CN105355876A - Preparation method and application of composite conductive polymer coated elemental sulfur - Google Patents
Preparation method and application of composite conductive polymer coated elemental sulfur Download PDFInfo
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- CN105355876A CN105355876A CN201510753077.0A CN201510753077A CN105355876A CN 105355876 A CN105355876 A CN 105355876A CN 201510753077 A CN201510753077 A CN 201510753077A CN 105355876 A CN105355876 A CN 105355876A
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- aluminium foil
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 71
- 230000008569 process Effects 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000767 polyaniline Polymers 0.000 claims abstract description 20
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 20
- 229920000123 polythiophene Polymers 0.000 claims abstract description 18
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 17
- 229930192474 thiophene Natural products 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000005030 aluminium foil Substances 0.000 claims description 83
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000005864 Sulphur Substances 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002019 doping agent Substances 0.000 claims description 16
- 238000002848 electrochemical method Methods 0.000 claims description 16
- 239000004576 sand Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 150000003233 pyrroles Chemical class 0.000 claims description 13
- 239000002322 conducting polymer Substances 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003801 milling Methods 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 3
- 229910052782 aluminium Inorganic materials 0.000 abstract 3
- 239000011888 foil Substances 0.000 abstract 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 86
- 229920000642 polymer Polymers 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method and application of composite conductive polymer coated elemental sulfur, and belongs to the field of electrochemical energy storage. The method specifically relates to a method for preparing a polypyrrole/polyaniline/polythiophene composite conductive polymer film coated with elemental sulfur on the surface of an aluminum foil, wherein suspension containing pyrrole, aniline, thiophene monomer and elemental sulfur is used as supporting electrolyte, a platinum electrode is used as an auxiliary electrode, the aluminum foil is used as a working electrode, a saturated calomel electrode is used as a reference electrode, electrochemical parameters are adjusted to control the polymerization of the conductive polymer monomer and control the synchronous aggregation of the elemental sulfur, and the elemental sulfur can be combined with the polythiophene through an S-S bond. The composite conductive polymer film wrapped with elemental sulfur can be directly used as a positive pole piece of a lithium-sulfur battery, and the aluminum foil is used as a positive current collector; the process saves the process of compounding elemental sulfur and a conductive polymer, and also saves the later preparation process of introducing an adhesive in the preparation process of the pole piece.
Description
Technical field
The invention belongs to electrochemical energy storage field, specifically the preparation method and its usage of the coated elemental sulfur of a kind of composite conductive polymer.
Background technology
In recent years, the fast development of electronic product makes the future developments such as electrochemical power source is light towards quality, volume is little, the life-span is long; Simultaneously under the pressure of Environment and energy safety, new-energy automobile starts development in 2014 swift and violent, and developing a kind of energy density is high, fail safe is high, the life-span is long electrokinetic cell also becomes the ultimate aim that each cart enterprise pursues.Far away can not practical requirement at present conventional lithium ion battery, lithium-sulfur cell starts to enter into the researcher visual field gradually, elemental sulfur has 1675mAh/g theoretical specific capacity, its theoretical energy density can reach 2600wh/kg, it is nearly about 10 times of current commercial li-ion battery (NCM ternary battery, cobalt acid lithium battery etc.) energy density; Meanwhile, elemental sulfur has rich reserves, cheap, advantages of environment protection, and thus lithium-sulfur cell becomes one of attractive system of most in following battery system.
But there is more problem and restrict its commercialization and promote in lithium-sulfur cell, it is mainly reflected in: poor (the conductance only 5*10 under room temperature of (a) elemental sulfur conductivity in actual applications
-30s/cm); B the intermediate product in () electrochemical reaction process---polysulfide can dissolve in the electrolytic solution, the carrying out with reaction is diffused into negative terminal surface and cathode of lithium generation side reaction, i.e. " effect of shuttling back and forth ", causes coulombic efficiency and reversible capacity all step-downs; Insulating properties insoluble matter Li in (c) cyclic process
2s and Li
2s
2in the deposition on positive electrode surface, cause the electrical contact of active material to worsen, cyclical stability declines; D () change in volume causes active material efflorescence and comes off.The existence of these problems causes the rapid decline of lithium-sulfur cell performance.
For solving these restricted shortcomings of lithium-sulfur cell, current researcher proposes multiple improvement project: (a) optimizes electrolyte, effectively can slow down effect of shuttling back and forth as added in ethers electrolyte by lithium nitrate, thus improves the coulombic efficiency of battery; B () negative pole is protected, carry out surface treatment to cathode of lithium, and isolation polysulfide reacts with it, and reduces self discharge; C the modification of () positive electrode, adopts carbon, metal oxide, conducting polymer etc. to carry out Combined Processing to elemental sulfur, the composite material of preparation sulfur loaded is as positive electrode.Because conducting polymer has the electrology characteristic of metal, the pliability of organic polymer and machinability, provides the effect of conductive network and relieve stresses and storage lithium performance, these features determine conducting polymer and can play an important role at raising lithium-sulfur cell aspect of performance, are a kind of lithium-sulphur cell positive electrode carrier materials with important application prospect.
Patent CN104638236A discloses a kind of polyaniline/sulphur composite material of hollow core-shell structure, patent CN103259000A also discloses a kind of pyrroles tiny balloon/sulphur composite material, found that no matter be that polyaniline or polypyrrole can both play facilitation to lithium-sulfur cell capacity and cycle performance to a certain extent.But the polypyrrole of separately preparation and the firm property of polyaniline due to chain and the strong interaction of interchain, there is shortcoming that is poorly soluble, processing difficulties; Polyaniline and film of poly pyrrole structure can be caused in the process of battery cycle charge-discharge to destroy simultaneously, make decrease in efficiency.The conducting polymer synthetic method that patent CN104638236A and CN103259000A adopts is all the chemical oxidation of gold of being polymerized by initator trigger monomer, first prepare conducting polymer subsequently with elemental sulfur compound by other means, it is many to there is operating procedure in this method, the shortcomings such as easy introducing impurity, and can not ensure that the compound of elemental sulfur is even and absorption is firm, limit the extensive development of this method.
Summary of the invention
The object of the present invention is to provide the preparation method and its usage of the coated elemental sulfur of a kind of composite conductive polymer, to solve the problem proposed in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in acid solution by pyrrole monomer and dopant, regulates pH value of solution to 1 ~ 5, obtains solution A;
(2) preparation of aaerosol solution B: by pyrroles, aniline, thiophene monomer and dopant join in acid solution, add elemental sulfur, emulsifying agent, adopt sand mill to carry out sand milling, the D50 scope in particle diameter that controls is 50 ~ 100nm, control pH value of solution to 4.5 ~ 6.5, obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering to aluminium foil respectively, after process is clean, dries for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, adopts electrochemical method polymerization, forms preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, elemental sulfur is selected from the one in high purity sulphur, sublimed sulfur, its content is 30 ~ 80% of conducting polymer monomer mass, employing electrochemical method is polymerized, and can form polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is enclosed with elemental sulfur at preliminary treatment aluminium foil surface.
Preferably, described dopant be selected from neopelex, lauryl sodium sulfate, sodium naphthalene sulfonate wherein one or both, wherein dopant quality accounting 1 ~ 3% in solution A, dopant quality accounting 5 ~ 8% in solution B.
Preferably, in described solution A, acid solution is selected from sulfuric acid, p-methyl benzenesulfonic acid, oxalic acid a kind of; In described solution A, pyrrole monomer concentration range is 0.05 ~ 0.5mol/L.
Preferably, in described solution B, thiophene monomer content accounts for 2 ~ 5% of conducting polymer monomer molar concentration; Described pyrroles and aniline monomer concentration ratio are 1:5 ~ 5:1; Described conducting polymer total monomer is 0.1 ~ 1mol/L.
Preferably, in described solution B, acid solution is selected from sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, the one in salicylic acid, oxalic acid.
Preferably, described emulsifying agent to be selected from polyethylene glycol-propylene glycol-polyethylene glycol, poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer, ethylene oxide-butylene oxide copolymer one or more; Described emulsifying agent accounts for 3 ~ 5% of aaerosol solution B quality.
Preferably, the electrochemical polymerization that described aluminium foil preprocessing process adopts is galvanostatic method, and control current density is 0.3 ~ 0.8mA/cm2, and generated time is 5 ~ 10s.
Preferably, described electrochemical polymerization is cyclic voltammetry, and the electrochemical parameter wherein controlled is: scanning potential range-0.5 ~ 1.6VSCE, sweep speed 10 ~ 30mV/s, scanning times 8 ~ 15 times.
Preferably, described electrochemical polymerization is galvanostatic method, and the electrochemical parameter wherein controlled is: current density 0.1 ~ 0.35mA/cm2, generated time 10 ~ 15min.
The purposes being coated with the composite conductive polymer of elemental sulfur that the coated simple substance sulphur preparing process of described composite conductive polymer is prepared, the described preliminary treatment aluminium foil being coated with the polypyrrole/polyaniline/polythiophene composite conductive polymer film of elemental sulfur can directly use as positive pole plate of lithium-sulfur cell, and described aluminium foil can be used as collector.
Compared with prior art, the invention has the beneficial effects as follows:
First the present invention carries out electrochemical pre-treatment to aluminium foil, forms polypyrrole reaction interface at aluminium foil surface; In the suspension solution containing pyrroles, aniline, thiophene monomer and elemental sulfur, electrochemical polymerization is carried out to preliminary treatment aluminium foil subsequently, utilize pyrroles can promote aniline and the thiophene monomer feature that simultaneous polymerization generates in film at aluminium foil interface growth simultaneously, control elemental sulfur and synchronously also assemble film forming with the formation of conductive polymer membrane, thus the film of the polypyrrole/polyaniline/coated elemental sulfur of polythiophene composite conductive polymer of composite conducting can be prepared.Usefulness of the present invention is that controlling composite conductive polymer control elemental sulfur while the polymerization of aluminium foil working electrode surface synchronously assembles film forming, elemental sulfur can be dispersed in the reticulated conductive network of composite conductive polymer structure, be combined by S-S bond with the polythiophene in composite conductive polymer simultaneously, reach the effect of load stabilization, the stripping of elemental sulfur in cyclic process can be reduced, reduce " effect of shuttling back and forth ", the swelling problem of lithium-sulphur cell positive electrode can be effectively reduced; Preliminary treatment aluminium foil simultaneously for the polypyrrole/polyaniline/polythiophene composite conductive polymer film being coated with elemental sulfur can directly use as positive pole plate of lithium-sulfur cell, this lithium sulfur battery anode material preparation technology eliminates the process of elemental sulfur and conducting polymer compound, also eliminate the later stage preparation process introducing bonding agent in pole piece preparation process simultaneously, simple to operate.
Accompanying drawing explanation
Accompanying drawing 1: the coated elemental sulfur of composite conductive polymer prepared by embodiment 6 is applied to initial charge/discharge curve under positive pole plate of lithium-sulfur cell 0.1C multiplying power;
Accompanying drawing 2: the coated elemental sulfur of composite conductive polymer prepared by embodiment 6 is applied to cyclic curve under positive pole plate of lithium-sulfur cell 0.5C multiplying power.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in sulfuric acid by the pyrrole monomer of 0.05mol/L and the neopelex of 1wt%, regulates pH value of solution to be obtain solution A after 1;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio of aniline=1:5, and the thiophene monomer of 3% molar ratio joins in sulfuric acid solution together, controlling three kinds of monomer solubility is 0.1mol/L; Add the dopant neopelex of polymer monomer total amount 5%, the emulsifying agent polyethylene glycol-propylene glycol-polyethylene glycol triblock copolymer of 3% and the sublimed sulfur of 30% subsequently, controlling pH value of solution is 4.5; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 50nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.3mA/cm
2, the constant current time is 10s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts cyclic voltammetry electrochemical method to process preliminary treatment aluminium foil: scanning potential range-0.5 ~ 1.6VSCE, sweep speed 10mV/s, scanning times 15 times; Polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is coated with elemental sulfur can be formed at preliminary treatment aluminium foil surface.
Embodiment 2
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in oxalic acid by the pyrrole monomer of 0.15mol/L and the lauryl sodium sulfate of 2wt%, regulates pH value of solution to be obtain solution A after 3;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio of aniline=1:3, and the thiophene monomer of 3% molar ratio joins in oxalic acid solution together, controlling three kinds of monomer solubility is 0.3mol/L; Add the dopant lauryl sodium sulfate of polymer monomer total amount 6%, the emulsifying agent poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer of 4% and the high purity sulphur of 50% subsequently, controlling pH value of solution is 5; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 80nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.6mA/cm
2, the constant current time is 8s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts galvanostatic method electrochemical method to process preliminary treatment aluminium foil: current density 0.1mA/cm2, generated time 15min; Polypyrrole/polyaniline/polythiophene composite conductive polymer the film of the coated elemental sulfur of one deck can be formed at preliminary treatment aluminium foil surface.
Embodiment 3:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in p-methyl benzenesulfonic acid by the pyrrole monomer of 0.25mol/L and the sodium naphthalene sulfonate of 3wt%, regulates pH value of solution to be obtain solution A after 5;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio of aniline=3:1, and the thiophene monomer of 2% molar ratio joins in salicylic acid solution together, controlling three kinds of monomer solubility is 0.5mol/L; Add the dopant sodium naphthalene sulfonate of polymer monomer total amount 7%, the emulsifying agent poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer of 3% and the sublimed sulfur of 80% subsequently, controlling pH value of solution is 5.5; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 100nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.5mA/cm
2, the constant current time is 7s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts galvanostatic method electrochemical method to process preliminary treatment aluminium foil: current density 0.2mA/cm2, generated time 12min; Polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is coated with elemental sulfur can be formed at preliminary treatment aluminium foil surface.
Embodiment 4:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in sulfuric acid by the pyrrole monomer of 0.35mol/L and the sodium naphthalene sulfonate of 1wt%, regulates pH value of solution to be obtain solution A after 1;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio of aniline=5:1, and the thiophene monomer of 3% molar ratio joins in hydrochloric acid solution together, controlling three kinds of monomer solubility is 0.7mol/L; Add the dopant lauryl sodium sulfate of polymer monomer total amount 8%, the emulsifying agent poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer of 4% and the sublimed sulfur of 50% subsequently, controlling pH value of solution is 6; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 80nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.6mA/cm
2, the constant current time is 6s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts cyclic voltammetry electrochemical method to process preliminary treatment aluminium foil: scanning potential range-0.5 ~ 1.6VSCE, sweep speed 20mV/s, scanning times 8 times; Polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is coated with elemental sulfur can be formed at preliminary treatment aluminium foil surface.
Embodiment 5:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in oxalic acid by the pyrrole monomer of 0.45mol/L and the lauryl sodium sulfate of 2wt%, regulates pH value of solution to be obtain solution A after 3;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio ratio of aniline=1:1, and the thiophene monomer of 5% molar ratio joins in p-methyl benzenesulfonic acid solution together, controlling three kinds of monomer solubility is 1mol/L; Add subsequently the dopant sodium naphthalene sulfonate of polymer monomer total amount 5%, the emulsifying agent ethylene oxide-butylene oxide copolymer of 5% and 30% high purity sulphur, control pH value of solution be 6; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 50nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.8mA/cm
2, the constant current time is 5s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts galvanostatic method electrochemical method to process preliminary treatment aluminium foil: current density 0.35mA/cm2, generated time 10min; Polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is coated with elemental sulfur can be formed at preliminary treatment aluminium foil surface.
Embodiment 6:
The coated simple substance sulphur preparing process of composite conductive polymer, comprises the steps:
(1) preparation of solution A: be dissolved in p-methyl benzenesulfonic acid by the pyrrole monomer of 0.5mol/L and the neopelex of 3wt%, regulates pH value of solution to be obtain solution A after 5;
(2) preparation of aaerosol solution B: by monomer according to pyrroles: the molar ratio of aniline=1:1, and the thiophene monomer of 3% molar ratio joins in oxalic acid solution together, controlling three kinds of monomer solubility is 0.8mol/L; Add the dopant lauryl sodium sulfate of polymer monomer total amount 6%, the emulsifying agent polyethylene glycol-propylene glycol-polyethylene glycol triblock copolymer of 4% and the sublimed sulfur of 60% subsequently, controlling pH value of solution is 6.5; Finally solution is adopted sand mill sand milling, controlling solution particle diameter D50 is 50nm; Obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering process respectively to aluminium foil, dry for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, and adopt galvanostatic method electrochemical method to process aluminium foil, current density is 0.5mA/cm
2, the constant current time is 8s; Form preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, adopts cyclic voltammetry electrochemical method to process preliminary treatment aluminium foil: scanning potential range-0.5 ~ 1.6VSCE, sweep speed 30mV/s, scanning times 12 times; Polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is coated with elemental sulfur can be formed at preliminary treatment aluminium foil surface.
The preliminary treatment aluminium foil of the polypyrrole/polyaniline being coated with elemental sulfur/polythiophene composite conductive polymer film prepared by embodiment 1 ~ 6 can directly use as positive pole plate of lithium-sulfur cell.Described aluminium foil can be used as collector.
For detecting the chemical property of the polypyrrole/polyaniline being coated with elemental sulfur/polythiophene composite conductive polymer film prepared by the present invention, with 2016 button cells, electrochemistry evaluation and test is carried out to it.Be formed with one deck using surface prepared by embodiment 6 and be coated with the aluminium foil of the polypyrrole/polyaniline/polythiophene composite conductive polymer film of elemental sulfur as anode pole piece, metal lithium sheet is to electrode, clegard2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell being full of in Ar glove box, adopt Land battery test system to carry out constant current charge-discharge test.As shown in Figure 1, charging/discharging voltage scope is that under 0.3 ~ 2.7V, 0.1C multiplying power, first discharge specific capacity is 11970mAh/g to result;
Have studied again its cyclic curve under 0.5C multiplying power, as shown in Figure 2,0.5C still also maintains the specific discharge capacity of 601mAh/g to result after circulation in 40 weeks after time circulation, be the capability retention of 50.2% of initial discharge specific capacity.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the coated simple substance sulphur preparing process of composite conductive polymer, is characterized in that, comprise the steps:
(1) preparation of solution A: be dissolved in acid solution by pyrrole monomer and dopant, regulates pH value of solution to 1 ~ 5, obtains solution A;
(2) preparation of aaerosol solution B: by pyrroles, aniline, thiophene monomer and dopant join in acid solution, add elemental sulfur, emulsifying agent, adopt sand mill to carry out sand milling, the D50 scope in particle diameter that controls is 50 ~ 100nm, control pH value of solution to 4.5 ~ 6.5, obtain aaerosol solution B;
(3) aluminium foil process: adopt ultrasonic wave to carry out acetone oil removing and ethanol dewatering to aluminium foil respectively, after process is clean, dries for subsequent use;
(4) preparation of preliminary treatment aluminium foil C: adopt three-electrode system, aluminium foil after processing with step 3 is for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution A as supporting electrolyte, controlling reaction temperature is-5 ~ 5 DEG C, adopts electrochemical method polymerization, forms preliminary treatment aluminium foil C;
(5) coated elemental sulfur: adopt three-electrode system, with preliminary treatment aluminium foil C for work electrode, platinized platinum is auxiliary electrode, saturated calomel electrode is reference electrode, take solution B as supporting electrolyte, controlling synthesis temperature is-5 ~ 5 DEG C, elemental sulfur is selected from the one in high purity sulphur, sublimed sulfur, its content is 30 ~ 80% of conducting polymer monomer mass, employing electrochemical method is polymerized, and can form polypyrrole/polyaniline/polythiophene composite conductive polymer film that one deck is enclosed with elemental sulfur at preliminary treatment aluminium foil surface.
2. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, it is characterized in that: described dopant be selected from neopelex, lauryl sodium sulfate, sodium naphthalene sulfonate wherein one or both, wherein dopant quality accounting 1 ~ 3% in solution A, dopant quality accounting 5 ~ 8% in solution B.
3. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, is characterized in that: in described solution A, acid solution is selected from sulfuric acid, p-methyl benzenesulfonic acid, oxalic acid a kind of; In described solution A, pyrrole monomer concentration range is 0.05 ~ 0.5mol/L.
4. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, is characterized in that: in described solution B, thiophene monomer content accounts for 2 ~ 5% of conducting polymer monomer molar concentration; Described pyrroles and aniline monomer concentration ratio are 1:5 ~ 5:1; Described conducting polymer total monomer is 0.1 ~ 1mol/L.
5. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, is characterized in that: in described solution B, acid solution is selected from sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, the one in salicylic acid, oxalic acid.
6. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, is characterized in that: described emulsifying agent to be selected from polyethylene glycol-propylene glycol-polyethylene glycol, poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer, ethylene oxide-butylene oxide copolymer one or more; Described emulsifying agent accounts for 3 ~ 5% of aaerosol solution B quality.
7. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, it is characterized in that: the electrochemical polymerization that described aluminium foil preprocessing process adopts is galvanostatic method, control current density is 0.3 ~ 0.8mA/cm2, and generated time is 5 ~ 10s.
8. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, it is characterized in that: described electrochemical polymerization is cyclic voltammetry, the electrochemical parameter wherein controlled is: scanning potential range-0.5 ~ 1.6VSCE, sweep speed 10 ~ 30mV/s, scanning times 8 ~ 15 times.
9. the coated simple substance sulphur preparing process of composite conductive polymer according to claim 1, it is characterized in that: described electrochemical polymerization is galvanostatic method, the electrochemical parameter wherein controlled is: current density 0.1 ~ 0.35mA/cm2, generated time 10 ~ 15min.
10. the purposes being coated with the composite conductive polymer of elemental sulfur prepared of the coated simple substance sulphur preparing process of the composite conductive polymer according to any one of claim 1 ~ 9, it is characterized in that: described in be coated with the polypyrrole/polyaniline/polythiophene composite conductive polymer film of elemental sulfur preliminary treatment aluminium foil can directly as positive pole plate of lithium-sulfur cell use, described aluminium foil can be used as collector.
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