CN103840125A - Lithium-sulfur battery positive electrode structure and preparation method thereof - Google Patents
Lithium-sulfur battery positive electrode structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a lithium-sulfur battery positive electrode structure and a preparation method thereof. According to the lithium-sulfur battery positive electrode structure, a current collector is adopted as a substrate, two carbon-sulfur complex layers with different pore sizes are attached onto the substrate, the structure sequentially comprises the current collector, the large pore size carbon-sulfur complex layer and the small pore size carbon-sulfur complex layer, the thickness of the large pore size carbon-sulfur complex layer is 50-500 mum, the thickness of the small pore size carbon-sulfur complex layer is 10-200 mum, the large pore size carbon material is a carbon material with a pore size of greater than 100 nm and less than 1 mum and a pore volume accounting for 50-90% of the total pore volume, and the small pore size carbon material is a carbon material with a pore size of 0.5-100 nm and a pore volume accounting for more than 50-90% of the total pore volume. With the lithium-sulfur battery positive electrode structure, the mass transfer curvature of the lithium ions in the electrode is effectively increased, the lithium ion transmission path is prolonged, provision of the capacity of the high supporting capacity active substance is easily achieved, and the energy density of the battery is increased.
Description
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 products, requires chemical power source used to have the features such as quality is light, volume is little, capacity is large.Want to adapt to social demand, increase substantially the energy density of battery, the exploitation of new material and new system is necessary.
Lithium-sulfur cell be a kind of taking lithium metal as negative pole, elemental sulfur is anodal secondary cell, its specific energy can reach 2600Wh/kg in theory, actual energy density can reach 300Wh/kg at present, in the coming years, very likely bring up to 600Wh/kg left and right, simultaneously elemental sulfur positive electrode have that source is abundant, low price, advantages of environment protection, be considered to one of secondary cell system of current tool research attraction.
But also there are a lot of problems in the development of lithium-sulfur cell.For example, actual lithium-sulfur cell energy density is not high is one of key factor limiting its practical application.Want to improve the energy density of whole battery, will improve positive active material load amount.The electrode causing is thus chapped from the cold, electric charge and ion-transfer resistance higher, the problems such as capacity performance is not high, circulating battery poor stability are bitten to be solved.
At present, lithium-sulphur cell positive electrode is normally by sulphurous materials, conductive additive and binding agent are dispersed in and make slurry in solvent according to certain ratio, and slurry is directly coated in aluminum foil current collector and is dried obtains.
Chinese patent (application number 201210032447.8) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.The method has only been improved 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 method be on sheet metal collector in depositing carbon film gas phase mix sulphur.Although do not contain the binding agent of poorly conductive in electrode prepared by this invention, due to the equipment price costliness of its application, and preparation process is wayward, thereby has limited 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, has reduced the infiltration resistance of electrolyte to pole piece.But still can not improve electrode and do the transfer resistance of thick rear electric charge and lithium ion.
To sum up, improve the structure of anode pole piece, prepare the compound gradient electrode of carbon-sulfur compound layer of wide-aperture carbon-sulfur compound layer and small-bore, can not only improve electric charge in anode pole piece and the transfer resistance of lithium ion.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, the cyclical stability of raising lithium-sulfur cell.Therefore, the structure of modified electrode is effectively to improving the energy density of battery, but no matter existing lithium-sulphur cell positive electrode is in the preparation method of product or aspect commercial value, all to have palpus improvements.
The present invention is directed to above-mentioned shortcoming, a kind of novel lithium-sulphur cell positive electrode structure is provided, this electrode structure is gradient electrode, comprises two parts, and one deck is the wide-aperture carbon-sulfur compound layer on collector, the carbon-sulfur compound layer that one deck is 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, circulates 20 times, and 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, comprise two parts, one deck is the wide-aperture carbon-sulfur compound layer on collector, the carbon-sulfur compound layer that one deck is small-bore.Wide-aperture carbon-sulfur compound layer is conducive to the transmission of lithium ion and is contained in the volumetric expansion that in discharge process, polysulfide causes, improves the discharge-rate of battery; The carbon-sulfur compound layer of small-bore is conducive to improve the utilance of active material, improves discharge capacity, and can effectively suppress " effect of shuttling back and forth " of many lithium sulfides, improves cyclical stability and coulomb efficiency of battery.The performance of the active material capacity of the high load amount that is just highly advantageous to of this structure, the energy density of raising battery.This structure applications, in lithium-sulfur cell, is conducive to reduce the mass transfer polarization of battery, improves discharge-rate and the cyclical stability of battery.
A kind of lithium-sulphur cell positive electrode structure, 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, the carbon-sulfur compound layer that one deck is small-bore.Described carbon-sulfur compound layer is that sulfur content is the mixture of 10 ~ 95% carbon-sulfur compound, conductive agent and binding agent, and 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 be the preferred 80-200 μ of 50 ~ 500 μ m(m), the carbon-sulfur compound layer thickness of small-bore be the preferred 20-50 μ of 10 μ m ~ 200 μ m(m); Described carbon-sulfur compound is to adopt 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 the material with carbon element that is greater than 100nm and accounts for to the pore volume of 1 μ m total pore volume 50-90%; Small-bore material with carbon element refers to that aperture is that the pore volume of 0.5nm ~ 100nm accounts for the material with carbon element that total pore volume 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 in dispersant by a certain percentage, fully stir, obtain slurry A, wherein, solid content is 5 ~ 50%;
2) slurry A is evenly coated on collector, after temperature is dry under 20 DEG C ~ 90 DEG C conditions, obtains pole piece B;
3) carbon-sulfur compound of small-bore, conductive agent and binding agent are joined in dispersant by a certain percentage, fully stir, obtain slurry C, wherein, solid content is 5 ~ 50%;
4) slurry C is evenly coated in to pole piece B, after temperature is dry under 50 DEG C ~ 120 DEG C conditions, 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 forced air drying, vacuumize, the heating platform open type one in dry.
Compared with prior art, tool of the present invention has the following advantages:
(1). the gradient electrode being obtained by the inventive method, comprise two parts, one deck is the wide-aperture carbon-sulfur compound layer on collector, the carbon-sulfur compound layer that one deck is small-bore.Wide-aperture carbon-sulfur compound layer is conducive to the transmission of lithium ion and is contained in the volumetric expansion that in discharge process, polysulfide causes, improves the discharge-rate of battery; The carbon-sulfur compound layer of small-bore is conducive to improve the utilance of active material, improves discharge capacity, and can effectively suppress " effect of shuttling back and forth " of many lithium sulfides, improves cyclical stability and coulomb efficiency of battery.The performance of the active material capacity of the high load amount that is just highly advantageous to of this structure, the energy density of raising battery.This structure applications, in lithium-sulfur cell, is conducive to reduce the mass transfer polarization of battery, improves discharge-rate and the cyclical stability of battery.
(2). the gradient electrode structure of being prepared by the present invention, compared with the lithium-sulphur cell positive electrode of preparing with prior art, can effectively increase lithium ion in electrode mass transfer curvature, 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 of being prepared by the present invention, adopt the carbon-sulfur compound of Different Pore Structures, can realize the desirable reticulated cell structure of structure " aperture storage sulphur, middle macropore diversion ", when 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, in battery discharge press 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 and the cathode of lithium that adopt the present invention to prepare 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.
Brief description of the drawings
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.
By elemental sulfur and ordered mesopore carbon, (aperture is 50nm, specific surface is 60) by the compound carbon-sulfur compound A that is prepared into of hot melt, filling sulfur content is 70%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 15%, by even 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 μ m.
By elemental sulfur and activated carbon, (aperture is 0.5nm, specific surface is 300) by the compound carbon-sulfur compound C that is prepared into of hot melt, filling sulfur content is 50%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 8%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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 has extended the bang path of lithium ion really, reduce electric charge and ion-transfer resistance, improved discharge voltage plateau, improved 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 circles circulations, the capability retention of battery is greater than 80%, and substantially remains unchanged, and improves 10% compared with traditional electrode capability retention.The anode pole piece of the high load amount active material sulphur of therefore, preparing by the present invention has excellent cyclical stability.
By elemental sulfur and Graphene by the compound carbon-sulfur compound A that is prepared into of hot melt, filling sulfur content is 95%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 10%, by even 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 μ m.
By elemental sulfur and carbon nano-tube by the compound carbon-sulfur compound C that is prepared into of hot melt, filling sulfur content is 10%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 10%, by even 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 μ m.
Electrochemical property test: taking metal lithium sheet as negative pole, be assembled into flexible-packed battery in the glove box that is 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%.
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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 5%, by even 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 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 10%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 1C.
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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 10%, by even 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 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 8%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.5C.
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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 10%, by even slurry blade coating on foamy carbon collector, after 60 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μ m.
Elemental sulfur and carbon nano-fiber are prepared into carbon-sulfur compound C by decompression Charging sulphur method, filling sulfur content is 75%, get C, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 8%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is full of argon gas, be assembled into CR2016 button cell, 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 be by blade coating of the carbon-sulfur compound of identical sulphur load amount to aluminium foil.
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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 50%, by even slurry blade coating on foamy carbon collector, after 90 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 50 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 5%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 50%, slurry is evenly sprayed on carbon cloth collector, 20 DEG C dry after, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 300 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 5%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 15%, slurry even roller is pressed in aluminum foil current collector, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 10%, by even slurry D laser printing 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 1C.
Embodiment 9
By elemental sulfur and ordered mesopore carbon by the compound carbon-sulfur compound A that is prepared into of hot melt, filling sulfur content is 60%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 1:1:0.01 ball milling is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 5%, by even 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 μ m.
By elemental sulfur and activated carbon by the compound carbon-sulfur compound C that is prepared into of hot melt, filling sulfur content is 50%, get C, acetylene black, Kynoar in mass ratio for 1:0:0.5 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 50%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
By elemental sulfur and Graphene by the compound carbon-sulfur compound A that is prepared into of mechanical mixing, filling sulfur content is 95%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 50%, by even 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 μ m.
By elemental sulfur and carbon nano-tube by the compound carbon-sulfur compound C that is prepared into of hot melt, filling sulfur content is 10%, get C, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 50%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 50%, slurry even roller is pressed on carbon cloth collector, 90 DEG C dry after, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μ m.
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 is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 50%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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
By elemental sulfur and ordered mesopore carbon, by the compound carbon-sulfur compound A that is prepared into of hot melt, filling sulfur content is 60%,
Get A, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling is scattered in 1-METHYLPYRROLIDONE after mixing, stir and obtain anodal active layer slurry B, wherein in slurry, solid content is 50%, slurry even roller is pressed on carbon cloth collector, 90 DEG C dry after, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 100 μ m.
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 is scattered in the aqueous solution after mixing, stir and obtain anodal active layer slurry D, wherein in slurry, solid content is 50%, by even 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 μ m.
Electrochemical property test: anode pole piece is struck out to the pole piece that diameter is 14mm.Taking metal lithium sheet as negative pole, in the glove box that is 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 order collector, large aperture carbon-sulfur compound layer, small-bore carbon-sulfur compound layer;
Wide-aperture carbon-sulfur compound layer thickness is 50 ~ 500 μ m, and the carbon-sulfur compound layer thickness of small-bore is 10 μ m ~ 200 μ m;
Described carbon-sulfur compound is to adopt 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, for being greater than 100nm, is less than 1 μ m, 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%.
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, and 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 material with carbon element specific surface of described large aperture material with carbon element is 60-2000m
2/ g, small-bore material with carbon element specific surface is 300-3000m
2/ g.
4. according to the anode structure described in claim 1 or 3, it 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 foamy carbon, carbon paper, carbon cloth, nickel foam, the one in aluminium foil.
7. anode structure according to claim 1, is characterized in that: described carbon-sulfur compound is to adopt 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 or decompression 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 stirs, and wherein, solids content is 5 ~ 50wt.%, obtains slurry A;
(2) slurry A is evenly coated on collector, drying processing obtains pole piece B;
(3) by carbon-sulfur compound, conductive agent and binding agent 1:(0 ~ 1 in mass ratio that adopts small-bore material with carbon element to prepare): (0.01 ~ 0.5) joins in dispersant, fully stirs, and wherein, solids content is 5 ~ 50%, obtains slurry C;
(4) slurry C is evenly coated in to pole piece B scribbles the one side of slurry A, is dry under 50 DEG C ~ 120 DEG C conditions through temperature, obtains 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 forced air drying, vacuumize, the heating platform open type one in dry.
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