ferrous metals organic backbone includes the following steps：By 0.351~1.053g fumaric acid, terephthalic acid (TPA) or
Trimesic acid and 0.81~2.43g FeCl3·6H2O is packed into reaction kettle after being mixed in water, reaction kettle is then put into 100
10~12h is reacted in~150 DEG C of baking oven, precipitation obtained by the reaction is dry after deionized water is cleaned, obtain ferrous metals
Organic backbone.
9. a kind of preparation method of ferriferous oxide/carbon fibre composite as described in claim 1 is preparing lithium ion battery
Application in cathode.
10. a kind of preparation method of ferriferous oxide/carbon fibre composite as described in claim 1 is in preparing flexible electrode
Application.
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| CN109616636A (en) * | 2018-12-04 | 2019-04-12 | 苏州大学 | Manganese oxide-carbon composite and its preparation method and application with yolk shell structure of carbon fiber package |
| CN109817958A (en) * | 2019-03-29 | 2019-05-28 | 陕西科技大学 | A kind of hollow nanobelt of kalium ion battery negative electrode material C cladding Co-MOF, preparation method and application |
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