CN104362316B - A kind of lithium-sulfur battery composite anode material and preparation method and application - Google Patents
A kind of lithium-sulfur battery composite anode material and preparation method and application Download PDFInfo
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- CN104362316B CN104362316B CN201410589010.3A CN201410589010A CN104362316B CN 104362316 B CN104362316 B CN 104362316B CN 201410589010 A CN201410589010 A CN 201410589010A CN 104362316 B CN104362316 B CN 104362316B
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Abstract
The invention belongs to electrochemical field, discloses a kind of multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole and preparation method thereof and its application in lithium-sulphur cell positive electrode piece is prepared.The lithium-sulfur battery composite anode material is multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole, with sandwich structure；The present invention adopts situ aggregation method coated with conductive polyaniline on multi-walled carbon nano-tubes/sulphur composite, forms multi-walled carbon nano-tubes/sulphur/polyaniline composite positive pole；The multi-walled carbon nano-tubes/sulphur composite is prepared using chemical codeposition method.The preparation method process is simple, low cost, product consistency, stability are high.Gained lithium-sulfur battery composite anode material electronics and ionic conductivity are strong, carry sulfur content height, can be used to prepare lithium battery anode composite piece；Gained lithium battery anode composite piece cyclical stability and capability retention are high.
Description
Technical field
The invention belongs to electrochemical field, is related to a kind of lithium-sulfur battery composite anode material, and in particular to a kind of many wall carbon
Nanotube/sulphur/polyaniline composite positive pole and preparation method thereof, with its application in lithium-sulphur cell positive electrode piece is prepared.
Background technology
With widely available, the fast development of energy storage technology and electric automobile, to currently of portable type electronic product
(with transition metal oxide as positive pole, graphite is negative pole, lithium hexafluoro phosphate and traditional carbon to the traditional lithium ion battery for rising
Acid esters is electrolyte) energy density and power density propose higher and higher requirement.As elemental sulfur has high theory
Specific capacity is 1672mAh/g, is assembled into battery with lithium metal, and Theoretical Mass specific energy meets portable electric up to 2600Wh/kg
Requirement of the sub- product to battery " light, thin, little ", also complies with the requirement of energy-accumulating power station and electric automobile to battery；And sulphur has
The advantages of wide material sources, low cost, pollution-free nonhazardous.However, sulphur and its reduzate lithium sulfide have electronic conductivity it is low,
The shortcomings of dissolving of intermediate product polysulfide.Therefore, researcher develop various sulfenyl composites solve with
Upper problem, mainly from composite electronics and ionic conductivity is improved, limits the dissolving and diffusion of intermediate product polysulfide, excellent
Change the aspects such as the structure design of composite to improve, so as to effectively increase the capability retention and stable circulation of composite
Property.
The product and preparation method of the lithium-sulfur battery composite anode material of report, comes with some shortcomings at present, such as composite wood
The load sulfur content of material is low, and electron conduction difference causes cyclical stability and capability retention low, and existing process is more complicated, technique
High cost, finished product stability are poor.
The content of the invention
In order to overcome the shortcoming of prior art and deficiency, the primary and foremost purpose of the present invention is to provide a kind of lithium-sulfur cell to be combined
The preparation method of positive electrode, the lithium-sulfur battery composite anode material are multi-walled carbon nano-tubes/sulphur/polyaniline anode composite material
Material, preparation method are simple, stable；
Another object of the present invention is to providing a kind of above-mentioned preparation method obtains lithium-sulfur battery composite anode material；
It is still another object of the present invention to provide above-mentioned lithium-sulfur battery composite anode material is in positive plate of lithium battery is prepared
Application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of lithium-sulfur battery composite anode material, comprises the steps：
(1) ammonium persulfate is completely dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution；
(2) multi-walled carbon nano-tubes/sulphur composite is added to into ultrasonic disperse in watery hydrochloric acid, then sequentially add aniline and
Ascorbic acid, is stirred vigorously in ice bath, while step (1) ammonium persulfate-dilute hydrochloric acid solution is added dropwise carries out polymerisation；
Polymerisation is filtered after terminating, and cleans filtration successively with watery hydrochloric acid, absolute ethyl alcohol and deionized water, and then vacuum drying is produced
Thing multi-walled carbon nano-tubes/sulphur/polyaniline composite material, as described lithium-sulfur battery composite anode material；
In the preparation method of above-mentioned lithium-sulfur battery composite anode material, it is preferred that the ammonium persulfate and aniline mole
Than for (0.75～1)：1；
Preferably, the ammonium persulfate and the mol ratio of ascorbic acid are (9～11)：1；
Preferably, in step (1), the amount of watery hydrochloric acid is the minimum for making added ammonium persulfate fully dissolve；
Preferably, the temperature of step (2) ice bath is 5～15 DEG C；
Preferably, the time of step (2) polymerisation 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) is that 30～40 drops are per minute；
Preferably, step (2) multi-walled carbon nano-tubes/sulphur composite and the mass ratio of the aniline are (2～6):
1；
Preferably, step (2) the vacuum drying temperature is 60 DEG C, and drying time is 24h；
Step (2) multi-walled carbon nano-tubes/sulphur composite can be prepared according to prior art；To reach obtaining property
The more preferable lithium-sulfur battery composite anode material of energy, the multi-walled carbon nano-tubes/sulphur composite can be by the preferred method of the present invention
It is prepared, the preparation method of the multi-walled carbon nano-tubes/sulphur composite comprises the steps：
A multi-walled carbon nano-tubes is added ultrasonic disperse in mixed acid of the red fuming nitric acid (RFNA) with the concentrated sulfuric acid by (), heat in oil bath
Backflow, filters, and deionized water is cleaned to neutrality, vacuum drying, obtains purification of Multi-wall Carbon Nanotubes；
B the purification of Multi-wall Carbon Nanotubes is carried out ultrasonic disperse process in deionized water by (), add five water thio
Sodium sulphate and surfactant, it is adjoint to be stirred vigorously；Then reacted with dropwise addition watery hydrochloric acid, reaction is filtered after terminating, and uses third
Ketone and deionized water are cleaned successively to neutrality, vacuum drying, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；
The reaction of the generation in the step is：S2O3 2-+2H+=S ↓+H2O+SO2；
(c) by gained preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace, inert atmosphere high temperature heat at
Reason, obtains the multi-walled carbon nano-tubes/sulphur composite；
In the preparation method of above-mentioned multi-walled carbon nano-tubes/sulphur composite, it is preferred that step (a) multi-wall carbon nano-tube
A diameter of 10～20nm of pipe, length are 5～15 μm；
Preferably, step (a) red fuming nitric acid (RFNA) and the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid in the mixed acid of the concentrated sulfuric acid are 3:
1；
Preferably, the time of step (a) ultrasonic disperse is 2～3h；
Preferably, the temperature being heated to reflux in step (a) oil bath is 100 DEG C, and return time is 6～8h；
Preferably, step (a) the vacuum drying temperature is 100 DEG C；
Preferably, the mass ratio of step (b) the five water sodium thiosulfate and the purification of Multi-wall Carbon Nanotubes for (7～
70)：1；
Preferably, in step (b) the five water sodium thiosulfate and step (b) watery hydrochloric acid mol ratio for (0.4～
0.45):1, to guarantee that sulphur is precipitated out completely；
Preferably, the concentration of step (b) watery hydrochloric acid is 2mol/L, and rate of addition is that 30～40 drops are per minute；Step
1～2h of sustained response after (b) described watery hydrochloric acid completion of dropping；
Preferably, step (b) surfactant be cetyl trimethylammonium bromide solution, the cetyl three
The mass fraction of methyl bromide ammonium salt solution is 5%, and addition is 5～10mL/100mL deionized waters；
Preferably, the time that step (b) ultrasonic disperse is processed is 8h；
Preferably, step (b) the vacuum drying temperature is 60 DEG C for temperature, and drying time is 24h；
Preferably, step (c) inert atmosphere is argon gas (Ar), and flow velocity is 150～200cc/min；
Preferably, the temperature of step (c) heat treatment is 155 DEG C, and heat treatment time is 12h；
The quality of sulphur and multi-walled carbon nano-tubes in the multi-walled carbon nano-tubes obtained according to above-mentioned preparation method/sulphur composite
Than for 5:5～9:1.
The lithium-sulfur battery composite anode material obtained according to the preparation method of above-mentioned lithium-sulfur battery composite anode material is many
Wall carbon nano tube/sulphur/polyaniline composite positive pole, with " sandwich " nanostructured, the lithium-sulfur cell anode composite material
In material, multi-walled carbon nano-tubes/sulphur composite and the mass ratio of polyaniline are 4:1～6:1.
Above-mentioned lithium-sulfur battery composite anode material can be used to prepare lithium-sulphur cell positive electrode piece；
Can be used to prepare the multi-walled carbon nano-tubes/sulphur/polyaniline of lithium battery using above-mentioned lithium-sulfur battery composite anode material
Anode composite piece, concrete preparation method comprise the steps：
(I) lithium-sulfur battery composite anode material is mixed with conductive agent, is stirred, obtain mixture；
(II) 1-METHYLPYRROLIDONE (NMP) is added dropwise to into binding agent, stirring and dissolving is into thin pulp；
Wherein, the dripping quantity of the 1-METHYLPYRROLIDONE is the minimum for being completely dissolved binding agent；
(III), during the mixture for obtaining step (I) adds thin pulp obtained by step (II), slurry is stirred into, slurry is entered
Row ball milling, adds the viscosity of 1-METHYLPYRROLIDONE allotment slurry to require to meet blade coating film forming, then by ball milling during stirring
The slurry for completing scratches and coating is formed in current collector aluminum foil, and vacuum drying obtains the multi-walled carbon nano-tubes/sulphur/polyaniline
Anode composite piece；
Preferably, step (I) conductive agent is carbon black conductive agent, specially in acetylene black, Super-P or Ketjen black
It is a kind of；
Preferably, step (II) binding agent be sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) mixture,
One kind in Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE) or polyethylene glycol oxide (PEO), wherein the carboxymethyl cellulose
Plain sodium is 1 with the mass ratio of sodium carboxymethylcellulose in butadiene-styrene rubber mixture and butadiene-styrene rubber:(1.5～2)；
Preferably, the time of step (III) ball milling is 5～6h, and ball milling speed is 300～500rpm；
Preferably, the thickness of step (III) coating is 15～20 μm；
Preferably, step (III) the vacuum drying temperature is 60 DEG C, and drying time is 24h.
The present invention is had the following advantages relative to prior art and effect：
(1) lithium-sulfur battery composite anode material of the present invention is multi-walled carbon nano-tubes/sulphur/polyaniline composite material, will
Multi-walled carbon nano-tubes/sulphur composite coated with conductive polyaniline, forms multi-walled carbon nano-tubes/sulphur/polyaniline sandwich structure, rises
To the electronics and ionic conductivity that both increased composite, while and improve the dissolving for carrying sulfur content and limiting polysulfide
And diffusion, the cyclical stability of the combination electrode prepared using lithium-sulfur battery composite anode material of the present invention can be effectively improved
And capability retention.
(2) preparation method process is simple of the present invention, chemical precipitation method carry sulphur and situ aggregation method coated with conductive polyphenyl
Amine can be carried out in same container successively, greatly reduced process costs, simplified technological operation, while improve composite
Uniformity, stability.
Description of the drawings
Fig. 1 is sulphur, multi-walled carbon nano-tubes/sulphur composite, the thermogravimetric of multi-walled carbon nano-tubes/sulphur/polyaniline composite material
Curve map.
Fig. 2 is that multi-walled carbon nano-tubes/sulphur anode composite piece and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece exist
0.05C (1C=1672mA g-1) first charge-discharge curve.
Fig. 3 is that multi-walled carbon nano-tubes/sulphur anode composite piece and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece exist
0.2C (1C=1672mA g-1) cyclical stability.
Fig. 4 be multi-walled carbon nano-tubes/sulphur anode composite piece and multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece from
0.05C to 2C (1C=1672mA g-1) rate charge-discharge performance.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
A kind of multi-walled carbon nano-tubes/sulphur composite, its preparation method are as follows：
(1) 4g raw material multi-walled carbon nano-tubes is added mixed acid (red fuming nitric acid (RFNA) and the dense sulphur of 400mL red fuming nitric acid (RFNA)s and the concentrated sulfuric acid
The volume ratio 3 of acid:1) 6h is heated to reflux in 100 DEG C of oil bath after ultrasound 2h in, is filtered, deionized water is cleaned to neutrality,
100 DEG C of vacuum drying, obtain purification of Multi-wall Carbon Nanotubes；
(2) weigh 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in ultrasound 8h in 100mL deionized waters, be subsequently adding 3.87g
Five water sodium thiosulfate and the cetyl trimethylammonium bromide solution that 5mL concentration is 5wt%, it is adjoint to be stirred vigorously；Use 19mL
Watery hydrochloric acid drop reaction 2h of the concentration for 2mol/L, rate of titration control are per minute in 30-40 drops, filter, third after reaction completely
Ketone, deionized water are cleaned successively to neutrality, 60 DEG C of vacuum drying 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；Send out
Raw reaction is S2O3 2-+2H+=S ↓+H2O+SO2；
(3) by prepare preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace 155 under high-purity argon atmosphere
DEG C constant temperature 12h is heat-treated, and obtains the multi-walled carbon nano-tubes/sulphur composite.
The sulfur content of resultant multi-wall CNT/sulphur composite is 48%.
Embodiment 2
A kind of multi-walled carbon nano-tubes/sulphur composite, its preparation method are as follows：
(1) 4g raw material multi-walled carbon nano-tubes is added mixed acid (red fuming nitric acid (RFNA) and the dense sulphur of 400mL red fuming nitric acid (RFNA)s and the concentrated sulfuric acid
The volume ratio 3 of acid:1) 6h is heated to reflux in 100 DEG C of oil bath after ultrasound 2h in, is filtered, deionized water is cleaned to neutrality,
100 DEG C of vacuum drying, obtain purification of Multi-wall Carbon Nanotubes；
(2) weigh 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in ultrasound 8h in 100mL deionized waters, be subsequently adding 5.81g
Five water sodium thiosulfate and the cetyl trimethylammonium bromide solution that 6mL concentration is 5wt%, it is adjoint to be stirred vigorously；Use 28mL
Watery hydrochloric acid drop reaction 2h of the concentration for 2mol/L, rate of titration control are per minute in 30-40 drops, filter, third after reaction completely
Ketone, deionized water are cleaned successively to neutrality, 60 DEG C of vacuum drying 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；Send out
Raw reaction is S2O3 2-+2H+=S ↓+H2O+SO2；
(3) by prepare preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace 155 under high-purity argon atmosphere
DEG C constant temperature 12h is heat-treated, and obtains the multi-walled carbon nano-tubes/sulphur composite.
The sulfur content of resultant multi-wall CNT/sulphur composite is 57%.
Embodiment 3
A kind of multi-walled carbon nano-tubes/sulphur composite, its preparation method are as follows：
(1) 4g raw material multi-walled carbon nano-tubes is added mixed acid (red fuming nitric acid (RFNA) and the dense sulphur of 400mL red fuming nitric acid (RFNA)s and the concentrated sulfuric acid
The volume ratio 3 of acid:1) 6h is heated to reflux in 100 DEG C of oil bath after ultrasound 2h in, is filtered, deionized water is cleaned to neutrality,
100 DEG C of vacuum drying, obtain purification of Multi-wall Carbon Nanotubes；
(2) weigh 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in ultrasound 8h in 100mL deionized waters, be subsequently adding 9.03g
Five water sodium thiosulfate and the cetyl trimethylammonium bromide solution that 7mL concentration is 5wt%, it is adjoint to be stirred vigorously；Use 44mL
Watery hydrochloric acid drop reaction 2h of the concentration for 2mol/L, rate of titration control are per minute in 30-40 drops, filter, third after reaction completely
Ketone, deionized water are cleaned successively to neutrality, 60 DEG C of vacuum drying 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；Send out
Raw reaction is S2O3 2-+2H+=S ↓+H2O+SO2；
(3) by prepare preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace 155 under high-purity argon atmosphere
DEG C constant temperature 12h is heat-treated, and obtains the multi-walled carbon nano-tubes/sulphur composite.
The sulfur content of resultant multi-wall CNT/sulphur composite is 66%.
Embodiment 4
A kind of multi-walled carbon nano-tubes/sulphur composite, its preparation method are as follows：
(1) 4g raw material multi-walled carbon nano-tubes is added mixed acid (red fuming nitric acid (RFNA) and the dense sulphur of 400mL red fuming nitric acid (RFNA)s and the concentrated sulfuric acid
The volume ratio 3 of acid:1) 6h is heated to reflux in 100 DEG C of oil bath after ultrasound 2h in, is filtered, deionized water is cleaned to neutrality,
100 DEG C of vacuum drying, obtain purification of Multi-wall Carbon Nanotubes；
(2) weigh 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in ultrasound 8h in 100mL deionized waters, be subsequently adding 15.48g
Five water sodium thiosulfate and the cetyl trimethylammonium bromide solution that 8mL concentration is 5wt%, it is adjoint to be stirred vigorously；Use 75mL
Watery hydrochloric acid drop reaction 2h of the concentration for 2mol/L, rate of titration control are per minute in 30-40 drops, filter, third after reaction completely
Ketone, deionized water are cleaned successively to neutrality, 60 DEG C of vacuum drying 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；Send out
Raw reaction is S2O3 2-+2H+=S ↓+H2O+SO2；
(3) by prepare preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace 155 under high-purity argon atmosphere
DEG C constant temperature 12h is heat-treated, and obtains the multi-walled carbon nano-tubes/sulphur composite.
The sulfur content of resultant multi-wall CNT/sulphur composite is 83%.
Embodiment 5
A kind of multi-walled carbon nano-tubes/sulphur composite, its preparation method are as follows：
(1) 4g raw material multi-walled carbon nano-tubes is added mixed acid (red fuming nitric acid (RFNA) and the dense sulphur of 400mL red fuming nitric acid (RFNA)s and the concentrated sulfuric acid
The volume ratio 3 of acid:1) 6h is heated to reflux in 100 DEG C of oil bath after ultrasound 2h in, is filtered, deionized water is cleaned to neutrality,
100 DEG C of vacuum drying, obtain purification of Multi-wall Carbon Nanotubes；
(2) weigh 0.5g purification of Multi-wall Carbon Nanotubes and be dispersed in ultrasound 8h in 100mL deionized waters, be subsequently adding 34.84g
Five water sodium thiosulfate and the cetyl trimethylammonium bromide solution that 8mL concentration is 5wt%, it is adjoint to be stirred vigorously；Use 168mL
Watery hydrochloric acid drop reaction 2h of the concentration for 2mol/L, rate of titration control are per minute in 30-40 drops, filter, third after reaction completely
Ketone, deionized water are cleaned successively to neutrality, 60 DEG C of vacuum drying 24h, obtain preliminary multi-walled carbon nano-tubes/sulphur composite；Send out
Raw reaction is S2O3 2-+2H+=S ↓+H2O+SO2；
(3) by prepare preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace 155 under high-purity argon atmosphere
DEG C constant temperature 12h is heat-treated, and obtains the multi-walled carbon nano-tubes/sulphur composite.
The sulfur content of resultant multi-wall CNT/sulphur composite is 87%.
Embodiment 6
A kind of preparation method of lithium-sulfur battery composite anode material, comprises the steps：
(1) 1.838g ammonium persulfates are completely dissolved in watery hydrochloric acid, form ammonium persulfate-dilute hydrochloric acid solution；
(2) multi-walled carbon nano-tubes obtained by Example 4/sulphur composite 2.0g is added to 100mL concentration for 2mol/L
Watery hydrochloric acid in ultrasonic disperse, then sequentially add 1.0g aniline and 0.412g ascorbic acid, be stirred vigorously in 15 DEG C of ice baths,
Step (1) ammonium persulfate-dilute hydrochloric acid solution is added dropwise simultaneously carries out polymerisation, the dropwise addition of ammonium persulfate-dilute hydrochloric acid solution
Speed is that 30～40 drops are per minute, and polymerization reaction time is 8h；Polymerisation is filtered after terminating, with the watery hydrochloric acid of 2mol/L, nothing
Water-ethanol and deionized water clean filtration successively to neutrality, be then vacuum dried in 60 DEG C 24h obtain product multi-walled carbon nano-tubes/
Sulphur/polyaniline composite material, as described lithium-sulfur battery composite anode material.
The sulfur content of gained lithium-sulfur battery composite anode material is 68%.
Take sulphur simple substance, 4 resultant multi-wall CNT of embodiment/sulphur composite and many wall carbon of the present embodiment products therefrom to receive
Mitron/sulphur/polyaniline composite material carries out thermogravimetric analysis, and gained thermogravimetric curve figure is as shown in Figure 1.
As can be drawn from Figure 1, the sulfur content of resultant multi-wall CNT/sulphur composite is 83%, many walls of products therefrom
CNT/sulphur/polyaniline composite material sulfur content is 68%.
Embodiment 7
A kind of preparation method of lithium-sulfur battery composite anode material, comprises the steps：
(1) 2.755g ammonium persulfates are completely dissolved in watery hydrochloric acid, form ammonium persulfate-dilute hydrochloric acid solution；
(2) multi-walled carbon nano-tubes obtained by Example 5/sulphur composite 2.0g is added to 100mL concentration for 2mol/L
Watery hydrochloric acid in ultrasonic disperse, then sequentially add 1.506g aniline and 0.216g ascorbic acid, acutely stir in 15 DEG C of ice baths
Mix, while step (1) ammonium persulfate-dilute hydrochloric acid solution is added dropwise carries out polymerisation, the drop of ammonium persulfate-dilute hydrochloric acid solution
Acceleration is that 30～40 drops are per minute, and polymerization reaction time is 8h；Polymerisation is filtered after terminating, with the watery hydrochloric acid of 2mol/L,
Absolute ethyl alcohol and deionized water clean filtration successively to neutrality, are then vacuum dried 24h in 60 DEG C and obtain product multi-wall carbon nano-tube
Pipe/sulphur/polyaniline composite material, as 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 piece, its preparation method are as follows：
Multi-walled carbon nano-tubes obtained by Example 4/sulphur composite positive pole 0.5g, conductive agent acetylene black 0.0625g are mixed
Close, stir, obtain mixture；Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to into 0.0625g binding agent polyvinylidene fluorides
Alkene (PVDF), stirring make Kynoar fully be dissolved into thin pulp；To stir, size mixing, ball during the mixture for obtaining adds thin pulp
5～6h of mill, repeatedly adds 1-METHYLPYRROLIDONE and is required to blade coating film forming is met with allocating the viscosity of slurry, then during stirring
Slurry after ball milling is scratched in current collector aluminum foil, coating layer thickness is 15～20 μm, obtains many after 60 DEG C of vacuum drying 24h
Wall carbon nano tube/sulphur anode composite piece.
Embodiment 9
A kind of multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece, its preparation method are as follows：
Lithium-sulfur battery composite anode material 0.5g, conductive agent acetylene black 0.0625g mixing obtained by Example 6, stirring
Uniformly, obtain mixture；Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to into 0.0625g binding agent Kynoar
(PVDF), stirring makes Kynoar fully be dissolved into thin pulp；To stir, size mixing, ball milling during the mixture for obtaining adds thin pulp
5～6h, repeatedly adds 1-METHYLPYRROLIDONE and is required to blade coating film forming is met with allocating the viscosity of slurry, then will during stirring
Slurry after ball milling is scratched in current collector aluminum foil, and coating layer thickness is 15～20 μm, obtains many walls after 60 DEG C of vacuum drying 24h
CNT/sulphur/polyaniline anode composite piece.
By the multi-walled carbon nano-tubes/sulphur obtained by 8 resultant multi-wall CNT of embodiment/sulphur anode composite piece and embodiment 9/
Polyaniline anode composite piece strikes out the disk of diameter 12mm respectively, with metal lithium sheet as negative pole, the double fluoroform sulphurs of 1mol/L
Imide li LiTFSI (LiTFSI) and 0.1mol/L lithium nitrates are dissolved in glycol dimethyl ether (DME) and 1,3- dioxolanes
(DOL) volume ratio is 1:Electrolyte is formulated as in 1 mixed liquor, with polypropylene screen as barrier film, in the glove box full of argon gas
CR2025 button cells are assembled into respectively, its chemical property is tested at room temperature, in 0.05C (1C=1672mA g-1) head
Secondary charging and discharging curve is as shown in Fig. 2 in 0.2C (1C=1672mA g-1) cyclical stability test as shown in figure 3, from 0.05C
To 2C (1C=1672mA g-1) rate charge-discharge ability it is as shown in Figure 4.
As can be drawn from Figure 2：The discharge capacity first of 8 resultant multi-wall CNT of embodiment/sulphur anode composite piece is
855.3mAh/g, coulombic efficiency are 86%；And the head of the multi-walled carbon nano-tubes/sulphur obtained by embodiment 9/polyaniline anode composite piece
Secondary discharge capacity is 896mAh/g, and coulombic efficiency is up to 96%；
As can be drawn from Figure 3：Multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece obtained by embodiment 9 is circulated in 0.2C
After 205 times, 545.5mAh/g is there remains, far above 8 resultant multi-wall CNT of embodiment/sulphur anode composite piece
353.4mAh/g；
As can be drawn from Figure 4：The multiplying power charge and discharge of the multi-walled carbon nano-tubes/sulphur obtained by embodiment 9/polyaniline anode composite piece
Electrical property is far above 8 resultant multi-wall CNT of embodiment/sulphur anode composite piece, in 0.5C charge and discharge cycles, 9 institute of embodiment
The average discharge capacity of the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece for obtaining is 473.7mAh/g, more than 8 institute of embodiment
Obtain the 293.2mAh/g of multi-walled carbon nano-tubes/sulphur anode composite piece；
Embodiment 10
A kind of multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece, its preparation method are as follows：
Lithium-sulfur battery composite anode material 0.5g, conductive agent acetylene black 0.0625g mixing obtained by Example 7, stirring
Uniformly, obtain mixture；Appropriate 1-METHYLPYRROLIDONE (NMP) is added dropwise to into 0.0625g binding agent Kynoar
(PVDF), stirring makes Kynoar fully be dissolved into thin pulp；To stir, size mixing, ball milling during the mixture for obtaining adds thin pulp
5～6h, repeatedly adds 1-METHYLPYRROLIDONE and is required to blade coating film forming is met with allocating the viscosity of slurry, then will during stirring
Slurry after ball milling is scratched in current collector aluminum foil, and coating layer thickness is 15～20 μm, obtains many walls after 60 DEG C of vacuum drying 24h
CNT/sulphur/polyaniline anode composite piece.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of lithium-sulfur battery composite anode material, it is characterised in that comprise the steps：
(1) ammonium persulfate is completely dissolved in watery hydrochloric acid, forms ammonium persulfate-dilute hydrochloric acid solution；
(2) multi-walled carbon nano-tubes/sulphur composite is added to into ultrasonic disperse in watery hydrochloric acid, then sequentially adds aniline and anti-bad
Hematic acid, is stirred vigorously in ice bath, while step (1) ammonium persulfate-dilute hydrochloric acid solution is added dropwise carries out polymerisation；Polymerization
Reaction is filtered after terminating, and cleans filtrations successively with watery hydrochloric acid, absolute ethyl alcohol and deionized water, is then vacuum dried that to obtain product more
Wall carbon nano tube/sulphur/polyaniline composite material, as described lithium-sulfur battery composite anode material；
The multi-walled carbon nano-tubes/sulphur composite is obtained by following preparation method, is comprised the steps：
A multi-walled carbon nano-tubes is added ultrasonic disperse in mixed acid of the red fuming nitric acid (RFNA) with the concentrated sulfuric acid by (), be heated to reflux in oil bath,
Filter, deionized water is cleaned to neutrality, vacuum drying, obtains purification of Multi-wall Carbon Nanotubes；
B the purification of Multi-wall Carbon Nanotubes is carried out ultrasonic disperse process in deionized water by (), add five water thiosulfuric acids
Sodium and surfactant, it is adjoint to be stirred vigorously；Then reacted with dropwise addition watery hydrochloric acid, reaction is filtered after terminating, with acetone and
Deionized water is cleaned successively to neutrality, vacuum drying, obtains preliminary multi-walled carbon nano-tubes/sulphur composite；
The reaction of the generation in the step is：S2O3 2-+2H+=S ↓+H2O+SO2；
C (), by gained preliminary multi-walled carbon nano-tubes/sulphur composite material sealing in tube furnace, inert atmosphere high temperature is heat-treated,
Obtain the multi-walled carbon nano-tubes/sulphur composite.
2. the preparation method of lithium-sulfur battery composite anode material according to claim 1, it is characterised in that：The persulfuric acid
Ammonium is (0.75～1) with the mol ratio of aniline：1；The ammonium persulfate is (9～11) with the mol ratio of ascorbic acid：1；Step
(2) multi-walled carbon nano-tubes/sulphur composite and the mass ratio of the aniline are (2～6):1.
3. the preparation method of lithium-sulfur battery composite anode material according to claim 1, it is characterised in that：Step (1) and
The concentration of 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)
It is per minute for 30～40 drops；The temperature of step (2) ice bath is 5～15 DEG C；The time of step (2) polymerisation is 6
～8h；Step (2) the vacuum drying temperature is 60 DEG C, and drying time is 24h.
4. the preparation method of lithium-sulfur battery composite anode material according to claim 1, it is characterised in that：Step (a) institute
A diameter of 10～20nm of multi-walled carbon nano-tubes is stated, length is 5～15 μm；The mixing of step (a) red fuming nitric acid (RFNA) and the concentrated sulfuric acid
In acid, the volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid is 3:1；The time of step (a) ultrasonic disperse is 2～3 hours；Step (a) institute
The temperature being heated to reflux in stating oil bath is 100 DEG C, and return time is 6～8h；Step (a) the vacuum drying temperature is 100
℃。
5. the preparation method of lithium-sulfur battery composite anode material according to claim 1, it is characterised in that：Step (b) institute
The mass ratio that five water sodium thiosulfate are stated with the purification of Multi-wall Carbon Nanotubes is (7～70)：1；Step (b) five water is thio
Sodium sulphate is (0.4～0.45) with the mol ratio of watery hydrochloric acid in step (b):1；The concentration of step (b) watery hydrochloric acid is 2mol/
L, rate of addition are that 30～40 drops are per minute；Step (b) surfactant be cetyl trimethylammonium bromide solution, institute
The mass fraction for stating cetyl trimethylammonium bromide solution is 5%, and addition is 5～10mL/100mL deionized waters；Step
B time that () described ultrasonic disperse is processed is 8h；Step (b) the vacuum drying temperature is 60 DEG C, and drying time is 24h；
Step (c) inert atmosphere is argon gas, and flow velocity is 150～200cc/min；The temperature of step (c) heat treatment is 155
DEG C, heat treatment time is 12h.
6. the lithium that a kind of preparation method of the lithium-sulfur battery composite anode material according to any one of Claims 1 to 5 is obtained
Sulphur battery composite anode material, the lithium-sulfur battery composite anode material are multi-walled carbon nano-tubes/sulphur/polyaniline anode composite material
Material, in the lithium-sulfur battery composite anode material, multi-walled carbon nano-tubes/sulphur composite and the mass ratio of polyaniline are 4:1～
6:1。
7. application of the lithium-sulfur battery composite anode material according to claim 6 in lithium-sulphur cell positive electrode piece is prepared.
8. application according to claim 7, it is characterised in that：Lithium electricity is prepared using above-mentioned lithium-sulfur battery composite anode material
Multi-walled carbon nano-tubes/the sulphur in pond/polyaniline anode composite piece, concrete preparation method comprise the steps：
(I) lithium-sulfur battery composite anode material is mixed with conductive agent, is stirred, obtain mixture；
(II) 1-METHYLPYRROLIDONE is added dropwise to into binding agent, stirring and dissolving is into thin pulp；
Wherein, the dripping quantity of the 1-METHYLPYRROLIDONE is the minimum for being completely dissolved binding agent；
(III), during the mixture for obtaining step (I) adds thin pulp obtained by step (II), slurry is stirred into, slurry is carried out into ball
Mill, adds the viscosity of 1-METHYLPYRROLIDONE allotment slurry to require to meet blade coating film forming, then completes ball milling during stirring
Slurry scratch coating formed in current collector aluminum foil, vacuum drying obtains the multi-walled carbon nano-tubes/sulphur/polyaniline and is combined
Positive plate.
9. application according to claim 8, it is characterised in that：Use being prepared using above-mentioned lithium-sulfur battery composite anode material
In the preparation method of the multi-walled carbon nano-tubes/sulphur/polyaniline anode composite piece of lithium battery, step (I) conductive agent is charcoal
Black conductive agent；Step (II) binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber mixture, Kynoar, polytetrafluoro
One kind in ethene or polyethylene glycol oxide, wherein the sodium carboxymethylcellulose and carboxymethylcellulose calcium in butadiene-styrene rubber mixture
Sodium is 1 with the mass ratio of butadiene-styrene rubber:(1.5～2)；The time of step (III) ball milling is 5～6h, and ball milling speed is 300
～500rpm；The thickness of step (III) coating is 15～20 μm；Step (III) the vacuum drying temperature is 60 DEG C,
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 |
| CN106058151B (en) * | 2016-08-12 | 2019-02-12 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulphur/polyaniline composite electrode, preparation method and application |
| CN106356555B (en) * | 2016-11-02 | 2019-09-10 | 武汉理工大学 | The preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer |
| CN107482198A (en) * | 2017-08-07 | 2017-12-15 | 中国科学技术大学 | A kind of self-supporting, high-sulfur carrying capacity lithium sulfur battery anode material and preparation method thereof |
| CN110858651B (en) * | 2018-08-24 | 2021-04-02 | 清华大学 | Carbon nanotube composite structure and preparation method thereof |
| CN110061218B (en) * | 2019-04-28 | 2021-02-02 | 西安交通大学 | Lithium phosphate coated sulfur/carbon composite material and preparation method and application thereof |
| CN112542579B (en) * | 2020-12-24 | 2021-09-21 | 太原理工大学 | Conductive Janus film, preparation method and application of conductive Janus film in preparation of lithium-sulfur battery anode |
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