CN104362316A - Lithium-sulfur battery composite cathode material, and preparation method and application thereof - Google Patents
Lithium-sulfur battery composite cathode material, and preparation method and application thereof Download PDFInfo
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- CN104362316A CN104362316A CN201410589010.3A CN201410589010A CN104362316A CN 104362316 A CN104362316 A CN 104362316A CN 201410589010 A CN201410589010 A CN 201410589010A CN 104362316 A CN104362316 A CN 104362316A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention belongs to the field of electrochemistry and discloses multiwalled carbon nanotube/sulphur/polyaniline composite cathode material, a preparation method thereof, and the application thereof to the preparation of lithium sulphur batterypositive plates. The material adopts multiwalled carbon nanotube/sulphur/polyaniline composite cathode material and a sandwich structure; multiwalled carbon nanotube/sulphur composite material is coated with conductive polyaniline through in-situ polymerization, so that the multiwalled carbon nanotube/sulphur/polyaniline composite cathode material is formed; the multiwalled carbon nanotube/sulphur composite material is prepared through chemical co-deposition. The method is simple in technology, low in cost and high in consistency and stability of products. The material is high in electronic and ionic conductivity and high in sulphur carrying capacity, and can be applied to the preparation of lithium battery composite positive plates; the positive plate is high in cycling stability and capacity retention ratio.
Description
Technical field
The invention belongs to electrochemical field, relate to a kind of lithium-sulfur battery composite anode material, be specifically related to a kind of multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole and preparation method thereof, preparing the application in lithium-sulphur cell positive electrode sheet with it.
Background technology
Along with extensively popularizing of portable type electronic product, the fast development of energy storage technology and electric automobile, (take transition metal oxide as positive pole to the traditional lithium ion battery risen at present, graphite is negative pole, and lithium hexafluoro phosphate and traditional carbonic ester are electrolyte) energy density and power density propose more and more higher requirement.Be 1672mAh/g because elemental sulfur has high theoretical specific capacity, battery is assembled into lithium metal, Theoretical Mass specific energy can reach 2600Wh/kg, meets the requirement of portable type electronic product to battery " light, thin, little ", also meets energy-accumulating power station and electric automobile to the requirement of battery; And sulphur has the advantages such as wide material sources, cost is low, nonhazardous is pollution-free.But sulphur and reduzate lithium sulfide thereof have the shortcomings such as electronic conductivity is low, the dissolving of intermediate product polysulfide.Therefore, researcher develops various sulfenyl composite material and solves above problem, mainly from raising composite material electronics and ionic conductivity, the dissolving of restriction intermediate product polysulfide and diffusion, optimize the aspects such as the structural design of composite material to improve, thus effectively improve capability retention and the cyclical stability of composite material.
The product of the lithium-sulfur battery composite anode material of current report and preparation method, come with some shortcomings, and year sulfur content as composite material is low, electron conduction difference cause cyclical stability and capability retention low, and existing technique is comparatively complicated, process costs is high, and finished product stability is poor.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of lithium-sulfur battery composite anode material, described lithium-sulfur battery composite anode material is multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole, and preparation method is simple, stable;
Another object of the present invention is to provide a kind of above-mentioned preparation method to obtain lithium-sulfur battery composite anode material;
Another object of the present invention is to provide above-mentioned lithium-sulfur battery composite anode material preparing the application in positive plate of lithium battery.
Object of the present invention is achieved through the following technical solutions:
A preparation method for lithium-sulfur battery composite anode material, comprises the steps:
(1) ammonium persulfate is fully dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution;
(2) multi-walled carbon nano-tubes/sulphur composite material is joined ultrasonic disperse in watery hydrochloric acid, then aniline and ascorbic acid is added successively, vigorous stirring in ice bath, drips the described ammonium persulfate-dilute hydrochloric acid solution of step (1) simultaneously and carries out polymerization reaction; Polymerization reaction terminates rear filtration, and with watery hydrochloric acid, absolute ethyl alcohol and deionized water successively cleaning and filtering, then vacuumize obtains product multi-walled carbon nano-tubes/sulphur/polyaniline composite material, is described lithium-sulfur battery composite anode material;
In the preparation method of above-mentioned lithium-sulfur battery composite anode material, preferably, the mol ratio of described ammonium persulfate and aniline is (0.75 ~ 1): 1;
Preferably, the mol ratio of described ammonium persulfate and ascorbic acid is (9 ~ 11): 1;
Preferably, in step (1), the amount of watery hydrochloric acid is the minimum that added ammonium persulfate is fully dissolved;
Preferably, the temperature of step (2) described ice bath is 5 ~ 15 DEG C;
Preferably, the time of step (2) described polymerization reaction is 6 ~ 8h;
Preferably, the concentration of step (1) and the watery hydrochloric acid described in step (2) is 2mol/L;
Preferably, the rate of addition of ammonium persulfate-dilute hydrochloric acid solution described in step (2) be 30 ~ 40 per minute;
Preferably, the mass ratio of step (2) described multi-walled carbon nano-tubes/sulphur composite material and described aniline is (2 ~ 6): 1;
Preferably, the described vacuum drying temperature of step (2) is 60 DEG C, and drying time is 24h;
Step (2) described multi-walled carbon nano-tubes/sulphur composite material can conventionally be prepared; Obtain the better lithium-sulfur battery composite anode material of performance for reaching, described multi-walled carbon nano-tubes/sulphur composite material can be prepared by the preferred method of the present invention, and the preparation method of described multi-walled carbon nano-tubes/sulphur composite material, comprises the steps:
A multi-walled carbon nano-tubes is added ultrasonic disperse in the mixed acid of red fuming nitric acid (RFNA) and the concentrated sulfuric acid by (), then add hot reflux in oil bath, filters, and by washed with de-ionized water to neutral, vacuumize, obtains purification of Multi-wall Carbon Nanotubes;
B described purification of Multi-wall Carbon Nanotubes is carried out ultrasonic disperse process by () in deionized water, then add five water sodium thiosulfate and surfactants, with vigorous stirring; Then react with dropping watery hydrochloric acid, reaction terminates rear filtration, cleans successively to neutrality, vacuumize, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material with acetone and deionized water;
The reaction of the generation in this step is: S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
C (), by preliminary for gained multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace, high-temperature heat treatment in inert atmosphere, obtains described multi-walled carbon nano-tubes/sulphur composite material;
In the preparation method of above-mentioned multi-walled carbon nano-tubes/sulphur composite material, preferably, the diameter of the described multi-walled carbon nano-tubes of step (a) is 10 ~ 20nm, and length is 5 ~ 15 μm;
Preferably, in the mixed acid of the described red fuming nitric acid (RFNA) of step (a) and the concentrated sulfuric acid, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3:1;
Preferably, the time of the described ultrasonic disperse of step (a) is 2 ~ 3h;
Preferably, the temperature adding hot reflux in the described oil bath of step (a) is 100 DEG C, and return time is 6 ~ 8h;
Preferably, the described vacuum drying temperature of step (a) is 100 DEG C;
Preferably, the mass ratio of the described five water sodium thiosulfate of step (b) and described purification of Multi-wall Carbon Nanotubes is (7 ~ 70): 1;
Preferably, the mol ratio of the described five water sodium thiosulfate of step (b) and the middle watery hydrochloric acid of step (b) is (0.4 ~ 0.45): 1, to guarantee that sulphur is precipitated out completely;
Preferably, the concentration of the described watery hydrochloric acid of step (b) is 2mol/L, rate of addition be 30 ~ 40 per minute; The described watery hydrochloric acid of step (b) dropwises rear sustained response 1 ~ 2h;
Preferably, the described surfactant of step (b) is softex kw solution, and the mass fraction of described softex kw solution is 5%, and addition is 5 ~ 10mL/100mL deionized water;
Preferably, the time of the described ultrasonic disperse process of step (b) is 8h;
Preferably, the described vacuum drying temperature of step (b) is temperature is 60 DEG C, and drying time is 24h;
Preferably, the described inert atmosphere of step (c) is argon gas (Ar), and flow velocity is 150 ~ 200cc/min;
Preferably, the described heat treated temperature of step (c) is 155 DEG C, and heat treatment time is 12h;
Mass ratio according to sulphur in multi-walled carbon nano-tubes/sulphur composite material that above-mentioned preparation method obtains and multi-walled carbon nano-tubes is 5:5 ~ 9:1.
Be multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole according to the lithium-sulfur battery composite anode material that the preparation method of above-mentioned lithium-sulfur battery composite anode material obtains, have " sandwich " nanostructure, in described lithium-sulfur battery composite anode material, the mass ratio of multi-walled carbon nano-tubes/sulphur composite material and polyaniline is 4:1 ~ 6:1.
Above-mentioned lithium-sulfur battery composite anode material can be used for preparing lithium-sulphur cell positive electrode sheet;
Adopt above-mentioned lithium-sulfur battery composite anode material to can be used for preparing the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of lithium battery, concrete preparation method comprises the steps:
(I) described lithium-sulfur battery composite anode material is mixed with conductive agent, stir, obtain mixture;
(II) 1-METHYLPYRROLIDONE (NMP) is added dropwise to binding agent, stirring and dissolving becomes thin pulp;
Wherein, the dripping quantity of described 1-METHYLPYRROLIDONE is the minimum of dissolving binding agent completely;
(III) mixture that step (I) obtains is added in step (II) gained thin pulp, stir into slurry, slurry is carried out ball milling, the viscosity of 1-METHYLPYRROLIDONE allotment slurry is added to meet the requirement of blade coating film forming during stirring, then the slurry blade coating completed by ball milling forms coating in current collector aluminum foil, and namely vacuumize obtain described multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet;
Preferably, step (I) described conductive agent is carbon black conductive agent, is specially the one in acetylene black, Super-P or Ketjen black;
Preferably, step (II) described binding agent is sodium carboxymethylcellulose (CMC) and the one in butadiene-styrene rubber (SBR) mixture, Kynoar (PVDF), polytetrafluoroethylene (PTFE) or polyethylene glycol oxide (PEO), and in wherein said sodium carboxymethylcellulose and butadiene-styrene rubber mixture, the mass ratio of sodium carboxymethylcellulose and butadiene-styrene rubber is 1:(1.5 ~ 2);
Preferably, the time of step (III) described ball milling is 5 ~ 6h, and ball milling speed is 300 ~ 500rpm;
Preferably, the thickness of step (III) described coating is 15 ~ 20 μm;
Preferably, the described vacuum drying temperature of step (III) is 60 DEG C, and drying time is 24h.
The present invention has following advantage and effect relative to prior art:
(1) lithium-sulfur battery composite anode material of the present invention is multi-walled carbon nano-tubes/sulphur/polyaniline composite material, by multi-walled carbon nano-tubes/sulphur composite material coated with conductive polyaniline, form multi-walled carbon nano-tubes/sulphur/polyaniline sandwich structure, play the electronics and ionic conductivity that both add composite material, turn improve dissolving and the diffusion of carrying sulfur content and limiting polysulfide simultaneously, effectively can improve cyclical stability and the capability retention of the combination electrode adopting lithium-sulfur battery composite anode material of the present invention to prepare.
(2) preparation method's technique of the present invention is simple, chemical precipitation method carries sulphur and situ aggregation method coated with conductive polyaniline can carry out successively in same container, greatly reduce process costs, simplify technological operation, improve the consistency of composite material, stability simultaneously.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric curve figure of sulphur, multi-walled carbon nano-tubes/sulphur composite material, multi-walled carbon nano-tubes/sulphur/polyaniline composite material.
Fig. 2 is that multi-walled carbon nano-tubes/sulphur anode composite sheet and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet are at 0.05C (1C=1672mA g
-1) first charge-discharge curve.
Fig. 3 is that multi-walled carbon nano-tubes/sulphur anode composite sheet and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet are at 0.2C (1C=1672mA g
-1) cyclical stability.
Fig. 4 is multi-walled carbon nano-tubes/sulphur anode composite sheet and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet (1C=1672mA g from 0.05C to 2C
-1) rate charge-discharge performance.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of multi-walled carbon nano-tubes/sulphur composite material, its preparation method is as follows:
(1) 4g raw material multi-walled carbon nano-tubes is added in the mixed acid (the volume ratio 3:1 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid) of 400mL red fuming nitric acid (RFNA) and the concentrated sulfuric acid and in the oil bath of 100 DEG C, add hot reflux 6h after ultrasonic 2h, filter, by washed with de-ionized water to neutral, 100 DEG C of vacuumizes, obtain purification of Multi-wall Carbon Nanotubes;
(2) take 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in 100mL deionized water for ultrasonic 8h, then add the softex kw solution that 3.87g five water sodium thiosulfate and 5mL concentration are 5wt%, with vigorous stirring; With the watery hydrochloric acid drop reaction 2h that 19mL concentration is 2mol/L, rate of titration controls to drip at 30-40 per minute, and filter after reacting completely, acetone, deionized water clean successively to neutrality, 60 DEG C of vacuumize 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material; The reaction occurred is S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
(3) by preparation preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace under high-purity argon atmosphere 155 DEG C of constant temperature 12h heat-treat, obtain described multi-walled carbon nano-tubes/sulphur composite material.
The sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 48%.
Embodiment 2
A kind of multi-walled carbon nano-tubes/sulphur composite material, its preparation method is as follows:
(1) 4g raw material multi-walled carbon nano-tubes is added in the mixed acid (the volume ratio 3:1 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid) of 400mL red fuming nitric acid (RFNA) and the concentrated sulfuric acid and in the oil bath of 100 DEG C, add hot reflux 6h after ultrasonic 2h, filter, by washed with de-ionized water to neutral, 100 DEG C of vacuumizes, obtain purification of Multi-wall Carbon Nanotubes;
(2) take 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in 100mL deionized water for ultrasonic 8h, then add the softex kw solution that 5.81g five water sodium thiosulfate and 6mL concentration are 5wt%, with vigorous stirring; With the watery hydrochloric acid drop reaction 2h that 28mL concentration is 2mol/L, rate of titration controls to drip at 30-40 per minute, and filter after reacting completely, acetone, deionized water clean successively to neutrality, 60 DEG C of vacuumize 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material; The reaction occurred is S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
(3) by preparation preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace under high-purity argon atmosphere 155 DEG C of constant temperature 12h heat-treat, obtain described multi-walled carbon nano-tubes/sulphur composite material.
The sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 57%.
Embodiment 3
A kind of multi-walled carbon nano-tubes/sulphur composite material, its preparation method is as follows:
(1) 4g raw material multi-walled carbon nano-tubes is added in the mixed acid (the volume ratio 3:1 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid) of 400mL red fuming nitric acid (RFNA) and the concentrated sulfuric acid and in the oil bath of 100 DEG C, add hot reflux 6h after ultrasonic 2h, filter, by washed with de-ionized water to neutral, 100 DEG C of vacuumizes, obtain purification of Multi-wall Carbon Nanotubes;
(2) take 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in 100mL deionized water for ultrasonic 8h, then add the softex kw solution that 9.03g five water sodium thiosulfate and 7mL concentration are 5wt%, with vigorous stirring; With the watery hydrochloric acid drop reaction 2h that 44mL concentration is 2mol/L, rate of titration controls to drip at 30-40 per minute, and filter after reacting completely, acetone, deionized water clean successively to neutrality, 60 DEG C of vacuumize 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material; The reaction occurred is S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
(3) by preparation preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace under high-purity argon atmosphere 155 DEG C of constant temperature 12h heat-treat, obtain described multi-walled carbon nano-tubes/sulphur composite material.
The sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 66%.
Embodiment 4
A kind of multi-walled carbon nano-tubes/sulphur composite material, its preparation method is as follows:
(1) 4g raw material multi-walled carbon nano-tubes is added in the mixed acid (the volume ratio 3:1 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid) of 400mL red fuming nitric acid (RFNA) and the concentrated sulfuric acid and in the oil bath of 100 DEG C, add hot reflux 6h after ultrasonic 2h, filter, by washed with de-ionized water to neutral, 100 DEG C of vacuumizes, obtain purification of Multi-wall Carbon Nanotubes;
(2) take 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in 100mL deionized water for ultrasonic 8h, then add the softex kw solution that 15.48g five water sodium thiosulfate and 8mL concentration are 5wt%, with vigorous stirring; With the watery hydrochloric acid drop reaction 2h that 75mL concentration is 2mol/L, rate of titration controls to drip at 30-40 per minute, and filter after reacting completely, acetone, deionized water clean successively to neutrality, 60 DEG C of vacuumize 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material; The reaction occurred is S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
(3) by preparation preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace under high-purity argon atmosphere 155 DEG C of constant temperature 12h heat-treat, obtain described multi-walled carbon nano-tubes/sulphur composite material.
The sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 83%.
Embodiment 5
A kind of multi-walled carbon nano-tubes/sulphur composite material, its preparation method is as follows:
(1) 4g raw material multi-walled carbon nano-tubes is added in the mixed acid (the volume ratio 3:1 of red fuming nitric acid (RFNA) and the concentrated sulfuric acid) of 400mL red fuming nitric acid (RFNA) and the concentrated sulfuric acid and in the oil bath of 100 DEG C, add hot reflux 6h after ultrasonic 2h, filter, by washed with de-ionized water to neutral, 100 DEG C of vacuumizes, obtain purification of Multi-wall Carbon Nanotubes;
(2) take 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in 100mL deionized water for ultrasonic 8h, then add the softex kw solution that 34.84g five water sodium thiosulfate and 8mL concentration are 5wt%, with vigorous stirring; With the watery hydrochloric acid drop reaction 2h that 168mL concentration is 2mol/L, rate of titration controls to drip at 30-40 per minute, and filter after reacting completely, acetone, deionized water clean successively to neutrality, 60 DEG C of vacuumize 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material; The reaction occurred is S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
(3) by preparation preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace under high-purity argon atmosphere 155 DEG C of constant temperature 12h heat-treat, obtain described multi-walled carbon nano-tubes/sulphur composite material.
The sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 87%.
Embodiment 6
A preparation method for lithium-sulfur battery composite anode material, comprises the steps:
(1) 1.838g ammonium persulfate is fully dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution;
(2) multi-walled carbon nano-tubes/sulphur composite material 2.0g of Example 4 gained joins 100mL concentration is ultrasonic disperse in the watery hydrochloric acid of 2mol/L, then 1.0g aniline and 0.412g ascorbic acid is added successively, vigorous stirring in 15 DEG C of ice baths, drip the described ammonium persulfate-dilute hydrochloric acid solution of step (1) simultaneously and carry out polymerization reaction, the rate of addition of ammonium persulfate-dilute hydrochloric acid solution be 30 ~ 40 per minute, polymerization reaction time is 8h; Polymerization reaction terminates rear filtration, with the watery hydrochloric acid of 2mol/L, absolute ethyl alcohol and deionized water successively cleaning and filtering to neutral, then obtain product multi-walled carbon nano-tubes/sulphur/polyaniline composite material in 60 DEG C of vacuumize 24h, be described lithium-sulfur battery composite anode material.
The sulfur content of gained lithium-sulfur battery composite anode material is 68%.
Get sulphur simple substance, embodiment 4 gained multi-walled carbon nano-tubes/sulphur composite material and the present embodiment products therefrom multi-walled carbon nano-tubes/sulphur/polyaniline composite material and carry out thermogravimetric analysis, gained thermogravimetric curve figure as shown in Figure 1.
As can be drawn from Figure 1, the sulfur content of gained multi-walled carbon nano-tubes/sulphur composite material is 83%, and products therefrom multi-walled carbon nano-tubes/sulphur/polyaniline composite material sulfur content is 68%.
Embodiment 7
A preparation method for lithium-sulfur battery composite anode material, comprises the steps:
(1) 2.755g ammonium persulfate is fully dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution;
(2) multi-walled carbon nano-tubes/sulphur composite material 2.0g of Example 5 gained joins 100mL concentration is ultrasonic disperse in the watery hydrochloric acid of 2mol/L, then 1.506g aniline and 0.216g ascorbic acid is added successively, vigorous stirring in 15 DEG C of ice baths, drip the described ammonium persulfate-dilute hydrochloric acid solution of step (1) simultaneously and carry out polymerization reaction, the rate of addition of ammonium persulfate-dilute hydrochloric acid solution be 30 ~ 40 per minute, polymerization reaction time is 8h; Polymerization reaction terminates rear filtration, with the watery hydrochloric acid of 2mol/L, absolute ethyl alcohol and deionized water successively cleaning and filtering to neutral, then obtain product multi-walled carbon nano-tubes/sulphur/polyaniline composite material in 60 DEG C of vacuumize 24h, be described lithium-sulfur battery composite anode material.
The sulfur content of gained lithium-sulfur battery composite anode material is 75%.
Embodiment 8
A kind of multi-walled carbon nano-tubes/sulphur anode composite sheet, its preparation method is as follows:
The multi-walled carbon nano-tubes of Example 4 gained/sulphur composite positive pole 0.5g, conductive agent acetylene black 0.0625g mixes, and stirs, obtains mixture; Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to 0.0625g binding agent Kynoar (PVDF), stirs and make Kynoar fully be dissolved into thin pulp; The mixture obtained is added in thin pulp, stir, size mixing, ball milling 5 ~ 6h, 1-METHYLPYRROLIDONE is repeatedly added to allocate the viscosity of slurry to meeting the requirement of blade coating film forming during stirring, then by the slurry blade coating after ball milling in current collector aluminum foil, coating layer thickness is 15 ~ 20 μm, namely obtains multi-walled carbon nano-tubes/sulphur anode composite sheet after 60 DEG C of vacuumize 24h.
Embodiment 9
A kind of multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet, its preparation method is as follows:
Lithium-sulfur battery composite anode material 0.5g, the conductive agent acetylene black 0.0625g of Example 6 gained mix, and stir, obtain mixture; Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to 0.0625g binding agent Kynoar (PVDF), stirs and make Kynoar fully be dissolved into thin pulp; The mixture obtained is added in thin pulp, stir, size mixing, ball milling 5 ~ 6h, 1-METHYLPYRROLIDONE is repeatedly added to allocate the viscosity of slurry to meeting the requirement of blade coating film forming during stirring, then by the slurry blade coating after ball milling in current collector aluminum foil, coating layer thickness is 15 ~ 20 μm, namely obtains multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet after 60 DEG C of vacuumize 24h.
Multi-walled carbon nano-tubes/sulphur/polyaniline anode composite the sheet of embodiment 8 gained multi-walled carbon nano-tubes/sulphur anode composite sheet and embodiment 9 gained is struck out respectively the disk of diameter 12mm, take metal lithium sheet as negative pole, the two trifluoromethanesulfonimide lithium LiTFSI (LiTFSI) of 1mol/L and 0.1mol/L lithium nitrate are dissolved in glycol dimethyl ether (DME) and 1, 3-dioxolane (DOL) volume ratio is be formulated as electrolyte in the mixed liquor of 1:1, take polypropylene screen as barrier film, CR2025 button cell is assembled into respectively in the glove box being full of argon gas, at room temperature test its chemical property, at 0.05C (1C=1672mA g
-1) first charge-discharge curve as shown in Figure 2, at 0.2C (1C=1672mA g
-1) cyclical stability test as shown in Figure 3, (1C=1672mA g from 0.05C to 2C
-1) rate charge-discharge ability as shown in Figure 4.
As can be drawn from Figure 2: the discharge capacity first of embodiment 8 gained multi-walled carbon nano-tubes/sulphur anode composite sheet is 855.3mAh/g, and coulombic efficiency is 86%; And the discharge capacity first of the multi-walled carbon nano-tubes/sulphur of embodiment 9 gained/polyaniline anode composite sheet is 896mAh/g, coulombic efficiency is up to 96%;
As can be drawn from Figure 3: the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of embodiment 9 gained circulates after 205 times at 0.2C, still maintains 545.5mAh/g, far above the 353.4mAh/g of embodiment 8 gained multi-walled carbon nano-tubes/sulphur anode composite sheet;
As can be drawn from Figure 4: the rate charge-discharge performance of the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of embodiment 9 gained is far above embodiment 8 gained multi-walled carbon nano-tubes/sulphur anode composite sheet, when 0.5C charge and discharge cycles, the average discharge capacity of the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of embodiment 9 gained is 473.7mAh/g, is greater than the 293.2mAh/g of embodiment 8 gained multi-walled carbon nano-tubes/sulphur anode composite sheet;
Embodiment 10
A kind of multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet, its preparation method is as follows:
Lithium-sulfur battery composite anode material 0.5g, the conductive agent acetylene black 0.0625g of Example 7 gained mix, and stir, obtain mixture; Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to 0.0625g binding agent Kynoar (PVDF), stirs and make Kynoar fully be dissolved into thin pulp; The mixture obtained is added in thin pulp, stir, size mixing, ball milling 5 ~ 6h, 1-METHYLPYRROLIDONE is repeatedly added to allocate the viscosity of slurry to meeting the requirement of blade coating film forming during stirring, then by the slurry blade coating after ball milling in current collector aluminum foil, coating layer thickness is 15 ~ 20 μm, namely obtains multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet after 60 DEG C of vacuumize 24h.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for lithium-sulfur battery composite anode material, is characterized in that comprising the steps:
(1) ammonium persulfate is fully dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution;
(2) multi-walled carbon nano-tubes/sulphur composite material is joined ultrasonic disperse in watery hydrochloric acid, then aniline and ascorbic acid is added successively, vigorous stirring in ice bath, drips the described ammonium persulfate-dilute hydrochloric acid solution of step (1) simultaneously and carries out polymerization reaction; Polymerization reaction terminates rear filtration, and with watery hydrochloric acid, absolute ethyl alcohol and deionized water successively cleaning and filtering, then vacuumize obtains product multi-walled carbon nano-tubes/sulphur/polyaniline composite material, is described lithium-sulfur battery composite anode material.
2. the preparation method of lithium-sulfur battery composite anode material according to claim 1, is characterized in that: the mol ratio of described ammonium persulfate and aniline is (0.75 ~ 1): 1; The mol ratio of described ammonium persulfate and ascorbic acid is (9 ~ 11): 1; The mass ratio of step (2) described multi-walled carbon nano-tubes/sulphur composite material and described aniline is (2 ~ 6): 1.
3. the preparation method of lithium-sulfur battery composite anode material according to claim 1, is characterized in that: the concentration of step (1) and the watery hydrochloric acid described in step (2) is 2mol/L; The rate of addition of ammonium persulfate-dilute hydrochloric acid solution described in step (2) be 30 ~ 40 per minute; The temperature of step (2) described ice bath is 5 ~ 15 DEG C; The time of step (2) described polymerization reaction is 6 ~ 8h; The described vacuum drying temperature of step (2) is 60 DEG C, and drying time is 24h.
4. the preparation method of lithium-sulfur battery composite anode material according to claim 1, is characterized in that: described multi-walled carbon nano-tubes/sulphur composite material is obtained by following preparation method, comprises the steps:
A multi-walled carbon nano-tubes is added ultrasonic disperse in the mixed acid of red fuming nitric acid (RFNA) and the concentrated sulfuric acid by (), then add hot reflux in oil bath, filters, and by washed with de-ionized water to neutral, vacuumize, obtains purification of Multi-wall Carbon Nanotubes;
B described purification of Multi-wall Carbon Nanotubes is carried out ultrasonic disperse process by () in deionized water, then add five water sodium thiosulfate and surfactants, with vigorous stirring; Then react with dropping watery hydrochloric acid, reaction terminates rear filtration, cleans successively to neutrality, vacuumize, obtain preliminary multi-walled carbon nano-tubes/sulphur composite material with acetone and deionized water;
The reaction of the generation in this step is: S
2o
3 2-+ 2H
+=S ↓+H
2o+SO
2;
C (), by preliminary for gained multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace, high-temperature heat treatment in inert atmosphere, obtains described multi-walled carbon nano-tubes/sulphur composite material.
5. the preparation method of lithium-sulfur battery composite anode material according to claim 4, is characterized in that: the diameter of the described multi-walled carbon nano-tubes of step (a) is 10 ~ 20nm, and length is 5 ~ 15 μm; In the mixed acid of the described red fuming nitric acid (RFNA) of step (a) and the concentrated sulfuric acid, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3:1; The time of the described ultrasonic disperse of step (a) is 2 ~ 3 hours; The temperature adding hot reflux in the described oil bath of step (a) is 100 DEG C, and return time is 6 ~ 8h; The described vacuum drying temperature of step (a) is 100 DEG C.
6. the preparation method of lithium-sulfur battery composite anode material according to claim 4, is characterized in that: the mass ratio of the described five water sodium thiosulfate of step (b) and described purification of Multi-wall Carbon Nanotubes is (7 ~ 70): 1; The mol ratio of the described five water sodium thiosulfate of step (b) and the middle watery hydrochloric acid of step (b) is (0.4 ~ 0.45): 1; The concentration of the described watery hydrochloric acid of step (b) is 2mol/L, rate of addition be 30 ~ 40 per minute; The described surfactant of step (b) is softex kw solution, and the mass fraction of described softex kw solution is 5%, and addition is 5 ~ 10mL/100mL deionized water; The time of the described ultrasonic disperse process of step (b) is 8h; The described vacuum drying temperature of step (b) is 60 DEG C, and drying time is 24h; The described inert atmosphere of step (c) is argon gas, and flow velocity is 150 ~ 200cc/min; The described heat treated temperature of step (c) is 155 DEG C, and heat treatment time is 12h.
7. the lithium-sulfur battery composite anode material that obtains of the preparation method of the lithium-sulfur battery composite anode material according to any one of claim 1 ~ 6, described lithium-sulfur battery composite anode material is multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole, and in described lithium-sulfur battery composite anode material, the mass ratio of multi-walled carbon nano-tubes/sulphur composite material and polyaniline is 4:1 ~ 6:1.
8. lithium-sulfur battery composite anode material according to claim 7 is preparing the application in lithium-sulphur cell positive electrode sheet.
9. application according to claim 8, is characterized in that: adopt above-mentioned lithium-sulfur battery composite anode material to prepare the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of lithium battery, concrete preparation method comprises the steps:
(I) described lithium-sulfur battery composite anode material is mixed with conductive agent, stir, obtain mixture;
(II) 1-METHYLPYRROLIDONE is added dropwise to binding agent, stirring and dissolving becomes thin pulp;
Wherein, the dripping quantity of described 1-METHYLPYRROLIDONE is the minimum of dissolving binding agent completely;
(III) mixture that step (I) obtains is added in step (II) gained thin pulp, stir into slurry, slurry is carried out ball milling, the viscosity of 1-METHYLPYRROLIDONE allotment slurry is added to meet the requirement of blade coating film forming during stirring, then the slurry blade coating completed by ball milling forms coating in current collector aluminum foil, and namely vacuumize obtain described multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet.
10. application according to claim 9, it is characterized in that: in the preparation method adopting above-mentioned lithium-sulfur battery composite anode material for the preparation of the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite sheet of lithium battery, step (I) described conductive agent is carbon black conductive agent; Step (II) described binding agent is the one in sodium carboxymethylcellulose and butadiene-styrene rubber mixture, Kynoar, polytetrafluoroethylene or polyethylene glycol oxide, and in wherein said sodium carboxymethylcellulose and butadiene-styrene rubber mixture, the mass ratio of sodium carboxymethylcellulose and butadiene-styrene rubber is 1:(1.5 ~ 2); The time of step (III) described ball milling is 5 ~ 6h, and ball milling speed is 300 ~ 500rpm; The thickness of step (III) described coating is 15 ~ 20 μm; The described vacuum drying temperature of step (III) is 60 DEG C, and drying time is 24h.
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| CN105609775A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation method for three-dimensional carbon nanotube/graphene/sulfur electrode slice |
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
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