CN103840125B - A kind of lithium-sulphur cell positive electrode structure and preparation method thereof - Google Patents

A kind of lithium-sulphur cell positive electrode structure and preparation method thereof Download PDF

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CN103840125B
CN103840125B CN201210482976.8A CN201210482976A CN103840125B CN 103840125 B CN103840125 B CN 103840125B CN 201210482976 A CN201210482976 A CN 201210482976A CN 103840125 B CN103840125 B CN 103840125B
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carbon
sulfur compound
sulfur
compound layer
slurry
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CN103840125A (en
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张华民
王美日
张益宁
曲超
王倩
李婧
聂红娇
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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
    • H01M4/13—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to a kind of lithium-sulphur cell positive electrode structure and preparation method thereof, using collector as substrate, be attached with the carbon-sulfur compound layer of two-layer different pore size thereon, be followed successively by collector, large aperture carbon-sulfur compound layer, small-bore carbon-sulfur compound layer in order; Wide-aperture carbon-sulfur compound layer thickness is 50 ~ 500 μm, and the carbon-sulfur compound layer thickness of small-bore is 10 μm ~ 200 μm; Large aperture material with carbon element refers to that aperture is for being greater than 100nm, is less than 1 μm, and its mesopore volume accounts for the material with carbon element of total pore volume 50-90%; Small-bore material with carbon element refers to that aperture is 0.5nm ~ 100nm, and its mesopore volume accounts for the material with carbon element that total pore volume is greater than 50 ~ 90%.The positive pole of this structure effectively increases lithium ion mass transfer curvature in the electrodes, extends lithium ion ground bang path, is conducive to the performance of the active material capacity of high load amount, improves the energy density of battery.

Description

A kind of lithium-sulphur cell positive electrode structure and preparation method thereof
Technical field
The present invention relates to lithium-sulphur cell positive electrode and preparation method thereof, particularly a kind of anode structure and preparation method thereof.
Background technology
In recent years, along with the continuous progress of science and technology, the fast development of various electronic product, requires that chemical power source used has the features such as quality is light, volume is little, capacity is large.Want the demand adapting to society, increase substantially the energy density of battery, the exploitation of new material and new system is necessary.
The secondary cell that lithium-sulfur cell is a kind of take lithium metal as negative pole, elemental sulfur is positive pole, its specific energy can reach 2600Wh/kg in theory, actual energy density can reach 300Wh/kg at present, very likely about 600Wh/kg is brought up in the coming years, elemental sulfur positive electrode has abundance, low price, advantages of environment protection simultaneously, is considered to one of secondary cell system of current most research attraction.
But also there is a lot of problem in the development of lithium-sulfur cell.Such as, actual lithium-sulfur cell energy density is not high is one of key factor limiting its practical application.Want the energy density improving whole battery, positive active material load amount will be improved.The electrode caused thus is chapped from the cold, electric charge and ion-transfer resistance higher, capacity plays the problems such as not high, circulating battery poor stability and bites to be solved.
At present, slurry normally by sulphurous materials, conductive additive and binding agent are made slurry in a solvent according to the dispersion of certain ratio, and to be directly coated in aluminum foil current collector and to dry and obtain by lithium-sulphur cell positive electrode.
Chinese patent (application number 201210032447.8) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.The method only improves the corrosion resistance of collector, can not improve the electric charge of active material and the transfer resistance of lithium ion of high load amount.
Chinese patent (application number 201010513866.4) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.The while that the method being depositing carbon film on sheet metal collector, gas phase mixes sulphur.Although the binding agent not containing poorly conductive in electrode prepared by this invention, because the equipment price of its application is expensive, and preparation process is wayward, thus limits its development.
Chinese patent (application number 200710122444.2) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.This invention, using gelatin as binding agent, reduces the infiltration resistance of electrolyte to pole piece.But still the transfer resistance that electrode does thick rear electric charge and lithium ion can not be improved.
To sum up, improve the structure of anode pole piece, prepare the gradient electrode of the carbon-sulfur compound layer compound of wide-aperture carbon-sulfur compound layer and small-bore, the transfer resistance of electric charge in anode pole piece and lithium ion can not only be improved.Improve the discharge capacity of active material, improve the energy density of battery; And the pore property of gradient electrode can effectively suppress shuttling back and forth of polysulfide, improve the cyclical stability of lithium-sulfur cell.Therefore, the energy density of structure to raising battery of modified electrode is effective, but no matter existing lithium-sulphur cell positive electrode is in the preparation method of product or in commercial value, all have palpus improvements.
The present invention is directed to above-mentioned shortcoming, provide a kind of novel lithium-sulphur cell positive electrode structure, this electrode structure is gradient electrode, comprises two parts, and one deck is the wide-aperture carbon-sulfur compound layer on collector, and one deck is the carbon-sulfur compound layer of small-bore.When it is used as lithium sulfur battery anode material, be 4.2mg-S/cm in the load amount of active material 2under condition, it is discharge capacity 1100mAh/g-S first, and circulate 20 times, discharge capacitance is greater than 80%.
Summary of the invention
The object of the present invention is to provide a kind of novel lithium-sulphur cell positive electrode structure and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: prepare gradient electrode, comprises two parts, and one deck is the wide-aperture carbon-sulfur compound layer on collector, and one deck is the carbon-sulfur compound layer of small-bore.Wide-aperture carbon-sulfur compound layer is conducive to the transmission of lithium ion and is contained in the volumetric expansion that polysulfide in discharge process causes, and improves the discharge-rate of battery; The carbon-sulfur compound layer of small-bore is conducive to the utilance improving active material, improves discharge capacity, and can effectively suppress " effect of shuttling back and forth " of many lithium sulfides, improves cyclical stability and the coulombic efficiency of battery.The performance of the active material capacity of the high load amount that is just highly advantageous to of this structure, improves the energy density of battery.This structure is applied to lithium-sulfur cell, is conducive to the mass transfer polarization reducing battery, improves discharge-rate and the cyclical stability of battery.
A kind of lithium-sulphur cell positive electrode structure, it is characterized in that, this pole piece is gradient electrode, comprises two parts, and one deck is the wide-aperture carbon-sulfur compound layer on collector, and one deck is the carbon-sulfur compound layer of small-bore.Described carbon-sulfur compound layer to be sulfur content the be carbon-sulfur compound of 10 ~ 95%, the mixture of conductive agent and binding agent, wherein the mass ratio of carbon-sulfur compound, conductive agent and binding agent is 1:(0 ~ 1): (0.01 ~ 0.5);
Described wide-aperture carbon-sulfur compound layer thickness is 50 ~ 500 μm (preferred 80-200 μm), and the carbon-sulfur compound layer thickness of small-bore is 10 μm ~ 200 μm (preferred 20-50 μm); Described carbon-sulfur compound adopts material with carbon element and sulfur materials to be prepared from, the material with carbon element that in the carbon-sulfur compound layer of described large aperture, carbon-sulfur compound adopts is large aperture material with carbon element, and the material with carbon element that in the carbon-sulfur compound layer of described small-bore, carbon-sulfur compound adopts is small-bore material with carbon element; Large aperture material with carbon element refers to that aperture is be greater than 100nm accounts for total pore volume 50-90% material with carbon element to the pore volume of 1 μm; Small-bore material with carbon element refers to that aperture is the material with carbon element that the pore volume of 0.5nm ~ 100nm accounts for total pore volume and is greater than 50% to 90%.The material with carbon element specific surface of described large aperture material with carbon element is 60m 2/ g-2000m 2/ g, small-bore material with carbon element specific surface is 300m 2/ g-3000m 2/ g.
The material with carbon element of described large aperture material with carbon element is one or more mixtures in active carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon; The material with carbon element of described small-bore material with carbon element is one or more mixtures in active carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon.Described conductive agent is one or more in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon.Described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, polyacrylic one or more.The preparation method of described carbon-sulfur compound is the one in mechanical mixing, solution composite approach, fusion method, reaction in-situ composite algorithm, gel precipitation composite algorithm, Charging sulphur method and decompression Charging sulphur method.
A preparation method for lithium-sulphur cell positive electrode structure, its preparation process is:
1) wide-aperture carbon-sulfur compound, conductive agent and binding agent are joined by a certain percentage in dispersant, fully stir, obtain slurry A, wherein, solid content is 5 ~ 50%;
2) slurry A is evenly applied on a current collector, be under 20 DEG C ~ 90 DEG C conditions after drying through temperature, obtain pole piece B;
3) carbon-sulfur compound of small-bore, conductive agent and binding agent are joined by a certain percentage in dispersant, fully stir, obtain slurry C, wherein, solid content is 5 ~ 50%;
4) slurry C is evenly coated in pole piece B, is under 50 DEG C ~ 120 DEG C conditions after drying through temperature, obtains the anode pole piece of lithium-sulfur cell.
Described dispersant is the one in 1-METHYLPYRROLIDONE, water.Described painting method is the one in knife coating, spraying process, silk screen print method, roll-in method, laser printing method; Described collector is foamy carbon, carbon paper, carbon cloth, nickel foam.One in aluminium foil; Described drying mode is the one in forced air drying, vacuumize, the drying of heating platform open type.
Compared with prior art, tool of the present invention has the following advantages:
(1). the gradient electrode obtained by the inventive method, comprises two parts, and one deck is the wide-aperture carbon-sulfur compound layer on collector, and one deck is the carbon-sulfur compound layer of small-bore.Wide-aperture carbon-sulfur compound layer is conducive to the transmission of lithium ion and is contained in the volumetric expansion that polysulfide in discharge process causes, and improves the discharge-rate of battery; The carbon-sulfur compound layer of small-bore is conducive to the utilance improving active material, improves discharge capacity, and can effectively suppress " effect of shuttling back and forth " of many lithium sulfides, improves cyclical stability and the coulombic efficiency of battery.The performance of the active material capacity of the high load amount that is just highly advantageous to of this structure, improves the energy density of battery.This structure is applied to lithium-sulfur cell, is conducive to the mass transfer polarization reducing battery, improves discharge-rate and the cyclical stability of battery.
(2). the gradient electrode structure prepared by the present invention, compared with the lithium-sulphur cell positive electrode prepared with prior art, effectively can increase lithium ion mass transfer curvature in the electrodes, extend lithium ion ground bang path, reduce the transfer resistance of electric charge and lithium ion, improve the discharge voltage plateau of battery, improve the discharge capacity of the active material of high load amount in unit are, improve the energy density of battery.
(3). the gradient electrode structure prepared by the present invention, adopt the carbon-sulfur compound of Different Pore Structures, the desirable networked pore structures building " aperture storage sulphur, middle macropore diversion " can be realized, while improving battery discharge multiplying power and discharge capacity, improve the cyclical stability of battery.
(4). anode prepared by the present invention has higher utilization efficiency and good cyclical stability.In active material sulphur load amount higher than 4mg/cm 2condition under, press in battery discharge higher than 2V, discharge capacity is greater than 1100mAh/g-S, circulation 20 circle after, discharge capacitance is greater than 80%.
(5). the lithium-sulphur cell positive electrode adopting the present invention to prepare and cathode of lithium are assembled into button cell or flexible-packed battery, in battery pole piece unit are, the amount of active material raises, discharge voltage plateau raises, discharge capacity and discharge-rate improve, the cyclical stability of battery also improves, and the energy density of final battery is greatly improved.
Accompanying drawing explanation
Fig. 1. the present invention prepares ground gradient electrode ground structure schematic diagram;
Wherein 1-aperture carbon-sulfur compound layer, 2-macropore carbon-sulfur compound layer, 3-collector, 4-elemental sulfur, 5-conductive carbon
Fig. 2. the gradient electrode of high load amount active material sulphur prepared by the present invention and the first circle discharge capacity of traditional electrode contrast (gradient electrode cut-ff voltage is 1.5V, and traditional electrode cut-ff voltage is 1.2V), discharge-rate 0.5C, room temperature condition;
Fig. 3. the gradient electrode of high load amount active material sulphur prepared by the present invention and the cyclical stability of traditional electrode contrast (gradient electrode cut-ff voltage is 1.5V, and traditional electrode cut-ff voltage is 1.2V), discharge-rate 0.5C, room temperature.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
By elemental sulfur and ordered mesopore carbon, (aperture is 50nm, specific surface is 60) be prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 70%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 15%, by even for slurry blade coating in aluminum foil current collector, after 80 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 50 μm.
By elemental sulfur and activated carbon, (aperture is 0.5nm, specific surface is 300) be prepared into carbon-sulfur compound C by hot melt compound, filling sulfur content is 50%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 8%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 100 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 10 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
As seen from Figure 2, the first circle discharge capacity of the anode pole piece of high load amount active material sulphur prepared by the present invention is greater than 1100mAh/g-S, and the utilance of elemental sulfur is 66%, and discharge voltage plateau is 2.0V; And traditional electrode polarization is very serious, discharge voltage plateau only has 1.6V, cut-off 1.2V, discharge capacity also only has 1000mAh/g-S, visible gradient electrode extends the bang path of lithium ion really, reduce electric charge and ion-transfer resistance, improve discharge voltage plateau, improve the utilance of elemental sulfur.
As seen from Figure 3, the anode pole piece of high load amount active material sulphur prepared by the present invention after 20 circle circulations, the capability retention of battery is greater than 80%, and substantially remains unchanged, and comparatively traditional electrode capability retention improves 10%.Therefore, the anode pole piece of the high load amount active material sulphur prepared by the present invention has excellent cyclical stability.
Embodiment 2
Elemental sulfur and Graphene are prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 95%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 10%, by even for slurry blade coating in aluminum foil current collector, after 50 ° of C vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 500 μm.
Elemental sulfur and carbon nano-tube are prepared into carbon-sulfur compound C by hot melt compound, filling sulfur content is 10%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 10%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 200 μm.
Electrochemical property test: take metal lithium sheet as negative pole, be assembled into flexible-packed battery in the glove box being full of argon gas, at room temperature carry out constant current charge-discharge test with 0.2C, circulate 20 times, capability retention is greater than 70%.
Embodiment 3
Elemental sulfur and conductive black are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 10%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 1:1:0.5 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 5%, by even for slurry blade coating in aluminum foil current collector, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by reaction in-situ composite algorithm, filling sulfur content is 95%, get C, acetylene black, Kynoar in mass ratio for 1:1:0.05 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 10%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 10 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 1C.
Embodiment 4
Elemental sulfur and carbon aerogels are prepared into carbon-sulfur compound A by solution composite approach, filling sulfur content is 50%, get A, electrically conductive graphite, polyvinyl alcohol in mass ratio for 1:0.5:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 10%, by even for slurry blade coating on nickel foam collector, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by gel precipitation composite algorithm, filling sulfur content is 70%, get C, acetylene black, polyacrylic acid in mass ratio for 1:0.5:0.5 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 8%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 100 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.5C.
Embodiment 5
Elemental sulfur and expanded graphite are prepared into carbon-sulfur compound A by Charging sulphur method, filling sulfur content is 75%, get A, acetylene black, polyacrylic acid in mass ratio for 9:0.4:0.6 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 10%, by even for slurry blade coating on carbon foam current collector, after 60 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by the Charging sulphur method that reduces pressure, filling sulfur content is 75%, get C, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 8%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 50 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, be assembled into CR2016 button cell in the glove box being full of argon gas, at room temperature carry out constant current charge-discharge test with 0.5C, circulate 20 times, capability retention is greater than 80% (as Fig. 2, Fig. 3).
Traditional electrode in comparative example is on aluminium foil by carbon-sulfur compound blade coating of identical sulphur load amount.
Embodiment 6
Elemental sulfur and mesoporous carbon are prepared into carbon-sulfur compound A by Charging sulphur method, filling sulfur content is 75%, get A, polyacrylic acid in mass ratio for 9:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by even for slurry blade coating on carbon foam current collector, after 90 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 50 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by hot melt, filling sulfur content is 70%, get C, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 5%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 50 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 200 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.1C.
Embodiment 7
Elemental sulfur and graphite oxide are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 50%, get A, polyacrylic acid in mass ratio for 9:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by slurry even application on carbon cloth collector, after 20 DEG C of dryings, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 300 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by hot melt, filling sulfur content is 70%, get C, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 5%, by even for slurry D silk screen printing on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 20 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
Embodiment 8
Elemental sulfur and conductive black are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 60%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 96:0:4 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 15%, is pressed in aluminum foil current collector by slurry even roller, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by reaction in-situ composite algorithm, filling sulfur content is 95%, get C, acetylene black, Kynoar in mass ratio for 1:1:0.05 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 10%, slurry D uniform laser is printed on the carbon-sulfur compound layer of large aperture, after 80 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 10 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 1C.
Embodiment 9
Elemental sulfur and ordered mesopore carbon are prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 60%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 1:1:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 5%, by even for slurry blade coating in aluminum foil current collector, after 90 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 500 μm.
Elemental sulfur and activated carbon are prepared into carbon-sulfur compound C by hot melt compound, filling sulfur content is 50%, get C, acetylene black, Kynoar in mass ratio for 1:0:0.5 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 50%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 50 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 10 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
Embodiment 10
Elemental sulfur and Graphene are prepared into carbon-sulfur compound A by mechanical mixing compound, filling sulfur content is 95%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by even for slurry blade coating in aluminum foil current collector, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 300 μm.
Elemental sulfur and carbon nano-tube are prepared into carbon-sulfur compound C by hot melt compound, filling sulfur content is 10%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 50%, by even for slurry D blade coating on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 50 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
Embodiment 11
Elemental sulfur and graphite oxide are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 50%, get A, polyacrylic acid in mass ratio for 1:0:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, is pressed in by slurry even roller on carbon cloth collector, after 90 DEG C of dryings, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by hot melt, filling sulfur content is 70%, get C, acetylene black, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 50%, by even for slurry D silk screen printing on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 20 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.5C.
Embodiment 12
Elemental sulfur and ordered mesopore carbon are prepared into carbon-sulfur compound A by hot melt compound, and filling sulfur content is 60%,
Get A, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, slurry even roller is pressed on carbon cloth collector, after 90 DEG C of dryings, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μm.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by hot melt, filling sulfur content is 70%, get C, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry D, wherein in slurry, solid content is 50%, by even for slurry D silk screen printing on the carbon-sulfur compound layer of large aperture, after 120 DEG C of vacuumizes, compacting obtains anode pole piece, and its small-bore carbon-sulfur compound layer thickness is 20 μm.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.5C.

Claims (10)

1. a lithium-sulfur cell anode structure, it is characterized in that: described anode structure is using collector as substrate, be attached with the carbon-sulfur compound layer of two-layer different pore size thereon, be followed successively by collector, large aperture carbon-sulfur compound layer, small-bore carbon-sulfur compound layer in order; Wide-aperture carbon-sulfur compound layer thickness is 50 ~ 500mm, and the carbon-sulfur compound layer thickness of small-bore is 10mm ~ 200mm; Described carbon-sulfur compound adopts material with carbon element and sulfur materials to be prepared from, the material with carbon element that in the carbon-sulfur compound layer of described large aperture, carbon-sulfur compound adopts is large aperture material with carbon element, and the material with carbon element that in the carbon-sulfur compound layer of described small-bore, carbon-sulfur compound adopts is small-bore material with carbon element; Large aperture material with carbon element refers to aperture to be 100nm to the pore volume of 1 μm accounts for the material with carbon element of total pore volume 50-90%; Small-bore material with carbon element refers to that aperture is the material with carbon element that the pore volume of 0.5nm to 100nm accounts for total pore volume and is greater than 50-90%.
2. anode structure according to claim 1, it is characterized in that, described carbon-sulfur compound layer comprises carbon-sulfur compound, binding agent, wherein also can add or not add conductive agent, the mass ratio of carbon-sulfur compound, conductive agent and binding agent is 1:(0 ~ 1): (0.01 ~ 0.5); Carbon-sulfur compound sulfur content is 10 ~ 95wt%.
3. anode structure according to claim 1, is characterized in that, the specific area of described large aperture material with carbon element is 60-2000m2/g, and small-bore material with carbon element specific surface is 300-3000m2/g.
4. the anode structure according to claim 1 or 3, is characterized in that: described material with carbon element is one or two or more kinds in active carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon.
5. anode structure according to claim 2, is characterized in that: described conductive agent is one or two or more kinds in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon.
6. anode structure according to claim 2, is characterized in that: described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, polyacrylic one or two or more kinds; Described collector is the one in foamy carbon, carbon paper, carbon cloth, nickel foam, aluminium foil.
7. anode structure according to claim 1, is characterized in that: described carbon-sulfur compound adopts material with carbon element and sulfur materials to be prepared from, and sulfur materials is sulphur simple substance; The preparation method of described carbon-sulfur compound is the one in mechanical mixing, solution composite approach, fusion method, reaction in-situ composite algorithm, gel precipitation composite algorithm, Charging sulphur method.
8. a preparation method for anode structure described in claim 1, is characterized in that:
(1) be 1:(0 ~ 1 in mass ratio by the carbon-sulfur compound, conductive agent and the binding agent that adopt large aperture material with carbon element to prepare): (0.01 ~ 0.5) joins in dispersant, fully stir, wherein, solids content is 5 ~ 50wt.%, obtains slurry A;
(2) evenly applied on a current collector by slurry A, drying process obtains pole piece B;
(3) carbon-sulfur compound, conductive agent and binding agent 1:(0 ~ 1 in mass ratio will small-bore material with carbon element being adopted to prepare): (0.01 ~ 0.5) joins in dispersant, fully stir, wherein, solids content is 5 ~ 50%, obtains slurry C;
(4) slurry C is evenly coated in the one side that pole piece B scribbles slurry A, dry under temperature is 50 DEG C ~ 120 DEG C conditions, obtain anode structure.
9. preparation method according to claim 8, is characterized in that: described dispersant is 1-METHYLPYRROLIDONE or water.
10. preparation method according to claim 8, is characterized in that, described painting method is the one in knife coating, spraying process, silk screen print method, roll-in method, laser printing method; Described drying mode is the one in forced air drying, vacuumize, the drying of heating platform open type.
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