CN101587951A - Novel carbon-sulfur compound for lithium-sulfur battery - Google Patents
Novel carbon-sulfur compound for lithium-sulfur battery Download PDFInfo
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Abstract
The invention relates to a novel carbon-sulfur compound for an anode material of a lithium-sulfur battery and a preparation method thereof. Sulfur is filled into a nano and micron hole of a matrix in an elementary substance way by taking a macroporous carbon material with high pore volume, electrical conductivity and specific surface area as the matrix, and the sulfur and carbon can also carry out combination reaction so as to prepare the novel carbon-sulfur compound of which the sulfur exists in one or more chemical states in a carbon material. The novel carbon-sulfur compound used as the anode material of the lithium-sulfur battery has the advantages that the high pore volume has large contained sulfur contents and can ensure high electric capacity; the small granularity of the sulfur can reduce a conductive distance between ions and electrons and increase the utilization ratio of the sulfur; and the adsorption characteristics of the high specific surface of the carbon material can inhibit a discharging intermediate product from dissolving and moving towards a cathode, reduce the self discharge, prevent a nonconductive discharging product, namely lithium sulfide from largely accumulating outside carbon particles and reduce internal resistance, therefore, the material can improve the specific energy, the specific power and the cycle performance of the lithium-sulfur battery.
Description
Technical field
The present invention relates to a kind of high specific energy lithium battery sulfur-bearing positive electrode and preparation method thereof.
Background technology
The theoretical specific capacity of elemental sulfur is 1675mAh/g, and the theoretical specific energy of forming battery with lithium can reach 2600Wh/kg, is a kind of high specific energy battery material, in addition, the advantage that also has cheapness, low toxicity, therefore, the lithium-sulfur cell system just received publicity as far back as last century 70, the eighties.R.D.Rauh etc. think and dissolve in the stability that many lithium sulfides in the electrolyte do not influence lithium metal to possess possibility (J.Electrochem.Soc.1979,126 (4): 523-527) of making secondary cell.Yamin and Peled etc. have studied the electrochemical reaction mechanism of many lithium sulfides, think that its process that is reduced to rudimentary sulfide is very complicated, have both comprised the electrochemical process of multistep electron exchange, also have the chemical conversion between the sulfide; As the primary cell positive electrode, specific capacity can reach 330mAh/g under the room temperature, and 60 ℃ are issued to 430mAh/g (J.Electrochem.Soc., 1988,135 (5): 1045-1048; J.Power Sources, 1989,26:267-271).Because the improvement to the lithium-sulfur cell cycle performance lacks means, research once stayed cool.
The beginning of the nineties in last century, occur with the fracture of sulphur sulfide linkage and compoundly put, the research of the organic sulfur compound of energy storage.This type of material is representative with dimercaptothiodiazole (DMcT), and molecular structure is controlled, polyaniline, poly-give a tongue-lashing to cough up etc. its oxidation-reduction process is had tangible catalysis.But the theoretical specific capacity of material is between 300～600mAh/g, and actual specific capacity has only about 200mAh/g, is not suitable for the battery system of high specific energy; The S-S group of this compounds is in main chain, and the micromolecule sulfide that the fracture of S-S group generates during discharge easily is dissolved in the electrolyte, causes harmful effect (J.Electrochem.Soc., 1991,138 (7), 1896 such as self discharge and capacity attenuation; J.Electrochem.Soc., 1997,144 (4), 1185).
Charcoal sulphur polymer can obtain higher specific capacity.CS such as Skotheim
2(USP 5601947 to generate poly-nitric sulfid (Polycarbon Sulfide) with the sodium metal reduction in solvent, 1997), again acetylene and elemental sulfur are reacted in the Sodamide liquid ammonia solution and generate polyacetylene copolymerization sulphur (Polyacetylene-co-Polysulfur) (USP 6117590,2000), head is put specific capacity and can be reached 800～1000mAh/g.This two classes electrode material all is a still mixture not really clearly of structure, use a large amount of sodium metals in synthetic, reaction condition requires harsh, process is more numerous and diverse, what have comprises a large amount of micromolecule, the structure that contains S-S in the main chain that has, the molten mistake of depolymerization when discharge easily causes anodal disintegration, cycle performance to descend.
For addressing the above problem, we have proposed the organic sulfur compound structural design thinking of " main chain conduction, side chain energy storage ", be main chain promptly with conducting polymer or conductive structure, to improve the conductivity and the structural stability of positive electrode, and taking place, redox S-S group is connected on the carbon atom of main chain in the mode of side chain, skeleton is not degraded during discharge, thereby guarantees that anodal external form is stablized and most of sulphur is trapped in positive polar region, and cyclicity will strengthen to some extent.Under instructing, this thinking designed and synthesized a series of sulfur-bearing conducting polymer composites such as carbyne polysulfide, many sulfo-s polyaniline, many sulfo-s polyhenylene and many sulfo-s polystyrene.Carbyne polysulfide circulates through 50 times still the specific capacity of 350mAh/g, and the synthetic and performance of many sulfo-s polyaniline also has remarkable break-throughs.Because the conductive polymer minor structure has accounted for big deal in material, the theoretical specific capacity of these materials is all not as good as 40% (applied chemistry, 2005,22 (4): 367-371 of elemental sulfur; SCI, 2005,26 (5): 918; SCI, 2005,26 (11): 2117-2121).
Based on the cheapness and the height ratio capacity characteristic of elemental sulfur, in recent years, be that the research of lithium-sulfur rechargeable battery of positive electrode is gradually many with the elemental sulfur, the Samsung company of Sion Power company, Polyplus company and the Korea S of the U.S. is all at this type of battery of active development.Sion Power company claimed that the sample battery of demonstration can be supported HP TC1000 notebook computer continuous operation 8h in 2003, and the specific energy that discharges first reaches 350Wh/kg, and declares and will release commodity the end of the year 2007.The business-like main cause of restriction lithium-sulfur cell is that its cycle performance is poor.The system of reporting in most of articles is reduced to (J.Electrochem.Soc., 2004,151 (12): A2067-A2073 below 70% through 50 circulation back capability retentions; J.Power Sources, 2005,139:269-273).The subject matter that the lithium-sulfur cell system exists is that the insulating properties of sulphur causes the utilance of material not high, and the circulation volume decay is serious, and its reason one is the Li that generates in discharge process
2S
X(2＜x≤8) are dissolved in electrolyte, cause positive electrode structure and profile that great variation has taken place, and active matter is through repeatedly breaking away from conductive agent after the circulation; The 2nd, deposit more and more thick Li at the conductive agent particle surface after the repeated charge
2S
2With Li
2The electric insulation layer of S, cause between the conductive agent particle and and collector between isolate gradually, finally cause capacity attenuation; The 3rd, " Li
2S
XThe effect of shuttling back and forth " (the Li that charging generates on the positive pole
2S
XDissolving also diffuses to negative pole, and with lithium generation self discharge reaction, the product after the self discharge moves again gets back to positive pole, is recharged again and is oxidized to Li
2S
X) cause efficiency for charge-discharge low, even be difficult to determine the charging terminal point.As seen, the insulating properties of positive electrode elemental sulfur and discharging product thereof and dissolubility are the roots of lithium-sulfur cell mis-behave.
Summary of the invention
At the problems referred to above, the present invention proposes a kind of novel carbon-sulfur compound and preparation method thereof, by the middle macropore carbon material with high pore volume, high conductivity, high-ratio surface is matrix, the form of sulphur with simple substance is filled in the nanometer and micrometer grade hole of matrix, the combination reaction of sulphur and carbon also can take place simultaneously, makes the novel carbon-sulfur compound that sulphur exists with one or more states in the raw material of wood-charcoal material.Have the following advantages with the positive electrode of this novel carbon-sulfur compound as lithium-sulfur cell: a large amount of sulphur in the high pore volume guarantee high-capacitance; Little sulphur granularity can reduce the conduction distance of ion, electronics, increases the utilance of sulphur; The characterization of adsorption of raw material of wood-charcoal material high-ratio surface suppresses the dissolving of discharge intermediate product and to the migration of negative pole, can reduce self discharge, and avoid the bulk deposition of nonconducting discharging product lithium sulfide outside carbon granule, reduces internal resistance.Therefore, this material can improve specific energy, specific power and the cycle performance of lithium-sulfur cell.
As the active carbon of elemental sulfur carrier, require to possess following character: (1) pore volume height to support a large amount of sulphur, guarantees that material has height ratio capacity.Typical active carbon specific area is about 1500m
2About/the g, average pore size is about 1nm, and pore volume is not more than 0.4cm
3/ g is even (proportion is with 2g/cm for the porose middle whole fill sulphur of institute
3Meter), sulfur content is the highest in the composite material of making also can only reach 44% (in fact can not reach), obviously can not satisfy the requirement of height ratio capacity, must adopt the active carbon of high pore volume; (2) specific area is big, micromolecular discharging product can be adsorbed on positive polar region, and minimizing directly contacts the self discharge that takes place because of discharging product with negative pole; (3) good conductivity to improve the electrical insulation property of elemental sulfur, improves the utilance of sulphur.
The carbon-sulfur compound that the present invention is used for the lithium-sulphur cell positive electrode material is a matrix with the macropore carbon material, and the specific area of middle macropore carbon material is 50～1900m
2/ g, pore volume are 0.1～3cm
3/ g, conductivity is 0.01～200S/cm; With content is that 10%～95% elemental sulfur is filled in the nanometer and submicron order hole of matrix, and the combination reaction that sulphur and carbon also can take place simultaneously makes.
Lithium-sulfur cell of the present invention is positive electrode with the novel carbon-sulfur compound, with the alloy of lithium metal, lithium and other alkali metal or alkaline-earth metal and Li/Al, Li/Si, Li/Pb, Li/Sn, Li/Sb, Li/Bi, Li/Zn, Li/Cd, Li/C is negative material, forms lithium-sulfur cell with organic bath; Organic bath is liquid state, gel, solid-state electrolyte system or ionic liquid, liquid electrolyte is selected for use and is contained PC, EC, DEC, 1, the mixture of one or more organic solvents of 3-dioxolane, dimethoxy-ethane, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, oxolane, ortho-xylene, supporting electrolyte can be lithium perchlorate, trifluoromethayl sulfonic acid lithium, lithium hexafluoro phosphate or lithium trifluoromethanesulp,onylimide.
The preparation method of carbon sulphur composite material comprises that the common hot method of ultrasonic immersing method, charcoal sulphur, sulfur vapor filling method, the sulphur of sulfur-bearing solution react method of formation in the hole among the present invention.
1. the ultrasonic immersing method of sulfur-bearing solution
(1) sulphur is dissolved in CS
2In, make concentration and be 5% to saturated solution;
(2) middle macropore carbon material is added the CS of sulphur
2In the solution, the C/S mass ratio is 1: 0.2～10;
(3) under 100～1000W action of ultrasonic waves, make the sulphur of dissolving can fully immerse in the hole of macropore carbon;
(4) remove by filter solvent, with product air drying under vacuum.
2. charcoal sulphur is total to hot method
(1) middle macropore carbon is evenly mixed with elemental sulfur, the C/S mass ratio is 1: 0.2～20;
(2) with the heating of the mixture in (1), heating can be carried out under normal pressure, adopts inert gas such as N
2Or the Ar protection, also can be as heating in the autoclave in closed container.Heating-up temperature is 100～500 ℃, and the time is 1h～10h.
3. sulfur vapor filling method
Elemental sulfur is heated to 100～500 ℃, at inert gas such as N
2Or the sulfur vapor filling is condensed in the macropore carbon in advancing, make the C/S mass ratio reach 1: 0.1～20.
4. sulphur reacts method of formation in the hole
(1) fortified aqueous with thiosulfate is impregnated in the middle macropore powdered carbon;
(2) middle macropore powdered carbon is leached, with hydrogen chloride gas or dilute acid soln and its reaction, sulphur precipitates in middle macropore carbon;
(3) compound is filtered, washs to there not being acid ion.
The kind of thiosulfate can be sylvite or sodium salt, and sulphur reacts the used diluted acid of generation in the hole can be the weak solution of hydrochloric acid, sulfuric acid, nitric acid, acetate or phosphoric acid.
The present invention is prepared carbon sulphur composite material as positive electrode active material, be assembled into battery, check its chemical property with lithium.Because this composite material has conductivity preferably, so can use conductive agent less than other positive electrode; Conductive agent can be selected conductive carbon black, graphite powder etc. for use.Binding agent among the present invention can be selected PEO, PTFE, ethylene-propylene rubber, Kynoar or gelatin for use.
Have the following advantages with the positive electrode of this novel carbon-sulfur compound as lithium-sulfur cell: a large amount of sulphur in the high pore volume guarantee high-capacitance; Little sulphur granularity can reduce the conduction distance of ion, electronics, increases the utilance of sulphur; The characterization of adsorption of raw material of wood-charcoal material high-ratio surface suppresses the dissolving of discharge intermediate product and to the migration of negative pole, can reduce self discharge, and avoid the bulk deposition of nonconducting discharging product lithium sulfide outside carbon granule, reduces internal resistance.Therefore, this material can improve specific energy, specific power and the cycle performance of lithium-sulfur cell.
Embodiment
Example 1
The 12.0g sublimed sulfur is joined 150ml CS
2In, under the effect of 250W ultrasonic wave, sulphur is dissolved into CS rapidly
2In the solvent.8.0g macropore material with carbon element is joined above CS
2In the solution, continue ultrasonic wave effect 1h the sulphur of dissolving can fully be immersed in the hole of macropore carbon, remove by filter solvent, with 30ml ether washing 3 times, with product air drying 10h under vacuum, sulfur content is 43% carbon-sulfur compound.
Example 2
Respectively macropore carbon and elemental sulfur 1.0g and 5.0g in the weighing, ball milling 2h make its mix (drum's speed of rotation be 500 change/min), place tube furnace to heat composite material.Speed with 5 ℃/min under nitrogen protection is warming up to 350 ℃, back constant temperature 3h; Be cooled to room temperature and obtain carbon sulphur composite material, wherein sulfur content is 48%.
Example 3
Distinguish macropore carbon and elemental sulfur 1.5g and 7.5g in the weighing, middle macropore carbon is placed on an end (glass pipe range 20mm) of the glass tube of both ends open, elemental sulfur is placed on the other end of glass tube; One end of elemental sulfur is placed on heating position in the tube furnace, and the speed with 5 ℃/min under nitrogen protection is warming up to 400 ℃, back constant temperature 2.5h, during sulfur vapor under stream of nitrogen gas drives, directly contact and enter in its hole with middle macropore carbon; Be cooled to room temperature and obtain carbon sulphur composite material, wherein sulfur content is 75%.
Example 4
Take by weighing 15.8g Na
2S
2O
3Be dissolved in the 100ml water, add macropore powdered carbon among the 2g, leave standstill 0.5h behind the stirring 0.5h under the room temperature and leach.At room temperature drip 1M HCL solution 250ML while stirring in leaching thing, drip and remove by filter solvent.To there not being chloride ion, 70 ℃ of dry 8h obtain carbon sulphur composite material under vacuum afterwards with the deionized water wash product.The sulfur content of composite material is 54%.
Example 5
The novel carbon-sulfur composite material of preparation in the example 1 is mixed with 90%: 10% (weight ratio) with adhesive (LA132), mixed solvent (the water: normal propyl alcohol=1: 4 volume ratio) that adds entry and normal propyl alcohol, ball milling mixes makes anode sizing agent, solids content is 25% in the slurry, blade coating is on aluminum foil current collector then, placed under the room temperature 8 hours, and treated after the solvent evaporates again in following 50 ℃ of dryings of vacuum condition 10 hours standby.Prepared pole piece coating layer thickness is 40～45 μ m.With above-mentioned pole piece is positive pole, is negative pole with Li, and barrier film is selected Celgard 2400 films for use, and electrolyte is the LiClO of 1M
4/ 50% 1, the diethylene glycol dimethyl ether of 3-dioxolanes+50%.Be assembled into battery in glove box, open circuit voltage is 2.5V.
Example 6
Carry out the charge-discharge performance test under the battery room temperature with example 5 preparations, deboost is 2.8V to 1.0V, and discharge curve has 3 discharge platforms at 2.3V, 2.1V and 1.7V place.When charging and discharging currents density is 0.4mA/cm
2The time, the head of battery is put capacity and is reached 1101.1mAh/g (calculating with sulphur), after 20 circulations, leaves the specific capacity of 756mAh/g.
Claims (4)
1. a carbon-sulfur compound that is used for the lithium-sulphur cell positive electrode material is characterized in that this compound is a matrix with middle macropore carbon material, and the specific area of middle macropore carbon material is 50～1900m
2/ g, pore volume are 0.1～3cm
3/ g, conductivity is 0.01～200S/cm; With content is that 10%～95% elemental sulfur is filled in the nanometer and submicron order hole of matrix, and the combination reaction that sulphur and carbon also can take place simultaneously makes.
2. the carbon-sulfur compound that is used for the lithium-sulphur cell positive electrode material according to claim 1, it is characterized in that with the novel carbon-sulfur compound being positive electrode, with the alloy of lithium metal, lithium and other alkali metal or alkaline-earth metal and Li/Al, Li/Si, Li/Pb, Li/Sn, Li/Sb, Li/Bi, Li/Zn, Li/Cd, Li/C is negative material, forms lithium-sulfur cell with organic bath; Organic bath is liquid state, gel, solid-state electrolyte system or ionic liquid, liquid electrolyte is selected for use and is contained PC, EC, DEC, 1, the mixture of one or more organic solvents of 3-dioxolane, dimethoxy-ethane, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, oxolane, ortho-xylene, supporting electrolyte can be lithium perchlorate, trifluoromethayl sulfonic acid lithium, lithium hexafluoro phosphate or lithium trifluoromethanesulp,onylimide.
3. a preparation method who is used for the carbon-sulfur compound of lithium-sulphur cell positive electrode material is characterized in that this preparation method, comprises that the common hot method of ultrasonic immersing method, charcoal sulphur, sulfur vapor filling method, the sulphur of sulfur-bearing solution reacts method of formation in the hole:
The ultrasonic immersing method of sulfur-bearing solution: (1) is dissolved in CS with sulphur
2In, make concentration and be 5% to saturated solution; (2) middle macropore carbon material is added the CS of sulphur
2In the solution, the C/S mass ratio is 1: 0.2～10; (3) under 100～1000W action of ultrasonic waves, make the sulphur of dissolving can fully immerse in the hole of macropore carbon; (4) remove by filter solvent, with product air drying under vacuum;
Charcoal sulphur is hot method altogether: evenly mix middle macropore carbon with elemental sulfur (1), and the C/S mass ratio is 1: 0.2～20; (2) with the heating of the mixture in (1), heating can be carried out under normal pressure, adopts inert gas such as N
2Or the Ar protection, also can be as heating in the autoclave in closed container.Heating-up temperature is 100～500 ℃, and the time is 1h～10h;
Sulfur vapor filling method: elemental sulfur is heated to 100～500 ℃, at inert gas such as N
2Or the sulfur vapor filling is condensed in the macropore carbon in advancing, make the C/S mass ratio reach 1: 0.1～20;
Sulphur reacts method of formation in the hole: (1) is impregnated into the fortified aqueous of thiosulfate in the middle macropore powdered carbon; (2) middle macropore powdered carbon is leached, with hydrogen chloride gas or dilute acid soln and its reaction, sulphur precipitates in middle macropore carbon; (3) compound is filtered, washs to there not being acid ion.
4. the preparation method who is used for the carbon-sulfur compound of lithium-sulphur cell positive electrode material according to claim 3, it is characterized in that thiosulfate can be sylvite or sodium salt, sulphur reacts the used diluted acid of generation in the hole can be the weak solution of hydrochloric acid, sulfuric acid, nitric acid, acetate or phosphoric acid.
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2008
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