CN104900848A - Long-service-life lithium-sulfur battery anode and manufacturing method of lithium-sulfur battery - Google Patents
Long-service-life lithium-sulfur battery anode and manufacturing method of lithium-sulfur battery Download PDFInfo
- Publication number
- CN104900848A CN104900848A CN201510364024.XA CN201510364024A CN104900848A CN 104900848 A CN104900848 A CN 104900848A CN 201510364024 A CN201510364024 A CN 201510364024A CN 104900848 A CN104900848 A CN 104900848A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- sulfur
- glucose
- melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the field of batteries and provides a long-service-life lithium-sulfur battery anode and a manufacturing method of a lithium-sulfur battery. The long-service lithium-sulfur battery anode is characterized in that electroconductive polymer polyaniline is taken as a binder, and Li+type Nafion resin covers the surface of the anode. The manufacturing method includes: cutting the anode into wafers, disposing the wafers into a button-type battery shell, and enabling a substrate aluminum film of the anode to contact with the battery shell; disposing a microporous polypropylene membrane on the anode, disposing a lithium cathode with the surface being subjected to nitriding, and enabling a lithium nitride layer of a metal lithium sheet to face the membrane; after cushioning a foamed nickel sheet, adding electrolyte, and sealing a sealing ring and a battery cover to obtain the button-type lithium-sulfur battery. By using a high-performance polyaniline modified sulfur electrode, cycle life and high-rate discharge performance of the lithium-sulfur battery can be improved effectively, the lithium-sulfur battery can be used for electromobiles to serve as a power battery and can be widely applied to large unstable-state power generation stations of wind power generation, solar power generation and tidal power generation to play a role in power adjusting.
Description
Technical field
The invention relates to field of batteries, relate to a kind of lithium anode using surfaces nitrided process, nitrogenous macropore carbon carries sulphur as positive electrode, particularly utilizes melamine and glucose polycondensation, take nano pipe/polyhenylethylene as template, a heat treated obtains the method for nitrogenous macropore carbon; Be binding agent with conductive polymer polyanilinc, make polyaniline network connect nitrogenous macropore carbon and carry the high connductivity positive pole that sulphur particle formed, and there is the long-life positive pole of type lithium ion perfluorinated sulfonic resin protection and the method for lithium-sulfur cell thereof.
Background technology
Lithium-sulfur cell is the one of lithium ion battery, using element sulphur as the positive electrode of battery, has the advantages such as lightweight, capacity is large, memory-less effect.The specific energy of lithium-sulfur cell is far above the lithium ion battery of commercial extensive use.Further, sulphur is a kind of environmental friendliness element, does not substantially pollute environment.Lithium-sulfur cell is the very promising lithium ion battery of one.
Lithium-sulfur cell take lithium metal as negative material, adopt liquid electrolyte, during electric discharge, negative reaction is that lithium loses electronics and becomes lithium ion, and positive pole reaction generates sulfide for sulphur and lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is the discharge voltage that lithium-sulfur cell provides.Under applied voltage effect, the positive pole of lithium-sulfur cell and negative reaction counter movement, be charging process.Elemental sulfur according to unit mass becomes S completely
2-the electricity that can provide can show that the theoretical discharge specific discharge capacity of sulphur is 1675mAh g
-1, the theoretical discharge specific discharge capacity of simple substance lithium is 3860mAh g
-1.Sulphur and lithium complete reaction generate lithium sulfide (Li
2s), time, the theoretical discharge specific energy of corresponding lithium-sulfur cell is 2600Wh kg
-1.Sulphur positive pole and lithium anode are separated the traditional lithium-sulfur cell of formation by micro-pore septum.
The charging and discharging reaction of sulfur electrode is more complicated, and its discharge process mainly comprises two steps, respectively corresponding two discharge platforms: (1) corresponding S
8circulus become S
n 2-the chain structure of (3≤n≤7) ion, and and Li
+in conjunction with the poly-lithium sulfide (Li of generation
2s
n), the discharge platform of this reaction on discharge curve near corresponding 2.4 ~ 2.1V; (2) corresponding S
n 2-the chain structure of ion becomes S
2-and S
2 2-and and Li
+in conjunction with generation Li
2s
2and Li
2s, discharge platform longer near 2.1 ~ 1.8V in the corresponding discharge curve of this reaction, this platform is the main discharge region of lithium-sulfur cell.Be positioned at the further reduction that the corresponding elemental sulfur reduction of 2.5 ~ 2.05V potential region generates solvable polysulfide and polysulfide upon discharging, the polysulfide reduction being positioned at 2.05 ~ 1.5V potential region corresponding solvable generates lithium sulfide solid film, and it covers conductive carbon based surface.During charging, Li in sulfur electrode
2s and Li
2s
2oxidized S
8and S
m 2-(6≤m≤7), can not be completely oxidized to S
8, the charging platform of this charging reaction in charging curve near corresponding 2.5 ~ 2.4V.The maximum problem of current lithium-sulfur cell is: in charge and discharge process, form the poly-lithium sulfide being dissolved in electrolyte, poly-lithium sulfide and the negative metal lithium of dissolving react, and cause capacitance loss, cause lithium-sulfur cell capacity fast decay, show the cycle life of extreme difference.
Utilize nano-calcium carbonate to do template, glucose is heated carbonization, finally removing template with acid, is the common method preparing macropore carbon.Because acid treatment causes macropore carbon complicated process of preparation, and produce a large amount of waste liquid, to environment.Therefore, be necessary to improve macropore carbon preparation technology.
The conductivity extreme difference of the sulphur in sulfur electrode and lithium sulfide, the sulfur electrode material preparation method usually using porous carbon to support sulphur improves the conductivity of sulfur electrode.But the conductivity how improving sulphur and lithium sulfide in porous carbon does not have good method, reduce the particle diameter of sulphur and lithium sulfide, it is an effective method that increase contacts with porous carbon wall.Carrying in sulphur process, have elemental sulfur to be adsorbed on porous carbon particle exterior surface unavoidably, cause resistance between particle to increase, the conductivity of sulfur electrode is deteriorated, and the electrode prepared thus demonstrates very large impedance, and the usefulness having had a strong impact on macropore material with carbon element high connductivity plays.
Polyaniline (PAN) is obtained through chemical oxidation or electrochemical oxidation in acidic aqueous solution by aniline (An) monomer, and conventional oxidant is ammonium persulfate (APS).Polyaniline is dissolved in 1-METHYLPYRROLIDONE.
Ion exchange resin be a kind of containing ionic group, to have ion and select through the macromolecule resin of ability.Ion exchange resin needs larger exchange capacity (ion-selective permeability is good, and conductive capability is strong), suitable imbibition ability, and conductivity is high, and selective penetrated property is good, has higher mechanical strength and chemical and thermal stability.Representative amberplex has proton exchange resins, as perfluorinated sulfonic resin, is commonly called as Nafion, is the product that E.I.Du Pont Company produces.It is the raw material of the proton exchange membrane used in fuel cell.Nafion resin through ion-exchange, by Li
+substitute the proton in Nafion film, can Li be obtained
+type Nafion resin, for lithium-sulfur cell as barrier film [Energy Environ.Sci., 7 (2014) 347-353.], stops polysulfide ion to shuttle back and forth.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and provide a kind of surfaces nitrided process lithium sheet to be negative pole, nitrogenous macropore carbon is sulfur-donor, and conductive polymer polyanilinc is binding agent, surface coverage Li
+the positive pole of type Nafion resin and the preparation method of lithium-sulfur cell.
In order to technical solution problem, solution of the present invention is:
There is provided a kind of preparation method of long-life lithium-sulphur cell positive electrode, it is characterized in that, this positive pole take conductive polymer polyanilinc as binding agent, surface coverage Li
+type Nafion resin, the preparation process of this positive pole is:
(1) getting the concentration that 20g aniline (An) is added to 20mL is in the hydrochloric acid solution of 0.5mol/L, and mixing obtains aniline solution; Moved into after in there-necked flask and put into rotor, be placed on magnetic stirring apparatus;
Getting the concentration that neopelex (LAS) 2g is dissolved in 5.74mL is the hydrochloric acid solution of 1mol/L, obtains neopelex solution; Joined in aforementioned there-necked flask, stirred;
Getting the concentration that ammonium persulfate 24.47g (be 1: 2 by the mol ratio of aniline and ammonium persulfate (APS)) joins 40mL is in the hydrochloric acid solution of 1mol/L, and mixing obtains ammonium persulfate solution;
Ammonium persulfate solution is moved to titration bottle, dropwise adds in aforementioned there-necked flask, rate of titration 0.5 ~ 0.7mL/min; Through suction filtration and 80 DEG C of dry 24h after reaction 2h, obtain electrically conductive polyaniline;
(2) get the nitrogenous macropore carbon of 1g and carry sulfur materials, mix with 0.1 ~ 0.3g electrically conductive polyaniline (in mass ratio 1: 0.1 ~ 0.3) and grind evenly, add 2g 1-METHYLPYRROLIDONE (NMP) again as dispersant, be coated to equably after being modulated into pasty state on aluminium film, dry 2 hours for 70 DEG C under vacuo, obtain Polyaniline-modified sulfur electrode;
(3) getting 10g LiOH is added in the 5wt% perfluor sulfoacid resin solution (Nafion originates from E.I.Du Pont Company) of 100mL, stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+type perfluor sulfoacid resin solution; Aforementioned Polyaniline-modified sulfur electrode be impregnated in Li
+in type perfluor sulfoacid resin solution 2 hours, taking-up was dried, and obtains long-life lithium-sulphur cell positive electrode.
In the present invention, it is utilize melamine and glucose polycondensation that described nitrogenous macropore carbon carries sulfur materials, take nano pipe/polyhenylethylene as template, and heat treated obtains; Concrete steps are:
(1) getting after melamine 10g is heated to 80 DEG C is dissolved in the watery hydrochloric acid of the 5wt% of 50mL; Getting 5 ~ 50g glucose is dissolved in 5 ~ 50mL deionized water, melamine solution is added in glucose solution, makes the mass ratio of melamine and glucose be 1: 0.5 ~ 5; Mixed solution is placed in 90 DEG C of water-baths and fully stirs; To react after 45 minutes liquid viscosity to increase, color from milky white through pale yellow become bronzing after cool, obtain glucose melamine prepolymer solution;
(2) polystyrene (PS) of 5 ~ 10g is dissolved in ethyl acetate (40mL) as decentralized photo A, the ethanol solution (100mL) of the dodecyl sodium sulfate of configuration containing 30wt% is as continuous phase B simultaneously, prepares emulsion C by homogenizer at 8000rpm; Be transferred in ultrasonic cleaner by milky solution C, ultrasonic process 15min obtains Polystyrene suspension;
(3) be dispersed in by Polystyrene suspension in glucose melamine prepolymer solution, stirring reaction 50 minutes under 85 DEG C of heating water baths, then spraying dry, obtains nitrogenous macropore carbon matrix precursor;
(4) under blanket of nitrogen, by nitrogenous macropore carbon matrix precursor with the speed of 10 DEG C/min after room temperature to 160 DEG C, be incubated 2 hours, carry out the polymerization of the glucose melamine degree of depth; Then after being warming up to 900 DEG C with the speed of 10 DEG C/min, be incubated 2 hours, carry out carbonization (generation cracking gas is decomposed in now polystyrene cracking, thus forms through hole); Take out after cooling, after ball milling, obtain the nitrogenous macropore carbon of black;
Be that 7: 3 mechanical mixture are even in mass ratio by elemental sulfur and nitrogenous macropore carbon, be placed in the reactor of 316 stainless steels, after being vacuumized by reactor, be heated to 80 DEG C, react and complete supporting of sulphur after 5 hours; Product is cooled to 25 DEG C, obtained nitrogenous macropore carbon carries sulfur materials.
Invention further provides the method utilizing aforementioned positive electrode to prepare lithium-sulfur cell, concrete number of assembling steps is:
Long-life lithium-sulphur cell positive electrode is cut into the disk that diameter is 18mm, is placed in city dealer's button cell shell (CR2025), the base material aluminium film of positive pole is contacted with battery case; By diameter be 19mm city dealer microporous polypropylene membrane be placed on positive pole, the cathode of lithium getting surfaces nitrided process is placed in (the nitrogen lithium layer of metal lithium sheet is towards barrier film) on polypropylene diaphragm; Be padded with that diameter is 18mm, thick 1mm, voidage are after the foam nickel sheet of 98%, add 0.2mL electrolyte, then potting circle and battery cover realize sealing, obtain button lithium-sulfur cell;
Described electrolyte is with Li [CF
3sO
2)
2n] (LiTFSI) be solute, with dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent, the volume ratio of dioxolanes and EGME is 1: 1, containing one mole of (263g) Li [CF in often liter of electrolyte
3sO
2)
2n].
In the present invention, the preparation method of the negative pole of described surfaces nitrided process is: under argon atmospher protection, with 10Kg/cm
2pressure metal lithium sheet is pressed onto on copper film, formed diameter be the negative pole of 18mm; The copper film being compounded with metal lithium sheet is placed in purity 99.999% High Purity Nitrogen atmosphere, at 25 DEG C, processes 1 hour, form nitrogenize lithium layer on the metal lithium sheet surface covered without copper film, obtain negative pole.
Compared with prior art, beneficial effect of the present invention:
The present invention utilizes melamine and glucose polycondensation, take nano pipe/polyhenylethylene as template, a heat treated can obtain nitrogenous macropore carbon, uses SiO without the need to tradition
2and CaCO
3template needs pickling to remove template, is a green macropore carbon synthesis technique.When nitrogenous macropore carbon carries after sulfur materials to mix with polyaniline and be modulated into pasty state with NMP, polyaniline is dissolved in NMP, be coated to dry on aluminium film after form polyaniline network, macropore carbon is carried sulphur particle and is linked to be entirety by polyaniline network.And polyaniline is fabulous electric conducting material, the nitrogen on polyaniline also possesses the affinity interaction very strong to polysulfide ion, can adsorb the polysulfide ion of escaping from macropore carbon further, strengthens positive pole thus further to the effect of contraction of polysulfide ion.
Further, due to Li
+type perfluorinated sulfonic resin is lithium ion (cation) conduction, stops polysulfide ion (anion) migration, at Polyaniline-modified sulfur electrode surface coverage Li
+type perfluorinated sulfonic resin, stops polysulfide ion to be escaped from macropore carbon further, thus improves the life-span of sulfur electrode further.
Use high-performance Polyaniline-modified sulfur electrode of the present invention, effectively can improve cycle life and the high-rate discharge ability of lithium-sulfur cell, both can be used for electric motor car etc. as electrokinetic cell, also the large-scale unstable state generating such as wind power generation, solar power generation, tidal power generation power station can be widely used in, play the effect of electric adjustment, also can be applicable to stable state generating power station, the peak-trough electricity of balance electricity consumption, improve generating efficiency, reduce cost of electricity-generating.
Accompanying drawing explanation
Fig. 1 is the multiplying power discharging property of the lithium-sulfur cell of assembling in embodiment ten, and rate of charge is 0.2C.
Fig. 2 is the cycle life of the lithium-sulfur cell of assembling in embodiment ten, and charge-discharge magnification is 1C.
Reference numeral in figure is: 1-1 discharge-rate 0.2C; 1-2 discharge-rate 1C; 1-3 discharge-rate 2C; 1-4 discharge-rate 5C; 1-5 discharge-rate 10C.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment one: glucose melamine pre-polymerization
Get melamine 10g to be heated to 80 DEG C and to be dissolved in (50mL) in the watery hydrochloric acid of 5wt%, glucose 5g is dissolved in 5mL deionized water, and the mass ratio of melamine and glucose is 1: 0.5.Melamine solution is added in glucose solution, be placed in 90 DEG C of water-baths, fully stir.React after 45 minutes, liquid viscosity obviously increases, color from milky white through pale yellow become bronzing after, cooling obtain glucose melamine prepolymer solution.
Embodiment two: prepared by Polystyrene suspension
The polystyrene (PS) of 5g is dissolved in ethyl acetate (40mL) as decentralized photo A, the ethanol solution (100mL) of the dodecyl sodium sulfate of configuration containing 30wt% is as continuous phase B simultaneously, preparing emulsion C. by homogenizer at 8000rpm is transferred in ultrasonic cleaner by milky solution C, and ultrasonic process 15min obtains PS suspension.
Embodiment three: prepared by macropore carbon matrix precursor
Get melamine 10g to be heated to 80 DEG C and to be dissolved in (50mL) in the watery hydrochloric acid of 5wt%, glucose 20g is dissolved in 20mL deionized water, and the mass ratio of melamine and glucose is 1: 2.Melamine solution is added in glucose solution, be placed in 90 DEG C of water-baths, fully stir.React after 45 minutes, liquid viscosity obviously increases, color from milky white through pale yellow become bronzing after, cooling obtain glucose melamine prepolymer solution.
The polystyrene (PS) of 7.5g is dissolved in ethyl acetate (40mL) as decentralized photo A, the ethanol solution (100mL) of the dodecyl sodium sulfate of configuration containing 30wt% is as continuous phase B simultaneously, preparing emulsion C. by homogenizer at 8000rpm is transferred in ultrasonic cleaner by milky solution C, and ultrasonic process 15min obtains PS suspension.
PS uniform suspension is scattered in above-mentioned glucose melamine prepolymer solution, water-bath 85 DEG C heating, stirring reaction after 50 minutes spraying dry obtain nitrogenous macropore carbon matrix precursor.
Embodiment four: nitrogenous macropore carbon preparation
Get melamine 10g to be heated to 80 DEG C and to be dissolved in (50mL) in rare salt of 5wt%, glucose 50g is dissolved in 50mL deionized water, and the mass ratio of melamine and glucose is 1: 5.Melamine solution is added in glucose solution, be placed in 90 DEG C of water-baths, fully stir.React after 45 minutes, liquid viscosity obviously increases, color from milky white through pale yellow become bronzing after, cooling obtain glucose melamine prepolymer solution.
The polystyrene (PS) of 10g is dissolved in ethyl acetate (40mL) as decentralized photo A, the ethanol solution (100mL) of the dodecyl sodium sulfate of configuration containing 30wt% is as continuous phase B simultaneously, preparing emulsion C. by homogenizer at 8000rpm is transferred in ultrasonic cleaner by milky solution C, and ultrasonic process 15min obtains PS suspension.
PS uniform suspension is scattered in above-mentioned glucose melamine prepolymer solution, water-bath 85 DEG C heating, stirring reaction after 50 minutes spraying dry obtain nitrogenous macropore carbon matrix precursor.
Under nitrogen atmosphere, nitrogenous macropore carbon matrix precursor is warming up to 110 DEG C from room temperature with the speed of 10 DEG C/min, is incubated 2 hours, carry out the polymerization of the glucose melamine degree of depth.Then be warming up to 900 DEG C with the speed of 10 DEG C/min, be incubated 2 hours, carry out carbonization, generation cracking gas is decomposed in PS cracking simultaneously, forms through hole, takes out, obtain the nitrogenous macropore carbon of black after ball milling after cooling.
Embodiment five: prepared by sulfur electrode material
Be that 7: 3 mechanical mixture are even in mass ratio by the nitrogenous macropore carbon obtained in elemental sulfur and embodiment four, be placed in the reactor of 316 stainless steels, then 80 DEG C are heated to after being vacuumized by reactor, react and complete supporting of sulphur after 5 hours, again product is cooled to 25 DEG C, namely obtained nitrogenous macropore carbon carries sulfur materials.
Embodiment six: prepared by polyaniline
Getting the concentration that 20g aniline (An) solution is added to 20mL is obtain An solution in the hydrochloric acid solution of 0.5mol/L, puts into there-necked flask, is fixed on magnetic stirring apparatus by rotor.Get hydrochloric acid solution (1mol/L) that neopelex (LAS) 2g is dissolved in 5.74mL to obtain LAS solution and join in there-necked flask and stir.The mol ratio of aniline and ammonium persulfate (APS) is n (APS): n (An)=1:2, gets APS 24.47g.Concentration APS being joined 40mL is stir in the hydrochloric acid solution of 1mol/L to obtain APS solution, whole dissolving titration bottle of falling people afterwards, titration bottle is fixed on the shelf of blender, dropwise add in there-necked flask, regulate rate of titration (about 0.5mL/min) to make the titration in 1h of APS solution complete.Namely electrically conductive polyaniline is obtained through suction filtration, 80 DEG C of dry 24h after reaction 2h.
Embodiment seven: prepared by Polyaniline-modified sulfur electrode
Getting the concentration that 20g aniline (An) solution is added to 20mL is obtain An solution in the hydrochloric acid solution of 0.5mol/L, puts into there-necked flask, is fixed on magnetic stirring apparatus by rotor.Get hydrochloric acid solution (1mol/L) that neopelex (LAS) 2g is dissolved in 5.74mL to obtain LAS solution and join in there-necked flask and stir.The mol ratio of aniline and ammonium persulfate (APS) is n (APS): n (An)=1:2, gets APS 24.47g.Concentration APS being joined 40mL is stir in the hydrochloric acid solution of 1mol/L to obtain APS solution, whole dissolving titration bottle of falling people afterwards, titration bottle is fixed on the shelf of blender, dropwise add in there-necked flask, regulate rate of titration (about 0.6mL/min) to make the titration in 1h of APS solution complete.Namely electrically conductive polyaniline is obtained through suction filtration, 80 DEG C of dry 24h after reaction 2h.
In Example five, the nitrogenous macropore carbon of preparation carries sulfur materials (1g), grind evenly after at 1: 0.1 in mass ratio with above-mentioned polyaniline (0.1g), add the 1-METHYLPYRROLIDONE (NMP:2g) as dispersant, then be coated to equably after being modulated into pasty state on aluminium film, at 70 DEG C, vacuum obtained Polyaniline-modified sulfur electrode after 2 hours.
Embodiment eight: the Li of Polyaniline-modified sulfur electrode
+type perfluorinated sulfonic resin covers
Getting the concentration that 20g aniline (An) solution is added to 20mL is obtain An solution in the hydrochloric acid solution of 0.5mol/L, puts into there-necked flask, is fixed on magnetic stirring apparatus by rotor.Get hydrochloric acid solution (1mol/L) that neopelex (LAS) 2g is dissolved in 5.74mL to obtain LAS solution and join in there-necked flask and stir.The mol ratio of aniline and ammonium persulfate (APS) is n (APS): n (An)=1:2, gets APS 24.47g.Concentration APS being joined 40mL is stir in the hydrochloric acid solution of 1mol/L to obtain APS solution, whole dissolving titration bottle of falling people afterwards, titration bottle is fixed on the shelf of blender, dropwise add in there-necked flask, regulate rate of titration (about 0.7mL/min) to make the titration in 1h of APS solution complete.Namely electrically conductive polyaniline is obtained through suction filtration, 80 DEG C of dry 24h after reaction 2h.
In Example five, the nitrogenous macropore carbon of preparation carries sulfur materials (1g), grind evenly after at 1: 0.2 in mass ratio with above-mentioned polyaniline (0.2g), add the 1-METHYLPYRROLIDONE (NMP:2g) as dispersant, then be coated to equably after being modulated into pasty state on aluminium film, at 70 DEG C, vacuum obtained Polyaniline-modified sulfur electrode after 2 hours.
Getting 10g LiOH is added in 5wt% perfluorinated sulfonic resin (Nafion) solution (originating from E.I.Du Pont Company) of 100mL, stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+type perfluor sulfoacid resin solution; Above-mentioned electrode be impregnated in Li
+in type perfluor sulfoacid resin solution 2 hours, taking-up was dried, and obtains Li
+the polypyrrole modifying sulfur electrode that type perfluorinated sulfonic resin covers.
Embodiment nine: prepared by negative pole
Under argon atmospher protection, at 10Kg/cm
2pressure under metal lithium sheet is pressed onto on copper film, formed diameter be the negative pole of 18mm; Metal lithium sheet is processed in the atmosphere that 25 DEG C are placed in High Purity Nitrogen (purity 99.999%) negative pole obtaining for 1 hour possessing the protection of nitrogenize lithium layer, forms nitrogenize lithium layer in the negative terminal surface covered without copper film.
Embodiment ten: lithium-sulfur cell is assembled
By the Li obtained in embodiment eight
+the polypyrrole modifying sulfur electrode that type perfluorinated sulfonic resin covers, cut-off footpath is the disk of 18mm, and be placed in city dealer's button cell shell (CR2025) as positive pole, positive-pole base material aluminium film contacts with by battery case; City being bought to resell microporous polypropylene membrane (diameter is 19mm) is placed on sulfur electrode; The negative pole of preparation in embodiment nine is placed in (the nitrogen lithium layer of lithium sheet is towards barrier film) on barrier film; On pad, diameter is 18mm, thick 1mm, voidage be after the foam nickel sheet of 98%, adds electrolyte 0.2mL, seals after adding sealing ring and battery cover, obtain button lithium-sulfur cell.As shown in Figure 1, Fig. 2 is its cycle life to its rate discharge curves, and charge-discharge magnification is 1C, C=1675mAh/g.
Finally, above announcement is only specific embodiments of the invention.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. a preparation method for long-life lithium-sulphur cell positive electrode, is characterized in that, this positive pole take conductive polymer polyanilinc as binding agent, surface coverage Li
+type Nafion resin, the preparation process of this positive pole is:
(1) getting the concentration that 20g aniline is added to 20mL is in the hydrochloric acid solution of 0.5mol/L, and mixing obtains aniline solution; Moved into after in there-necked flask and put into rotor, be placed on magnetic stirring apparatus;
Getting the concentration that neopelex 2g is dissolved in 5.74mL is the hydrochloric acid solution of 1mol/L, obtains neopelex solution; Joined in aforementioned there-necked flask, stirred;
Getting the concentration that ammonium persulfate 24.47g joins 40mL is in the hydrochloric acid solution of 1mol/L, and mixing obtains ammonium persulfate solution;
Ammonium persulfate solution is moved to titration bottle, dropwise adds in aforementioned there-necked flask, rate of titration 0.5 ~ 0.7mL/min; Through suction filtration and 80 DEG C of dry 24h after reaction 2h, obtain electrically conductive polyaniline;
(2) get the nitrogenous macropore carbon of 1g and carry sulfur materials, mix with 0.1 ~ 0.3g electrically conductive polyaniline and grind evenly, add 2g 1-METHYLPYRROLIDONE (NMP) again as dispersant, be coated to equably after being modulated into pasty state on aluminium film, dry 2 hours for 70 DEG C under vacuo, obtain Polyaniline-modified sulfur electrode;
(3) getting 10g LiOH is added in the 5wt% perfluor sulfoacid resin solution of 100mL, stirs after 30 minutes, and superfluous LiOH is fallen in centrifugation, obtains Li
+type perfluor sulfoacid resin solution; Aforementioned Polyaniline-modified sulfur electrode be impregnated in Li
+in type perfluor sulfoacid resin solution 2 hours, taking-up was dried, and obtains long-life lithium-sulphur cell positive electrode.
2. method according to claim 1, is characterized in that, it is utilize melamine and glucose polycondensation that described nitrogenous macropore carbon carries sulfur materials, take nano pipe/polyhenylethylene as template, and heat treated obtains; Concrete steps are:
(1) getting after melamine 10g is heated to 80 DEG C is dissolved in the watery hydrochloric acid of the 5wt% of 50mL; Getting 5 ~ 50g glucose is dissolved in 5 ~ 50mL deionized water, melamine solution is added in glucose solution, makes the mass ratio of melamine and glucose be 1: 0.5 ~ 5; Mixed solution is placed in 90 DEG C of water-baths and fully stirs; To react after 45 minutes liquid viscosity to increase, color from milky white through pale yellow become bronzing after cool, obtain glucose melamine prepolymer solution;
(2) polystyrene of 5 ~ 10g is dissolved in as decentralized photo A in 40mL ethyl acetate, configures 100mL simultaneously and contain the ethanol solution of the dodecyl sodium sulfate of 30wt% as continuous phase B, prepare emulsion C by homogenizer at 8000rpm; Be transferred in ultrasonic cleaner by milky solution C, ultrasonic process 15min obtains Polystyrene suspension;
(3) be dispersed in by Polystyrene suspension in glucose melamine prepolymer solution, stirring reaction 50 minutes under 85 DEG C of heating water baths, then spraying dry, obtains nitrogenous macropore carbon matrix precursor;
(4) under blanket of nitrogen, by nitrogenous macropore carbon matrix precursor with the speed of 10 DEG C/min after room temperature to 160 DEG C, be incubated 2 hours, carry out the polymerization of the glucose melamine degree of depth; Then, after being warming up to 900 DEG C with the speed of 10 DEG C/min, being incubated 2 hours, carrying out carbonization; Take out after cooling, after ball milling, obtain the nitrogenous macropore carbon of black;
Be that 7: 3 mechanical mixture are even in mass ratio by elemental sulfur and nitrogenous macropore carbon, be placed in the reactor of 316 stainless steels, after being vacuumized by reactor, be heated to 80 DEG C, react and complete supporting of sulphur after 5 hours; Product is cooled to 25 DEG C, obtained nitrogenous macropore carbon carries sulfur materials.
3. utilize positive pole described in claim 1 to prepare the method for lithium-sulfur cell, it is characterized in that, the number of assembling steps of this lithium-sulfur cell is:
Long-life lithium-sulphur cell positive electrode is cut into the disk that diameter is 18mm, is placed in city dealer button cell shell, the base material aluminium film of positive pole is contacted with battery case; By diameter be 19mm city dealer microporous polypropylene membrane be placed on positive pole, the cathode of lithium getting surfaces nitrided process is placed on polypropylene diaphragm, and the nitrogen lithium layer of metal lithium sheet is towards barrier film; Be padded with that diameter is 18mm, thick 1mm, voidage are after the foam nickel sheet of 98%, add 0.2mL electrolyte, then potting circle and battery cover realize sealing, obtain button lithium-sulfur cell;
Described electrolyte is with Li [CF
3sO
2)
2n] be solute, with the mixture of dioxolanes and EGME for solvent, the volume ratio of dioxolanes and EGME is 1: 1, containing one mole of Li [CF in often liter of electrolyte
3sO
2)
2n].
4. method according to claim 3, is characterized in that, the preparation method of the negative pole of described surfaces nitrided process is: under argon atmospher protection, with 10Kg/cm
2pressure metal lithium sheet is pressed onto on copper film, formed diameter be the negative pole of 18mm; The copper film being compounded with metal lithium sheet is placed in purity 99.999% High Purity Nitrogen atmosphere, at 25 DEG C, processes 1 hour, form nitrogenize lithium layer on the metal lithium sheet surface covered without copper film, obtain negative pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510364024.XA CN104900848B (en) | 2015-06-25 | 2015-06-25 | The preparation method of long-life lithium-sulphur cell positive electrode and lithium-sulfur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510364024.XA CN104900848B (en) | 2015-06-25 | 2015-06-25 | The preparation method of long-life lithium-sulphur cell positive electrode and lithium-sulfur cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104900848A true CN104900848A (en) | 2015-09-09 |
| CN104900848B CN104900848B (en) | 2017-07-18 |
Family
ID=54033368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510364024.XA Expired - Fee Related CN104900848B (en) | 2015-06-25 | 2015-06-25 | The preparation method of long-life lithium-sulphur cell positive electrode and lithium-sulfur cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104900848B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898774A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | One kind peels off carbon block and its preparation and application |
| CN107845773A (en) * | 2016-09-19 | 2018-03-27 | 天津大学 | A kind of method that lithium sulphur battery electrode is directly prepared using sulfide hydrogen regenerant |
| CN109638205A (en) * | 2018-12-21 | 2019-04-16 | 河南景创新能源科技有限公司 | A kind of lithium-sulfur cell modified diaphragm of fibrous web-like and its preparation method and application |
| CN110112390A (en) * | 2019-05-10 | 2019-08-09 | 浙江大学 | The preparation method and applications of easily-activated high carrying capacity lithium sulfide carbon composite |
| CN111952540A (en) * | 2020-08-26 | 2020-11-17 | 复阳固态储能科技(溧阳)有限公司 | Lithium-free positive electrode lithium battery system and preparation method of electrode in-situ lithium nitride film |
| CN111952517A (en) * | 2020-08-26 | 2020-11-17 | 复阳固态储能科技(溧阳)有限公司 | Diaphragm containing lithium nitride thin film layer and preparation method and application thereof |
| CN112635770A (en) * | 2020-12-17 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Lithium ion battery pre-lithiation positive pole piece and preparation method of lithium ion battery |
| CN115036447A (en) * | 2022-07-15 | 2022-09-09 | 中国科学技术大学 | Lithium/sodium metal battery electrode plate protective coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362316A (en) * | 2014-10-28 | 2015-02-18 | 华南师范大学 | Lithium-sulfur battery composite cathode material, and preparation method and application thereof |
| CN104466138A (en) * | 2014-12-24 | 2015-03-25 | 华南师范大学 | Spherical composite positive pole material for lithium sulfur battery and preparation method and application of spherical composite positive pole material |
| CN104638236A (en) * | 2015-01-16 | 2015-05-20 | 中国计量学院 | Preparation method of polyaniline/sulfur composite material with hollow core-shell structure |
-
2015
- 2015-06-25 CN CN201510364024.XA patent/CN104900848B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362316A (en) * | 2014-10-28 | 2015-02-18 | 华南师范大学 | Lithium-sulfur battery composite cathode material, and preparation method and application thereof |
| CN104466138A (en) * | 2014-12-24 | 2015-03-25 | 华南师范大学 | Spherical composite positive pole material for lithium sulfur battery and preparation method and application of spherical composite positive pole material |
| CN104638236A (en) * | 2015-01-16 | 2015-05-20 | 中国计量学院 | Preparation method of polyaniline/sulfur composite material with hollow core-shell structure |
Non-Patent Citations (1)
| Title |
|---|
| GAORAN LI等: ""A multi functional binder with lithium ion conductive polymer and polysulfide absorbents to improve cycleability of lithium-sulfur batteries"", 《JOURNAL OF POWER SOURCE》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898774A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | One kind peels off carbon block and its preparation and application |
| CN107845773A (en) * | 2016-09-19 | 2018-03-27 | 天津大学 | A kind of method that lithium sulphur battery electrode is directly prepared using sulfide hydrogen regenerant |
| CN109638205A (en) * | 2018-12-21 | 2019-04-16 | 河南景创新能源科技有限公司 | A kind of lithium-sulfur cell modified diaphragm of fibrous web-like and its preparation method and application |
| CN109638205B (en) * | 2018-12-21 | 2021-05-11 | 河南景创新能源科技有限公司 | Fiber-mesh-shaped modified diaphragm of lithium-sulfur battery and preparation method and application thereof |
| CN110112390A (en) * | 2019-05-10 | 2019-08-09 | 浙江大学 | The preparation method and applications of easily-activated high carrying capacity lithium sulfide carbon composite |
| CN110112390B (en) * | 2019-05-10 | 2020-08-25 | 浙江大学 | Preparation method and application of easily-activated high-load lithium sulfide carbon composite material |
| CN111952540A (en) * | 2020-08-26 | 2020-11-17 | 复阳固态储能科技(溧阳)有限公司 | Lithium-free positive electrode lithium battery system and preparation method of electrode in-situ lithium nitride film |
| CN111952517A (en) * | 2020-08-26 | 2020-11-17 | 复阳固态储能科技(溧阳)有限公司 | Diaphragm containing lithium nitride thin film layer and preparation method and application thereof |
| CN111952540B (en) * | 2020-08-26 | 2022-04-12 | 复阳固态储能科技(溧阳)有限公司 | Lithium-free positive electrode lithium battery system and preparation method of electrode in-situ lithium nitride film |
| CN112635770A (en) * | 2020-12-17 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Lithium ion battery pre-lithiation positive pole piece and preparation method of lithium ion battery |
| CN115036447A (en) * | 2022-07-15 | 2022-09-09 | 中国科学技术大学 | Lithium/sodium metal battery electrode plate protective coating and preparation method thereof |
| CN115036447B (en) * | 2022-07-15 | 2023-08-29 | 中国科学技术大学 | Lithium/sodium metal battery electrode plate protective coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104900848B (en) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104900848A (en) | Long-service-life lithium-sulfur battery anode and manufacturing method of lithium-sulfur battery | |
| Wang et al. | A lightweight multifunctional interlayer of sulfur–nitrogen dual-doped graphene for ultrafast, long-life lithium–sulfur batteries | |
| CN104592541B (en) | Micropore polybenzimidazole membrane and modified polyphenyl and imidazoles are the lithium-sulfur cell of barrier film | |
| CN104577083B (en) | Positive electrode sulfur-carrying material of lithium-sulfur battery and preparation method of lithium-sulfur battery | |
| CN108963205A (en) | A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application | |
| CN104617247B (en) | Preparation method of tandem laminated lithium-sulfur battery | |
| CN102938475B (en) | Sodium-sulfur battery and manufacture method thereof | |
| CN108899579A (en) | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| CN104900847B (en) | Sulfur electrode preparation method by in-situ polymerization of pyrrole monomer | |
| CN104600349A (en) | High-safety flexibly-packaged lithium-sulfur battery and anode material thereof | |
| CN105047984B (en) | It is a kind of to suppress the high-lithium ion conduction lithium-sulfur cell that polysulfide ion shuttles | |
| CN108232254A (en) | A kind of preparation method of used in proton exchange membrane fuel cell proton exchange membrane | |
| CN108630928A (en) | A kind of self-supporting grading-hole positive electrode, preparation method and its application on lithium-sulfur cell | |
| CN105006558A (en) | Lithium negative electrode with hydrotreated surface and solution-type half-flow lithium-sulfur battery thereof | |
| CN112239230B (en) | Hierarchical structure coating diaphragm for lithium-sulfur battery and preparation method thereof | |
| CN110085864A (en) | The preparation method and application of potassium or based lithium-ion battery positive plate | |
| CN114188541A (en) | Positive electrode plate of lithium ion battery and preparation method thereof | |
| CN109802078A (en) | A kind of soft graphite alkenyl composite polyimide material of membrane structure, preparation method and applications | |
| CN111584876B (en) | Metal negative electrode and application thereof | |
| CN112242554A (en) | Composite solid electrolyte membrane, preparation method thereof and solid battery | |
| CN116470130A (en) | NH 2- Hydrogen bond crosslinking quasi-solid mixed base lithium ion battery and diaphragm preparation method | |
| CN105742619A (en) | Amorphous-form manganese oxide coated iron oxide lithium/sodium ion battery anode material and preparation method thereof | |
| CN104993167B (en) | A kind of lithium electrode and its lithium-sulfur cell of pyrroles's surface treatment | |
| CN104610569A (en) | Novel sodium-sulfur battery and preparation method of separator of battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170718 Termination date: 20190625 |