CN109244405A - A kind of lithium sulfur battery anode material and its lithium-sulfur cell - Google Patents
A kind of lithium sulfur battery anode material and its lithium-sulfur cell Download PDFInfo
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- CN109244405A CN109244405A CN201811063571.4A CN201811063571A CN109244405A CN 109244405 A CN109244405 A CN 109244405A CN 201811063571 A CN201811063571 A CN 201811063571A CN 109244405 A CN109244405 A CN 109244405A
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Abstract
The invention belongs to the technical field of materials chemistry, it is specifically related to a kind of lithium sulfur battery anode material and its lithium-sulfur cell.This kind of lithium sulfur battery anode material, using being made following preparation method: utilizing N, dinethylformamide is as solvent, polyacrylonitrile and silica are dissolved in N in proportion, spinning precursor liquid is prepared in dinethylformamide solution, silicon dioxide-poly acrylonitril membrane is prepared using electrostatic spinning process, carbonization treatment is carried out to silicon dioxide-poly acrylonitril membrane and obtains carbon fiber-silicon dioxide composite material, then porous carbon fiber material is formed with hydrofluoric acid dips carbon fiber-silicon dioxide composite material, it finally carries out porous carbon fiber material and mixes sulphur, prepare situ Nitrogen Doping porous carbon sulphur positive electrode.The lithium sulfur battery anode material has porous structure, provides a large amount of ion channels and high-specific surface area, effectively improves the shuttle effect of polysulfide in lithium-sulfur cell, improve the utilization rate of active material in the cycle life and positive electrode of lithium-sulfur cell.
Description
Technical field
The invention belongs to the technical field of materials chemistry, it is specifically related to a kind of lithium sulfur battery anode material and its lithium sulphur electricity
Pond.
Background technique
With the rapid development of science and technology and communication, exploitation high-energy-density energy storage new material becomes eager demand.Lithium sulphur
Battery theoretical specific capacity reaches 1672mAh/g (theoretical energy density can reach 2600Wh/kg), is existing lithium ion battery specific volume
The several times of amount, and sulphur has rich reserves, cheap and advantages of environment protection.Therefore lithium-sulfur cell has become most
Has one of the energy storage system of researching value.
However there are elemental sulfur poorly conductive and the intermediate product poorly conductives of charge and discharge process for lithium-sulfur cell, it is vulcanize more
Object during the reaction shuttle effect the problems such as, cause the utilization rate of lithium sulfur battery anode material to be constantly in lower level,
Therefore how improving the cycle life of lithium-sulfur cell, improving positive electrode active material utilization and improving Volumetric expansion becomes
The key of lithium-sulfur cell.
The scheme for improving lithium-sulfur cell performance in the prior art mainly has optimization and the sulfur-based positive electrode material of sulfur-based positive electrode structure
The modification of material is usually carried out elemental sulfur and porous material with high pore structure by the method for filling, mixing or cladding
It is mechanical compound, anode composite material is formed, which is made of nano-sulfur and porous carbon fiber, wherein sulphur
It loads in the hole of porous carbon fiber, porous carbon fiber has excellent electric conductivity and chemical stability, and porous structure mentions
For a large amount of ionization paths, the shortcomings that can make up for it elemental sulfur poorly conductive, simultaneously can play sulfur fixation, improve polysulfide and reacting
Shuttle effect in the process, which improves the utilization rates of positive active material, so as to improve the lithium-ion electric of sulfur-based positive electrode
The cycle performance of conductance and battery, and then improve the chemical property of lithium-sulfur cell.
Have about the carbon sulphur positive electrode prior art disclosed, CN104752702A discloses a kind of lithium-sulphur cell positive electrode material
Material and preparation method thereof is to generate metal oxide nanotubes, is combined after calcining with sulphur.CN105489863A is disclosed
One kind being based on C/Ti4O7The lithium sulfur battery anode material of composite nano fiber, prepares C/Ti4O7Composite nano fiber, then will be fine
Dimension is mixed with elemental sulfur obtains the positive electrode through Overheating Treatment.But the generally existing disadvantage of above-mentioned technology is: preparation work
Skill is relative complex, so as to cause its high production cost, influences its extensive use in lithium-sulfur cell；And the anode prepared
Material surface area is small, its microscopic appearance difficult to control, Study of Volume Expansion is still had in charge and discharge process, to limit it
Chemical property.
Summary of the invention
It is low it is an object of the invention to be directed to existing lithium sulfur battery anode material utilization rate, influence lithium-sulfur cell electrochemistry
Can the problem of and a kind of lithium sulfur battery anode material and its lithium-sulfur cell are provided.The lithium sulfur battery anode material has porous knot
Structure provides a large amount of ion channels and high-specific surface area, effectively improves the shuttle effect of polysulfide in lithium-sulfur cell, improves
The utilization rate of active material in the cycle life and positive electrode of lithium-sulfur cell.
The technical solution of the present invention is as follows: a kind of lithium sulfur battery anode material, use are made following preparation method: utilizing N, N-
Dimethylformamide (DMF) is used as solvent, by polyacrylonitrile (PAN) and silica (SiO2) it is dissolved in N, N- diformazan in proportion
Spinning precursor liquid is prepared in base formamide solution, silicon dioxide-poly acrylonitril membrane is prepared using electrostatic spinning process, to dioxy
SiClx-polyacrylonitrile film carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, then impregnates carbon with hydrofluoric acid (HF)
Fiber-silicon dioxide composite material forms porous carbon fiber material, finally carries out porous carbon fiber material and mixes sulphur, prepares porous
Carbon sulphur positive electrode.
The mass ratio of the polyacrylonitrile and silica is 0.1~0.7.
The preparation method specifically includes the following steps:
(1) electrostatic spinning prepares silicon dioxide-poly acrylonitril membrane: polyacrylonitrile is dissolved in n,N-Dimethylformamide solution
In obtain polyacrylonitrile/n,N-Dimethylformamide solution, 25 DEG C~50 DEG C at a temperature of by partial size be 1~50nm SiO2
Particle stirring and dissolving obtains polymer solution into polyacrylonitrile/n,N-Dimethylformamide solution, wherein polyacrylonitrile with
SiO2Mass ratio be 0.1~0.7；By in resulting polymers solution inhalation syringe, electrostatic spinning is carried out using following parameter
Silicon dioxide-poly acrylonitril membrane is made: adjusting the distance between needle point and receiving barrel is 25cm, and application voltage is 18KV, injection
Pump rate is 0.3mL/h, and collector revolving speed is 500rpm；
(2) pre-oxidation treatment of silicon dioxide-poly acrylonitril membrane: silicon dioxide-poly acrylonitril membrane obtained by step (1) is set
Stablize 1~10h at 200~300 DEG C in air, wherein the rate of heat addition is 1~10 DEG C/min；
(3) carbonization treatment of silicon dioxide-poly acrylonitril membrane: in a nitrogen atmosphere to the silicon dioxide-poly after pre-oxidation
Acrylonitril membrane carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, and wherein the rate of heat addition is 1~10 DEG C/min, instead
Answering temperature is 500~1200 DEG C, and soaking time is 1~5h；
(4) preparation of porous carbon fiber material: by carbon fiber-silicon dioxide composite material mass fraction be 10%~
1~24 hour is impregnated in 20% hydrofluoric acid to remove SiO2, and be washed with distilled water, 12h is then dried at 50~120 DEG C
Obtain porous carbon fiber material；
(5) porous carbon fiber material mixes sulphur: first in mass ratio 1~5:1 weighs porous carbon fiber material and nano-sulfur, mixes
Together in 1~30min is ground in agate mortar, 0.05~1ml carbon disulfide is instilled for dissolving sulphur, continues to be ground to without obvious sulphur
Yellow is put into reaction kettle after then drying 1~20min in a vacuum drying oven and anti-full of removing is shaken in argon gas glove box
The oxygen in kettle is answered, reaction kettle is finally placed in 155 DEG C of heating 12h in Constant Temp. Oven, prepares porous carbon sulphur anode
Material.
Porous carbon fiber material is activated before step (5) porous carbon fiber material mixes sulphur in the preparation method
Processing, it is specific as follows: porous carbon fiber material obtained by step (4) is immersed 1 in the KOH solution that mass fraction is 20%~45%
High-temperature process is carried out after~5 hours in a nitrogen atmosphere, wherein being heated to 500~800 from room temperature with the rate of 1~10 DEG C/min
DEG C, it then cooling to room temperature, the porous carbon fiber material after activation is washed with distilled water water and removes remaining potassium, and 50~
Dry 1~12h at 120 DEG C.Mass fraction is used to carry out chemical activation to porous carbon fiber for 20%~45% KOH solution,
Largely suitable micropore (being less than 2nm) structure is formed in carbon fiber surface, the specific surface area of porous material can be further increased,
Pore structure abundant, which is conducive to increase, carries sulfur content, the transmission for accelerating ion and absorption polysulfide, effectively increases lithium-sulfur cell
Chemical property.
A kind of lithium-sulfur cell prepared using the positive electrode.
The invention has the benefit that the present invention, which prepares silicon dioxide-poly acrylonitril membrane by electrostatic spinning, to be had very
Reticular structure pattern abundant forms netlike carbon fiber-silicon dioxide composite material after carbonization treatment, is then corroded with hydrofluoric acid
Silica forms porous carbon nanofiber, obtains porous carbon fiber material, finally carries out mixing sulphur technique obtaining porous carbon sulphur just
Pole material, the positive electrode have many advantages, such as large specific surface area, hole abundant, low manufacture cost and reproducible.As anode
Material is applied in lithium-sulfur cell, effectively fixes the shuttle of polysulfide, improves the utilization rate of positive active material.It is filling
Reticular structure helps to reduce the polarization phenomena during electrode electro Chemical in discharge process, so that electrode material body be effectively relieved
It the problem of product expansion, is avoided to a certain extent due to electrode material volume expansion problem and is brought to electrode material negative
It influences, so that reaction invertibity is improved, improves the cycle performance of electrode, and then enhance the electrochemistry of lithium-sulfur cell
Energy.
The present invention forms original position N doping carbon fiber using original N element in PAN fiber in the carbonized, it not only has
Excellent electric conductivity and experiments have shown that N doping can effectively inhibit and adsorb polysulfide, and utilize nano silica
Particle forms a large amount of pore structure by hf etching as template on carbon fiber, with high specific surface area and by force
Big conductive network can greatly improve the chemical property of battery using the synergistic effect of the two in this way.
Detailed description of the invention
Fig. 1 is the SEM figure of porous carbon fiber in the embodiment of the present invention 1.
Fig. 2 is the graph of pore diameter distribution of porous carbon fiber in the embodiment of the present invention 1.
Fig. 3 is porous carbon fiber/sulphur composite material XRD diagram in the embodiment of the present invention 1.
Fig. 4 is porous carbon fiber/sulphur composite material specific capacity voltage pattern in the embodiment of the present invention 1.
Specific embodiment
The present invention is further illustrated with attached drawing with reference to embodiments, but embodiment does not do any form to the present invention
Restriction.Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
The lithium sulfur battery anode material is made using the preparation method included the following steps:
(1) electrostatic spinning prepares silicon dioxide-poly acrylonitril membrane: polyacrylonitrile is dissolved in n,N-Dimethylformamide solution
In obtain polyacrylonitrile/n,N-Dimethylformamide solution, 25 DEG C~50 DEG C at a temperature of by partial size be 30nm SiO2?
Grain stirring and dissolving obtains polymer solution into polyacrylonitrile/n,N-Dimethylformamide solution, wherein polyacrylonitrile and SiO2
Mass ratio be 0.5；By in resulting polymers solution inhalation syringe, electrostatic spinning is carried out using following parameter, titanium dioxide is made
Silicon-polyacrylonitrile film: adjusting the distance between needle point and receiving barrel is 25cm, and application voltage is 18KV, and injection pump rate is
0.3mL/h, collector revolving speed are 500rpm；
(2) pre-oxidation treatment of silicon dioxide-poly acrylonitril membrane: silicon dioxide-poly acrylonitril membrane obtained by step (1) is set
Stablize 1~10h at 200~300 DEG C in air, wherein the rate of heat addition is 1~10 DEG C/min；
(3) carbonization treatment of silicon dioxide-poly acrylonitril membrane: in a nitrogen atmosphere to the silicon dioxide-poly after pre-oxidation
Acrylonitril membrane carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, and wherein the rate of heat addition is 1~10 DEG C/min, instead
Answering temperature is 500~1200 DEG C, and soaking time is 1~5h；
(4) preparation of porous carbon fiber material: the hydrogen for being 15% in mass fraction by carbon fiber-silicon dioxide composite material
1~24 hour is impregnated in fluoric acid to remove SiO2, and be washed with distilled water, then at 50~120 DEG C dry 12h obtain it is porous
Carbon fibre material；
(5) porous carbon fiber material mixes sulphur: first in mass ratio 3:1 weighs porous carbon fiber material and nano-sulfur, mixing
1~30min is ground in agate mortar, is instilled 0.25ml carbon disulfide and is used to dissolve sulphur, continues to be ground to without obvious Sulfur color,
Then reaction kettle is put into after drying 1~20min in a vacuum drying oven and is removing reaction kettle full of shaking in argon gas glove box
In oxygen, reaction kettle is finally placed in 155 DEG C of heating 12h in Constant Temp. Oven, prepares porous carbon sulphur positive electrode.
Porous carbon fiber material is activated before step (5) porous carbon fiber material mixes sulphur in the preparation method
Processing, it is specific as follows: it is small in 45% KOH solution 1~5 that porous carbon fiber material obtained by step (4) being immersed into mass fraction
When after carry out high-temperature process in a nitrogen atmosphere, wherein being heated to 500~800 DEG C from room temperature with the rate of 1~10 DEG C/min, so
After be cooled to room temperature, the porous carbon fiber material after activation is washed with distilled water water and removes remaining potassium, and at 50~120 DEG C
Dry 1~12h.
Embodiment 2
The lithium sulfur battery anode material is made using the preparation method included the following steps:
(1) electrostatic spinning prepares silicon dioxide-poly acrylonitril membrane: polyacrylonitrile is dissolved in n,N-Dimethylformamide solution
In obtain polyacrylonitrile/n,N-Dimethylformamide solution, 25 DEG C~50 DEG C at a temperature of by partial size be 30nm SiO2?
Grain stirring and dissolving obtains polymer solution into polyacrylonitrile/n,N-Dimethylformamide solution, wherein polyacrylonitrile and SiO2
Mass ratio be 0.5；By in resulting polymers solution inhalation syringe, electrostatic spinning is carried out using following parameter, titanium dioxide is made
Silicon-polyacrylonitrile film: adjusting the distance between needle point and receiving barrel is 25cm, and application voltage is 18KV, and injection pump rate is
0.3mL/h, collector revolving speed are 500rpm；
(2) pre-oxidation treatment of silicon dioxide-poly acrylonitril membrane: silicon dioxide-poly acrylonitril membrane obtained by step (1) is set
Stablize 1~10h at 200~300 DEG C in air, wherein the rate of heat addition is 1~10 DEG C/min；
(3) carbonization treatment of silicon dioxide-poly acrylonitril membrane: in a nitrogen atmosphere to the silicon dioxide-poly after pre-oxidation
Acrylonitril membrane carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, and wherein the rate of heat addition is 1~10 DEG C/min, instead
Answering temperature is 500~1200 DEG C, and soaking time is 1~5h；
(4) preparation of porous carbon fiber material: the hydrogen for being 15% in mass fraction by carbon fiber-silicon dioxide composite material
1~24 hour is impregnated in fluoric acid to remove SiO2, and be washed with distilled water, then at 50~120 DEG C dry 12h obtain it is porous
Carbon fibre material；
(5) porous carbon fiber material mixes sulphur: first in mass ratio 4:1 weighs porous carbon fiber material and nano-sulfur, mixing
1~30min is ground in agate mortar, is instilled 0.25ml carbon disulfide and is used to dissolve sulphur, continues to be ground to without obvious Sulfur color,
Then reaction kettle is put into after drying 1~20min in a vacuum drying oven and is removing reaction kettle full of shaking in argon gas glove box
In oxygen, reaction kettle is finally placed in 155 DEG C of heating 12h in Constant Temp. Oven, prepares porous carbon sulphur positive electrode.
Porous carbon fiber material is activated before step (5) porous carbon fiber material mixes sulphur in the preparation method
Processing, it is specific as follows: it is small in 45% KOH solution 1~5 that porous carbon fiber material obtained by step (4) being immersed into mass fraction
When after carry out high-temperature process in a nitrogen atmosphere, wherein being heated to 500~800 DEG C from room temperature with the rate of 1~10 DEG C/min, so
After be cooled to room temperature, the porous carbon fiber material after activation is washed with distilled water water and removes remaining potassium, and at 50~120 DEG C
Dry 1~12h.
Comparative example 1
The lithium sulfur battery anode material is made using the preparation method included the following steps:
(1) electrostatic spinning prepares silicon dioxide-poly acrylonitril membrane: polyacrylonitrile is dissolved in n,N-Dimethylformamide solution
In obtain polyacrylonitrile/n,N-Dimethylformamide solution, 50 DEG C at a temperature of by partial size be 30nm SiO2Particle stirring
It is dissolved into polyacrylonitrile/n,N-Dimethylformamide solution and obtains polymer solution, wherein polyacrylonitrile and SiO2Quality
Than being 0.3；By in resulting polymers solution inhalation syringe, electrostatic spinning is carried out using following parameter, silicon dioxide-poly is made
Acrylonitril membrane: adjusting the distance between needle point and receiving barrel is 25cm, and application voltage is 18KV, and injection pump rate is 0.3mL/h,
Collector revolving speed is 500rpm；
(2) pre-oxidation treatment of silicon dioxide-poly acrylonitril membrane: silicon dioxide-poly acrylonitril membrane obtained by step (1) is set
Stablize 4h at 230 DEG C in air, wherein the rate of heat addition is 5 DEG C/min；
(3) carbonization treatment of silicon dioxide-poly acrylonitril membrane: in a nitrogen atmosphere to the silicon dioxide-poly after pre-oxidation
Acrylonitril membrane carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, and wherein the rate of heat addition is 5 DEG C/min, reaction temperature
Degree is 1200 DEG C, soaking time 1h；
(4) preparation of porous carbon fiber material: the hydrogen for being 15% in mass fraction by carbon fiber-silicon dioxide composite material
24 hours are impregnated in fluoric acid to remove SiO2, and be washed with distilled water, then dry 12h obtains porous carbon fiber at 110 DEG C
Material；
(5) porous carbon fiber material mixes sulphur: first in mass ratio 3:1 weighs porous carbon fiber material and nano-sulfur, mixing
30min is ground in agate mortar, is instilled 0.25ml carbon disulfide for dissolving sulphur, is continued to be ground to without obvious Sulfur color, so
Reaction kettle is put into after drying 20min in a vacuum drying oven afterwards and full of the oxygen shaken in removing reaction kettle in argon gas glove box
Reaction kettle is finally placed in 180 DEG C of heating 12h in Constant Temp. Oven, prepares porous carbon sulphur positive electrode by gas.
Comparative example 2
The lithium sulfur battery anode material is made using the preparation method included the following steps:
(1) electrostatic spinning prepares polyacrylonitrile film: polyacrylonitrile being dissolved in n,N-Dimethylformamide solution and is gathered
Polymer solution；By in resulting polymers solution inhalation syringe, electrostatic spinning is carried out using following parameter, polyacrylonitrile film is made:
Adjusting the distance between needle point and receiving barrel is 25cm, and application voltage is 18KV, and injection pump rate is 0.3mL/h, and collector turns
Speed is 500rpm；
(2) pre-oxidation treatment of polyacrylonitrile film: polyacrylonitrile film obtained by step (1) is placed in air at 230 DEG C
Stablize 4h, wherein the rate of heat addition is 5 DEG C/min；
(3) carbonization treatment of polyacrylonitrile film: the polyacrylonitrile film after pre-oxidation is carried out at carbonization in a nitrogen atmosphere
Reason obtains carbon fiber, and wherein the rate of heat addition is 5 DEG C/min, and reaction temperature is 1200 DEG C, soaking time 1h；
(4) activation processing of carbon fiber: carbon fiber obtained by step (3) is immersed 5 in the KOH solution that mass fraction is 45%
High-temperature process is carried out in a nitrogen atmosphere after hour, wherein being heated to 600 DEG C from room temperature with the rate of 5 DEG C/min, is then cooled down
To room temperature, the carbon fiber after activation is washed with distilled water water and removes remaining potassium, and the dry 12h at 110 DEG C；
(5) carbon fiber mixes sulphur: first in mass ratio 3:1 weighs activated carbon fiber and nano-sulfur, is mixed in agate mortar
30min is ground, 0.25ml carbon disulfide is instilled for dissolving sulphur, continues to be ground to without obvious Sulfur color, then be dried in vacuo
Reaction kettle is put into case after dry 20min and is removing the oxygen in reaction kettle full of shaking in argon gas glove box, it finally will be anti-
It answers kettle to be placed in 180 DEG C of heating 12h in Constant Temp. Oven, prepares carbon sulphur positive electrode.
The lithium-sulfur cell prepared using lithium sulfur battery anode material described in each embodiment and each comparative example is passed through below new
Prestige test macro carries out electric performance test, and constant current charge/discharge test is in different current density (1C=1672mAh g-1)
With 1.0-3.0V Li+It is carried out under the voltage of/Li.Specific discharge capacity test result is shown in Table 1:
The lithium-sulfur cell electric performance test result that table 1 is prepared using embodiment and comparative example positive electrode
Fig. 1 is the scanning electron microscope (SEM) photograph of porous carbon fiber material (PCNF) made from embodiment 1, can see carbon from Fig. 1 a, b
The diameter of fiber is about 200~300nm, and rough surface is uneven, this is because material surface pore structure abundant and formed
Special appearance.
Fig. 2 is the graph of pore diameter distribution of porous carbon fiber material made from embodiment 1, it is seen that the aperture of material concentrates on 2~
3nm, micropore in porous carbon fiber material and it is mesoporous be conducive to improve carry sulfur content and ion transmission, BET specific surface is
531.868m2/g。
Fig. 3 be embodiment 1 obtained by porous carbon fiber/sulphur composite material XRD diagram, PCNF shown at 24 ° compared with
Strong broad peak shows weak characteristic peak at 43 °, corresponds to (002) and (100) plane, shows the stone in PCNF obtained
Ink structure is occupied an leading position.The Fddd orthorhombic crystalline structure of elementary sulfur is shown in S/PCNF composite material, since S/PCNF is multiple
Well dispersed nano-sulfur feature in condensation material.
Fig. 4 is specific capacity voltage pattern of the material at 0.2C obtained by embodiment 1, as can be seen from the figure this original position
There are two platforms near 2.4V and 2.1V for nitrogen-doped carbon fiber/sulphur, this is two reduction peaks common in lithium-sulfur cell,
Initial discharge capacity is more than 1500mAh/g under 0.2C multiplying power, and the reversible capacity of 1000mAh/g is still maintained after circulation 100 times, is filled
Discharging efficiency is always close to 100%.This is because the porous carbon fiber/sulphur composite material can not only mention for the electrolyte of liquid
It, also can be in charge and discharge process, by multi-stage porous come the more sulphur of intermediate product during sorption cycle for porous ion channel
Compound, to improve the performance of battery.
Claims (5)
1. a kind of lithium sulfur battery anode material, which is characterized in that use is made following preparation method: utilizing N, N-
Dimethylformamide is dissolved in N, N- dimethyl formyl as solvent, by polyacrylonitrile and silica in proportion
Spinning precursor liquid is prepared in amine aqueous solution, prepares silicon dioxide-poly acrylonitril membrane using electrostatic spinning process, it is right
Silicon dioxide-poly acrylonitril membrane carries out carbonization treatment and obtains carbon fiber-silicon dioxide composite material, then uses hydrogen fluorine
Acid soak carbon fiber-silicon dioxide composite material forms porous carbon fiber material, finally carries out porous carbon fiber material
Material mixes sulphur, prepares porous carbon sulphur positive electrode.
2. lithium sulfur battery anode material according to claim 1, which is characterized in that the polyacrylonitrile and dioxy
The mass ratio of SiClx is 0.1~0.7.
3. lithium sulfur battery anode material according to claim 1, which is characterized in that the preparation method is specifically wrapped
Include following steps:
(1) electrostatic spinning prepares silicon dioxide-poly acrylonitril membrane: polyacrylonitrile is dissolved in n,N-Dimethylformamide
Polyacrylonitrile/n,N-Dimethylformamide solution is obtained in solution, 25 DEG C~50 DEG C at a temperature of by partial size
For the SiO of 10~50nm2Particle stirring and dissolving is gathered into polyacrylonitrile/n,N-Dimethylformamide solution
Polymer solution, wherein the mass ratio of polyacrylonitrile and silica is 0.1~0.7；By resulting polymers solution
In inhalation syringe, electrostatic spinning is carried out using following parameter, silicon dioxide-poly acrylonitril membrane: metering needle is made
The distance between point and receiving barrel are 25cm, and application voltage is 18KV, and injection pump rate is 0.3mL/h, are received
Storage revolving speed is 500rpm；
(2) pre-oxidation treatment of silicon dioxide-poly acrylonitril membrane: by silicon dioxide-poly acrylonitrile obtained by step (1)
Film, which is placed in air at 200~300 DEG C, stablizes 1~10h, and wherein the rate of heat addition is 1~10 DEG C/min；
(3) carbonization treatment of silicon dioxide-poly acrylonitril membrane: in a nitrogen atmosphere to the silica-after pre-oxidation
Polyacrylonitrile film carry out carbonization treatment obtain carbon fiber-silicon dioxide composite material, wherein the rate of heat addition be 1~
10 DEG C/min, reaction temperature is 500~1200 DEG C, and soaking time is 1~5h；
(4) preparation of porous carbon fiber material: by carbon fiber-silicon dioxide composite material mass fraction be 10%~
1~24 hour is impregnated in 20% hydrofluoric acid to remove SiO2, and be washed with distilled water, then at 50~120 DEG C
Lower dry 12h obtains porous carbon fiber material；
(5) porous carbon fiber material mixes sulphur: first in mass ratio 1~5:1 weighs nano-sulfur and porous carbon fiber material
Material is mixed in 1~30min of grinding in agate mortar, instills 0.05~1ml carbon disulfide and is used to dissolve sulphur,
Continue to be ground to without obvious Sulfur color, is put into reaction kettle simultaneously after then drying 1~20min in a vacuum drying oven
Full of the oxygen removed in reaction kettle is shaken in argon gas glove box, it is dry that reaction kettle is finally placed in electric heating constant temperature
155 DEG C of heating 12h, prepare porous carbon sulphur positive electrode in case.
4. lithium sulfur battery anode material according to claim 3, which is characterized in that in step in the preparation method
Suddenly (5) porous carbon fiber material is activated porous carbon fiber material before mixing sulphur, specific as follows:
Porous carbon fiber material obtained by step (4) is immersed 1~5 in the KOH solution that mass fraction is 20%~45%
High-temperature process is carried out in a nitrogen atmosphere after hour, wherein being heated to the rate of 1~10 DEG C/min from room temperature
It 500~800 DEG C, then cools to room temperature, it is residual that the porous carbon fiber material after activation is washed with distilled water water removing
Remaining potassium, and dry 1~12h at 50~120 DEG C.
5. a kind of lithium-sulfur cell prepared using positive electrode described in claim 1.
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