CN105355876B - Composite conductive polymer coats the preparation method and its usage of elemental sulfur - Google Patents
Composite conductive polymer coats the preparation method and its usage of elemental sulfur Download PDFInfo
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- CN105355876B CN105355876B CN201510753077.0A CN201510753077A CN105355876B CN 105355876 B CN105355876 B CN 105355876B CN 201510753077 A CN201510753077 A CN 201510753077A CN 105355876 B CN105355876 B CN 105355876B
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Abstract
The invention discloses a kind of preparation method and its usage of composite conductive polymer cladding elemental sulfur, belong to electrochemical energy storage field.More particularly to contain pyrroles, the suspension of aniline, thiophene monomer and elemental sulfur is supporting electrolyte, platinum electrode is auxiliary electrode, aluminium foil is working electrode, saturated calomel electrode is reference electrode, adjust electrochemical parameter controllable elemental sulfur while the polymerization of conducting polymer monomer is controlled synchronously to assemble, one layer of polypyrrole/polyaniline/polythiophene composite conductive polymer film for being enclosed with elemental sulfur can be formed in aluminium foil surface, elemental sulfur can be bonded with S S with polythiophene and be closed.Being enclosed with the composite conductive polymer film of elemental sulfur can use directly as positive pole plate of lithium-sulfur cell, and aluminium foil is as plus plate current-collecting body；This technique eliminates elemental sulfur and the compound process of conducting polymer, while also eliminates the later stage preparation process that bonding agent is introduced in pole piece preparation process, and the present invention is simple to operate, can effectively reduce the swelling problem of lithium-sulphur cell positive electrode.
Description
Technical field
The invention belongs to electrochemical energy storage field, specifically a kind of composite conductive polymer cladding simple substance sulphur preparing process
And application thereof.
Background technology
In recent years, the fast development of electronic product causes electrochemical power source towards directions such as light weight, small volume, long lifespans
Development；Simultaneously under the pressure of environment and energy security, new-energy automobile starts in development in 2014 rapidly, to develop a kind of energy
High, safe, long lifespan the electrokinetic cell of density also turns into the ultimate aim that each cart enterprise is pursued.For currently used lithium
Ion battery far can not meet actual demand, and lithium-sulfur cell starts gradually to enter into the researcher visual field, and elemental sulfur has
1675mAh/g theoretical specific capacities, its theoretical energy density can reach 2600wh/kg, be current commercial li-ion battery (NCM tri-
First battery, cobalt acid lithium battery etc.) nearly 10 times or so of energy density；Meanwhile elemental sulfur has rich reserves, cheap, ring
The advantages that border close friend, thus lithium-sulfur cell turns into one of most attractive system in following battery system.
However, lithium-sulfur cell has the problem of more in actual applications restricts its commercialization popularization, it is mainly reflected in：
(a) poor (the conductance only 5*10 at room temperature of elemental sulfur electric conductivity-30S/cm)；(b) the middle production in electrochemical reaction process
Thing --- polysulfide can dissolve in the electrolytic solution, and pair occurs instead with cathode of lithium with the negative terminal surface that is diffused of reaction
Should, i.e., " shuttle effect ", cause coulombic efficiency and reversible capacity all step-downs；(c) insulating properties insoluble matter Li in cyclic process2S and
Li2S2Deposition on positive electrode surface, the electrical contact of active material is caused to deteriorate, cyclical stability declines；(d) Volume Changes
Cause active material efflorescence and come off.The presence of these problems causes the rapid decline of lithium-sulfur cell performance.
To solve lithium-sulfur cell these restricted shortcomings, researcher proposes a variety of improvement projects at present：(a) optimization electrolysis
Liquid, such as lithium nitrate, which is added in ethers electrolyte, can effectively slow down shuttle effect, so as to improve the coulombic efficiency of battery；(b)
Negative pole is protected, and cathode of lithium is surface-treated, and isolation polysulfide reacts, and reduces self discharge；(c) positive pole
Material modification, Combined Processing is carried out to elemental sulfur using carbon, metal oxide, conducting polymer etc., prepares the compound of sulfur loaded
Material is as positive electrode.Because conducting polymer has the electrology characteristic of metal, the pliability of organic polymer and can process
Property, provide conductive network and alleviate stress effect and storage lithium performance, these features determine conducting polymer improve lithium sulphur
It can be played an important role in terms of battery performance, be a kind of lithium-sulphur cell positive electrode carrier material with important application prospect.
Patent CN104638236A discloses a kind of polyaniline of hollow core-shell structure/sulphur composite, patent CN
103259000 A also disclose that a kind of pyrroles's tiny balloon/sulphur composite, as a result find either polyaniline or polypyrrole
Facilitation can be played to lithium-sulfur cell capacity and cycle performance to a certain extent.But the polypyrrole being manufactured separately and
The shortcomings that poor dissolubility, processing difficulties be present due to the firm property of chain and the strong interaction of interchain in polyaniline；Simultaneously in battery
Polyaniline and film of poly pyrrole structure can be caused to destroy during cycle charge-discharge so that efficiency declines.Patent
CN104638236A is all to trigger monomer to polymerize by initiator with the conducting polymer synthetic method that CN 103259000A are used
Chemical oxidation of gold, it is then compound by other means with elemental sulfur first to prepare conducting polymer, and this method has operation
Step is more, the shortcomings of being readily incorporated impurity, and cannot be guaranteed elemental sulfur it is compound uniformly and absorption is firm, limit this side
The extensive development of method.
The content of the invention
It is an object of the invention to provide a kind of composite conductive polymer cladding elemental sulfur preparation method and its usage, with
Solve the problems, such as to propose in above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：Pyrrole monomer and dopant are dissolved into acid solution, regulation pH value of solution obtains to 1~5
To solution A；
(2) aaerosol solution B preparation：By pyrroles, aniline, thiophene monomer and dopant are added in acid solution, are added
Enter elemental sulfur, emulsifying agent, be sanded using sand mill, it is 50~100nm to control D50 scopes in particle diameter, and control pH value of solution is extremely
4.5~6.5, obtain aaerosol solution B；
(3) aluminium foil is handled：Acetone oil removing and ethanol dewatering are carried out to aluminium foil using ultrasonic wave respectively, after processing is clean, dried in the air
It is dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, it is polymerize using electrochemical method, forms pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, and elemental sulfur is selected from height
One kind in bright sulfur, sublimed sulfur, its content are the 30~80% of conducting polymer monomer mass, are polymerize using electrochemical method,
It is thin one layer of polypyrrole/polyaniline/polythiophene composite conductive polymer for being enclosed with elemental sulfur can be formed in pretreatment aluminium foil surface
Film.
Preferably, the dopant is selected from neopelex, lauryl sodium sulfate, sodium naphthalene sulfonate one of which
Or two kinds, dopant quality accounting 1~3% wherein in solution A, dopant quality accounting 5~8% in solution B.
Preferably, acid solution is a kind of in sulfuric acid, p-methyl benzenesulfonic acid, oxalic acid in the solution A；In the solution A
Pyrrole monomer concentration range is 0.05~0.5mol/L.
Preferably, thiophene monomer content accounts for the 2~5% of conducting polymer monomer molar concentration in the solution B；The pyrrole
It is 1 to cough up with aniline monomer concentration ratio:5~5:1；The conducting polymer total monomer is 0.1~1mol/L.
Preferably, acid solution is selected from sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid in the solution B, and one in salicylic acid, oxalic acid
Kind.
Preferably, the emulsifying agent is selected from polyethylene glycol propane diols-polyethylene glycol, PEO-polycyclic oxygen third
It is one or more in alkane-PEO triblock copolymer, ethylene oxide-butylene oxide copolymer；The emulsifying agent accounts for outstanding
The 3~5% of floating solution B quality.
Preferably, the electrochemical polymerization that the aluminium foil preprocessing process uses is galvanostatic method, control electric current density
For 0.3~0.8mA/cm2, generated time is 5~10s.
Preferably, the electrochemical polymerization is cyclic voltammetry, wherein the electrochemical parameter controlled is：Scan current potential
Scope -0.5~1.6VSCE, 10~30mV/s of sweep speed, scanning times 8~15 times.
Preferably, the electrochemical polymerization is galvanostatic method, wherein the electrochemical parameter controlled is：Current density
0.1~0.35mA/cm2, 10~15min of generated time.
The composite guide for being coated with elemental sulfur that described composite conductive polymer cladding simple substance sulphur preparing process is prepared
The purposes of electric polymer, the pretreatment of the polypyrrole/polyaniline/polythiophene composite conductive polymer film for being coated with elemental sulfur
Aluminium foil can use directly as positive pole plate of lithium-sulfur cell, and the aluminium foil can be used as collector.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention carries out electrochemical pre-treatment to aluminium foil first, and polypyrrole reaction interface is formed in aluminium foil surface；Then exist
Electrochemical polymerization is carried out to pretreatment aluminium foil in suspension solution containing pyrroles, aniline, thiophene monomer and elemental sulfur, utilizes pyrrole
Cough up aluminium foil interface growth can promote simultaneously aniline and thiophene monomer in film simultaneous polymerization generate the characteristics of, control elemental sulfur
It is synchronous also to assemble film forming with the formation of conductive polymer membrane, so as to prepare polypyrrole/polyaniline/polythiophene of composite conducting
Composite conductive polymer coats the film of elemental sulfur.The present invention is advantageous in that control composite conductive polymer is in aluminium foil work
Make to control elemental sulfur synchronously to assemble film forming while electrode surface polymerization, elemental sulfur can be dispersed in composite conductive polymer
In the reticulated conductive network of construction, while it is combined together with the polythiophene in composite conductive polymer by S -- S, reaches negative
Stable effect is carried, dissolution of the elemental sulfur in cyclic process can be reduced, reduces " shuttle effect ", lithium-sulfur cell can be effectively reduced
The swelling problem of positive pole；Simultaneously for the pre- of the polypyrrole/polyaniline/polythiophene composite conductive polymer film for being coated with elemental sulfur
Processing aluminium foil can use directly as positive pole plate of lithium-sulfur cell, and this lithium sulfur battery anode material preparation technology eliminates elemental sulfur
The compound process with conducting polymer, while also eliminate the later stage preparation process that bonding agent is introduced in pole piece preparation process, behaviour
Make simple.
Brief description of the drawings
Accompanying drawing 1：Composite conductive polymer cladding elemental sulfur prepared by embodiment 6 is applied to positive pole plate of lithium-sulfur cell 0.1C
Initial charge/discharge curve under multiplying power；
Accompanying drawing 2：Composite conductive polymer cladding elemental sulfur prepared by embodiment 6 is applied to positive pole plate of lithium-sulfur cell 0.5C
Cyclic curve under multiplying power.
Embodiment
With reference to embodiments, the present invention is described in detail.
Embodiment 1：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The neopelex of 0.05mol/L pyrrole monomer and 1wt% is dissolved into sulphur
In acid, regulation pH value of solution obtains solution A after being 1；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=1:5 molar ratio, and 3% molar ratio
Thiophene monomer be added to together in sulfuric acid solution, it is 0.1mol/L to control three kinds of monomer solubility；Then add polymer monomer
The dopant neopelex of total amount 5%, 3% emulsifying agent polyethylene glycol propane diols-polyethylene glycol three block are total to
Polymers and 30% sublimed sulfur, it is 4.5 to control pH value of solution；Finally solution is sanded using sand mill, control solution particle diameter D50
For 50nm；Obtain aaerosol solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.3mA/cm2, the constant current time is 10s；
Form pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using cyclic voltammetric
Method electrochemical method is handled pretreatment aluminium foil：Potential range -0.5~1.6VSCE is scanned, sweep speed 10mV/s, is swept
Retouch number 15 times；One layer of polypyrrole/polyaniline/polythiophene composite guide for being coated with elemental sulfur can be formed in pretreatment aluminium foil surface
Electric polymer film.
Embodiment 2
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The lauryl sodium sulfate of 0.15mol/L pyrrole monomer and 2wt% is dissolved into oxalic acid
In, regulation pH value of solution obtains solution A after being 3；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=1:3 molar ratio, and 3% molar ratio
Thiophene monomer be added to together in oxalic acid solution, it is 0.3mol/L to control three kinds of monomer solubility；Then add polymer monomer
The dopant lauryl sodium sulfate of total amount 6%, 4% emulsifying agent PEO-PPOX-PEO three are embedding
Section copolymer and 50% high purity sulphur, it is 5 to control pH value of solution；Finally solution is sanded using sand mill, controls solution particle diameter
D50 is 80nm；Obtain aaerosol solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.6mA/cm2, the constant current time is 8s；Shape
Into pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using galvanostatic method
Electrochemical method is handled pretreatment aluminium foil：Current density 0.1mA/cm2, generated time 15min；Can be in pretreatment aluminium foil
Surface forms polypyrrole/polyaniline/polythiophene composite conductive polymer film of one layer of cladding elemental sulfur.
Embodiment 3：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The sodium naphthalene sulfonate of 0.25mol/L pyrrole monomer and 3wt% is dissolved into p-methyl benzenesulfonic acid
In, regulation pH value of solution obtains solution A after being 5；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=3:1 molar ratio, and 2% molar ratio
Thiophene monomer be added to together in salicylic acid solution, it is 0.5mol/L to control three kinds of monomer solubility；Then add polymer list
The dopant sodium naphthalene sulfonate of body total amount 7%, 3% emulsifying agent PEO-PPOX-PEO three block are total to
Polymers and 80% sublimed sulfur, it is 5.5 to control pH value of solution；Finally solution is sanded using sand mill, control solution particle diameter D50
For 100nm；Obtain aaerosol solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.5mA/cm2, the constant current time is 7s；Shape
Into pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using galvanostatic method
Electrochemical method is handled pretreatment aluminium foil：Current density 0.2mA/cm2, generated time 12min；Can be in pretreatment aluminium foil
Surface forms one layer of polypyrrole/polyaniline/polythiophene composite conductive polymer film for being coated with elemental sulfur.
Embodiment 4：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The sodium naphthalene sulfonate of 0.35mol/L pyrrole monomer and 1wt% is dissolved into sulfuric acid, adjusted
Section pH value of solution obtains solution A after being 1；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=5:1 molar ratio, and 3% molar ratio
Thiophene monomer be added to together in hydrochloric acid solution, it is 0.7mol/L to control three kinds of monomer solubility；Then add polymer monomer
The dopant lauryl sodium sulfate of total amount 8%, 4% emulsifying agent PEO-PPOX-PEO three are embedding
Section copolymer and 50% sublimed sulfur, it is 6 to control pH value of solution；Finally solution is sanded using sand mill, controls solution particle diameter
D50 is 80nm；Obtain aaerosol solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.6mA/cm2, the constant current time is 6s；Shape
Into pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using cyclic voltammetric
Method electrochemical method is handled pretreatment aluminium foil：Potential range -0.5~1.6VSCE is scanned, sweep speed 20mV/s, is swept
Retouch number 8 times；One layer of polypyrrole/polyaniline/polythiophene composite guide for being coated with elemental sulfur can be formed in pretreatment aluminium foil surface
Electric polymer film.
Embodiment 5：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The lauryl sodium sulfate of 0.45mol/L pyrrole monomer and 2wt% is dissolved into oxalic acid
In, regulation pH value of solution obtains solution A after being 3；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=1:1 molar ratio ratio, and 5% mole
The thiophene monomer of ratio is added in p-methyl benzenesulfonic acid solution together, and it is 1mol/L to control three kinds of monomer solubility；Then add poly-
The dopant sodium naphthalene sulfonate of monomer adduct total amount 5%, 5% emulsifying agent ethylene oxide-butylene oxide copolymer and 30%
High purity sulphur, it is 6 to control pH value of solution；Finally solution is sanded using sand mill, it is 50nm to control solution particle diameter D50；Suspended
Solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.8mA/cm2, the constant current time is 5s；Shape
Into pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using galvanostatic method
Electrochemical method is handled pretreatment aluminium foil：Current density 0.35mA/cm2, generated time 10min；Can be in pre-treating aluminium
Paper tinsel surface forms one layer of polypyrrole/polyaniline/polythiophene composite conductive polymer film for being coated with elemental sulfur.
Embodiment 6：
Composite conductive polymer coats simple substance sulphur preparing process, comprises the following steps：
(1) preparation of solution A：The neopelex of 0.5mol/L pyrrole monomer and 3wt% is dissolved into pair
In toluenesulfonic acid, regulation pH value of solution obtains solution A after being 5；
(2) aaerosol solution B preparation：By monomer according to pyrroles：Aniline=1:1 molar ratio, and 3% molar ratio
Thiophene monomer be added to together in oxalic acid solution, it is 0.8mol/L to control three kinds of monomer solubility；Then add polymer monomer
The dopant lauryl sodium sulfate of total amount 6%, 4% emulsifying agent polyethylene glycol propane diols-polyethylene glycol triblock copolymer
Thing and 60% sublimed sulfur, it is 6.5 to control pH value of solution；Finally solution is sanded using sand mill, controls the solution particle diameter D50 to be
50nm；Obtain aaerosol solution B；
(3) aluminium foil is handled：Carry out acetone oil removing and ethanol dewatering processing respectively to aluminium foil using ultrasonic wave, dry standby；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step 3 is working electrode, platinum
Piece is auxiliary electrode, and saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5
DEG C, aluminium foil is handled using galvanostatic method electrochemical method, current density 0.5mA/cm2, the constant current time is 8s；Shape
Into pretreatment aluminium foil C；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode,
Saturated calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, using cyclic voltammetric
Method electrochemical method is handled pretreatment aluminium foil：Potential range -0.5~1.6VSCE is scanned, sweep speed 30mV/s, is swept
Retouch number 12 times；One layer of polypyrrole/polyaniline/polythiophene composite guide for being coated with elemental sulfur can be formed in pretreatment aluminium foil surface
Electric polymer film.
Polypyrrole/polyaniline/polythiophene composite conductive polymer the film for being coated with elemental sulfur prepared by embodiment 1~6
Aluminium foil is pre-processed to use directly as positive pole plate of lithium-sulfur cell.The aluminium foil is as collector.
Polypyrrole/polyaniline/polythiophene the composite conductive polymer for being coated with elemental sulfur prepared for the detection present invention is thin
The chemical property of film, electrochemistry evaluation and test is carried out to it with 2016 button cells.The surface prepared with embodiment 6 is formed with one layer
The aluminium foil of polypyrrole/polyaniline/polythiophene composite conductive polymer film of elemental sulfur is coated with as anode pole piece, lithium metal
Piece is that clegard2400 is barrier film, and 1mol/L LiPF6/EC+DMCWEI is electrolyte, in full of Ar glove boxes to electrode
Button cell is assembled into, constant current charge-discharge test is carried out using Land battery test systems.As a result as shown in figure 1, discharge and recharge is electric
Pressure scope is 0.3~2.7V, and first discharge specific capacity is 11970m Ah/g under 0.1C multiplying powers；
Its cyclic curve under 0.5C multiplying powers is have studied again, as a result as shown in Fig. 2 0.5C time circulations after circulation in 40 weeks
601mAh/g specific discharge capacity is still also maintained afterwards, is 50.2% capability retention of initial discharge specific capacity.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (6)
1. composite conductive polymer coats simple substance sulphur preparing process, it is characterised in that comprises the following steps：
(1) preparation of solution A：Pyrrole monomer and dopant are dissolved into acid solution, regulation pH value of solution obtains molten to 1~5
Liquid A, the dopant is selected from neopelex, lauryl sodium sulfate, sodium naphthalene sulfonate one of which or two kinds, solution
Dopant quality accounting 1~3% in A, acid solution is a kind of in sulfuric acid, p-methyl benzenesulfonic acid, oxalic acid in the solution A；Institute
It is 0.05~0.5mol/L to state pyrrole monomer concentration range in solution A；
(2) aaerosol solution B preparation：By pyrroles, aniline, thiophene monomer and dopant are added in acid solution, are added single
Matter sulphur, emulsifying agent, are sanded using sand mill, and it is 50~100nm to control D50 scopes in particle diameter, and control pH value of solution to 4.5~
6.5, aaerosol solution B is obtained, the dopant is selected from neopelex, lauryl sodium sulfate, sodium naphthalene sulfonate wherein
One or two, dopant quality accounting 5~8% in solution B, acid solution is selected from sulfuric acid, hydrochloric acid, to first in the solution B
Benzene sulfonic acid, one kind in salicylic acid, oxalic acid, the emulsifying agent are selected from polyethylene glycol propane diols-polyethylene glycol, polycyclic oxygen second
It is one or more in alkane-PPOX-PEO triblock copolymer, ethylene oxide-butylene oxide copolymer；It is described
Emulsifying agent accounts for the 3~5% of aaerosol solution B mass；
(3) aluminium foil is handled：Acetone oil removing and ethanol dewatering are carried out to aluminium foil using ultrasonic wave respectively, after processing is clean, dried standby
With；
(4) aluminium foil C preparation is pre-processed：Using three-electrode system, the aluminium foil after being handled using step (3) is working electrode, platinized platinum
For auxiliary electrode, saturated calomel electrode is reference electrode, and using solution A as supporting electrolyte, controlling reaction temperature is -5~5 DEG C,
Pretreatment aluminium foil C is formed using electrochemical polymerization；
(5) elemental sulfur is coated：Using three-electrode system, to pre-process aluminium foil C as working electrode, platinized platinum is auxiliary electrode, saturation
Calomel electrode is reference electrode, and using solution B as supporting electrolyte, it is -5~5 DEG C to control synthesis temperature, and elemental sulfur is selected from high-purity
One kind in sulphur, sublimed sulfur, its content are the 30~80% of conducting polymer monomer mass, can using electrochemical polymerization
One layer of polypyrrole/polyaniline/polythiophene composite conductive polymer film for being enclosed with elemental sulfur is formed in pretreatment aluminium foil surface.
2. composite conductive polymer according to claim 1 coats simple substance sulphur preparing process, it is characterised in that：The step
Suddenly thiophene monomer content accounts for the 2~5% of conducting polymer monomer molar concentration in (2) solution B；The pyrroles and aniline monomer are dense
Degree is than being 1:5~5:1；The conducting polymer total monomer is 0.1~1mol/L.
3. composite conductive polymer according to claim 1 coats simple substance sulphur preparing process, it is characterised in that：The step
Suddenly for the electrochemical polymerization that (4) aluminium foil preprocessing process uses for galvanostatic method, control electric current density is 0.3~0.8mA/
cm2, generated time is 5~10s.
4. composite conductive polymer according to claim 1 coats simple substance sulphur preparing process, it is characterised in that：The step
Suddenly (5) electrochemical polymerization is cyclic voltammetry, wherein the electrochemical parameter controlled is：Scanning potential range -0.5~
1.6VSCE, 10~30mV/s of sweep speed, scanning times 8~15 times.
5. composite conductive polymer according to claim 1 coats simple substance sulphur preparing process, it is characterised in that：The step
Suddenly (5) electrochemical polymerization is galvanostatic method, wherein the electrochemical parameter controlled is：0.1~0.35mA/cm of current density2,
10~15min of generated time.
6. prepared by a kind of composite conductive polymer cladding simple substance sulphur preparing process according to any one of Claims 1 to 5
What is gone out is coated with the purposes of the composite conductive polymer of elemental sulfur, it is characterised in that：The polypyrrole/poly- for being coated with elemental sulfur
The pretreatment aluminium foil of aniline/polythiophene composite conductive polymer film uses directly as positive pole plate of lithium-sulfur cell, the aluminium foil
For collector.
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