CN109004205A - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- CN109004205A CN109004205A CN201810889071.XA CN201810889071A CN109004205A CN 109004205 A CN109004205 A CN 109004205A CN 201810889071 A CN201810889071 A CN 201810889071A CN 109004205 A CN109004205 A CN 109004205A
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Abstract
The present invention is a kind of preparation method of lithium sulfur battery anode material.This method utilizes N, dinethylformamide (DMF) is used as solvent, a certain proportion of polyacrylonitrile (PAN)/graphene oxide (GO) in situ is dissolved in preparation spinning precursor liquid in DMF, continuous nano-fibre film is prepared using electrostatic spinning process, carbonization treatment is carried out to electrostatic spinning PAN/GO fiber and prepares situ Nitrogen Doping carbon fiber/redox graphene composite material, it finally carries out mixing sulphur technique and prepares nitrogen-doped carbon fiber/redox graphene/sulphur composite positive pole, this composite material with excellent electric conductivity and the adsorption capacity to polysulfide, the shortcomings that poorly conductive of elemental sulfur can not only be made up, simultaneously can play sulfur fixation, improve the shuttle effect of polysulfide during the reaction, to improve the chemical property of lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium sulfur battery anode material, and in particular to a kind of to utilize electrostatic spinning technique
Situ Nitrogen Doping carbon fiber/redox graphene composite material is prepared, technical field of material chemistry is belonged to.
Background technique
With society it is increasingly developed, people have higher requirement to the high efficiency, portability and safety of the energy.
Lithium-sulfur cell theoretical specific capacity is up to 1672mAh/g (theoretical energy density can reach 2600Wh/kg), is existing lithium ion anode
The several times of material specific capacity, and elemental sulfur has resourceful, cheap and advantages of environment protection, becomes and is concerned
New type lithium ion battery.However, elemental sulfur conductivity is low and its soluble polysulfide has the effect that shuttles in charge and discharge process
It answers, the utilization rate of positive electrode is caused to be constantly in lower level.Currently, lithium sulfur battery anode material mostly uses greatly sulphur and carbon
It is compound, by the method for filling, mixing or cladding that the high carbon material progress of elemental sulfur and specific surface area is compound, so as to improve sulphur
The cycle performance of base anode material conductivity and battery.
Situ Nitrogen Doping carbon fiber/redox graphene the composite material is by redox graphene and nitrogen-doped carbon
Fiber composition, finally loads to nano-sulfur in carbon fiber and graphene sheet layer.Wherein nitrogen-doped carbon fiber has excellent
Electric conductivity, and N doping can be enhanced the Surface absorption to soluble poly sulfide and improve the electronic conductivity of carbon.Equally
Graphene oxide has excellent electric conductivity, can provide powerful electron-transport frame.It will using the method for high-temperature heat treatment
Graphene oxide (GO) is reduced to redox graphene (rGO), and most oxygen-containing functional group is reduced, so that the surface rGO
Existing defects show very strong absorption property, inhibit shuttle effect by absorption polysulfide.The present invention is gathered using in situ
Acrylonitrile is closed, so that polyacrylonitrile and graphene oxide can be very good to combine, by low temperature heat treatment in advance and high temperature cabonization
After obtain situ Nitrogen Doping carbon fiber/redox graphene composite material.Research about nitrogen-doped carbon material also has been reported that:
CN105702937A discloses a kind of SnO2The preparation method of/fiber C, with SiO2For pore creating material, it is quiet that progress is mixed with PAN, PVP
Electrospun forms composite fibre.After high-temperature calcination is carbonized, obtained N doping porous carbon fiber with it is a certain proportion of
SnCl4·5H2O is mixed with urea, and SnO is prepared using microwave method2/ fiber C.Manufactured SnO2/ fiber C diameter in 1mm,
Inside is SiO2Hollow structure after removing.The SnO of invention preparation2/ fiber C, not only surface distribution is uniform, but also as lithium
Ion battery material has height ratio capacity.CN107633959A discloses a kind of preparation method of electrode material, by nano inorganic
Material is scattered in n,N-Dimethylformamide, obtains dispersion liquid, adds polyacrylonitrile, and is heated 1 hour at 70 DEG C, is obtained
To mixing mucus, the mass fraction that gained mixes polyacrylonitrile in mucus is 15%, carries out electrostatic spinning to mixing mucus, and will
Obtained precursor is empty under conditions of 250 DEG C to be burnt 0.5 hour, by the precursor after heat treatment under conditions of 800 DEG C of nitrogen protections
Heating 3 hours, and cleaned, dry to obtain situ Nitrogen Doping carbon fiber/magnesium oxide composite material, gained composite material is made
Acid processing, can be obtained the nanoporous carbon fiber electrode material of situ Nitrogen Doping.But the generally existing disadvantage of above-mentioned technology is:
Preparation process is relative complex, so as to cause its high production cost, influences its extensive use in lithium-sulfur cell.And preparation
The electric conductivity of composite material is poor, preparation when be difficult to control its microscopic appearance, electrode material still has in charge and discharge process
Study of Volume Expansion, to limit its chemical property.
Summary of the invention
It is an object of the invention to provide a kind of be applied in lithium-sulfur cell for deficiency existing for current techniques center
The preparation method of positive electrode.This method is gathered a certain proportion of original position using n,N-Dimethylformamide (DMF) as solvent
Acrylonitrile (PAN)/graphene oxide (GO) is dissolved in preparation spinning precursor liquid in DMF, is prepared using electrostatic spinning process continuous
Nano fibrous membrane carries out carbonization treatment to electrostatic spinning PAN/GO fiber and prepares situ Nitrogen Doping carbon fiber/reduction-oxidation graphite
Alkene composite material finally carries out mixing sulphur technique preparing nitrogen-doped carbon fiber/redox graphene/sulphur composite positive pole, this
Kind has the composite material of excellent electric conductivity and the adsorption capacity to polysulfide, can not only make up the electric conductivity of elemental sulfur
The disadvantage of difference simultaneously can play sulfur fixation, improve the shuttle effect of polysulfide during the reaction, which improves anodes
The utilization rate of active material, to improve the chemical property of lithium-sulfur cell.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of lithium sulfur battery anode material, this method comprises the following steps:
Step 1 prepares graphene oxide, is then configured to the graphene oxide solution of 1~4mg/ml；
Step 2: in-situ polymerization acrylonitrile/graphene oxide composite material
Deionized water, acrylonitrile and GO solution are sequentially added in beaker and stirred, the concentrated sulfuric acid, thiosulfuric acid are then instilled
Sodium solution and potassium persulfate solution continue to stir, and are filtered by vacuum, are obtained after 0.5~1.5h of reaction at 50~100 DEG C
To solid be washed with deionized after it is dry, obtain PAN/GO composite material；
Wherein, volume ratio is deionized water: acrylonitrile and: GO solution: the concentrated sulfuric acid: hypo solution: potassium peroxydisulfate
Solution=50~150:5~20:1~50:0.5~2:1~5:5~25；The concentration of GO solution is 2mg/ml, and sodium thiosulfate is molten
The mass fraction of liquid is 1~10%, and the mass fraction of potassium persulfate solution is 1~2%；
Step 3: electrostatic spinning prepares polyacrylonitrile/graphene oxide fiber
By in spinning solution inhalation syringe, electrostatic spinning: the distance between needle point and receiving barrel is carried out using following parameter
For 25cm, apply voltage 18KV, injects pump rate 0.3mL/h, collector revolving speed 500rpm；Obtain polyacrylonitrile/graphite oxide
Alkene fiber；
Wherein, the group of the spinning solution becomes DMF and PAN/GO composite material, mass ratio PAN/GO:DMF=1:1
~10；
Step 4: polyacrylonitrile/graphene oxide fiber heat treatment in advance
Polyacrylonitrile/graphene oxide fiber that upper step obtains is placed in Muffle furnace, is warming up at 200~300 DEG C
Stablize 1~10h, the polyacrylonitrile aoxidized/graphene oxide fiber；
Step 5: high-temperature heat treatment prepares situ Nitrogen Doping carbon fiber/redox graphene composite material
Polyacrylonitrile/graphene oxide fiber is warming up to 500~1200 DEG C in a nitrogen atmosphere, 1~5h of soaking time；
Product is immersed in NaOH solution 1~5 hour, then product is washed with distilled water, then in 50~120 DEG C of dry 1~12h；
Obtain situ Nitrogen Doping carbon fiber/redox graphene composite material；
Step 6: situ Nitrogen Doping carbon fiber/redox graphene material mixes sulphur
After situ Nitrogen Doping carbon fiber/redox graphene and nano-sulfur are mixed, it is ground in the agate mortar not
Yellow is shown again, is then dried 1~20min in a vacuum drying oven, is placed into reaction kettle, argon atmosphere, closed reactor,
1~12h is heated at 100~160 DEG C, obtains situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material；
Wherein, quality is than situ Nitrogen Doping carbon fiber/redox graphene: nano-sulfur=3:1；The two milling time every
Carbon disulfide is added dropwise, the gross mass of the carbon disulfide of dropwise addition is the 10~55% of nano-sulfur quality；
Step 7: situ Nitrogen Doping carbon fiber/redox graphene/sulphur combination electrode material preparation
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode, conductive agent and bonding that step 6 is obtained
Agent Kynoar (PVDF) mixing, instills NMP, is made into slurry, and apply on a current collector, dries, rolls, cuts out, obtain
Lithium sulfur battery anode material；
Wherein, material proportion is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material: conductive agent: bonding
Agent=7~8.5:0.5~2:1；The gross mass of the NMP of dropwise addition is the 10~50% of above-mentioned material gross mass.(material is
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material, conductive agent and binder)
The conductive agent is acetylene black or Super P；The coating thickness of collector spreading mass is 0.01~0.1mm；Institute
The collector stated is aluminium foil, carbon containing aluminium foil, nickel foam or carbon cloth.
The heating rate in the step four and step 5 is 1~10 DEG C/min.
The concentration of NaOH solution in the step five is 0.5~2mol/L.
Substantive distinguishing features of the invention are as follows:
The present invention synthesizes PAN/GO composite material by AN monomers in situ, and PAN and GO are not mechanical mixing, utilizes PAN
Original N element forms original position N doping carbon fiber in the carbonized in fiber, it not only has excellent electric conductivity but also experiment card
Bright N doping can effectively inhibit and adsorb polysulfide, and GO has high specific surface area and powerful conductive network, warp
It crosses high-temperature heat treatment reduction and generates rGO, the defect existing for reduction site can equally adsorb polysulfide, sharp in this way
The chemical property of battery can be greatly improved with the synergistic effect of the two.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
The present invention prepares composite material by in-situ polymerization acrylonitrile/graphene oxide, prepares poly- third using electrostatic spinning
Alkene nitrile/graphene oxide fiber, carbonization treatment form situ Nitrogen Doping carbon fiber/redox graphene composite material, finally
It carries out mixing sulphur technique.This carbon sulfur materials have situ Nitrogen Doping, excellent electric conductivity and the absorption property to polysulfide, and
And have the characteristics that at low cost and reproducible.Applied to positive electrode is used as in lithium-sulfur cell, can have in charge and discharge process
Effect is fixed and adsorbs the shuttle of polysulfide, improves the utilization rate of positive active material, helps to reduce electrode electro Chemical mistake
Polarization phenomena in journey are avoided to a certain extent to which the volume expansion problem of electrode material be effectively relieved due to electrode material
The volume expansion problem of material and to brought by electrode material negatively affect so that reaction invertibity be improved, improve electricity
The cycle performance of pole, and then enhance the chemical property of lithium-sulfur cell.Electrochemical data in 1 in conjunction with the embodiments, battery is in 0.1C
Initial discharge capacity reaches 1230mAh/g under multiplying power；It is shown under the current density of 0.1C, 0.2C, 0.5C and 1C excellent
High rate performance, wherein being able to maintain the specific discharge capacity close to 800mAh/g under the high current density of 1C；It is worth noting that
The specific discharge capacity that 1260mAh/g is still maintained after recycling 300 times under the multiplying power of 0.1C, due to the activation of electrode, preceding
Specific discharge capacity gradually increases in 200 circulations, and highest specific discharge capacity reaches 1550mAh/g (close to theoretical specific capacity
1672mAh/g)。
Detailed description of the invention
Fig. 1 is situ Nitrogen Doping carbon fiber/redox graphene composite material micropore diameter obtained by embodiment 1 point
Butut；
Fig. 2 is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material X-ray obtained by embodiment 1
XPS Analysis (XPS) figure；Wherein, Fig. 2 a is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material
High-resolution XPS spectrum；Fig. 2 b is high-resolution C 1s；Fig. 2 c is high-resolution S 2p；Fig. 2 d is high-resolution N 1s；
Fig. 3 is situ Nitrogen Doping carbon fiber/redox graphene composite material infrared spectroscopy obtained by embodiment 1
(FTIR) figure；
Fig. 4 is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material obtained by embodiment 1 in 0.1C
Under constant current impulse electricity figure.
Fig. 5 be embodiment 1 obtained by situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material 0.1C,
Charging and discharging curve figure under 0.2C, 0.5C and 1C multiplying power；
Fig. 6 is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material obtained by embodiment 1 in 0.1C
Long circulating figure under multiplying power.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1:
Step 1 improves Hummers method and prepares graphene oxide:
By 1g graphite, the H that 27ml mass fraction is 95%2SO4, 3ml concentration be 0.1M H3PO4It is placed in three-necked flask,
And 6g potassium permanganate is added by several times, 1h is stirred in ice-water bath, temperature rises to 50 DEG C, insulation reaction 12h.Products therefrom is poured into
In ice water, it is 30% hydrogen peroxide that mass fraction is added while stirring, until solution colour becomes golden yellow, then filters, is used in combination
Product is washed till pH value close to 7 for 5%HCL and distilled water by volume fraction.Gained graphite oxide is dispersed in water, ultrasonic 8h,
The graphene oxide solution for being finally configured to 2mg/ml is spare；
Step 2: in-situ polymerization acrylonitrile/graphene oxide composite material
PAN/GO composite material is prepared by in-situ polymerization.Firstly, 125ml deionization is added into three-necked flask respectively
Water, 12.5ml acrylonitrile and concentration are the GO solution 50ml of 2mg/ml, and stir, and then instilling 1ml mass fraction is 95%
The concentrated sulfuric acid, mass fraction are 2% potassium persulfate solution 25ml of 10% hypo solution 5ml and mass fraction, continue to stir,
And so that temperature is maintained 60 DEG C with oil bath heating, be filtered by vacuum after reacting 1h and be washed with deionized for several times, finally will
Product is placed in drying in surface plate, finally obtains PAN/GO composite material,
Step 3: electrostatic spinning prepares polyacrylonitrile/graphene oxide fiber
Using DMF as the solvent of PAN/GO composite material, spinning forerunner is prepared for PAN/GO:DMF=1:4 in mass ratio
Liquid.By in above-mentioned spinning solution inhalation syringe, electrostatic spinning is carried out using following parameter: adjust between needle point and receiving barrel away from
From to distance 25cm is set, applies voltage 18KV, inject pump rate 0.3mL/h, collector revolving speed 500rpm obtains PAN/
GO electrospinning fibre.
Step 4: polyacrylonitrile/graphene oxide fiber heat treatment in advance
Polyacrylonitrile/graphene oxide fibrous material is placed in Muffle furnace at 260 DEG C and stablizes 4h, the rate of heat addition is 1
DEG C/min, the polyacrylonitrile aoxidized/graphene oxide fibrous material.
Step 5: high-temperature heat treatment prepares situ Nitrogen Doping carbon fiber/redox graphene composite material
Carbonization treatment is carried out to polyacrylonitrile/graphene oxide fiber in a nitrogen atmosphere, the rate of heat addition: 5 DEG C/min, instead
Answer temperature: 950 DEG C, soaking time 1h, so that electrospun fibers are carbonized.Carbon fiber samples are immersed to the NaOH solution of 1mol/L
In 5 hours, for obtaining micropore, last gained sample is washed with distilled water water and removes remaining potassium, and in 60 DEG C of dry 12h,
Obtain situ Nitrogen Doping carbon fiber/redox graphene composite material.
Step 6: situ Nitrogen Doping carbon fiber/redox graphene material mixes sulphur
Situ Nitrogen Doping carbon fiber/redox graphene composite material 3g and nano-sulfur 1g is weighed, agate is mixed in and grinds
It is ground in alms bowl, instills 0.2ml drop carbon disulfide (CS by several times2) for dissolving sulphur, 5min is ground every time, then instills CS2It repeats above-mentioned
If step grinds 6 times until without obvious Sulfur color, 20min is then dried in a vacuum drying oven, dried sample is put
Enter reaction kettle and shaking the oxygen removed in reaction kettle for several times full of argon gas glove box, reaction kettle is finally placed in electric heating constant temperature
155 DEG C of heating 12h prepare situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode in drying box.
Step 7: situ Nitrogen Doping carbon fiber/redox graphene/sulphur combination electrode material preparation
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode, conductive agent and bonding that step 6 is obtained
Agent Kynoar (PVDF) mixing, instilling NMP, (gross mass of the NMP of dropwise addition is the 10% of above-mentioned material gross mass.Described
Material refers to situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material, conductive agent and binder-following embodiment
Together), it is made into slurry, and coated on carbon containing aluminium foil, dries and rolls (pressure 5Mpa), cuts out, obtain lithium sulfur battery anode material；
Wherein, material proportion is quality than situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material: Super
P:PVDF=8:1:1 is 0.1mm in the coating thickness of carbon containing aluminum foil current collector spreading mass.
By positive plate obtained in step 7 and lithium cathode sheet, assembly obtains lithium-sulfur cell in the glove box full of argon gas.
C2025 button cell is assembled (to fill according to anode cover-positive plate-diaphragm-negative electrode tab-gasket-spring leaf-negative electrode casing sequence
With obtaining lithium-sulfur cell).
Wherein, Fig. 1 and micro- for the carbon fiber of situ Nitrogen Doping made from embodiment 1/redox graphene composite material
Graph of pore diameter distribution.The aperture of material concentrates on 1-1.2nm as seen from the figure, and aperture is both less than 2nm and belongs to poromerics, has in this way
Conducive to the load sulfur content for improving material.Fig. 2 is that situ Nitrogen Doping carbon fiber/redox graphene/sulphur obtained by embodiment 1 is multiple
X-ray photoelectron spectroscopic analysis (XPS) figure of condensation material.Find out from high-resolution C 1s, N 1s figure there are C-N/C-S key,
Pyridinic-N, pyrrolic-N and graphitic-N key illustrate that there are nitrogen-doped carbons in composite material.From the infrared of Fig. 3
Find out, due to the stretching vibration of C-N key, occur a 1620cm in spectrogram in spectrum-1New bands of a spectrum, this is also indicated that
Nitrogen-doped carbon is formed in carbonisation.Fig. 4 and Fig. 5 is respectively specific capacity voltage of the material obtained by embodiment 1 at 0.1C
Figure and the circulation figure under each current density.As can be seen from the figure this situ Nitrogen Doping carbon fiber/oxygen reduction fossil
There are two platforms near 2.3V and 2.0V for black alkene/sulphur, this is two reduction peaks common in lithium-sulfur cell, under 0.1C multiplying power
Initial discharge capacity reaches 1230mAh/g, and excellent times is equally shown under the current density of 0.1C, 0.2C, 0.5C and 1C
Rate performance.This is because nitrogen carbon fiber/redox graphene structure in situ can not only be provided for the electrolyte of liquid it is porous
Ion channel, also can be in charge and discharge process, by aperture come the intermediate product polysulfide during sorption cycle, thus whole
The performance of body raising battery.As shown in fig. 6, still maintaining the electric discharge of 1260mAh/g after recycling 300 times under the multiplying power of 0.1C
Specific capacity.
Embodiment 2:
Step 1 improves Hummers method and prepares graphene oxide:
By 1g graphite, the H that 27ml mass fraction is 95%2SO4, 3ml concentration be 0.1M H3PO4It is placed in three-necked flask,
And 6g potassium permanganate is added by several times, 1h is stirred in ice-water bath, temperature rises to 50 DEG C, insulation reaction 12h.Products therefrom is poured into
In ice water, it is 30% hydrogen peroxide that mass fraction is added while stirring, until solution colour becomes golden yellow, then filters, is used in combination
Product is washed till pH value close to 7 for 5%HCL and distilled water by volume fraction.Gained graphite oxide is dispersed in water, ultrasonic 8h,
The graphene oxide solution for being finally configured to 2mg/ml is spare；
Step 2: in-situ polymerization acrylonitrile/graphene oxide composite material
PAN/GO composite material is prepared by in-situ polymerization.Firstly, 125ml deionization is added into three-necked flask respectively
Water, 12.5ml acrylonitrile and concentration are the GO solution 50ml of 2mg/ml, and stir, and then instilling 1ml mass fraction is 95%
The concentrated sulfuric acid, mass fraction are 2% potassium persulfate solution 25ml of 10% hypo solution 5ml and mass fraction, continue to stir,
And so that temperature is maintained 60 DEG C with oil bath heating, be filtered by vacuum after reacting 1h and be washed with deionized for several times, finally will
Product is placed in drying in surface plate, finally obtains PAN/GO composite material,
Step 3: electrostatic spinning prepares polyacrylonitrile/graphene oxide fiber
Using DMF as the solvent of PAN/GO composite material, spinning forerunner is prepared for PAN/GO:DMF=1:5 in mass ratio
Liquid.By in above-mentioned spinning solution inhalation syringe, electrostatic spinning is carried out using following parameter: adjust between needle point and receiving barrel away from
From to distance 25cm is set, applies voltage 18KV, inject pump rate 0.3mL/h, collector revolving speed 500rpm obtains PAN/
GO electrospinning fibre.
Step 4: polyacrylonitrile/graphene oxide fiber heat treatment in advance
Polyacrylonitrile/graphene oxide fibrous material is placed in Muffle furnace at 280 DEG C and stablizes 4h, the rate of heat addition is 1
DEG C/min, the polyacrylonitrile aoxidized/graphene oxide fibrous material.
Step 5: high-temperature heat treatment prepares situ Nitrogen Doping carbon fiber/redox graphene composite material
Carbonization treatment is carried out to polyacrylonitrile/graphene oxide fiber in a nitrogen atmosphere, the rate of heat addition: 5 DEG C/min, instead
Answer temperature: 950 DEG C, soaking time 1h, so that electrospun fibers are carbonized.Carbon fiber samples are immersed to the NaOH solution of 1mol/L
In 5 hours, for obtaining micropore, last gained sample is washed with distilled water water and removes remaining potassium, and in 60 DEG C of dry 12h,
Obtain situ Nitrogen Doping carbon fiber/redox graphene composite material.
Step 6: situ Nitrogen Doping carbon fiber/redox graphene material mixes sulphur
Situ Nitrogen Doping carbon fiber/redox graphene composite material 3g and nano-sulfur 1g is weighed, agate is mixed in and grinds
It is ground in alms bowl, instills 0.2ml drop carbon disulfide (CS by several times2) for dissolving sulphur, 5min is ground every time, then instills CS2It repeats above-mentioned
Step grinding until without obvious Sulfur color, then dries 20min in a vacuum drying oven, dried sample is put several times
Enter reaction kettle and shaking the oxygen removed in reaction kettle for several times full of argon gas glove box, reaction kettle is finally placed in electric heating constant temperature
155 DEG C of heating 12h prepare situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode in drying box.
Step 7: situ Nitrogen Doping carbon fiber/redox graphene/sulphur combination electrode material preparation
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode, conductive agent and bonding that step 6 is obtained
Agent Kynoar (PVDF) mixing, instills NMP, is made into slurry, and coated on carbon containing aluminium foil, dries and roll (pressure
5Mpa), it cuts out, obtains lithium sulfur battery anode material；
Wherein material proportion is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material: Super P:PVDF
=7:2:1 is 0.1mm in the coating thickness of carbon containing aluminum foil current collector spreading mass.
The lithium-sulfur cell that the present embodiment is prepared is by the test of charge-discharge performance, under the multiplying power of 0.1C for the first time
Up to 1097mAh/g, and after 300 circulations, specific discharge capacity can still keep 1002mAh/g to specific discharge capacity.
Embodiment 3:
Step 1 improves Hummers method and prepares graphene oxide:
By 1g graphite, the H that 27ml mass fraction is 95%2SO4, 3ml concentration be 0.1M H3PO4It is placed in three-necked flask,
And 6g potassium permanganate is added by several times, 1h is stirred in ice-water bath, temperature rises to 50 DEG C, insulation reaction 12h.Products therefrom is poured into
In ice water, it is 30% hydrogen peroxide that mass fraction is added while stirring, until solution colour becomes golden yellow, then filters, is used in combination
Product is washed till pH value close to 7 for 5%HCL and distilled water by volume fraction.Gained graphite oxide is dispersed in water, ultrasonic 8h,
The graphene oxide solution for being finally configured to 2mg/ml is spare；
Step 2: in-situ polymerization acrylonitrile/graphene oxide composite material
PAN/GO composite material is prepared by in-situ polymerization.Firstly, 125ml deionization is added into three-necked flask respectively
Water, 12.5ml acrylonitrile and concentration are the GO solution 50ml of 2mg/ml, and stir, and then instilling 1ml mass fraction is 95%
The concentrated sulfuric acid, mass fraction are 2% potassium persulfate solution 25ml of 10% hypo solution 5ml and mass fraction, continue to stir,
And so that temperature is maintained 60 DEG C with oil bath heating, be filtered by vacuum after reacting 1h and be washed with deionized for several times, finally will
Product is placed in drying in surface plate, finally obtains PAN/GO composite material,
Step 3: electrostatic spinning prepares polyacrylonitrile/graphene oxide fiber
Using DMF as the solvent of PAN/GO composite material, spinning forerunner is prepared for PAN/GO:DMF=1:6 in mass ratio
Liquid.By in above-mentioned spinning solution inhalation syringe, electrostatic spinning is carried out using following parameter: adjust between needle point and receiving barrel away from
From to distance 25cm is set, applies voltage 18KV, inject pump rate 0.3mL/h, collector revolving speed 500rpm obtains PAN/
GO electrospinning fibre.
Step 4: polyacrylonitrile/graphene oxide fiber heat treatment in advance
Polyacrylonitrile/graphene oxide fibrous material is placed in Muffle furnace at 260 DEG C and stablizes 4h, the rate of heat addition is 1
DEG C/min, the polyacrylonitrile aoxidized/graphene oxide fibrous material.
Step 5: high-temperature heat treatment prepares situ Nitrogen Doping carbon fiber/redox graphene composite material
Carbonization treatment is carried out to polyacrylonitrile/graphene oxide fiber in a nitrogen atmosphere, the rate of heat addition: 5 DEG C/min, instead
Answer temperature: 1050 DEG C, soaking time 1h, so that electrospun fibers are carbonized.The NaOH that carbon fiber samples are immersed 1mol/L is molten
5 hours in liquid, for obtaining micropore, last gained sample is washed with distilled water water and removes remaining potassium, and in 60 DEG C of dryings
12h obtains situ Nitrogen Doping carbon fiber/redox graphene composite material.
Step 6: situ Nitrogen Doping carbon fiber/redox graphene material mixes sulphur
Situ Nitrogen Doping carbon fiber/redox graphene composite material 3g and nano-sulfur 1g is weighed, agate is mixed in and grinds
It is ground in alms bowl, instills 0.2ml drop carbon disulfide (CS by several times2) for dissolving sulphur, 5min is ground every time, then instills CS2It repeats above-mentioned
Step grinding until without obvious Sulfur color, then dries 20min in a vacuum drying oven, dried sample is put several times
Enter reaction kettle and shaking the oxygen removed in reaction kettle for several times full of argon gas glove box, reaction kettle is finally placed in electric heating constant temperature
155 DEG C of heating 12h prepare situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode in drying box.
Step 7: situ Nitrogen Doping carbon fiber/redox graphene/sulphur combination electrode material preparation
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode, conductive agent and bonding that step 6 is obtained
Agent Kynoar (PVDF) mixing, instills NMP, is made into slurry, and coated on carbon containing aluminium foil, dries and roll (pressure
5Mpa), it cuts out, obtains lithium sulfur battery anode material；
Wherein material proportion is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material: Super P:PVDF
=8:1:1 is 0.1mm in the coating thickness of carbon containing aluminum foil current collector spreading mass.
The lithium-sulfur cell that the present embodiment is prepared is by the test of charge-discharge performance, under the multiplying power of 0.1C for the first time
Up to 1265mAh/g, and after 300 circulations, specific discharge capacity can still keep 1237mAh/g to specific discharge capacity.
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of preparation method of lithium sulfur battery anode material, it is characterized in that this method comprises the following steps:
Step 1 prepares graphene oxide, is then configured to the graphene oxide solution of 1~4mg/ml；
Step 2: in-situ polymerization acrylonitrile/graphene oxide composite material
Deionized water, acrylonitrile and GO solution are sequentially added in beaker and stirred, it is molten then to instill the concentrated sulfuric acid, sodium thiosulfate
Liquid and potassium persulfate solution continue to stir, and are filtered by vacuum, are obtained after 0.5~1.5h of reaction at 50~100 DEG C
Solid is dry after being washed with deionized, and obtains PAN/GO composite material；
Wherein, volume ratio is deionized water: acrylonitrile and: GO solution: the concentrated sulfuric acid: hypo solution: potassium persulfate solution
=50~150:5~20:1~50:0.5~2:1~5:5~25；The concentration of GO solution is 2mg/ml, hypo solution
Mass fraction is 1~10%, and the mass fraction of potassium persulfate solution is 1~2%；
Step 3: electrostatic spinning prepares polyacrylonitrile/graphene oxide fiber
Following parameter in spinning solution inhalation syringe, will be used to carry out electrostatic spinning: the distance between needle point and receiving barrel for
25cm applies voltage 18KV, injects pump rate 0.3mL/h, collector revolving speed 500rpm；Obtain polyacrylonitrile/graphene oxide
Fiber；
Wherein, the group of the spinning solution becomes DMF and PAN/GO composite material, and mass ratio is PAN/GO:DMF=1:1~10；
Step 4: polyacrylonitrile/graphene oxide fiber heat treatment in advance
Polyacrylonitrile/graphene oxide fiber that upper step obtains is placed in Muffle furnace, is warming up to and stablizes 1 at 200~300 DEG C
~10h, the polyacrylonitrile aoxidized/graphene oxide fiber；
Step 5: high-temperature heat treatment prepares situ Nitrogen Doping carbon fiber/redox graphene composite material
Polyacrylonitrile/graphene oxide fiber is warming up to 500~1200 DEG C in a nitrogen atmosphere, 1~5h of soaking time；It will produce
Object immerses in NaOH solution 1~5 hour, then product is washed with distilled water, then in 50~120 DEG C of dry 1~12h；It obtains
Situ Nitrogen Doping carbon fiber/redox graphene composite material；
Step 6: situ Nitrogen Doping carbon fiber/redox graphene material mixes sulphur
After situ Nitrogen Doping carbon fiber/redox graphene and nano-sulfur are mixed, it is ground in the agate mortar no longer aobvious
Show yellow, then dries 1~20min in a vacuum drying oven, place into reaction kettle, argon atmosphere, closed reactor, 100
1~12h is heated at~160 DEG C, obtains situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material；
Wherein, quality is than situ Nitrogen Doping carbon fiber/redox graphene: nano-sulfur=3:1；The two milling time is every dropwise addition
Carbon disulfide, the gross mass of the carbon disulfide of dropwise addition are the 10~55% of nano-sulfur quality；
Step 7: situ Nitrogen Doping carbon fiber/redox graphene/sulphur combination electrode material preparation
Situ Nitrogen Doping carbon fiber/redox graphene/sulphur positive electrode, conductive agent and binder that step 6 obtains is gathered
Vinylidene (PVDF) mixing, instills NMP, is made into slurry, and apply on a current collector, dries, rolls, cuts out, obtain lithium sulphur
Cell positive material；
Wherein, material proportion is situ Nitrogen Doping carbon fiber/redox graphene/sulphur composite material: conductive agent: binder=
7~8.5:0.5~2:1.
2. the preparation method of lithium sulfur battery anode material as described in claim 1, it is characterized in that the conductive agent is acetylene
Black or Super P；The coating thickness of collector spreading mass is 0.01~0.1mm；The collector be aluminium foil, carbon containing aluminium foil,
Nickel foam or carbon cloth.
3. the preparation method of lithium sulfur battery anode material as described in claim 1, it is characterized in that the step four and step
The heating rate in five is 1~10 DEG C/min.
4. the preparation method of lithium sulfur battery anode material as described in claim 1, it is characterized in that in the step five
The concentration of NaOH solution is 0.5~2mol/L.
5. the preparation method of lithium sulfur battery anode material as described in claim 1, it is characterized in that the drop in the step seven
The gross mass of the NMP added is the 10~50% of above-mentioned quality of material.
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