CN104716324A - Lithium-sulfur battery positive electrode making method - Google Patents

Lithium-sulfur battery positive electrode making method Download PDF

Info

Publication number
CN104716324A
CN104716324A CN201310694530.6A CN201310694530A CN104716324A CN 104716324 A CN104716324 A CN 104716324A CN 201310694530 A CN201310694530 A CN 201310694530A CN 104716324 A CN104716324 A CN 104716324A
Authority
CN
China
Prior art keywords
carbon
ptfe
template
sulfur compound
carbon element
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
Application number
CN201310694530.6A
Other languages
Chinese (zh)
Other versions
CN104716324B (en
Inventor
王倩
张华民
张益宁
王美日
曲超
马艺文
吴宝山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201310694530.6A priority Critical patent/CN104716324B/en
Publication of CN104716324A publication Critical patent/CN104716324A/en
Application granted granted Critical
Publication of CN104716324B publication Critical patent/CN104716324B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/36—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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lithium-sulfur battery positive electrode making method, first, a carbon material is loaded onto the surface of one side or two sides of a metal aluminum foil of a positive electrode current collector; then a carbon sulfur complex, PTFE (polytetrafluoroethylene) and a carbon material are mixed, or the carbon sulfur complex is mixed with the PTFE to prepare a flexible electrode; the carbon-material-loaded surface of one side or two sides of the positive electrode current collector is attached with the flexible electrode to prepare a positive electrode body; and finally the flexible-electrode-attached surface of the positive electrode body is coated with a polymer film to prepare the lithium-sulfur battery positive electrode. According to the self characteristics of a lithium-sulfur battery, the battery positive electrode structure is improved, and the electrochemical performance is improved.

Description

A kind of manufacture method of lithium-sulphur cell positive electrode
Technical field
The present invention relates to a kind of lithium-sulfur cell field, particularly a kind of a kind of method of preparing of lithium-sulphur cell positive electrode.
Background technology
Modern science and technology develop rapidly, the demand of the energy is also increased day by day, traditional energy is petered out, although emerging energy focuses on environmental friendliness more, but all there is very important shortcoming, as wind-force and solar energy etc., all there is a problem, electric energy is unstable, and therefore chemical energy storage just highlights its importance.Lithium-sulfur cell relies on its high-energy-density and low material cost, becomes the focus of recent research.
Lithium-sulphur cell positive electrode active material is sulphur simple substance, but because the electric conductivity of elemental sulfur is poor, usually porous or the larger material with carbon element (as mesoporous carbon, carbon nano-fiber, carbon nano-tube, expanded graphite and Graphene etc.) of specific surface are synthesized carbon-sulfur compound as conductive agent and elemental sulfur by high-temperature liquid-phase or vapor phase method.The higher 1675mAh/g of specific discharge capacity due to sulphur positive electrode, the various graphite cathodes of industrialization cannot match, some height ratio capacity negative material such as silicon etc. is also in conceptual phase at present, and therefore lithium-sulfur cell many employings lithium metal (theoretical capacity 3800mAh/g) is as negative pole.
The exoelectrical reaction of lithium-sulfur cell is divided into two stages substantially, first stage, the electronics of elemental sulfur generates polysulfide root ion, dissolve in electrolyte, due to concentration diffusion, polysulfide root ion can move to negative pole, directly chemical reaction occurs with lithium metal, and this is also that self discharge and the low basic reason of coulombic efficiency occur; Second stage, the further electronics of polysulfide root ion also generates insoluble Li with the lithium ion in electrolyte 2s 2and Li 2s, carbon electrode deposits, and finally generates Li by S 2s 2and Li 2s, volumetric expansion, cause carbon matrix structure to cave in and with the stripping mutually of collector, contact internal resistance sharply raises, and causes the concentration of electrolyte and viscosity to increase due to the dissolving of the first step, the diffusion difficulty of ion in positive pole, therefore cause, product covers in carbon electrodes, prevents polysulfide root ion in the deposition of electrode interior active site, and this is also the basic reason of lithium-sulfur cell capacity attenuation.Polysulfide root ion how can be stoped to the diffusion of negative pole, strengthen the adhesion of collector and active material, and abundant duct can be produced in the electrodes, for the dissolving of intermediate product and the rapid diffusion mass transfer of lithium ion provide enough passages, become the emphasis that this is research.
Summary of the invention
For the problems referred to above, in conjunction with lithium-sulfur cell id reaction mechanism, the present invention proposes a kind of a kind of method preparing lithium-sulphur cell positive electrode.First, make between collector metal forming and active material electrode and cushion carbon, layer object be solve the change of active material volume causes in charge and discharge process anode structure cave in and with the stripping of collector; Second, added by template or pore creating material, for producing suitable pore passage structure in positive electrode, the transmission enabled as the dissolving of intermediate product and ion, electronics provides adequate space, for redox reaction provides broader active surface, thus reduce the polarization of course of reaction, improve energy and cycle performance; Finally, add at positive electrode surface and be coated with one layer of polymeric film, hinder the concentration diffusion of polysulfide root ion, thus effectively reduce self discharge, improve the Kunlun efficiency.
For achieving the above object, complete skill scheme provided by the invention is as follows:
First material with carbon element is supported on the surface, metal aluminum foil one or both sides of plus plate current-collecting body;
Carbon-sulfur compound, PTFE and material with carbon element are mixed, or just carbon-sulfur compound and PTFE mixing, obtained flexible electrode; Flexible electrode is amplexiformed on the surface, one or both sides being supported with material with carbon element in plus plate current-collecting body, obtained positive pole main body;
Finally have the surface of flexible electrode to add the film preparation of painting one layer of polymeric in positive pole main body to form.
Concrete preparation process is as follows,
1) collector process
Using the aluminium foil as plus plate current-collecting body, put into acid solution, corrode 1 ~ 10min, take out and immerse again in deionized water, ultrasonic 10 ~ 50s, air-dry stand-by;
By in the mixed solution of water-soluble for material with carbon element and ethanol, ultrasonic 10 ~ 60min, adds PTFE emulsion, fully mixes, ultrasonic 20 ~ 60min, treats that this mixed liquor is even, stand-by;
Be laid on 50 ~ 100 DEG C of heating plates by the aluminium foil after process, adopt the mode of spraying to be sprayed on aluminium foil side or two side surfaces ultrasonic uniform mixed liquor, material with carbon element load amount controls at 0.1-0.5mg/cm 2, dry, roll squeezer roll-in, to aluminium foil original thickness, obtains collector;
2) positive pole body making
Carbon-sulfur compound is as active material, and conductive agent is material with carbon element, and binding agent is PTFE; By in the mixed solution of carbon-sulfur compound or carbon-sulfur compound and the blended water-soluble and ethanol of conductive agent, ultrasonic 20 ~ 60min, adds PTFE emulsion, and ultrasonic at least 30min is to dissolution homogeneity;
In homogeneous solution, add template and/or pore creating material, mix;
Above-mentioned mixed liquor is heated to 40 ~ 80 DEG C of stirrings, by solvent evaporates, until remaining solid material becomes bulk; Use roll squeezer roll-forming, be finally pressed into 60 ~ 300 μm of film-form flexible electrodes, in air, shelve 1 ~ 30 minute, cut to required size, after superimposed with the collector made in step 1), put into hydraulic press;
If the current collector aluminum foil side surface spraying of step 1) has material with carbon element layer, then film-form flexible electrode and aluminium foil one side surface being coated with material with carbon element layer are fitted in opposite directions; If aluminium foil two side surface is all coated with material with carbon element layer, two film-form flexible electrodes are fitted in respectively two side surfaces of aluminium foil;
0.5 ~ 5MPa pressure compacting, 1 ~ 10min is adopted under room temperature; Dry at 50 ~ 100 DEG C; Obtain positive pole main body;
If add the electrode of template, after oven dry, need electrode to immerse in the cleaning fluid of this template, remove template, washed with de-ionized water, dry obtained positive pole main body for 40 ~ 80 DEG C;
3) protective layer makes
High molecular polymer is divided the jelly being dissolved in solvent and making between mass fraction 0.5% ~ 10%; Jelly is applied to the film-form flexible electrode surface of positive pole main body, dry to obtain electrode for 40 ~ 100 DEG C, it is 1 ~ 100 μm that jelly coating is done thick.
In step 1), acid solution is the oxalic acid of mass concentration 0.5% ~ 10%, acetic acid or hydrochloric acid solution; Aluminium foil original thickness is the thickness before not spraying, and thickness is 7 ~ 20 μm;
Step 1) and step 2) described material with carbon element comprise in amorphous carbon, the mesoporous carbon of template synthesis, carbon nano-fiber, carbon nano-tube, expanded graphite, Graphene one or two or more kinds; The volumetric concentration 1% ~ 20% of ethanol in the mixed solution of water and ethanol; In PTFE emulsion, the solids content of PTFE is 0.1% ~ 70%; The material with carbon element mass fraction dissolved in water described in step 1) and alcohol mixeding liquid is 0.1% ~ 1%; The mass ratio of material with carbon element: PTFE is 95 ~ 60:5 ~ 40.
Step 2) described carbon-sulfur compound is the carbon-sulfur compound adopting high-temperature liquid-phase Melting Synthesis;
Carbon-sulfur compound: conductive agent: PTFE mass ratio is 95 ~ 50:0 ~ 40:5 ~ 40, by water-soluble for three with the mixed solution of ethanol, solid content is between 0.5% ~ 10%.
Step 2) described pore creating material comprise in inorganic pore creating material, organic pore-forming agents, biological pore creating material one or two or more kinds; Wherein inorganic pore creating material is calcium carbonate, magnesium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium or ammonium chloride; Organic pore-forming agents is polyethylene glycol, and biological pore creating material is the starch containing ferment quality 1%; The quality of pore creating material is 0.1% ~ 10% of carbon-sulfur compound quality;
Step 2) described template is one or more in hard template, non-silicon oxide, inorganic salts, comprises different-shape, spherical or longilineal Ludox, nanometer silica gel, order mesoporous silicate and molecular sieve; Non-silicon oxide and the common hydroxide comprising nickel oxide, calcium oxide, magnesium oxide, manganese oxide and these metals, halide, carbonate compound, acetate compound and other organic acid salt compound of inorganic salts;
Template is 1% ~ 30% of carbon-sulfur compound quality; The cleaning fluid of template is deionized water, hydrofluoric acid or hydrochloric acid.
High molecular polymer described in step 3) is one or two or more kinds in naphthols, cyclodextrin, gelatin, poly(ethylene oxide), Kynoar, polytetrafluoroethylene, polyhexafluoropropylene, polymethyl methacrylate, polyethyl acrylate, polystyrene, polyvinyl alcohol, PVP, butylbenzene diene.
Described in step 3), the solvent of dissolve polymer comprises one or two or more kinds in water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, acetonitrile, 1-METHYLPYRROLIDONE, toluene.
By obtained positive plate and anode ear ultra-sonic welded, 60 DEG C of more than vacuum drying 24h, proceed to and are full of in the glove box of argon gas.
In glove box, put into barrier film by positive pole, in the middle of negative pole, after individual layer superposition, multi-layer stacks or individual layer superposition, the mode such as winding makes battery core, load in battery case, vacuum leaves standstill more than 12h after injecting electrolyte, and seal battery, so far battery completes.
Beneficial effect of the present invention:
The present invention, in conjunction with the feature of lithium-sulfur cell self, improves for battery cathode structure, respectively for lithium-sulfur cell key restriction factors, suits the remedy to the case, and effectively promotes its chemical property.
First, the carbon coating on aluminium foil, not only can the bonding force of enhanced activity electrode layer and collector, can also play certain cushioning effect, and be conducive to electrical conductivity, effectively reduce contact internal resistance when active material is reset in the electrodes;
Second, template and pore creating material method is adopted to carry out pore-creating to positive pole, can by selecting template and theory calculate, the control pore size of qualitative, quantitative, the pattern in hole and total pore volume, make to exist in electrode the micropore required for us, mesoporous, mesopore and macropore.This pore space structure of electrode is beneficial to the infiltration of electrolyte, and the transmission for ion and intermediate product provides abundant and passage fast, for redox reaction provides larger reactivity face, thus effectively reduces impedance and degree of polarization.
In addition, thin polymer film is swelling in the electrolytic solution, effect similar gels electrolyte, the lithium ion transport of small particle diameter is substantially unaffected, the diffusion of solvable large molecule polysulfide root ion is restricted, hinder polysulfide root ion to depart from positive pole to a certain extent, suppress to shuttle back and forth effect, play the effect of the solid sulphur of resistance sulphur.
Accompanying drawing explanation
Fig. 1 is electrode vertical section schematic diagram;
1-aluminum foil current collector; 2-carbon coating; 3-electrode body; 4-electrode interior duct; 5-protective finish.
Fig. 2 is the AC impedance comparison diagram of embodiment 1 and comparative example;
Fig. 3 is the circulation volume comparison diagram of embodiment 2 and comparative example.
Embodiment
Embodiment 1
1) collector process
Using the aluminium foil (20 μm) as lithium-sulphur cell positive electrode collector, put into the oxalic acid solution of 5%, corrode 1min, take out and immerse again in deionized water, ultrasonic 10s, air-dry stand-by;
Water and ethanol is body 1:9 mixed preparing mixed liquor by volume, and superP and AB is water-soluble with in the mixed liquor of ethanol according to the mixing of 1:1 mass ratio, mass fraction 0.5%, ultrasonic 20min; Select solid content 60%PTFE emulsion, by material with carbon element: PTFE(is solid) mass ratio 80%:20% add PTFE emulsion, fully mix, ultrasonic 30min, treat that this mixed liquor is even, stand-by;
Be laid on 80 DEG C of heating plates by the aluminium foil after process, adopt the mode of spraying to be sprayed on aluminium foil side or two side surfaces ultrasonic uniform mixed liquor, material with carbon element load amount controls at 0.2mg/cm 2, dry, roll squeezer roll-in, to aluminium foil original thickness (20 μm), obtains collector;
2) positive pole body making
Carbon-sulfur compound, the PTFE of conductive agent SuperP and solid content 60%, according to the ratio of mass ratio 8:1:1 take respectively 0.8g, 0.1g, 0.167g, first carbon-sulfur compound and conductive agent are dissolved in the deionized water of 100ml volume ratio 9:1 and the mixed solution of ethanol, ultrasonic 30min, add 0.167gPTFE emulsion (solid content 60%), ultrasonic more than 30min, to dissolution homogeneity.The particle diameter respectively taking 10mg is respectively the Silica hydrogel template of 100nm, 500nm and 1 μm, adds in this homogeneous solution.
The water-bath that above-mentioned mixed liquor puts into 70 DEG C heated, with stirring, aqueous solvent wherein and ethanol are volatilized away, remaining solid material becomes bulk.Use roll squeezer roll-forming, finally be pressed into 200 μm of film-form flexible electrodes, 10 minutes are shelved in air, cut required size, put into hydraulic press (film-form flexible electrode fits in material with carbon element layer side) with the current collector layers made in step 1), under room temperature, adopt 2MPa pressure to suppress 10min.Dry in 50 DEG C of air dry ovens.
Drying rear electrode immerses in 10%HF, soaks 30min, deionized water soaking and washing, 80 DEG C of oven dry.
3) protective layer makes
Select the Kynoar 0.1g of molecular weight about 900,000 to be scattered in 10gN-methyl pyrrolidone, make jelly.Use scraper adjustment thickness 100 μm, by its blade coating to step 2) the middle positive pole host film shape flexible electrode of the having dried surface made, 60 DEG C of vacuum dryings.
This electrode assembling is become battery, ac impedance measurement and 0.1C constant-current discharge are carried out to it.
Embodiment 2
1) collector process
As the aluminium foil (20 μm) of lithium-sulphur cell positive electrode collector, put into the oxalic acid solution of 5%, corrode 1min, take out and immerse again in deionized water, ultrasonic 10s, air-dry stand-by;
Water and ethanol is body 1:9 mixed preparing mixed liquor by volume, and superP and AB is water-soluble with in the mixed liquor of ethanol according to the mixing of 1:1 mass ratio, mass fraction 0.5%, ultrasonic 20min; Select solid content 60%PTFE emulsion, by material with carbon element: PTFE(is solid) mass ratio 80%:20% add PTFE emulsion, fully mix, ultrasonic 30min, treat that this mixed liquor is even, stand-by;
Be laid on 80 DEG C of heating plates by the aluminium foil after process, adopt the mode of spraying to be sprayed on aluminium foil side or two side surfaces ultrasonic uniform mixed liquor, material with carbon element load amount controls at 0.2mg/cm 2, dry, roll squeezer roll-in, to aluminium foil original thickness (20 μm), obtains collector;
2) positive pole body making
Carbon-sulfur compound, the PTFE of conductive agent SuperP and solid content 60%, according to the ratio of mass ratio 8:1:1 take respectively 0.8g, 0.1g, 0.167g, first carbon-sulfur compound and conductive agent are dissolved in the deionized water of 100ml volume ratio 9:1 and the mixed solution of ethanol, ultrasonic 30min, add 0.167gPTFE emulsion (solid content 60%), ultrasonic more than 30min, to dissolution homogeneity.Take the calcium carbonate of 60mg, add in this homogeneous solution.
The water-bath that above-mentioned mixed liquor puts into 50 DEG C heated, with stirring, aqueous solvent wherein and ethanol are volatilized away, remaining solid material becomes bulk.Use roll squeezer roll-forming, finally be pressed into 200 μm of film-form flexible electrodes, 10 minutes are shelved in air, cut required size, put into hydraulic press (film-form flexible electrode fits in material with carbon element layer side) with the current collector layers made in step 1), under room temperature, adopt 2MPa pressure to suppress 10min.Dry in 50 DEG C of air dry ovens.
Drying rear electrode immerses in 10% hydrochloric acid, soaks 10min, deionized water soaking and washing, 80 DEG C of oven dry.
3) protective layer makes
Select the gelatin of molecular weight 50W to be dissolved in deionized water, make mass fraction 5% jelly.Use scraper adjustment thickness 100 μm, by its blade coating to electrode surface, 60 DEG C of vacuum dryings.
This electrode assembling is become battery, and carry out ac impedance measurement and the electric discharge of 0.1C constant current cycle to it, cycle performance as shown in Figure 3.
Comparative example
Carbon-sulfur compound, conductive agent super P, binding agent PVDF(molecular weight 900,000), take a certain amount of according to the ratio of mass ratio 8:1:1, first that three kinds of dry powder blend are even, add NMP according to the ratio of solid content 15%, magnetic agitation 2h, on blade coating to untreated aluminium foil, on guarantor unit's area, the amount of active material is identical with embodiment.This electrode assembling is become battery, in its AC impedance of 100000 ~ 0.01Hz frequency range build-in test, adopts 0.1C current versus cell to carry out constant current cycle discharge and recharge.

Claims (7)

1. a manufacture method for lithium-sulphur cell positive electrode, is characterized in that:
First material with carbon element is supported on the surface, metal aluminum foil one or both sides of plus plate current-collecting body;
Carbon-sulfur compound, PTFE and material with carbon element are mixed, or just carbon-sulfur compound and PTFE mixing, obtained flexible electrode; Flexible electrode is amplexiformed on the surface, one or both sides being supported with material with carbon element in plus plate current-collecting body, obtained positive pole main body;
Finally have the surface of flexible electrode to add the film preparation of painting one layer of polymeric in positive pole main body to form.
2. according to manufacture method according to claim 1, it is characterized in that: concrete preparation process is as follows,
1) collector process
Using the aluminium foil as plus plate current-collecting body, put into acid solution, corrode 1 ~ 10min, take out and immerse again in deionized water, ultrasonic 10 ~ 50s, air-dry stand-by;
By in the mixed solution of water-soluble for material with carbon element and ethanol, ultrasonic 10 ~ 60min, adds PTFE emulsion, fully mixes, ultrasonic 20 ~ 60min, treats that this mixed liquor is even, stand-by;
Be laid on 50 ~ 100 DEG C of heating plates by the aluminium foil after process, adopt the mode of spraying to be sprayed on aluminium foil side or two side surfaces ultrasonic uniform mixed liquor, material with carbon element load amount controls at 0.1-0.5mg/cm 2, dry, roll squeezer roll-in, to aluminium foil original thickness, obtains collector;
2) positive pole body making
Carbon-sulfur compound is as active material, and conductive agent is material with carbon element, and binding agent is PTFE; By in the mixed solution of carbon-sulfur compound or carbon-sulfur compound and the blended water-soluble and ethanol of conductive agent, ultrasonic 20 ~ 60min, adds PTFE emulsion, and ultrasonic at least 30min is to dissolution homogeneity;
In homogeneous solution, add template and/or pore creating material, mix;
Above-mentioned mixed liquor is heated to 40 ~ 80 DEG C of stirrings, by solvent evaporates, until remaining solid material becomes bulk; Use roll squeezer roll-forming, be finally pressed into 60 ~ 300 μm of film-form flexible electrodes, in air, shelve 1 ~ 30 minute, cut to required size, after superimposed with the collector made in step 1), put into hydraulic press;
If the current collector aluminum foil side surface spraying of step 1) has material with carbon element layer, then film-form flexible electrode and aluminium foil one side surface being coated with material with carbon element layer are fitted in opposite directions; If aluminium foil two side surface is all coated with material with carbon element layer, two film-form flexible electrodes are fitted in respectively two side surfaces of aluminium foil;
0.5 ~ 5MPa pressure compacting, 1 ~ 10min is adopted under room temperature; Dry at 50 ~ 100 DEG C; Obtain positive pole main body;
If add the electrode of template, after oven dry, need electrode to immerse in the cleaning fluid of this template, remove template, washed with de-ionized water, dry obtained positive pole main body for 40 ~ 80 DEG C;
3) protective layer makes
High molecular polymer is divided the jelly being dissolved in solvent and making between mass fraction 0.5% ~ 10%; Jelly is applied to the film-form flexible electrode surface of positive pole main body, dry to obtain electrode for 40 ~ 100 DEG C, it is 1 ~ 100 μm that jelly coating is done thick.
3., according to manufacture method according to claim 2, it is characterized in that:
In step 1), acid solution is the oxalic acid of mass concentration 0.5% ~ 10%, acetic acid or hydrochloric acid solution; Aluminium foil original thickness is the thickness before not spraying, and thickness is 7 ~ 20 μm;
Step 1) and step 2) described material with carbon element comprise in amorphous carbon, the mesoporous carbon of template synthesis, carbon nano-fiber, carbon nano-tube, expanded graphite, Graphene one or two or more kinds; The volumetric concentration 1% ~ 20% of ethanol in the mixed solution of water and ethanol; In PTFE emulsion, the solids content of PTFE is 0.1% ~ 70%;
The material with carbon element mass fraction dissolved in water described in step 1) and alcohol mixeding liquid is 0.1% ~ 1%; The mass ratio of material with carbon element: PTFE is 95 ~ 60:5 ~ 40.
4., according to manufacture method according to claim 2, it is characterized in that:
Step 2) described carbon-sulfur compound is the carbon-sulfur compound adopting high-temperature liquid-phase Melting Synthesis;
Carbon-sulfur compound: conductive agent: PTFE mass ratio is 95 ~ 50:0 ~ 40:5 ~ 40, by water-soluble for three with the mixed solution of ethanol, solid content is between 0.5% ~ 10%.
5., according to manufacture method according to claim 2, it is characterized in that:
Step 2) described pore creating material comprise in inorganic pore creating material, organic pore-forming agents, biological pore creating material one or two or more kinds; Wherein inorganic pore creating material is calcium carbonate, magnesium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium or ammonium chloride; Organic pore-forming agents is polyethylene glycol, and biological pore creating material is the starch containing ferment quality 1%; The quality of pore creating material is 0.1% ~ 10% of carbon-sulfur compound quality;
Step 2) described template is one or more in hard template, non-silicon oxide, inorganic salts, comprises different-shape, spherical or longilineal Ludox, nanometer silica gel, order mesoporous silicate and molecular sieve; Non-silicon oxide and the common hydroxide comprising nickel oxide, calcium oxide, magnesium oxide, manganese oxide and these metals, halide, carbonate compound, acetate compound and other organic acid salt compound of inorganic salts;
Template is 1% ~ 30% of carbon-sulfur compound quality; The cleaning fluid of template is deionized water, hydrofluoric acid or hydrochloric acid.
6. according to manufacture method according to claim 2, it is characterized in that: high molecular polymer described in step 3) is one or two or more kinds in naphthols, cyclodextrin, gelatin, poly(ethylene oxide), Kynoar, polytetrafluoroethylene, polyhexafluoropropylene, polymethyl methacrylate, polyethyl acrylate, polystyrene, polyvinyl alcohol, PVP, butylbenzene diene.
7. according to manufacture method according to claim 2, it is characterized in that: described in step 3), the solvent of dissolve polymer comprises one or two or more kinds in water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, acetonitrile, 1-METHYLPYRROLIDONE, toluene.
CN201310694530.6A 2013-12-15 2013-12-15 Lithium-sulfur battery positive electrode making method Active CN104716324B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310694530.6A CN104716324B (en) 2013-12-15 2013-12-15 Lithium-sulfur battery positive electrode making method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310694530.6A CN104716324B (en) 2013-12-15 2013-12-15 Lithium-sulfur battery positive electrode making method

Publications (2)

Publication Number Publication Date
CN104716324A true CN104716324A (en) 2015-06-17
CN104716324B CN104716324B (en) 2017-02-01

Family

ID=53415445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310694530.6A Active CN104716324B (en) 2013-12-15 2013-12-15 Lithium-sulfur battery positive electrode making method

Country Status (1)

Country Link
CN (1) CN104716324B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105304906A (en) * 2015-09-24 2016-02-03 山东润昇电源科技有限公司 Flexible lithium ion battery cathode and manufacturing method thereof
CN105789557A (en) * 2016-05-26 2016-07-20 厦门大学 Lithium-sulfur pole piece with function protection layer and preparation method and application thereof
CN107845774A (en) * 2016-09-21 2018-03-27 中国科学院大连化学物理研究所 Self-supporting porous electrode preparation method and its electrode and application
CN109285993A (en) * 2017-07-19 2019-01-29 中国科学院过程工程研究所 A kind of sulphur carbon flexible electrode material and its preparation method and application
CN110911682A (en) * 2019-11-06 2020-03-24 华南理工大学 Electrode of lithium-sulfur battery and preparation method and application thereof
CN111029526A (en) * 2019-11-28 2020-04-17 西南科技大学 Preparation method of porous positive pole piece for lithium-sulfur battery and product thereof
CN111653728A (en) * 2019-03-04 2020-09-11 中南大学 Lithium-sulfur battery porous positive electrode and preparation method and application thereof
CN112103555A (en) * 2020-10-21 2020-12-18 中国科学技术大学 All-solid-state lithium ion battery and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1499659A (en) * 2002-10-28 2004-05-26 三星Sdi株式会社 Positive electrode of Li-S cell and Li-S cell including such positive electrode
CN102569816A (en) * 2012-02-14 2012-07-11 中南大学 Positive electrode of lithium sulfur battery and preparation method thereof
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1499659A (en) * 2002-10-28 2004-05-26 三星Sdi株式会社 Positive electrode of Li-S cell and Li-S cell including such positive electrode
CN102569816A (en) * 2012-02-14 2012-07-11 中南大学 Positive electrode of lithium sulfur battery and preparation method thereof
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105304906A (en) * 2015-09-24 2016-02-03 山东润昇电源科技有限公司 Flexible lithium ion battery cathode and manufacturing method thereof
CN105789557A (en) * 2016-05-26 2016-07-20 厦门大学 Lithium-sulfur pole piece with function protection layer and preparation method and application thereof
CN107845774A (en) * 2016-09-21 2018-03-27 中国科学院大连化学物理研究所 Self-supporting porous electrode preparation method and its electrode and application
CN109285993A (en) * 2017-07-19 2019-01-29 中国科学院过程工程研究所 A kind of sulphur carbon flexible electrode material and its preparation method and application
CN111653728A (en) * 2019-03-04 2020-09-11 中南大学 Lithium-sulfur battery porous positive electrode and preparation method and application thereof
CN111653728B (en) * 2019-03-04 2022-02-01 中南大学 Lithium-sulfur battery porous positive electrode and preparation method and application thereof
CN110911682A (en) * 2019-11-06 2020-03-24 华南理工大学 Electrode of lithium-sulfur battery and preparation method and application thereof
CN110911682B (en) * 2019-11-06 2021-03-30 华南理工大学 Electrode of lithium-sulfur battery and preparation method and application thereof
CN111029526A (en) * 2019-11-28 2020-04-17 西南科技大学 Preparation method of porous positive pole piece for lithium-sulfur battery and product thereof
CN112103555A (en) * 2020-10-21 2020-12-18 中国科学技术大学 All-solid-state lithium ion battery and preparation method thereof

Also Published As

Publication number Publication date
CN104716324B (en) 2017-02-01

Similar Documents

Publication Publication Date Title
CN104716324B (en) Lithium-sulfur battery positive electrode making method
Zhang et al. Flexible, mechanically robust, solid-state electrolyte membrane with conducting oxide-enhanced 3D nanofiber networks for lithium batteries
Wu et al. LiI embedded meso-micro porous carbon polyhedrons for lithium iodine battery with superior lithium storage properties
Zheng et al. Ultralight carbon flakes modified separator as an effective polysulfide barrier for lithium-sulfur batteries
CN104488117B (en) Carbon sulfur material nano-complex negative electrode for the doping of Li S batteries
Sun et al. High-performance lithium-sulfur batteries based on self-supporting graphene/carbon nanotube foam@ sulfur composite cathode and quasi-solid-state polymer electrolyte
Wang et al. Composite polymer electrolyte with three-dimensional ion transport channels constructed by NaCl template for solid-state lithium metal batteries
CN103855358B (en) Cathode of lithium battery and preparation method thereof, lithium battery and application
Li et al. Improving the electrochemical performance of a lithium–sulfur battery with a conductive polymer-coated sulfur cathode
Li et al. Suppressing shuttle effect using Janus cation exchange membrane for high-performance lithium–sulfur battery separator
Chen et al. Perchlorate based “oversaturated gel electrolyte” for an aqueous rechargeable hybrid Zn–Li battery
CN111916640B (en) WS2/CNTs modified diaphragm of lithium-sulfur battery and preparation method thereof
Yang et al. High‐rate aqueous aluminum‐ion batteries enabled by confined iodine conversion chemistry
Wang et al. Design and construction of a three‐dimensional electrode with biomass‐derived carbon current collector and water‐soluble binder for high‐sulfur‐loading lithium‐sulfur batteries
CN108123104A (en) A kind of three continuous Si/C porous electrodes and its application
CN104269559A (en) TiO2 coated sulfur/ordered mesoporous carbon composite cathode material and preparation method thereof
Zhu et al. Enhanced performance of Li‐S battery by constructing inner conductive network and outer adsorption layer sulfur‐carbon composite
Wang et al. Robust Room‐Temperature Sodium‐Sulfur Batteries Enabled by a Sandwich‐Structured MXene@ C/Polyolefin/MXene@ C Dual‐functional Separator
Wang et al. Nano architectured halloysite nanotubes enable advanced composite separator for safe lithium metal batteries
Chen et al. Synergistic effect of cerium oxide with core-shell structure embedded in porous carbon for high-performance lithium-sulfur batteries
Yao et al. Controllably regulating ion transport in lithium metal batteries via pore effect of metal–organic framework-based separators
CN109461865A (en) A kind of preparation method of coating polyetherimide diaphragm and the application in lithium-sulfur cell
Dong et al. The free-standing N-doped Murray carbon framework with the engineered quasi-optimal Se/C interface for high–Se-loading Li/Na–Se batteries at elevated temperature
Kim et al. Selective ion transport of catalytic hybrid aerofilm interlayer for long-stable Li-S batteries
CN112421044B (en) Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur 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
C14 Grant of patent or utility model
GR01 Patent grant