CN104332600A - Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode - Google Patents
Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode Download PDFInfo
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a graphene/sulfur/conductive polymer composite material used for the lithium-sulfur battery positive electrode. The method comprises the following steps: (1) mechanical mixing; (2) isostatic fusion; and (3) polymer cladding. According to the method, elemental sulfur is wrapped in a three-dimensional conductive network composed of graphene by using mechanical mixing, isostatic fusion, polymer cladding and other simple and practical means, so the excellent electrical contact between the elemental sulfur and the graphene can be kept, and the diffusion path of lithium ions is shortened, thereby ensuring that the electron conduction of an electrode material can not be lost. In addition, the elemental sulfur is cladded completely and uniformly by the conductive polymer, so that the direct contact between the polysulfide ion and the electrolyte in reactions is prevented effectively, and thus the initial charging/discharging efficiency and cyclic performance of the material are enhanced.
Description
Technical field
The present invention relates to lithium sulphur battery electrode field of material preparation technology, refer in particular to a kind of Graphene/sulphur/conducting polymer composite material preparation method for lithium-sulphur cell positive electrode.
Background technology
Lithium ion battery is widely used in the various mobile electronic devices such as notebook computer, camera, mobile phone, panel computer.Due to the fast development of mobile electronic device, require more and more higher to the specific capacity of battery and specific energy.Current commercial Li-ion battery can not meet due to the restriction of self theoretical capacity, so the secondary cell in the urgent need to developing height ratio capacity high-energy-density, and lithium-sulfur cell (theoretical specific capacity is 1675.0 mAh/g, specific energy is 2500 Wh/kg, 2800 Wh/L) be considered to one of the most promising high-energy battery.It is completely different from traditional lithium ion battery, such as LiCoO2, the theoretical capacity of LiFePO4 and ternary material only has 149.0,170.0,270.0 mAh/g, the theoretical capacity of these materials is limited to the deintercalation quantity of lithium ion, when discharging Lithium-ion embeding these materials lattice in, deviate from during charging, deintercalation quantity can not be too many again, otherwise can cause these metal oxide materials structures that irreversible change occurs, finally cause battery to damage completely.And lithium-sulfur cell is by the fracture of sulphur sulfide linkage and is formed and come electric discharge and charging, so can realize more high power capacity charge and discharge.It is poor that the cycle performance caused is moved in the problem that lithium-sulfur cell is main at present or the dissolving of many sulphions.Address this problem future and mainly all constantly improved by both positive and negative polarity and electrolyte.Wherein make composite positive pole with conductive carbon material and sulphur, carbon-based material serves as conducting bridge, builds conductive network between particles, improves electronic conductivity; Carbon-based material carries out coated to sulfur granules, suppresses to fly the change of shuttle effect and electrode material volume in charge and discharge process thus the cycle life of raising battery.
Chinese patent ZL 201210485646.4 discloses a kind of carbon sulphur composite material for lithium-sulphur cell positive electrode, for injecting the elemental sulfur of porous hollow carbon ball, wherein porous hollow carbon ball is by simple Template synthesis, and elemental sulfur is injected in porous hollow carbon ball by the method adopting melting to spread.This positive electrode has that preparation method is simple, specific capacity is comparatively large, coulombic efficiency is high, good cycle, but, because have employed hollow carbon sphere, virtually greatly reduce volume energy density.
Chinese patent ZL201410229448.0 discloses a kind of preparation method of the sulphur composite modification material for lithium sulfur battery anode material, and by high-energy ball milling-microwave radiation technology, the means such as gas-phase polymerization is coated, prepare the method for positive pole material for high-performance lithium-sulfur battery.Preparation technology is simple, and manufacturing cycle is short, and product property is excellent.But Graphene is porous material, macropore is a lot, and the main precedence partition of elemental sulfur, in macropore, makes the utilance of elemental sulfur reduce.Capacity is not played well.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, its main purpose is to provide a kind of Graphene/sulphur/conducting polymer composite material preparation method for lithium-sulphur cell positive electrode, described composite material contains sulphur/Graphene particle/conducting polymer, the method is simple to operation, is very applicable to large-scale production.
For achieving the above object, the present invention adopts following technical scheme:
For Graphene/sulphur/conducting polymer composite material preparation method of lithium-sulphur cell positive electrode, comprise the following steps:
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 500 ~ 5000 r/min to carry out dispersion 1 ~ 4h, elemental sulfur is dispersed in graphene sheet layer;
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 100 ~ 200 MPa, be heated to 150 ~ 200 DEG C, pressure-maintaining and heat-preservation 10 ~ 20h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.5-1M, ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath formation suspension, get polymer monomer to join in above-mentioned suspension, then ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.5 ~ 1M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, and time for adding controls at 10 ~ 50 minutes, can obtain Graphene/sulphur/conducting polymer composite material after oven dry.
As a kind of preferred version, the elemental sulfur described in step (1) is the purity of 99%, and the granularity of elemental sulfur is 1 ~ 5um.
As a kind of preferred version, described in step (1), Graphene is single or multiple lift Graphene, and it adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method or chemical vapour deposition (CVD) to obtain.
As a kind of preferred version, described in step (3), polymer monomer is selected from least one in aniline, pyrroles, thiophene.
The present invention compared with prior art has obvious advantage and beneficial effect, specifically, as shown from the above technical solution:
1, the present invention adopts simple and easy to do mechanical mixture, isostatic pressed merges, being polymerized the means such as coated is wrapped in the three-dimensional conductive network that Graphene forms by elemental sulfur, the good electrical contact between elemental sulfur and Graphene can be maintained, shorten the evolving path of lithium ion, ensure that the electrical conductivity of electrode material can not be lost; Conducting polymer carries out coated completely uniformly to elemental sulfur simultaneously, effectively prevents the polysulfide ion in reaction to contact with the direct of electrolyte, thus improves first charge-discharge efficiency and the cycle performance of material.
2, introduce isostatic pressed to merge, the integration engineering of elemental sulfur and Graphene is made mainly to occur in mesopore and aperture, the capacity effectively avoiding elemental sulfur to cause in the reunion of graphenic surface can not be brought into play, and can improve volume energy density and high rate performance.
3, present invention process is simple, and easy to operate, production equipment is few, thus reduces costs further, easy to utilize, is suitable for large-scale production.
For more clearly setting forth architectural feature of the present invention and effect, below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the preferred embodiment of the present invention.
Embodiment
Please refer to shown in Fig. 1, the present invention discloses a kind of Graphene/sulphur/conducting polymer composite material preparation method for lithium-sulphur cell positive electrode, comprises the following steps:
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 500 ~ 5000 r/min to carry out dispersion 1 ~ 4h, elemental sulfur is dispersed in graphene sheet layer; Described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 1 ~ 5um, and described Graphene is single or multiple lift Graphene, and it adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method or chemical vapour deposition (CVD) to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 100 ~ 200 MPa, be heated to 150 ~ 200 DEG C, pressure-maintaining and heat-preservation 10 ~ 20h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.5-1M, ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath formation suspension, get polymer monomer to join in above-mentioned suspension, then ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.5 ~ 1M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 10 ~ 50 minutes, can obtain Graphene/sulphur/conducting polymer composite material after oven dry, this step (3) described polymer monomer is selected from least one in aniline, pyrroles, thiophene.
The present invention will be described to use specific embodiment below.
Embodiment 1
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 500r/min to carry out dispersion 4h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 1um, and described Graphene is single-layer graphene, and it adopts oxidation-reduction method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 100 MPa, be heated to 180 DEG C, pressure-maintaining and heat-preservation 10h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.5M, ultrasonic disperse 30 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 20 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.8M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 20 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from aniline.
Embodiment 2
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 1000 r/min to carry out dispersion 3h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 2um, and described Graphene is multi-layer graphene, and it adopts mechanical stripping method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 120 MPa, be heated to 160 DEG C, pressure-maintaining and heat-preservation 12h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.8M, ultrasonic disperse 20 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 30 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.5M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 30 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from pyrroles.
Embodiment 3
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 1500 r/min to carry out dispersion 1.6h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 3um, and described Graphene is single-layer graphene, and it adopts epitaxial growth method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 130 MPa, be heated to 170 DEG C, pressure-maintaining and heat-preservation 15h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.6M, ultrasonic disperse 40 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 10 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.7M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 40 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from thiophene.
Embodiment 4
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 2000 r/min to carry out dispersion 2h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 4um, and described Graphene is multi-layer graphene, and it adopts chemical vapour deposition (CVD) to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 140 MPa, be heated to 150 DEG C, pressure-maintaining and heat-preservation 11h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.7M, ultrasonic disperse 10 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 40 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.6M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 25 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from aniline and pyrroles.
Embodiment 5
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 3000 r/min to carry out dispersion 2.5h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 5um, and described Graphene is multi-layer graphene, and it adopts oxidation-reduction method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 150 MPa, be heated to 200 DEG C, pressure-maintaining and heat-preservation 14h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.9M, ultrasonic disperse 50 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 45 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 1M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 50 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from aniline.
Embodiment 6
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 4000 r/min to carry out dispersion 1h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 2um, and described Graphene is single-layer graphene, and it adopts mechanical stripping method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 170 MPa, be heated to 190 DEG C, pressure-maintaining and heat-preservation 18h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 1M, ultrasonic disperse 50 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 30 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.9M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 10 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from aniline, pyrroles and thiophene.
Embodiment 7
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 4500 r/min to carry out dispersion 2h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 3um, and described Graphene is multi-layer graphene, and it adopts mechanical stripping method to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 190 MPa, be heated to 190 DEG C, pressure-maintaining and heat-preservation 18h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.8M, ultrasonic disperse 30 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 40 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.6M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 40 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from pyrroles and thiophene.
Embodiment 8
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 5000 r/min to carry out dispersion 1h, elemental sulfur is dispersed in graphene sheet layer; In the present embodiment, described elemental sulfur is the purity of 99%, and the granularity of elemental sulfur is 1um, and described Graphene is single-layer graphene, and it adopts chemical vapour deposition (CVD) to obtain.
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 200 MPa, be heated to 150 DEG C, pressure-maintaining and heat-preservation 20h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.6M, ultrasonic disperse 20 minutes, and is aided with ice-water bath and forms suspension, gets polymer monomer and joins in above-mentioned suspension, then ultrasonic disperse 30 minutes, and is aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 1M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, time for adding controls at 30 minutes, Graphene/sulphur/conducting polymer composite material can be obtained after oven dry, in the present embodiment, described polymer monomer is selected from aniline, pyrroles and thiophene.
Comparative example 1
Use elemental sulfur directly as positive electrode.
Comparative example 2
Cover obtained composite material by carrying out aggregate packet after mechanical mixture, its preparation process does not carry out isostatic pressed.
For detecting the chemical property of Graphene/sulphur/conducting polymer composite material of the present invention, test by half-cell method of testing, composite material by above embodiment and comparative example: PVDF: Super-p=80: 5: 15(weight ratio), add appropriate: nitrogen methyl pyrrolidone reconciles into pulpous state, to coat on aluminium foil and within 12 hours, to make lithium-sulphur cell positive electrode sheet in vacuum drying chamber inner drying, negative pole is done with the lithium paper tinsel of 130 microns, the PE perforated membrane of 20 microns is barrier film, 1 of 1M LiSO3CF3, 3-dioxolanes/diethylene glycol dimethyl ether/sulfolane/dimethoxy-ethane (volume ratio 50/20/10/20) solution is as electrolyte, be lithium sheet to electrode, button cell is assembled in the glove box being full of argon gas.Carry out constant current charge-discharge experiment at LAND battery test system, charging/discharging voltage is limited in 1.5-3.0 V, and charging and discharging currents is 100mA/g, and the discharge and recharge cabinet computerizedd control carries out collection and the control of data.The data obtained are as shown in table 1 below:
The composite material of preparation of the embodiment 1 ~ 8 that table 1 represents and the chemical property of comparative example 1,2 composite material
As can be known from Table 1, compared with the comparative example 1 of elemental sulfur, the introducing of Graphene and conducting polymer is all significantly improved to battery capacity, high rate performance, cycle performance.Compared with the comparative example 2 of not carrying out isostatic pressed operation, the introducing of isostatic pressed operation can make the high rate performance of composite material be greatly improved.These results show that synthesized Graphene/sulphur/conducting polymer composite material effectively improves conductivity, inhibits volumetric expansion, decrease loss of shuttling back and forth.So the anode composite material of lithium sulfur battery that the present invention proposes has a good application prospect.
Design focal point of the present invention is: the present invention is by adopting simple and easy to do mechanical mixture, isostatic pressed merges, being polymerized the means such as coated is wrapped in the three-dimensional conductive network that Graphene forms by elemental sulfur, the good electrical contact between elemental sulfur and Graphene can be maintained, shorten the evolving path of lithium ion, ensure that the electrical conductivity of electrode material can not be lost; Conducting polymer carries out coated completely uniformly to elemental sulfur simultaneously, effectively prevents the polysulfide ion in reaction to contact with the direct of electrolyte, thus improves first charge-discharge efficiency and the cycle performance of material.And, introducing isostatic pressed merges, make the integration engineering of elemental sulfur and Graphene mainly occur in mesopore and aperture, the capacity effectively avoiding elemental sulfur to cause in the reunion of graphenic surface can not be brought into play, and can improve volume energy density and high rate performance.Present invention process is simple, and easy to operate, production equipment is few, thus reduces costs further, easy to utilize, is suitable for large-scale production.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (4)
1., for Graphene/sulphur/conducting polymer composite material preparation method of lithium-sulphur cell positive electrode, it is characterized in that: comprise the following steps:
(1) mechanical mixture
Elemental sulfur and Graphene are joined in homogenizer according to mass ratio, uses rotating speed 500 ~ 5000 r/min to carry out dispersion 1 ~ 4h, elemental sulfur is dispersed in graphene sheet layer;
(2) isostatic pressed merges
Elemental sulfur and Graphene mixture press-powder are filled in the rubber mold of iso-static pressure shaping machine, vibrated by high-frequency electromagnetic, press-powder is obtained closely knit, vacuumize after sealing, discharge the air between powder particle, put into the high-pressure bottle that water or oil are housed, be pressurized to 100 ~ 200 MPa, be heated to 150 ~ 200 DEG C, pressure-maintaining and heat-preservation 10 ~ 20h, after being cooled to room temperature, be pressed into block;
(3) be polymerized coated
After block being used Universalpulverizer fragmentation, joining concentration is in the HCl solution of 0.5-1M, ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath formation suspension, get polymer monomer to join in above-mentioned suspension, then ultrasonic disperse 10 ~ 50 minutes, and be aided with ice-water bath; Initiator ammonium persulfate being dissolved in concentration is in the HCl solution of 0.5 ~ 1M, and be slowly added drop-wise in reaction system, the mol ratio of polymer monomer and ammonium sulfate is 1:1, and time for adding controls at 10 ~ 50 minutes, can obtain Graphene/sulphur/conducting polymer composite material after oven dry.
2. Graphene/sulphur/conducting polymer composite material the preparation method for lithium-sulphur cell positive electrode according to claim 1, is characterized in that: the elemental sulfur described in step (1) is the purity of 99%, and the granularity of elemental sulfur is 1 ~ 5um.
3. Graphene/sulphur/conducting polymer composite material the preparation method for lithium-sulphur cell positive electrode according to claim 1, it is characterized in that: described in step (1), Graphene is single or multiple lift Graphene, it adopts oxidation-reduction method, mechanical stripping method, epitaxial growth method or chemical vapour deposition (CVD) to obtain.
4. Graphene/sulphur/conducting polymer composite material the preparation method for lithium-sulphur cell positive electrode according to claim 1, is characterized in that: described in step (3), polymer monomer is selected from least one in aniline, pyrroles, thiophene.
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| CN104701542A (en) * | 2015-02-05 | 2015-06-10 | 中南大学 | All-solid-state lithium-sulfur battery composite positive material, all-solid-state lithium-sulfur battery prepared from composite positive material and preparation method of composite positive material |
| CN106876675A (en) * | 2017-03-23 | 2017-06-20 | 福建翔丰华新能源材料有限公司 | A kind of lithium ion battery preparation method of lithium titanate composite cathode material of silicon/carbon/graphite |
| WO2017139940A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polythiophene/sulfur composite positive electrode material |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
| CN107403916A (en) * | 2017-07-14 | 2017-11-28 | 贵州鼎玺烯材高科技有限公司 | A kind of positive material for lithium-sulfur battery with the more lithium sulfides of graphene conductive network constraint |
| CN107768617A (en) * | 2017-09-15 | 2018-03-06 | 深圳启辰新能源科技有限公司 | Lithium-sulfur battery composite anode material and preparation method thereof |
| CN114583130A (en) * | 2020-03-13 | 2022-06-03 | 北京航空航天大学 | MXene coated sulfur composite material, preparation method of lithium-sulfur battery positive electrode material and battery |
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| CN104701542B (en) * | 2015-02-05 | 2017-10-20 | 中南大学 | A kind of all solid state lithium-sulfur battery composite anode material and all solid state lithium-sulfur cell and preparation method |
| CN104701542A (en) * | 2015-02-05 | 2015-06-10 | 中南大学 | All-solid-state lithium-sulfur battery composite positive material, all-solid-state lithium-sulfur battery prepared from composite positive material and preparation method of composite positive material |
| WO2017139940A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polythiophene/sulfur composite positive electrode material |
| CN106876675A (en) * | 2017-03-23 | 2017-06-20 | 福建翔丰华新能源材料有限公司 | A kind of lithium ion battery preparation method of lithium titanate composite cathode material of silicon/carbon/graphite |
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| CN107195874B (en) * | 2017-04-19 | 2019-05-28 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
| CN107403916B (en) * | 2017-07-14 | 2019-09-10 | 贵州鼎玺烯材高科技有限公司 | A kind of positive material for lithium-sulfur battery with the more lithium sulfides of graphene conductive network constraint |
| CN107403916A (en) * | 2017-07-14 | 2017-11-28 | 贵州鼎玺烯材高科技有限公司 | A kind of positive material for lithium-sulfur battery with the more lithium sulfides of graphene conductive network constraint |
| CN107768617B (en) * | 2017-09-15 | 2019-04-30 | 深圳启辰新能源科技有限公司 | Lithium-sulfur battery composite cathode material and preparation method thereof |
| CN107768617A (en) * | 2017-09-15 | 2018-03-06 | 深圳启辰新能源科技有限公司 | Lithium-sulfur battery composite anode material and preparation method thereof |
| CN114583130A (en) * | 2020-03-13 | 2022-06-03 | 北京航空航天大学 | MXene coated sulfur composite material, preparation method of lithium-sulfur battery positive electrode material and battery |
| CN114583130B (en) * | 2020-03-13 | 2023-11-03 | 北京航空航天大学 | MXene coated sulfur composite material, preparation method of lithium sulfur battery positive electrode material and battery |
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