CN104733695A - Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application - Google Patents
Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application Download PDFInfo
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Abstract
The invention discloses a carbon-sulfur composite cathode material with high capacity and long cycle life for a lithium-sulfur battery as well as a preparation method and an application. The preparation method comprises the following steps that by taking graphene oxide as a template, a surface dispersing agent is added, by taking glucose or cane sugar as a carbon source, a laminated structure carbon precursor is prepared through a hydrothermal method, the precursor is split at a high temperature in a nitrogen or argon atmosphere after being dried to form a microporous carbon material based on the support of graphene, wherein the microporous carbon material is in a platy shape, the carbon material is uniformly mixed with sublimate sulfur powder to obtain a mixture, and the mixture is heated and thermally preserved under a closed condition to obtain the laminated structural microporous carbon/sulfur composite material, wherein the thickness of the material laminate is 15nm to 25nm. The composite material sulfur is uniformly distributed in the laminated structure microporous carbon, the sulfur content is high, the material structure is stable, the charging-discharging specific capacity is high, and the cycling performance is excellent; moreover, the cost of raw materials for the preparation method is low, simplicity in preparation is realized, the process is easy to control, and the carbon-sulfur composite cathode material is suitable for mass production.
Description
Technical field
The present invention relates to lithium sulfur battery anode material and preparation field thereof, be specifically related to a kind of lithium-sulphur cell positive electrode carbon/sulphur composite material and preparation method and application.
Background technology
In order to adapt to the requirement of future society to efficient, clean, economy and safety energy system.Research and develop novel green, efficient energy conversion and high density energy storage medium and device and efficiency utilization new forms of energy, become the inexorable trend of the common problem paid close attention in the whole world and new energy materials development.Current extensive use be the lithium rechargeable battery of positive pole with embedded type transition metal oxide base (LiMn2O4, cobalt acid lithium, ternary, LiFePO4) material, due to the restriction of its theoretical capacity, cannot meet at present for the requirement of more high-energy-density power supply.Lithium-sulfur cell becomes the study hotspot of high-energy density secondary battery of future generation due to its high theoretical capacity.Lithium-sulfur cell take sulphur as positive pole, lithium is negative pole, its Theoretical Mass energy density 2680Wh/kg, volume energy density 2967Wh/L.Elemental sulfur has as positive electrode that high theoretical capacity (1675mAh/g), rich reserves, environmental friendliness, fail safe are high, low cost and other advantages.But due to sulphur as electrochemical applications time, itself and its product (Li
2s) be close to as insulator, electronics and ionic conductivity are extremely low, make to there is very large gap between its actual energy density and theoretical energy density.In addition, the polysulfide that sulphur positive electrode generates in charge and discharge process is dissolved in electrolyte solution and can causes " effect of shuttling back and forth ", thus makes capacity rapid decay.The Volumetric expansion of sulphur in removal lithium embedded process (80%) proposes higher design of material requirement to the cyclical stability improving sulphur simultaneously.
In order to the conductivity of the utilance and positive electrode that improve sulphur, most effective method exactly sulphur is carried out nano-scale dispersion and with nanometer conductive material compound.Electric conducting material is particularly outstanding with the material with carbon element performance with high-ratio surface sum high conductivity, and active carbon, conductive black, carbon nano-tube, carbon fiber, graphene oxide, Graphene, meso-porous carbon material etc. all have report.The material with carbon element of high-specific surface area can provide larger electrode reaction area for sulphur, reduces electrochemical polarization, and hinders the gathering of sulphur.Because sulphur fusing point is low, utilize it in 155 DEG C ~ 158 DEG C good mobility and capillarity, the method that the compound of porous carbon materials and sulphur adopts low-temperature heat to be incubated usually.
Grapheme material receives much concern in the research of sulphur positive electrode because its two-dimensional structure has the electric conductivity of superelevation.Compound based on modified graphene material and S has many reports.Publication number is that the Chinese patent application of CN 103700859A discloses a kind of lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and preparation method thereof, this technical scheme discloses a kind of by using graphene oxide and nano silicon as double-template, on graphene oxide growth in situ polypyrrole, obtain after high temperature cabonization, activation of potassium hydroxide pore-creating, its carbon nanosheet thickness is 10-25nm, and structure is the class sandwich type of Graphene as carbon nanosheet intermediate layer.But the sheet material with carbon element preparation process that this Graphene supports adopts double-template, and silica template will be removed, also will through follow-up high temperature hydrogen potassium oxide pore-creating, complex process, the requirement that material structure consistency controls is higher.
Publication number is that the Chinese patent application of CN 103682274A discloses a kind of Graphene/polyanilinecomposite composite material and preparation method thereof, take graphene oxide as oxidant, aniline monomer oxidation polymerization is attached to graphenic surface, and add sulphur source generate nano-sulfur particles be evenly distributed on polyaniline.But this composite material is the way by the solution sulphur being compound to base material carries out the compound with sulphur, and the content of sulphur is difficult to accurate control.In addition composite material cycle performance and capability retention also await further raising.
Summary of the invention
The invention provides a kind of lithium-sulphur cell positive electrode carbon/sulphur composite material and preparation method and application, take graphene oxide as support shuttering, adopt hydro thermal method simple and easy to control to prepare the good Graphene of conductivity in conjunction with high-temperature process and support sheet micro-pore carbon material as conductive substrates, prepare sheet C/S composite positive pole with after sulphur powder low-temperature heat compound.
A preparation method for lithium-sulphur cell positive electrode carbon/sulphur composite material, comprises the following steps:
1) graphene oxide, surfactant, carbon source is soluble in water, mix and obtain mixed liquor;
2) by step 1) in mixed liquor in 170 DEG C ~ 200 DEG C close insulation 12h ~ 18h, obtain precursor product after cooling;
3) by step 2) in precursor product filter, dry, then under nitrogen or argon gas atmosphere protection 700 DEG C ~ 900 DEG C calcining 1 ~ 3h, obtain Graphene support chip Rotating fields micro-pore carbon material after cooling;
4) by step 3) in Graphene support chip Rotating fields micro-pore carbon material mix with weight ratio 1:0.5 ~ 3 with sublimed sulfur powder, 150 DEG C ~ 170 DEG C close insulation 8h ~ 16h, obtain lithium-sulphur cell positive electrode carbon/sulphur composite material after cooling.
In order to obtain better invention effect, below as preferably of the present invention:
Step 1) in, described surfactant is lauryl sodium sulfate (SDS), and described carbon source is glucose, sucrose, citric acid or stearic acid;
The mass ratio of described graphene oxide, surfactant and carbon source three is 10:0.2 ~ 2:30 ~ 50, and further preferably, the mass ratio of described graphene oxide, surfactant and carbon source three is 10:1:30 ~ 50.
Described water adds is advisable in right amount, and as preferably, described graphene oxide and the mass ratio of water are 1:500 ~ 2000.
Step 3) in, 800 DEG C of calcining 2h under nitrogen or argon gas atmosphere protection, Pintsch process, forms the micro-pore carbon material supported based on Graphene, has better sheet-like morphology.
Described nitrogen or the flow of argon gas are 50 ~ 200mL/min, are further preferably 100mL/min.
Step 4) in, described Graphene support chip Rotating fields micro-pore carbon material mixes with weight ratio 1:1 ~ 1.5 with sublimed sulfur powder, closes insulation 12h at 158 DEG C.
Lithium-sulphur cell positive electrode carbon/sulphur composite material that preparation method of the present invention obtains, 1, there is sheet-like morphology, lamellar spacing is 15-25nm; Two, be the sulphur of 50% ~ 60% containing mass percent, the carbon of 50% ~ 40%.
Present invention also offers the application of a kind of C/S positive electrode of lithium-sulfur cell, using lithium-sulphur cell positive electrode carbon/sulphur composite material of the present invention as lithium sulfur battery anode material, there is the cycle performance that reversible capacity is high, charge and discharge process coulombic efficiency is high and stable, for the preparation of lithium-sulphur cell positive electrode.A preparation method for lithium-sulphur cell positive electrode, comprises the following steps:
By the mixing of the carbon/sulphur composite positive pole of preparation, conductive carbon black and polyvinylidene fluoride (PVDF), add 1-Methyl-2-Pyrrolidone (NMP) vacuum stirring again and make uniform slurry, then uniform slurry coating process is coated on aluminium foil, after oven dry through compacting, point cut into positive electrode.Be placed in vacuum drying oven in 60 DEG C of dry 12h.Lithium sulfur battery anode material and metal lithium sheet are assembled into lithium ion battery.Lithium ion battery adopts microporous polypropylene membrane (Cellgard 2300) to be barrier film, with the glycol dimethyl ether of volume ratio 1:1 (DME) and 1,3 dioxolanes (DOL) are as solvent, two trifluoromethanesulfonimide lithium (LiTFSI) is dissolved in solvent, obtain mixed liquor, then add LiNO to mixed liquor
3, obtained electrolyte, in electrolyte, the concentration of LiTFSI is 1mol/L, LiNO in electrolyte
3concentration is 0.2mol/L.Lithium ion battery assembling process completes in water volume content is lower than the dry glove box of 0.1ppm.The lithium ion battery assembled carries out constant current charge-discharge test after placing 24h, and charging/discharging voltage is 1.5V ~ 3.0V, and in 25 ± 2 DEG C of environment, Reversible lithium insertion capacity, the charge-discharge performance of lithium ion battery negative is measured in circulation.
Compared with prior art, tool of the present invention has the following advantages:
Graphene supports micro-pore carbon material as the base material of sulfur loaded as conducting matrix grain, effectively can improve the conductivity of material.Simultaneously by utilizing mobility and the capillarity of sulphur, adopt low temperature heat processing method with sulphur powder compound tense, because sheet-like morphology material with carbon element has large surface area and little vertical depth, shorter at the evolving path of flaky material sulphur in the radial direction, relative to the spherical of three-dimensional or tubular material substrate, this laminar structure is more conducive to sulphur being uniformly distributed in substrate material with carbon element, is also beneficial to the release of the material internal stress brought due to volumetric expansion in charge and discharge process simultaneously.In electrochemical reaction process, flaky material is the distribution in different directions in pole piece, can form the three-dimensional network of intersection, changes the transmission path of polysulfide, suppresses the movement of polysulfide, thus plays the effect of suppression " effect of shuttling back and forth " to a certain extent.
Lithium ion battery prepared by lithium sulfur battery anode material C/S of the present invention at room temperature 25 DEG C during 0.1C multiplying power current density first discharge specific capacity can reach 1380mAh/g.0.2C rate charge-discharge circulates after 150 times, capacity keeps more than 630mAh/g, there is good cyclical stability, the requirement of high capacity density secondary cell can be met, and preparation method of the present invention has, and needed raw material cost is lower, preparation method is simple, process is easy to control, low power consumption and other advantages, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is that C/S positive electrode of the present invention prepares schematic diagram;
Fig. 2 is the X-ray diffractogram of Graphene support sheet micro-pore carbon material, C/S composite material and distillation S powder prepared by embodiment 1.
Fig. 3 is (40K doubly) stereoscan photograph of lithium-sulfur cell C/S positive electrode prepared by embodiment 1;
Fig. 4 is the first charge-discharge curve of lithium-sulfur cell C/S positive electrode when 0.1C prepared by embodiment 1;
Fig. 5 is specific capacity and the coulombic efficiency curve of lithium-sulfur cell C/S positive electrode continuous 150 charge and discharge cycles under 0.2C current density prepared by embodiment 1.
Embodiment
As shown in Figure 1, for C/S positive electrode of the present invention prepares schematic diagram, first prepared by graphene oxide Graphene and support sheet microporous carbon, finally obtain carbon/sulphur composite material.
Embodiment 1
1) by 200mg graphene oxide, 20mg lauryl sodium sulfate and 8.0g glucose, be dissolved in 200ml (200g) deionized water, fully mix, obtain auburn suspension-turbid liquid.
2) by step 1) auburn suspension-turbid liquid be poured into containing in teflon-lined reactor, 170 DEG C insulation 18h, be then placed in room temperature 25 DEG C cool.After cooled suspension-turbid liquid is filtered cleaning, 100 DEG C of oven dry, obtain the presoma of carbon.
3) by the presoma of carbon in step 2 800 DEG C of calcining 2h under argon atmosphere, wherein the flow velocity of argon gas is 100ml/min, obtains Graphene and support sheet micro-pore carbon material after cooling.
4) Graphene in step 3 is supported sheet micro-pore carbon material to mix with mass ratio 4:6 with sublimed sulfur powder, be sealed in reactor and be heated to 158 DEG C of insulation 12h, obtain C/S composite material.
The X-ray diffraction (XRD) that Graphene prepared by the present embodiment supports sheet micro-pore carbon material, C/S composite material and sublimed sulfur powder contrasts collection of illustrative plates as shown in Figure 2.As seen from the figure, the diffraction maximum of prepared material with carbon element only has the steamed bun peak of two broadenings, illustrates that material with carbon element is amorphous state.After S compound, the diffraction maximum of diffraction maximum and sublimed sulfur powder matches, but diffracted intensity reduces.This illustrates that S is present among composite material with the crystalline form of very refinement, and S content is 60% (mass percent).As shown in Figure 3, this material pattern in the form of sheets, does not find the existence of S particle to the electron scanning micrograph (SEM) of the C/S composite material prepared by the present embodiment in figure, illustrates that S is evenly distributed in sheet material with carbon element.As shown in Figure 4, discharge curve has two obvious discharge platforms to the discharge curve first of C/S composite material 0.1C, and this is with S
8the electrochemical discharge curve that molecule shows is consistent, and this illustrates that in the composite material prepared by the present invention, sulphur is with S
8the form of molecule exists, consistent with XRD analysis result.The discharge capacity first of this composite material is 1380mAh/g.In addition, as shown in Figure 5, the C/S composite material prepared by the present invention has excellent cycle performance, and under 0.2C (335mA/g) current density after discharge and recharge 150 circulation, battery capacity keeps more than 630mAh/g.
Embodiment 2
1) by 200mg graphene oxide, 20mg lauryl sodium sulfate and 6.0g sucrose, be dissolved in 200ml (200g) deionized water, fully mix, obtain auburn suspension-turbid liquid.
2) by step 1) auburn suspension-turbid liquid be poured into containing in teflon-lined reactor, 190 DEG C insulation 14h, be then placed in room temperature 25 DEG C cool.After cooled suspension-turbid liquid is filtered cleaning, 100 DEG C of oven dry, obtain the presoma of carbon.
3) by the 800 DEG C of calcining 2h under nitrogen protection atmosphere of the presoma in step 2, wherein the flow velocity of nitrogen is 100ml/min, obtains Graphene and support sheet micro-pore carbon material after cooling.
4) Graphene in step 3 is supported sheet micro-pore carbon material to mix with mass ratio 1:1 with sublimed sulfur powder, be sealed in reactor and be heated to 158 DEG C of insulation 12h, obtain C/S composite material.
The stereoscan photograph of the C/S composite material that the present embodiment obtains is similar to the photo in embodiment 1, is sheet-like morphology, there is not the granule of independent S, and S content is 50% (mass percent).During 0.1C electric discharge, discharge capacity is 1430mAh/g first, and cyclical stability is good.
Embodiment 3
1) by 200mg graphene oxide, 20mg lauryl sodium sulfate and 8.0g citric acid, be dissolved in 200ml (200g) deionized water, fully mix, obtain auburn suspension-turbid liquid.
2) by step 1) auburn suspension-turbid liquid be poured into containing in teflon-lined reactor, 180 DEG C insulation 16h, be then placed in room temperature 25 DEG C cool.After cooled suspension-turbid liquid is filtered cleaning, 100 DEG C of oven dry, obtain the presoma of carbon.
3) by the 800 DEG C of calcining 2h under argon atmosphere of the presoma in step 2, wherein the flow velocity of argon gas is 100ml/min, obtains Graphene and support sheet micro-pore carbon material after cooling.
4) Graphene in step 3 is supported sheet micro-pore carbon material to mix with mass ratio 9:11 with sublimed sulfur powder, be sealed in reactor and be heated to 158 DEG C of insulation 12h, obtain C/S composite material.
The stereoscan photograph of the C/S composite material that the present embodiment obtains is similar to the photo in embodiment 1, is sheet-like morphology, there is not the granule of independent S, and S content is 55% (mass percent).During 0.1C electric discharge, discharge capacity is 1357mAh/g first, and cyclical stability is good.
Embodiment 4
1) by 200mg graphene oxide, 20mg lauryl sodium sulfate and 7.0g stearic acid, be dissolved in 200ml (200g) deionized water, fully mix, obtain auburn suspension-turbid liquid.
2) by step 1) auburn suspension-turbid liquid be poured into containing in teflon-lined reactor, 200 DEG C insulation 12h, be then placed in room temperature 25 DEG C cool.After cooled suspension-turbid liquid is filtered cleaning, 100 DEG C of oven dry, obtain the presoma of carbon.
3) by the 800 DEG C of calcining 2h under argon atmosphere of the presoma in step 2, wherein the flow velocity of argon gas is 100ml/min, obtains Graphene and support sheet micro-pore carbon material after cooling.
4) Graphene in step 3 is supported sheet micro-pore carbon material to mix with mass ratio 4:6 with sublimed sulfur powder, be sealed in reactor and be heated to 158 DEG C of insulation 12h, obtain C/S composite material.
The stereoscan photograph of the C/S composite material that the present embodiment obtains is similar to the photo in embodiment 1, is sheet-like morphology, there is not the granule of independent S, and S content is 60% (mass percent).During 0.1C electric discharge, discharge capacity is 1135mAh/g first, and cyclical stability is good.
Embodiment 5
1) by 200mg graphene oxide, 20mg lauryl sodium sulfate and 8.0g citric acid, be dissolved in 200ml (200g) deionized water, fully mix, obtain auburn suspension-turbid liquid.
2) by step 1) auburn suspension-turbid liquid be poured into containing in teflon-lined reactor, 180 DEG C insulation 16h, be then placed in room temperature 25 DEG C cool.After cooled suspension-turbid liquid is filtered cleaning, 100 DEG C of oven dry, obtain the presoma of carbon.
3) by the 800 DEG C of calcining 2h under nitrogen protection atmosphere of the presoma in step 2, wherein the flow velocity of nitrogen is 100ml/min, obtains Graphene and support sheet micro-pore carbon material after cooling.
4) Graphene in step 3 is supported sheet micro-pore carbon material to mix with mass ratio 1:1 with sublimed sulfur powder, be sealed in reactor and be heated to 158 DEG C of insulation 12h, obtain C/S composite material.
The stereoscan photograph of the C/S composite material that the present embodiment obtains is similar to the photo in embodiment 1, is sheet-like morphology, there is not the granule of independent S, and S content is 50%.During 0.1C electric discharge, discharge capacity is 1372mAh/g first, and cyclical stability is good.
Claims (9)
1. a preparation method for lithium-sulphur cell positive electrode carbon/sulphur composite material, is characterized in that, comprise the following steps:
1) graphene oxide, surfactant, carbon source is soluble in water, mix and obtain mixed liquor;
2) by step 1) in mixed liquor in 170 DEG C ~ 200 DEG C close insulation 12h ~ 18h, obtain precursor product after cooling;
3) by step 2) in precursor product filter, dry, then under nitrogen or argon gas atmosphere protection 700 DEG C ~ 900 DEG C calcining 1 ~ 3h, obtain Graphene support chip Rotating fields micro-pore carbon material after cooling;
4) by step 3) in Graphene support chip Rotating fields micro-pore carbon material mix with weight ratio 1:0.5 ~ 3 with sublimed sulfur powder, 150 DEG C ~ 170 DEG C close insulation 8h ~ 16h, obtain lithium-sulphur cell positive electrode carbon/sulphur composite material after cooling.
2. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 1, is characterized in that, step 1) in, described surfactant is lauryl sodium sulfate;
Described carbon source is glucose, sucrose, citric acid or stearic acid.
3. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 1, is characterized in that, step 1) in, the mass ratio of described graphene oxide, surfactant and carbon source three is 10:0.2 ~ 2:30 ~ 50.
4. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 3, is characterized in that, step 1) in, the mass ratio of described graphene oxide, surfactant and carbon source three is 10:1:30 ~ 50.
5. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 1, is characterized in that, step 1) in, described graphene oxide and the mass ratio of water are 1:500 ~ 2000.
6. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 1, is characterized in that, step 3) in, 800 DEG C of calcining 2h under nitrogen or argon gas atmosphere protection.
7. the preparation method of lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 1, it is characterized in that, step 4) in, described Graphene support chip Rotating fields micro-pore carbon material mixes with weight ratio 1:1 ~ 1.5 with sublimed sulfur powder, closes insulation 12h at 158 DEG C.
8. lithium-sulphur cell positive electrode carbon/sulphur composite material prepared by the preparation method according to any one of claim 1 ~ 7.
9. the application in lithium-sulphur cell positive electrode prepared by lithium-sulphur cell positive electrode carbon/sulphur composite material according to claim 8.
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