CN104716297B - Oleophylic sulfur electrode preparation method - Google Patents

Oleophylic sulfur electrode preparation method Download PDF

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CN104716297B
CN104716297B CN201310694702.XA CN201310694702A CN104716297B CN 104716297 B CN104716297 B CN 104716297B CN 201310694702 A CN201310694702 A CN 201310694702A CN 104716297 B CN104716297 B CN 104716297B
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carbon
silicone oil
electrode
sulfur
slurry
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CN104716297A (en
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王美日
张华民
张洪章
张益宁
马艺文
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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
    • H01M4/62—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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Abstract

The invention relates to an oleophylic sulfur electrode preparation method, silicone oil is penetrated into a positive porous electrode, and dried to obtain a porous oleophilic sulfur electrode, and the mass content of the silicone oil in the porous oleophilic sulfur electrode is 0.2-30%; by use of the oleophilic property of the silicone oil, an electrolyte uniformly infiltrates into the electrode, and especially lithium ion conduction in a high load sulfur electrode can be effectively achieved, so that the electrochemical performance of high load elemental sulfur can be played, and silicon oxygen bonds contained in the silicone oil can be effectively combined with lithium polysulfide in the discharge process, and self discharge phenomenon caused by dissolving and shuttling of the polysulfide can be suppressed, so that the objective of improving the lithium sulfur battery coulombic efficiency and cycle stability can be achieved.

Description

A kind of preparation method of oleophylic sulfur electrode
Technical field
The present invention relates to lithium-sulphur cell positive electrode and preparation method thereof, particularly to a kind of high lipophile sulfur electrode.
Background technology
In recent years, with scientific and technological continuous progress, the fast development of various electronic products is it is desirable to electrochmical power source used has The features such as have light weight, small volume, capacity big.Want to adapt to the demand of society, increase substantially the energy density of battery, green wood The exploitation of material and new system is necessary.
Lithium-sulfur cell be a kind of with lithium metal as negative pole, the secondary cell as positive pole for the elemental sulfur, its specific energy in theory may be used Reach 2600Wh/kg, actual energy density can reach 400Wh/kg at present, in the coming years, very likely bring up to 600Wh/kg Left and right, simultaneously elemental sulfur positive electrode have abundance, low price, advantages of environment protection it is considered to be current most One of secondary cell system of research attraction.
However, nearly 30 years of research, except fewer companies in recent years, in addition to the Applied D emonstration in high-end field, lithium-sulfur cell is still So can not commercially produce.This is because some intrinsic major defects of battery itself are not also well solved, for example, Actual lithium-sulfur cell energy density is not high to be to limit one of key factor of its practical application.Want to improve the energy of whole battery Metric density is it is necessary to improve positive active material load amount.The electrode thus causing is chapped from the cold, electric charge and ion-transfer resistance are higher, holds The problems such as amount plays not high, circulating battery stability difference is bitten to be solved.
Want to improve these problems, reaching practical level is not affecting discharge capacity of the cell it is necessary to try every possible means Under the conditions of improve positive active material load amount, therefore, improve high carrying capacity sulfur electrode lipophile, so that electrolyte is fully infiltrated, The conduction resistance reducing lithium ion is very urgent.
At present, the method improving lithium-sulfur cell lithium ion diffusional resistance is mainly the hole building hundred nanometers of poles in positive pole Road, but the consequence that this measure brings is to exacerbate the loss by dissolution of many lithium sulfides in discharge process, causes discharge capacity of the cell Reduce, the consequence that cyclical stability reduces.Therefore, the new method improving the conduction of lithium ion in lithium-sulfur cell of exploitation is necessary 's.
Content of the invention
New there is to electrolyte high infiltrating sulfur electrode and preparation method thereof it is an object of the invention to provide a kind of.
For achieving the above object, the technical solution used in the present invention is：By carbon-sulfur compound, conductive agent, binding agent molten Scratch after mixing in agent or coat to the carbon cloth or carbon paper of carbon dust leveling, be dried and positive pole porous electrode is obtained, then will Silicone oil infiltrates into inside porous electrode, and the oleophylic sulfur electrode of porous is obtained after being dried.Using the lipophile of silicone oil, make electrolyte equal The even conduction infiltrating to electrode interior, being especially effectively realized lithium ion in high carrying capacity sulfur electrode, thus ensure that high carrying capacity The performance of the chemical property of elemental sulfur.And, the silica bond energy containing in silicone oil is effectively combined many sulphur in discharge process Change lithium, the self-discharge phenomenon that suppression is caused due to polysulfide dissolving shuttle, it is achieved thereby that improve lithium-sulfur cell coulombic efficiency And cyclical stability ground purpose.
A kind of preparation method of oleophylic sulfur electrode, blade coating or coating on the carbon cloth or carbon paper of carbon dust leveling is combined by carbon sulphur Slurry that thing is mixed with binding agent or the slurry that carbon-sulfur compound, conductive agent are mixed with binding agent, are dried and positive pole porous electricity are obtained Pole, in electrode, sulphur load amount is（2.0-5.0）Mg/cm2, silicone oil is infiltrated into inside positive pole porous electrode, and porous is obtained after being dried Oleophylic sulfur electrode, in oleophylic sulfur electrode the mass content of silicone oil be 0.2～30%, wherein preferably 1～10%.
The preparation method of described oleophylic sulfur electrode,
(1) carbon dust and binding agent are added in dispersant, are sufficiently stirred for, wherein, solid content is 5～50%, obtains Slurry A;Carbon dust and binding agent mass ratio are (99:1)～(90:10)；
(2) slurry A is coated uniformly on carbon paper or carbon cloth, after being dried under the conditions of being 20 DEG C～90 DEG C through temperature, obtains Pole piece B with regulating course；
(3) carbon-sulfur compound and binding agent are added in dispersant, add or be added without conductive agent, fully stirred Mix, wherein, solid content is 5～50%, obtains slurry C；Described carbon-sulfur compound, conductive agent, the mass ratio of binding agent are (70- 90):(0-20)：10；
(4) slurry C is coated uniformly on pole piece B, after being dried under the conditions of being 50 DEG C～120 DEG C through temperature, obtains traditional The anode pole piece D of lithium-sulfur cell；
(5) by silicone oil with easy volatile solvent ultrasonic mixing uniformly, obtain silicone oil mixed liquor, pole piece D is placed on Buchner funnel On, drip silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum filtration 5-20 minute, treat that solvent infiltrates into electricity completely After in extremely, in drying box, 100-170 DEG C of insulation 10-120min, obtains oleophylic porous sulfur electrode.
Carbon dust in the carbon cloth of described carbon dust leveling or carbon paper is acetylene black, in oil oven carbon, Peal blackberry, section's qin carbon black One or two, its coating thickness on carbon paper or carbon cloth is 10-50 μm.Carbon in described carbon-sulfur compound is activity One of charcoal, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, CNT, carbon nano-fiber, mesoporous carbon or two kinds Thing mixed above, it accounts for the mass percent of carbon-sulfur compound is 10-50%；Described conductive agent is acetylene black, carbon black, stone One of ink, CNT, carbon nano-fiber, mesoporous carbon or more than two kinds, described binding agent is polytetrafluoroethylene (PTFE), gathers inclined fluorine Ethene, polyvinyl alcohol, sodium carboxymethylcellulose, polyacrylic one or two or more kinds.Described carbon paper or carbon cloth regulating course are used 's.Described dispersant is one of 1-METHYLPYRROLIDONE, water.Described silicone oil is dimethicone, aminomethyl phenyl silicon One of oil, Methyl Hydrogen Polysiloxane Fluid, diethyl silicone oil, ethyl containing hydrogen silicone oil, methyl alkoxy silicone oil, described silicon oil viscosity For 5-100mPa S；Described easy volatile solvent is isopropanol, carbon tetrachloride, dichloromethane, gasoline, kerosene, in acetone one Kind；Described silicone oil is 1 with the volume ratio of easy volatile solvent:（0.5-10）.
Compared with prior art, the invention has the advantages that:
Improve the lipophile of high carrying capacity sulfur electrode, so that electrolyte is fully infiltrated, reduce the conduction resistance of lithium ion, improve high The discharge capacity of carrying capacity sulfur electrode is the outstanding advantages of the present invention.
(1). what the present invention provided has high infiltrating sulfur electrode, preparation process simple possible to electrolyte, and raw material becomes This is low, is suitable for amplifying on a large scale.
(2). what the present invention provided has high infiltrating sulfur electrode, compared with traditional lithium-sulfur cell, especially to electrolyte It can be effectively realized the conduction of lithium ion in high carrying capacity sulfur electrode, thus ensure that the chemical property of high carrying capacity elemental sulfur Performance.Under the conditions of elemental sulfur load amount is more than 3.5mg/cm2 in the electrodes, the electrode discharge capacity adding silicone oil is compared with traditional electrode Improve 300mAh/g.
(3). what the present invention provided has high infiltrating sulfur electrode to electrolyte, and the silica bond energy containing in silicone oil is being put It is effectively combined many lithium sulfides, the self-discharge phenomenon that suppression is caused due to polysulfide dissolving shuttle, thus realize in electric process Raising lithium-sulfur cell coulombic efficiency and cyclical stability ground purpose.The electrode adding silicone oil is in cycle-index identical situation Under, capability retention improves 30% compared with traditional electrode.
Brief description
Fig. 1 is the oleophylic sulfur electrode of embodiment 3 preparation and traditional lithium-sulfur cell discharge capacity contrast (sulphur load amount 4.5mg/ cm2;Battery discharge multiplying power 0.1C；By voltage 1.5V～2.8V, electrolyte：1mol/l di-trifluoromethyl sulfonic acid acid imide Lithium/(diethylene glycol dimethyl ether：DOX, V:V=1:1), 30 DEG C of test temperature)；
Fig. 2. for oleophylic sulfur electrode and traditional lithium sulfur electrode coulombic efficiency and the cyclical stability contrast of embodiment 3 preparation (sulphur load amount 4.5mg/cm2, battery discharge multiplying power 0.1C；By voltage 1.5V～2.8V, electrolyte：1mol/l bis--fluoroform Base sulfonic acid imide li/(diethylene glycol dimethyl ether：DOX, V:V=1:1), 30 DEG C of test temperature).
Specific embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
Oil oven carbon (XC-72) is pressed 9 with Kynoar：1 ratio is added in 1-METHYLPYRROLIDONE, carries out fully Stirring, wherein, solid content is 5%, obtains slurry A;Slurry A is coated uniformly on Torry060 carbon paper, is 90 DEG C of bars through temperature After being dried under part, obtain pole piece B, its coating thickness on carbon paper is 10 μm；By 50% sulphur-carbon mano-tube composite, acetylene Black and Kynoar presses 7：2：1 is added in 1-METHYLPYRROLIDONE, is sufficiently stirred for, and wherein, solid content is 15%, obtains To slurry C；Slurry C is coated uniformly on pole piece B, after being dried under the conditions of being 50 DEG C through temperature, obtains traditional lithium-sulfur cell Anode pole piece D, sulphur load amount be 3.5mg/cm2.By Methyl Hydrogen Polysiloxane Fluid（Silicon oil viscosity is 5Pa S）Press 1 with isopropanol：10 Volume ratio ultrasonic mixing uniformly, obtains silicone oil mixed liquor, and pole piece D is put on a buchner funnel, and dropping silicone oil mixed liquor is in pole piece On, after it is uniformly dispersed, vacuum filtration 20 minutes, after solvent infiltrates in electrode completely, 100 DEG C of insulations in drying box 120min, obtains oleophylic porous sulfur electrode, and in sulfur electrode, the mass content of silicone oil is 0.2%.Battery testing, this material has relatively High coulombic efficiency and excellent cyclical stability.
Embodiment 2
Oil oven carbon (XC-72) is pressed 99 with polytetrafluoroethylene (PTFE)：1 ratio is added in 1-METHYLPYRROLIDONE, is filled Divide stirring, wherein, solid content is 50%, obtains slurry A;Slurry A is coated uniformly on Torry090 carbon paper, is 50 through temperature After being dried under the conditions of DEG C, obtain pole piece B, its coating thickness on carbon paper is 50 μm；By 90% sulphur-charcoal-aero gel compound, CNT presses 8 with polytetrafluoroethylene (PTFE)：1：1 is added in 1-METHYLPYRROLIDONE, is sufficiently stirred for, and wherein, solid content is 5%, obtain slurry C；Slurry C is coated uniformly on pole piece B, after being dried under the conditions of being 90 DEG C through temperature, obtains traditional lithium sulphur The anode pole piece D of battery, sulphur load amount is 0.5mg/cm2.By methyl phenyl silicone oil（Silicon oil viscosity is 100Pa S）With four chlorinations Carbon presses 1：0.5 volume ratio ultrasonic mixing uniformly, obtains silicone oil mixed liquor, and pole piece D is put on a buchner funnel, dropping silicone oil mixing , on pole piece, after it is uniformly dispersed, vacuum filtration 20 minutes, after solvent infiltrates in electrode completely, in drying box for liquid 170 DEG C of insulation 10min, obtain oleophylic porous sulfur electrode, and in sulfur electrode, the mass content of silicone oil is 30%.Battery testing, this material Material has higher coulombic efficiency and excellent cyclical stability.
Embodiment 3
Oil oven carbon (XC-72) is pressed 9 with Kynoar：1 ratio is added in 1-METHYLPYRROLIDONE, carries out fully Stirring, wherein, solid content is 10%, obtains slurry A;Slurry A is coated uniformly on Torry060 carbon paper, is 90 DEG C through temperature Under the conditions of be dried after, obtain pole piece B, its coating thickness on carbon paper be 10 μm；By 50% sulphur-activity carbon complex, acetylene Black and Kynoar presses 9：0：1 is added in 1-METHYLPYRROLIDONE, is sufficiently stirred for, and wherein, solid content is 15%, obtains To slurry C；Slurry C is coated uniformly on pole piece B, after being dried under the conditions of being 50 DEG C through temperature, obtains traditional lithium-sulfur cell Anode pole piece D, sulphur load amount be 4.5mg/cm2.By dimethicone（Silicon oil viscosity is 15Pa S）Press 1 with isopropanol：10 bodies Long-pending more uniform than ultrasonic mixing, obtain silicone oil mixed liquor, pole piece D is put on a buchner funnel, drip silicone oil mixed liquor on pole piece, After it is uniformly dispersed, vacuum filtration 20 minutes, after solvent infiltrates in electrode completely, 100 DEG C of insulations in drying box 30min, obtains oleophylic porous sulfur electrode, and in sulfur electrode, the mass content of silicone oil is 2%.Battery testing, this material has higher Coulombic efficiency and excellent cyclical stability.（Fig. 1, Fig. 2）, after Fig. 1 result can be seen that interpolation silicone oil, the head of battery Circle discharge capacity improves more than 300mAh/g compared with traditional electrode discharge capacity.Therefore, the method that the present invention provides is effective.
After the result of Fig. 2 can be seen that the circulating battery 20 times of method test providing using the present invention, battery coulomb is imitated Rate can reach more than 95%, improves 20%～30% compared with before-improvement；Circulation 20 times, capability retention is 90%, compared with before-improvement Improve 30%.It can be seen that, what the present invention provided has high infiltrating sulfur electrode to electrolyte, has preferable effect.Add After silicone oil, lithium-sulfur cell shows high coulombic efficiency and good cyclical stability.
Embodiment 4
Peal blackberry (BP2000) is pressed 9 with polyvinyl alcohol：1 ratio is added in 1-METHYLPYRROLIDONE, carries out fully Stirring, wherein, solid content is 10%, obtains slurry A;Slurry A is coated uniformly on carbon cloth, dry under the conditions of being 80 DEG C through temperature After dry, obtain pole piece B, its coating thickness on carbon cloth is 10 μm；70% sulphur-Graphene, acetylene black and polyvinyl alcohol are pressed 9：0：1 is added in 1-METHYLPYRROLIDONE, is sufficiently stirred for, and wherein, solid content is 50%, obtains slurry C；Slurry C is equal Even be coated on pole piece B, through temperature be 60 DEG C under the conditions of be dried after, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount For 5mg/cm2.By diethyl silicone oil（Silicon oil viscosity is 50Pa S）Press 1 with dichloromethane：2 volume ratio ultrasonic mixings uniformly, obtain To silicone oil mixed liquor, pole piece D is put on a buchner funnel, drip silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum Suction filtration 5 minutes, after solvent infiltrates in electrode completely, 120 DEG C of insulation 60min in drying box, obtain oleophylic porous sulphur electricity Pole, in sulfur electrode, the mass content of silicone oil is 5%.Battery testing, this material has higher coulombic efficiency and excellent circulation Stability.
Embodiment 5
Peal blackberry (BP2000) is pressed 9 with polyacrylic acid：1 ratio is added to the water, and is sufficiently stirred for, wherein, Gu Content is 10%, obtains slurry A;Slurry A is coated uniformly on carbon cloth, after being dried under the conditions of being 80 DEG C through temperature, obtains pole piece B, its coating thickness on carbon cloth is 20 μm；70% sulphur-nanofiber, graphite and polyacrylic acid are pressed 8：1：1 is added to water In, it is sufficiently stirred for, wherein, solid content is 20%, obtains slurry C；Slurry C is coated uniformly on pole piece B, through temperature is After being dried under the conditions of 60 DEG C, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 2mg/cm2.By ethyl containing hydrogen silicone oil （Silicon oil viscosity is 90Pa S）Press 1 with gasoline：10 volume ratio ultrasonic mixings uniformly, obtain silicone oil mixed liquor, pole piece D are placed on On Buchner funnel, drip silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum filtration 10 minutes, treat that solvent oozes completely After thoroughly to electrode, in drying box, 150 DEG C of insulation 20min, obtain oleophylic porous sulfur electrode, in sulfur electrode, the quality of silicone oil contains Measure as 10%.Battery testing, this material has higher coulombic efficiency and excellent cyclical stability.
Embodiment 6
Section's qin carbon black (KB300) is pressed 9 with sodium carboxymethylcellulose：1 ratio is added to the water, and is sufficiently stirred for, Wherein, solid content is 10%, obtains slurry A;Slurry A is coated uniformly on carbon cloth, after being dried under the conditions of being 80 DEG C through temperature, Obtain pole piece B, its coating thickness on carbon cloth is 50 μm；By 70% sulphur-graphite oxide, carbon black and sodium carboxymethylcellulose By 8：1：1 is added to the water, and is sufficiently stirred for, and wherein, solid content is 10%, obtains slurry C；Slurry C is coated uniformly on pole On piece B, after being dried under the conditions of being 90 DEG C through temperature, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 4mg/cm2. By methyl alkoxy silicone oil（Silicon oil viscosity is 10Pa S）Press 1 with acetone：10 volume ratio ultrasonic mixings uniformly, obtain silicone oil and mix Close liquid, pole piece D is put on a buchner funnel, drip silicone oil mixed liquor on pole piece, after it is uniformly dispersed, 10 points of vacuum filtration Clock, after solvent infiltrates in electrode completely, 150 DEG C of insulation 20min in drying box, obtain oleophylic porous sulfur electrode, sulphur electricity The mass content of extremely middle silicone oil is 20%.Battery testing, this material has higher coulombic efficiency and excellent cyclical stability.
Embodiment 7
Section's qin carbon black (KB600) is pressed 9 with sodium carboxymethylcellulose：1 ratio is added to the water, and is sufficiently stirred for, Wherein, solid content is 10%, obtains slurry A;Slurry A is coated uniformly on carbon cloth, after being dried under the conditions of being 80 DEG C through temperature, Obtain pole piece B, its coating thickness on carbon cloth is 20 μm；By 70% sulphur-graphite oxide, carbon black and sodium carboxymethylcellulose By 8：1：1 is added to the water, and is sufficiently stirred for, and wherein, solid content is 10%, obtains slurry C；Slurry C is coated uniformly on pole On piece B, after being dried under the conditions of being 90 DEG C through temperature, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 3.5mg/ cm2.By methyl alkoxy silicone oil（Silicon oil viscosity is 30Pa S）Press 1 with acetone：10 volume ratio ultrasonic mixings uniformly, obtain silicon Oily mixed liquor, pole piece D is put on a buchner funnel, drips silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum filtration 10 minutes, after solvent infiltrates in electrode completely, in drying box, 150 DEG C of insulation 20min, obtained oleophylic porous sulfur electrode, In sulfur electrode, the mass content of silicone oil is 0.5%.Battery testing, this material has higher coulombic efficiency and excellent circulation is steady Qualitative.
Embodiment 8
Acetylene black is pressed 9 with sodium carboxymethylcellulose：1 ratio is added to the water, and is sufficiently stirred for, wherein, admittedly containing Measure as 10%, obtain slurry A;Slurry A is coated uniformly on carbon cloth, after being dried under the conditions of being 80 DEG C through temperature, obtains pole piece B, Its coating thickness on carbon cloth is 20 μm；70% sulphur-nanofiber, CNT and sodium carboxymethylcellulose are pressed 8：1：1 It is added to the water, is sufficiently stirred for, wherein, solid content is 10%, obtains slurry C；Slurry C is coated uniformly on pole piece B, After being dried under the conditions of being 90 DEG C through temperature, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 4.0mg/cm2.By two Methyl-silicone oil（Silicon oil viscosity is 30Pa S）Press 1 with acetone：5 volume ratio ultrasonic mixings uniformly, obtain silicone oil mixed liquor, by pole Piece D is put on a buchner funnel, drips silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum filtration 10 minutes, and treat solvent After infiltrating in electrode completely, in drying box, 120 DEG C of insulation 30min, obtain oleophylic porous sulfur electrode, silicone oil in sulfur electrode Mass content is 1%.Battery testing, this material has higher coulombic efficiency and excellent cyclical stability.
Embodiment 9
Acetylene black is pressed 9 with sodium carboxymethylcellulose：1 ratio is added to the water, and is sufficiently stirred for, wherein, admittedly containing Measure as 10%, obtain slurry A;Slurry A is coated uniformly on carbon cloth, after being dried under the conditions of being 80 DEG C through temperature, obtains pole piece B, Its coating thickness on carbon cloth is 20 μm；70% sulphur-nanofiber, CNT and sodium carboxymethylcellulose are pressed 8：1：1 It is added to the water, is sufficiently stirred for, wherein, solid content is 10%, obtains slurry C；Slurry C is coated uniformly on pole piece B, After being dried under the conditions of being 90 DEG C through temperature, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 4.0mg/cm2.By first Base alkoxyl silicone oil（Silicon oil viscosity is 5Pa S）Press 1 with acetone：10 volume ratio ultrasonic mixings uniformly, obtain silicone oil mixed liquor, Pole piece D is put on a buchner funnel, drips silicone oil mixed liquor on pole piece, after it is uniformly dispersed, vacuum filtration 10 minutes, treat After solvent infiltrates in electrode completely, in drying box, 150 DEG C of insulation 20min, obtain oleophylic porous sulfur electrode, silicon in sulfur electrode The mass content of oil is 15%.Battery testing, this material has higher coulombic efficiency and excellent cyclical stability.
Embodiment 10
Peal blackberry (BP2000) is pressed 9 with polyvinyl alcohol：1 ratio is added in 1-METHYLPYRROLIDONE, carries out fully Stirring, wherein, solid content is 5%, obtains slurry A;Slurry A is coated uniformly on carbon cloth, is dried under the conditions of being 80 DEG C through temperature Afterwards, obtain pole piece B, its coating thickness on carbon cloth is 50 μm；60% sulphur-mesoporous carbon, acetylene black and polyvinyl alcohol are pressed 9： 0：1 is added in 1-METHYLPYRROLIDONE, is sufficiently stirred for, and wherein, solid content is 5%, obtains slurry C；Slurry C is uniform It is coated on pole piece B, after being dried under the conditions of being 60 DEG C through temperature, obtain the anode pole piece D of traditional lithium-sulfur cell, sulphur load amount is 3.86mg/cm2.By diethyl silicone oil（Silicon oil viscosity is 60Pa S）Press 1 with kerosene：1 volume ratio ultrasonic mixing uniformly, obtains Silicone oil mixed liquor, pole piece D is put on a buchner funnel, and dropping silicone oil mixed liquor on pole piece, after it is uniformly dispersed, take out by vacuum Filter 10 minutes, after solvent infiltrates in electrode completely, 170 DEG C of insulation 10min in drying box, obtain oleophylic porous sulphur electricity Pole, in sulfur electrode, the mass content of silicone oil is 3%.Battery testing, this material has higher coulombic efficiency and excellent circulation Stability.

Claims (6)

1. a kind of preparation method of oleophylic sulfur electrode, coats by carbon-sulfur compound and bonding on the carbon cloth or carbon paper of carbon dust leveling The slurry of agent mixing, or the slurry that carbon-sulfur compound, conductive agent are mixed with binding agent；It is dried and positive pole porous electrode, electrode are obtained Middle sulphur load amount is (2.0-5.0) mg/cm2It is characterised in that：Silicone oil is infiltrated into inside positive pole porous electrode, is obtained after being dried The oleophylic sulfur electrode of porous, in oleophylic sulfur electrode, the mass content of silicone oil is 0.2～30%.
2. according to claim 1 oleophylic sulfur electrode preparation method it is characterised in that：
1) carbon dust and binding agent are added in dispersant, are sufficiently stirred for, wherein, solid content is 5～50%, obtains slurry A；Carbon dust and binding agent mass ratio are (99: 1)～(90: 10)；
2) slurry A is coated uniformly on carbon paper or carbon cloth, after being dried under the conditions of being 20 DEG C～90 DEG C through temperature, obtains band leveling The pole piece B of layer；
3) carbon-sulfur compound and binding agent are added in dispersant, add or be added without conductive agent, be sufficiently stirred for, its In, solid content is 5～50%, obtains slurry C；Described carbon-sulfur compound, conductive agent, the mass ratio of binding agent are (70-90): (0-20)：10；
4) slurry C is coated uniformly on pole piece B, after being dried under the conditions of being 50 DEG C～120 DEG C through temperature, obtains traditional lithium sulphur electricity The anode pole piece D in pond；
5) by silicone oil with easy volatile solvent ultrasonic mixing uniformly, obtain silicone oil mixed liquor, pole piece D is put on a buchner funnel, drips Plus silicone oil mixed liquor is on pole piece, after it is uniformly dispersed, vacuum filtration 5-20 minute, treat that solvent infiltrates in electrode completely Afterwards, 100-170 DEG C of insulation 10-120min in drying box, obtains oleophylic porous sulfur electrode.
3. preparation method according to claim 1 it is characterised in that：Carbon in the described carbon cloth of carbon dust leveling or carbon paper Powder is one of acetylene black, oil oven carbon, Peal blackberry, section's qin carbon black or two kinds, and its coating thickness on carbon paper or carbon cloth is 10-50μm.
4. preparation method according to claim 1 it is characterised in that：Carbon in described carbon-sulfur compound be activated carbon, One of charcoal-aero gel, Graphene, graphite oxide, expanded graphite, CNT, carbon nano-fiber, mesoporous carbon or two kinds with Upper mixture, it accounts for the mass percent of carbon-sulfur compound is 10-50%；Described conductive agent is carbon black, graphite, carbon nanometer One of pipe, carbon nano-fiber, mesoporous carbon or more than two kinds, described binding agent is polytetrafluoroethylene (PTFE), Kynoar, poly- second Enol, sodium carboxymethylcellulose, polyacrylic one or two or more kinds.
5. preparation method according to claim 2 it is characterised in that：Described dispersant is 1-METHYLPYRROLIDONE, water One of.
6. preparation method according to claim 2 is it is characterised in that described silicone oil is dimethicone, aminomethyl phenyl One of silicone oil, Methyl Hydrogen Polysiloxane Fluid, diethyl silicone oil, ethyl containing hydrogen silicone oil, methyl alkoxy silicone oil, described silicone oil glues Spend for 5-100mPa S；Described easy volatile solvent is isopropanol, carbon tetrachloride, dichloromethane, gasoline, kerosene, in acetone A kind of；Described silicone oil is 1 with the volume ratio of easy volatile solvent: (0.5-10).
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