CN104716324B - Lithium-sulfur battery positive electrode making method - Google Patents

Lithium-sulfur battery positive electrode making method Download PDF

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Publication number
CN104716324B
CN104716324B CN201310694530.6A CN201310694530A CN104716324B CN 104716324 B CN104716324 B CN 104716324B CN 201310694530 A CN201310694530 A CN 201310694530A CN 104716324 B CN104716324 B CN 104716324B
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carbon
ptfe
electrode
sulfur compound
template
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CN104716324A (en
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王倩
张华民
张益宁
王美日
曲超
马艺文
吴宝山
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Dalian Institute of Chemical Physics of CAS
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    • 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

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 to a kind of a kind of method of lithium-sulphur cell positive electrode preparation.
Background technology
Modern science and technology develops rapidly, and the demand of the energy is also increasingly increased, traditional energy is petered out, although emerging energy Many emphasis environmental friendliness, but all have the shortcomings that very important, such as wind-force and solar energy etc., all have a problem that, electric energy Unstable, 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, generally will be many Hole or the larger material with carbon element (as mesoporous carbon, carbon nano-fiber, CNT, expanded graphite and Graphene etc.) of specific surface are as leading Electric agent and elemental sulfur pass through high-temperature liquid-phase or vapor phase method synthesizes carbon-sulfur compound.Because the specific discharge capacity of sulfur positive electrode is higher 1675mah/g, the various graphite cathodes of industrialization cannot be matching, and some height ratio capacity negative material such as silicon etc. are also located at present In conceptual phase, adopting lithium metal (theoretical capacity 3800mah/g) therefore lithium-sulfur cell as negative pole more.
The exoelectrical reaction of lithium-sulfur cell is divided into two stages substantially, the first stage, elemental sulfur be electronically generated polysulfide root from Son, dissolves in electrolyte, and due to concentration diffusion, polysulfide root ion can move to negative pole, directly occurs chemistry anti-with lithium metal Should, this is also that self discharge and the low basic reason of coulombic efficiency occur；Second stage, the further electronics of polysulfide root ion is simultaneously Generate soluble li with the lithium ion in electrolyte2s2And li2S, deposits on carbon electrode, ultimately generates li by s2s2With li2S, volumetric expansion, lead to carbon matrix structure to cave in and the mutually stripping with collector, contact internal resistance drastically raises, and due to The dissolving of the first step causes the concentration of electrolyte and viscosity to increase, and diffusion in positive pole for the ion is difficult, therefore leads to, product exists Carbon electrodes cover, and prevent polysulfide root ion in the deposition of electrode interior active site, this namely lithium-sulfur cell capacity attenuation Basic reason.How to stop the diffusion to negative pole for the polysulfide root ion, strengthen the adhesion of collector and active substance, and And abundant duct can be produced in the electrodes, the quick diffusion mass transfer of the dissolving for intermediate product and lithium ion provides enough Passage, become this be research an emphasis.
Content of the invention
For the problems referred to above, in conjunction with lithium-sulfur cell autoreactivity mechanism, the present invention proposes one kind and is just preparing lithium-sulfur cell A kind of method of pole.First, make buffering carbon between collector metal forming and active substance electrode, layer purpose is to solve discharge and recharge During the anode structure that causes of change of active substance volume cave in and the stripping with collector；Second, by template or Pore creating material adds, and is to produce suitable pore passage structure in anelectrode, enables the dissolving for intermediate product and ion, electronics Transmission adequate space is provided, provide broader active surface for redox reaction, thus reducing the polarization of course of reaction, Improve energy and cycle performance；Finally, in positive electrode surface plus painting one layer of polymeric thin film, the concentration of polysulfide root ion is hindered to expand Dissipating, thus effectively reducing self discharge, improving the Kunlun efficiency.
For achieving the above object, the complete skill scheme that the present invention provides is as follows:
Support material with carbon element on the metal aluminum foil one or both sides surface of plus plate current-collecting body first；
Carbon-sulfur compound, ptfe and material with carbon element are mixed, or just carbon-sulfur compound and ptfe mixing, prepared flexible electrical Pole；Amplexiform flexible electrode in the one or both sides surface that plus plate current-collecting body is supported with material with carbon element, prepared positive pole main body；
The last surface having flexible electrode in positive pole main body adds painting one layer of polymeric film preparation and forms.
Concrete preparation process is as follows,
1) collector is processed
Put into the aluminium foil as plus plate current-collecting body in acid solution, corrode 1～10min, take out and immerse deionized water again In, ultrasonic 10～50s, air-dry stand-by；
Material with carbon element is dissolved in water and the mixed solution of ethanol, ultrasonic 10～60min, adds ptfe emulsion, be sufficiently mixed, Ultrasonic 20～60min, treats this mixed liquor uniformly, stand-by；
Aluminium foil after processing is laid in 50～100 DEG C of heating plates, by ultrasonic uniform mixed liquor using the side spraying Formula is sprayed on aluminium foil side or two side surfaces, and material with carbon element load amount controls in 0.1-0.5mg/cm2, dry, roll squeezer roll-in is extremely Aluminium foil original thickness, obtains collector；
2) positive pole body making
As active substance, conductive agent is material with carbon element to carbon-sulfur compound, and binding agent is ptfe；By carbon-sulfur compound or carbon Sulfur compound and conductive agent blending are dissolved in water and the mixed solution of ethanol, and ultrasonic 20～60min adds ptfe emulsion, ultrasonic At least 30min is uniform to solution；
Template and/or pore creating material, mix homogeneously is added in homogeneous solution；
Above-mentioned mixed liquor is heated to 40～80 DEG C of stirrings, solvent is volatilized, until remaining solid material becomes bulk；Use Roll squeezer roll-forming, is finally pressed into 60～300 μm of film like flexible electrodes, and in the air is shelved 1～30 minute, cuts to institute Need size, put in hydraulic press after overlapping with the collector of making in step 1)；
If the current collector aluminum foil side surface spraying of step 1) has carbon material layer, by film like flexible electrode be coated with Aluminium foil one side surface of carbon material layer is fitted in opposite directions；If aluminium foil two side surface is all coated with carbon material layer, will be soft for two film like Property electrode fits in two side surfaces of aluminium foil respectively；
0.5～5mpa pressure is adopted to suppress 1～10min under room temperature；Dry at 50～100 DEG C；Obtain positive pole main body；
If adding the electrode of template, need after drying, in the cleanout fluid immerse electrode this template, to remove template agent removing, Deionized water cleans, and dries for 40～80 DEG C and positive pole main body is obtained；
3) protective layer makes
High molecular polymer is divided and is dissolved in the jelly made in solvent between mass fraction 0.5%～10%；By jelly It is applied to the film like flexible electrode surface of positive pole main body, dries to obtain electrode for 40～100 DEG C, it is 1～100 μ that jelly coating is done thick m.
In step 1), acid solution is oxalic acid, acetic acid or the hydrochloric acid solution of mass concentration 0.5%～10%；Aluminium foil original thickness is Thickness before not spraying, thickness is 7～20 μm；
Step 1) and step 2) described material with carbon element include amorphous carbon, template preparation mesoporous carbon, carbon nano-fiber, carbon One of nanotube, expanded graphite, Graphene or more than two kinds；The volumetric concentration 1% of ethanol in the mixed solution of water and ethanol ～20%；In ptfe emulsion, the solids content of ptfe is 0.1%～70%；Dissolving in water described in step 1) and alcohol mixeding liquid Material with carbon element mass fraction 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 carbon-sulfur compound using high-temperature liquid-phase Melting Synthesis；
Carbon-sulfur compound: conductive agent: ptfe mass ratio is 95～50:0～40:5～40, three is dissolved in water and ethanol In mixed solution, solid content is between 0.5%～10%.
Step 2) described pore creating material include one of inorganic pore creating material, organic pore-forming agents, biological pore creating material or two kinds with On；Wherein inorganic pore creating material is Calcium Carbonate, magnesium carbonate, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate or ammonium chloride；Organic pore-forming agents For Polyethylene Glycol, biological pore creating material is the starch containing ferment quality 1%；The quality of pore creating material is carbon-sulfur compound quality 0.1%～10%；
Step 2) described template be one of hard template, non-silicon oxide, inorganic salt or two or more, include difference Pattern, spherical or longilineal Ludox, nanometer silica gel, order mesoporous silicate and molecular sieve；Non-silicon oxide and inorganic salt Common includes nickel oxide, calcium oxide, the hydroxide of magnesium oxide, manganese oxide and these metals, halogenide, carbonate chemical combination Thing, acetate compound and other organic acid salt compound；
Template is the 1%～30% of carbon-sulfur compound quality；The cleanout fluid of template is deionized water, Fluohydric acid. or salt Acid.
High molecular polymer described in step 3) is naphthols, cyclodextrin, gelatin, poly(ethylene oxide), Kynoar, polytetrafluoro Ethylene, polyhexafluoropropylene, polymethyl methacrylate, polyethyl acrylate, polystyrene, polyvinyl alcohol, polyvinylpyrrolidine One of alkanone, butylbenzene diene or more than two kinds.
The solvent dissolving polymer described in step 3) includes water, methanol, ethanol, isopropanol, oxolane, acetonitrile, n- first One of base ketopyrrolidine, toluene or more than two kinds.
By the positive plate being obtained and anode ear ultra-sonic welded, 60 DEG C of more than vacuum drying 24h, proceed to the glove full of argon In case.
In glove box, put into barrier film by the middle of positive pole, negative pole, roll up after monolayer superposition, multi-layer stacks or monolayer superposition Around etc. mode make battery core, load in battery case, stand more than 12h after vacuum injection electrolyte, battery is sealed, so far Battery completes.
Beneficial effects of the present invention:
The present invention combines the feature of lithium-sulfur cell itself, improves for battery cathode structure, is respectively directed to lithium sulfur electricity Pond key restriction factors, suit the remedy to the case, and effectively lift its chemical property.
First, the carbon coating on aluminium foil, not only can strengthen the bonding force of layers of active electrodes and collector additionally it is possible to live Property material play certain cushioning effect when resetting in the electrodes, and be conducive to electronics to conduct, effectively reduce contact internal resistance；
Second, pore-creating is carried out to positive pole using template and pore creating material method, can pass through to select template and Theoretical Calculation, The control pore size of qualitative, quantitative, the pattern in hole and total pore volume, make there is our required micropore, Jie in electrode Hole, mesopore and macropore.This pore space structure of electrode is beneficial to the infiltration of electrolyte, is that the transmission of ion and intermediate product provides Abundant and quick passage, is that redox reaction provides bigger reactivity face, thus effectively reducing impedance and pole Change degree.
In addition, thin polymer film is swelling in the electrolytic solution, act on similar gels electrolyte, the lithium ion transport base of small particle This is unaffected, and the diffusion of solvable macromole polysulfide root ion is restricted, and hinders polysulfide root ion just to depart to a certain extent Pole, suppresses shuttle effect, plays the effect of the solid sulfur of resistance sulfur.
Brief description
Fig. 1 is electrode longitudinal section schematic diagram；
1- aluminum foil current collector；2- carbon coating；3- electrode body；4- electrode interior duct；5- protective coating.
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.
Specific embodiment
Embodiment 1
1) collector is processed
Put into the aluminium foil (20 μm) as lithium-sulphur cell positive electrode collector in 5% oxalic acid solution, corrode 1min, take out Immerse again in deionized water, ultrasonic 10s, air-dry stand-by；
Water and ethanol body 1:9 mixed preparing mixed liquor by volume, superp and ab are mixed molten according to 1:1 mass ratio In the mixed liquor of water and ethanol, mass fraction 0.5%, ultrasonic 20min；From solid content 60%ptfe emulsion, by material with carbon element: Ptfe(is solid) mass ratio 80%:20% add ptfe emulsion, be sufficiently mixed, ultrasonic 30min, treat this mixed liquor uniformly, stand-by；
Aluminium foil after processing is laid in 80 DEG C of heating plates, ultrasonic uniform mixed liquor is sprayed by the way of spraying To aluminium foil side or two side surfaces, material with carbon element load amount controls in 0.2mg/cm2, dry, roll squeezer roll-in is to the original thickness of aluminium foil Degree (20 μm), obtains collector；
2) positive pole body making
The ptfe of carbon-sulfur compound, conductive agent superp and solid content 60%, the ratio according to mass ratio 8:1:1 claims respectively Take 0.8g, 0.1g, 0.167g, first carbon-sulfur compound and conductive agent are dissolved in deionized water and the ethanol of 100ml volume ratio 9:1 Mixed solution in, ultrasonic 30min, add 0.167gptfe emulsion (solid content 60%), ultrasonic more than 30min, equal to solution Even.The particle diameter respectively weighing 10mg respectively is the Silica hydrogel template of 100nm, 500nm and 1 μm, adds in this homogeneous solution.
Above-mentioned mixed liquor is put into heating in 70 DEG C of water-bath, with stirring, aqueous solvent therein and ethanol are volatilized Go, remaining solid material becomes bulk.Using roll squeezer roll-forming, finally it is pressed into 200 μm of film like flexible electrodes, in the air Shelve 10 minutes, cut required size, put into (film like flexible electrode in hydraulic press with the current collector layers of making in step 1) Fit in carbon material layer side), adopt 2mpa pressure to suppress 10min under room temperature.50 DEG C of air dry ovens are dried.
Dry in rear electrode immersion 10%hf, soak 30min, deionized water soaking and washing, 80 DEG C of drying.
3) protective layer makes
Kynoar 0.1g from molecular weight about 900,000 is scattered in 10gn- methyl pyrrolidone, makes jelly. Using scraper adjust 100 μm of thickness, scratched to step 2) in make drying positive pole host film shape flexible electrode Surface, 60 DEG C of vacuum dryings.
This electrode group is dressed up battery, it is carried out with ac impedance measurement and 0.1c constant-current discharge.
Embodiment 2
1) collector is processed
Aluminium foil (20 μm) as lithium-sulphur cell positive electrode collector, puts in 5% oxalic acid solution, corrodes 1min, takes out again In immersion deionized water, ultrasonic 10s, air-dry stand-by；
Water and ethanol body 1:9 mixed preparing mixed liquor by volume, superp and ab are mixed molten according to 1:1 mass ratio In the mixed liquor of water and ethanol, mass fraction 0.5%, ultrasonic 20min；From solid content 60%ptfe emulsion, by material with carbon element: Ptfe(is solid) mass ratio 80%:20% add ptfe emulsion, be sufficiently mixed, ultrasonic 30min, treat this mixed liquor uniformly, stand-by；
Aluminium foil after processing is laid in 80 DEG C of heating plates, ultrasonic uniform mixed liquor is sprayed by the way of spraying To aluminium foil side or two side surfaces, material with carbon element load amount controls in 0.2mg/cm2, dry, roll squeezer roll-in is to the original thickness of aluminium foil Degree (20 μm), obtains collector；
2) positive pole body making
The ptfe of carbon-sulfur compound, conductive agent superp and solid content 60%, the ratio according to mass ratio 8:1:1 claims respectively Take 0.8g, 0.1g, 0.167g, first carbon-sulfur compound and conductive agent are dissolved in deionized water and the ethanol of 100ml volume ratio 9:1 Mixed solution in, ultrasonic 30min, add 0.167gptfe emulsion (solid content 60%), ultrasonic more than 30min, equal to solution Even.Weigh the Calcium Carbonate of 60mg, add in this homogeneous solution.
Above-mentioned mixed liquor is put into heating in 50 DEG C of water-bath, with stirring, aqueous solvent therein and ethanol are volatilized Go, remaining solid material becomes bulk.Using roll squeezer roll-forming, finally it is pressed into 200 μm of film like flexible electrodes, in the air Shelve 10 minutes, cut required size, put into (film like flexible electrode in hydraulic press with the current collector layers of making in step 1) Fit in carbon material layer side), adopt 2mpa pressure to suppress 10min under room temperature.50 DEG C of air dry ovens are dried.
Dry rear electrode to immerse in 10% hydrochloric acid, soak 10min, deionized water soaking and washing, 80 DEG C of drying.
3) protective layer makes
Gelatin from molecular weight 50w is dissolved in deionized water, makes mass fraction 5% jelly.Adjusted thick using scraper 100 μm of degree, is scratched to electrode surface, 60 DEG C of vacuum dryings.
This electrode group is dressed up battery, it is carried out with ac impedance measurement and the electric discharge of 0.1c constant current cycle, cycle performance is such as Shown in Fig. 3.
Comparative example
Carbon-sulfur compound, conductive agent super p, binding agent pvdf(molecular weight 900,000), according to the ratio of mass ratio 8:1:1 Weigh a certain amount of, first by three kinds of dry powder blend uniformly, the ratio according to solid content 15% adds nmp, magnetic agitation 2h, scratch to On untreated aluminium foil it is ensured that in unit area the amount of active substance identical with embodiment.This electrode group is dressed up battery, 100000～0.01hz its AC impedance of frequency range build-in test, carries out constant current cycle discharge and recharge using 0.1c current versus cell.

Claims (6)

1. a kind of manufacture method of lithium-sulphur cell positive electrode it is characterised in that:
Support material with carbon element on the metal aluminum foil one or both sides surface of plus plate current-collecting body first；
Carbon-sulfur compound, ptfe and material with carbon element are mixed, or carbon-sulfur compound and ptfe is mixed, prepared flexible electrode；
Amplexiform flexible electrode in the one or both sides surface that plus plate current-collecting body is supported with material with carbon element, prepared positive pole main body；
The last surface having flexible electrode in positive pole main body adds painting one layer of polymeric film preparation and forms；
Concrete preparation process is as follows,
1) collector is processed
Put into the aluminium foil as plus plate current-collecting body in acid solution, corrode 1～10min, take out and immerse again in deionized water, surpass
Sound 10～50s, air-dries stand-by；
Material with carbon element is dissolved in water and the mixed solution of ethanol, ultrasonic 10～60min, adds ptfe emulsion, be sufficiently mixed, surpass
Sound 20～60min, treats this mixed liquor uniformly, stand-by；
Aluminium foil after processing is laid in 50～100 DEG C of heating plates, ultrasonic uniform mixed liquor is sprayed by the way of spraying Apply
To aluminium foil side or two side surfaces, material with carbon element load amount controls in 0.1-0.5mg/cm2, dry, roll squeezer roll-in is to aluminium foil Original
Thickness, obtains collector；
2) positive pole body making
As active substance, conductive agent is material with carbon element to carbon-sulfur compound, and binding agent is ptfe；Will be multiple to carbon-sulfur compound or carbon sulfur
Compound and conductive agent blending are dissolved in water and the mixed solution of ethanol, and ultrasonic 20～60min adds ptfe emulsion, ultrasonic At least
30min is uniform to solution；
Template and/or pore creating material, mix homogeneously is added in homogeneous solution；
Above-mentioned mixed liquor is heated to 40～80 DEG C of stirrings, solvent is volatilized, until remaining solid material becomes bulk；Using roll-in
Machine roll-forming, is finally pressed into 60～300 μm of film like flexible electrodes, and in the air is shelved 1～30 minute, cuts to institute
Need size, with step 1) in make collector overlapping after put in hydraulic press；
If step 1) current collector aluminum foil side surface spraying have carbon material layer, by film like flexible electrode be coated with carbon materials
Aluminium foil one side surface of the bed of material is fitted in opposite directions；If aluminium foil two side surface is all coated with carbon material layer, will be soft for two film like Property electrode
Fit in two side surfaces of aluminium foil respectively；
0.5～5mpa pressure is adopted to suppress 1～10min under room temperature；Dry at 50～100 DEG C；Obtain positive pole main body；
If add template electrode, need after drying, in the cleanout fluid immerse electrode this template, to remove template agent removing, go from
Sub- water cleaning, dries for 40～80 DEG C and positive pole main body is obtained；
3) protective layer makes
High molecular polymer is dissolved in the jelly made in solvent between mass fraction 0.5%～10%；Jelly is applied to Just
The film like flexible electrode surface of pole main body, dries to obtain electrode for 40～100 DEG C, and jelly coating is done thickness and is 1～100 μm.
2. according to the manufacture method described in claim 1 it is characterised in that:
Step 1) in acid solution be the oxalic acid of mass concentration 0.5%～10%, acetic acid or hydrochloric acid solution；Aluminium foil original thickness is
Thickness before not spraying, thickness is 7～20 μm；
Step 1) and step 2) described material with carbon element include amorphous carbon, template preparation mesoporous carbon, carbon nano-fiber, carbon
One of nanotube, expanded graphite, Graphene or more than two kinds；In the mixed solution of water and ethanol, the volume of ethanol is dense Degree
1%～20%；In ptfe emulsion, the solids content of ptfe is 0.1%～70%；
Step 1) described in water and alcohol mixeding liquid in dissolving material with carbon element mass fraction be 0.1%～1%；Material with carbon element: ptfe
Mass ratio be 95～60:5～40.
3. according to the manufacture method described in claim 1 it is characterised in that:
Step 2) described carbon-sulfur compound is carbon-sulfur compound using high-temperature liquid-phase Melting Synthesis；
Carbon-sulfur compound: conductive agent: ptfe mass ratio is 95～50:0～40:5～40, three is dissolved in water and ethanol
In mixed solution, solid content is between 0.5%～10%.
4. according to the manufacture method described in claim 1 it is characterised in that:
Step 2) described pore creating material includes one of inorganic pore creating material, organic pore-forming agents, biological pore creating material or more than two kinds；Its In inorganic pore creating material be Calcium Carbonate, magnesium carbonate, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate or ammonium chloride；Organic pore-forming agents are poly- second Glycol, biological pore creating material is the starch containing ferment quality 1%；The quality of pore creating material be carbon-sulfur compound quality 0.1%～ 10%；
Step 2) described template be one of hard template, non-silicon oxide, inorganic salt or two or more, including not similar shape
Looks, spherical or longilineal Ludox, nanometer silica gel, order mesoporous silicate and molecular sieve；Non-silicon oxide and inorganic Salt is normal
That sees includes nickel oxide, calcium oxide, the hydroxide of magnesium oxide, manganese oxide and these metals, halogenide, carbonation Close
Thing, acetate compound and other organic acid salt compound；Template is the 1%～30% of carbon-sulfur compound quality；Mould The cleanout fluid of plate agent is deionized water, Fluohydric acid. or hydrochloric acid.
5. according to the manufacture method described in claim 1 it is characterised in that: step 3) described high molecular polymer is gelatin, poly- Oxirane, Kynoar, politef, polyhexafluoropropylene, polymethyl methacrylate, polyethyl acrylate, polyphenyl One of ethylene, polyvinyl alcohol, polyvinyl pyrrolidone or more than two kinds.
6. according to the manufacture method described in claim 1 it is characterised in that: step 3) described solvent include water, methanol, ethanol, One of isopropanol, oxolane, acetonitrile, n- methyl pyrrolidone, toluene or more than two kinds.
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CN111653728B (en) * 2019-03-04 2022-02-01 中南大学 Lithium-sulfur battery porous positive electrode 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
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