CN105826523A - Lithium-sulfur battery positive pole material and preparation method thereof - Google Patents
Lithium-sulfur battery positive pole material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium-sulfur battery positive pole material and a preparation method thereof, and belongs to the technical field of battery materials. The provided positive pole material has abundant micropores and mesopores; porous nano carbon thin sheets with a three-dimensional communicated net structure are taken as the skeleton; nano sulfur dots are filled into the pores of the net structure, and the outer layer of the skeleton is wrapped by reduced oxidized graphene. The preparation method comprises the following steps: mixing porous nano carbon thin sheets with a sulfur single substance, subjecting the mixture to ball milling, carrying out reactions at a temperature of 180 to 200 DEG C in an enclosed environment in the absence of oxygen and water under the protection of inert gas to obtain a porous nano carbon thin sheet/nano sulfur compound; dissolving the compound into an ethanol solution, dispersing the compound by ultrasonic waves, adding oxidized graphene, adjusting the pH to 10.1 by ammonia water, carrying out ultrasonic dispersion, carrying out hydrothermal reactions at a temperature of 80 to 100 DEG C, filtering, washing the reaction product until the reaction product becomes neutral, and drying to obtain the positive pole material. The positive material has the advantages of high specific capacity and stable electrochemical circulation performance, moreover, the preparation method is simple, the price is low, and the positive material is environment-friendly and can be easily produced in batches.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material and preparation method thereof, belong to battery material technical field.
Background technology
Along with the constantly progressive of new forms of energy and green science and technology and to electrokinetic cell and the growth of portable power source device requirement, research and develop environmentally friendly, have extended cycle life, secondary cell that specific capacity is high becomes more and more meaningful.Lithium rechargeable battery, because having the advantages such as high-energy-density, long-life and memory-less effect, becomes the first-selected power supply of each electronic product.Along with the further miniaturization of electronic equipment and electric automobile, the developing rapidly of large-scale energy-accumulating power station, its power supply is had higher requirement by people.Existing lithium ion battery is difficult to meet people's demand because limiting by theoretical specific capacity, and make the lithium-sulfur cell of positive pole with sulfur and there is the highest theoretical energy density (2600Wh/kg), theoretical specific capacity is up to 1675mAh/g, and sulfur rich reserves, cheap, environmentally friendly pollution-free in nature, become a class very in lithium battery of future generation with application potential.But, lithium-sulfur cell to obtain actual application widely and realize commercialization and must also overcome multiple problem.First, the electronic conductivity (5 × 10 of elemental sulfur-30S/cm, 25 DEG C) and ionic conductivity all ratios relatively low, and electric discharge ultimately generates the lithium sulfide (Li of insulation2S), electro-chemical activity and the utilization rate of sulfur are reduced.Secondly, in charge and discharge process, produced polysulfide can be dissolved in electrolyte and migrate, thus " effect of shuttling back and forth " occurs.The generation of " effect of shuttling back and forth ", directly results in the loss of active substance and the corrosion of cathode of lithium, makes circulating battery bad stability, and capacity attenuation accelerates.Additionally, cause 80% theoretical volume change to cause the destruction of electrode structure owing to sulfur positive pole transfers lithium sulfide completely in charge and discharge process, the specific discharge capacity of lithium-sulfur cell can be caused to decline.And in the factors affecting lithium-sulfur cell performance, the granular size of sulfur is very big on discharge performance impact, particle size is crossed conference and is slowed down ion migration speed, causes the utilization rate of sulfur to decline, thus causes the problems such as battery capacity decay is fast.Therefore, the size reducing sulfur has great significance to improving lithium-sulphur cell positive electrode performance.
For the problems referred to above, a kind of smaller size of sulfur nano anode of necessary research, improves the overall performance of lithium-sulfur cell.QingZhao et al. uses the method for electrochemical deposition to prepare sulfur nano dot in nickel foam and does lithium sulfur battery anode material and improve lithium-sulfur cell performance (QingZhao, etal.SulfurNanodotsElectrodepositedonNiFoamasHigh-Perfor manceCathodeforLi-SBatteries.NanoLett.2015,15,721-726.), but its complex technical process, the ratio that inert matter occupies is big.LiweiChen et al. adopts the chemical action of thiamine and prepares monodispersed sulfur nano dot, but its trace is precisely controlled and is unfavorable for large-scale production (HongweiChen, etal.MonodispersedSulfurNanoparticlesforLithium-SulfurBa tterieswithTheoreticalPerformance.NanoLett.2015,15,798 802.).
Summary of the invention
For problems of the prior art, an object of the present invention is to provide a kind of lithium sulfur battery anode material, described positive electrode is composited by porous nano carbon thin slice/nano-sulfur/redox graphene, can improve the overall performances such as the cyclical stability of lithium-sulfur cell, high rate performance.
The two of the purpose of the present invention are to provide the preparation method of a kind of lithium sulfur battery anode material, and described method, without adding binding agent and conductive agent direct compression, can be prepared by lithium-sulphur cell positive electrode.
It is an object of the invention to be achieved through the following technical solutions.
A kind of lithium sulfur battery anode material, described positive electrode is with porous nano carbon thin slice as skeleton, and described carbon thin slice has abundant micropore and mesoporous, for three-dimensional communication network structure, being filled with nano-sulfur point in the hole that described network structure is formed, skeleton outer layer reduced oxygen functionalized graphene is coated with.
Wherein, described porous nano carbon thin slice is prepared by the following method and obtains:
By metal simple-substance and carbon source mixing and ball milling, gained mixture reacts 4h～24h under the conditions of anaerobic anhydrous vacuum tightness environment, 450 DEG C～600 DEG C and obtains product, take the loose part in product upper strata and carry out ball milling, the material obtained after ball milling first cleans to bubble-free generation with excess dilute hydrochloric acid, it is neutral for cleaning to pH with water again, then at 80 DEG C～120 DEG C, it is dried more than 6h, obtains black powder the most described porous nano carbon thin slice；
Wherein, metal simple-substance is zinc and/or magnesium；Carbon source is glucose and/or sucrose.
Preferably metal simple-substance is 1:1～1:6 with the mass ratio of carbon source.
Anaerobic anhydrous vacuum tightness environment can use to be placed in the glove box of noble gas mixture and be sealed in autoclave, and autoclave is evacuated to 0.1MPa implemented below subsequently；
Described autoclave can use stainless steel autoclave；
Heating can use heating by electric cooker；
The preferably speed of ball milling is 200rpm～500rpm, ball milling 2h～8h.
Preferential ratio of grinding media to material is 15:1～5:1；
The preferably concentration of dilute hydrochloric acid is 0.01M～0.2M.
The preferably purity of water is more than deionized water purity.
A kind of preparation method of lithium sulfur battery anode material of the present invention, described method step is as follows:
(1) by porous nano carbon thin slice of the present invention and sulfur simple substance mixing and ball milling; gained mixture reacts 12h～36h at the anhydrous closed environment of anaerobic, inert gas shielding and 180 DEG C～200 DEG C, obtains porous nano carbon thin slice/nano-sulfur complex (ICPs/nS)；
The mass ratio of porous nano carbon thin slice and sulfur simple substance is 1:1～1:9；
Preferably ball milling speed is 100rpm～300rpm, ball milling 2h～8h；Preferably ratio of grinding media to material is 15:1～5:1；
Preferably noble gas is argon；
The anhydrous closed environment of described anaerobic can carry out evacuation realization to autoclave subsequently by being sealed in autoclave in the glove box of full noble gas by gained mixture, and autoclave can use stainless steel autoclave, and heating can use in electric furnace and carry out.
(2) being dissolved in ethanol solution by porous nano carbon thin slice/nano-sulfur complex, ultrasonic disperse is uniform, adds graphene oxide and with ammonia regulation pH value of solution to 10.1, and ultrasonic disperse is uniform obtains mixed solution；By mixed solution hydro-thermal reaction 24h～72h at 80 DEG C～100 DEG C, filter, washing is to neutral, more than 12h it is dried at 40 DEG C～80 DEG C, obtain porous nano carbon thin slice/nano-sulfur/redox graphene (ICPs/nS/rGO) composite, be lithium sulfur battery anode material of the present invention；
The most described ethanol solution is made up of the water that volume ratio is 1:1 and dehydrated alcohol；
The mass ratio of preferential oxidation Graphene and porous nano carbon thin slice/nano-sulfur complex is 1:7～1:13；
The most described ultrasonic time is 30min～90min；
Described hydro-thermal reaction can use to be had teflon-lined water heating kettle and carries out, and heating can use baking oven.
Filtration can use microporous filter membrane vacuum to filter, and slurry is preferably the water of more than deionization purity.
More than 12h it is dried the most in an oven at 40 DEG C～80 DEG C.
By direct for lithium sulfur battery anode material of the present invention cutting, tabletting lithium-sulphur cell positive electrode.
Beneficial effect:
1. the invention provides a kind of lithium sulfur battery anode material, described positive electrode uses has three-dimensional communication cancellated porous nano carbon thin slice as skeleton, it is ensured that electric conductivity that described positive electrode is good and catchment effect；
2. the invention provides a kind of lithium sulfur battery anode material, the described positive electrode cancellated hole of three-dimensional communication based on porous nano carbon thin slice can carry out confinement to sulfur simple substance, it is suppressed that polysulfide shuttling at inside battery, i.e. " shuttle effect "；
3. the invention provides a kind of lithium sulfur battery anode material, the active substance of described positive electrode is nano-sulfur of the present invention point, described nano-sulfur point has nanometer size effect, shortens electronics and the ion transmission path in positive electrode, thus improves the utilization rate of positive electrode；
4. the invention provides a kind of lithium sulfur battery anode material, the outermost layer of described positive electrode is redox graphene, is coated on nano-sized carbon thin slice, has good ductility, the specific energy of lithium-sulfur cell can be promoted as exempting from the flexible lithium sulphur battery positive electrode of binding agent and collector；
5. the invention provides the preparation method of a kind of lithium sulfur battery anode material, described method is simple, with low cost, environmental protection, it is easy to accomplish produce in enormous quantities；
6. the invention provides a kind of lithium-sulfur cell, the positive electrode of described lithium-sulfur cell is a kind of lithium sulfur battery anode material of the present invention, has height ratio capacity and stable electrochemistry cycle performance.
Accompanying drawing explanation
Fig. 1 is atomic force microscope (AFM) figure of the porous nano carbon thin slice that embodiment 1 prepares.
Fig. 2 is transmission electron microscope (TEM) figure of the lithium sulfur battery anode material that embodiment 1 prepares.
Fig. 3 is thermal gravimetric analysis curve (TG) figure of the lithium sulfur battery anode material that embodiment 1 prepares.
Fig. 4 is the cycle performance curve chart of the lithium ion battery that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further elaborated, but the present invention is not limited to following example.
It is as follows that porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell preparing following example carries out test respectively:
(1) atomic force microscope (AFM) test: the INSTRUMENT MODEL of atomic force microscope is the DimensionFastScan of Brooker, the U.S.；Test sample and preparation method: described porous nano carbon thin slice is scattered on mica sheet and makes sample drying, carry out the test of AFM；
(2) transmission electron microscope (TEM) test: the model of transmission electron microscope is JEM-2100F, 200kV, Japan；Test sample and preparation method: be scattered in dehydrated alcohol by described lithium sulfur battery anode material, drop in and dry on micro-grid of transmission electron microscope, carry out TEM test；
(3) lithium-sulphur cell positive electrode cycle performance test: use INSTRUMENT MODEL is Land, Wuhan, test parameter: charging/discharging voltage 1.7V～2.6V, charge and discharge multiplying power: 0.1C, discharge and recharge temperature: 30 DEG C.
(4) lithium ion battery negative cycle performance test: use INSTRUMENT MODEL is Land, Wuhan, test parameter: charging/discharging voltage 0.005V～3V, charge and discharge multiplying power: 0.1C, discharge and recharge temperature: 30 DEG C.
Ethanol solution described in following example is made up of the water that volume ratio is 1:1 and ethanol.
Embodiment 1
(1) by 1.15g zinc and 3.9g sucrose mixing and ball milling, ratio of grinding media to material is 10:1, and rotating speed is 300rpm, ball milling 6h, and gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas, subsequently described autoclave is evacuated to below 0.1MPa；Described autoclave electric furnace is heated to 550 DEG C, room temperature is naturally cooled to after reaction 8h, obtain product, take part ball milling 6h under the rotating speed of 300rpm that product upper strata is loose, the material obtained after ball milling first cleans to bubble-free generation with the dilute hydrochloric acid that concentration is 0.1M, it is neutral for cleaning to pH with deionized water again, is dried 10h, obtains porous nano carbon thin slice at 100 DEG C；By porous nano carbon thin slice and the sulfur simple substance mixing and ball milling of 1:4 in mass ratio; ratio of grinding media to material is 10:1; rotating speed 300rpm; ball milling 6h; gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas; it is heated to 180 DEG C with electric furnace, under argon shield, reacts 24h, obtain porous nano carbon thin slice/nano-sulfur complex.
(2) the porous nano carbon thin slice/nano-sulfur complex of 0.5g is dissolved in 100mL ethanol solution, ultrasonic 30min, adding concentration is the graphene oxide of 3mg/mL, the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:10, dropping ammonia regulation pH value is 10.1, ultrasonic 60min, obtains the mixed solution of black；Mixed solution is put into there is teflon-lined water heating kettle, it is heated to 95 DEG C of hydro-thermal reactions 48h in an oven and obtains product, the product microporous filter membrane vacuum in 22 μm apertures is filtered, be washed with deionized to pH value be 7,24h it is dried in 60 DEG C of baking ovens, obtain porous nano carbon thin slice/nano-sulfur/redox graphene composite, for lithium sulfur battery anode material of the present invention.Described lithium sulfur battery anode material tabletting is obtained lithium-sulphur cell positive electrode, it is not necessary to use binding agent and collector.
Dripping 0.1mL electrolyte on the lithium-sulphur cell positive electrode that the present embodiment prepares makes it absorb, and after infiltration 48h, described lithium-sulphur cell positive electrode, the barrier film of Celgard2325 model and metal lithium sheet is assembled into lithium-sulfur cell；Described electrolyte is the LiNO of 0.2M by double trifluoromethanesulfonimide lithiums (LiTFSI) that concentration is 1M and concentration3Being dissolved in the mixed solution of DOX (DOL) and glycol dimethyl ether (DME) formation, the volume ratio of DOX and glycol dimethyl ether is 1:1.
The porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell that prepare the present embodiment are tested, and result is as follows:
(1) atomic force microscope test:
As it is shown in figure 1, wherein, left figure is the atomic force microscope figure of porous nano carbon thin slice to test result, and right figure is the respective heights figure of dotted line position in left figure, and as shown in Figure 1, the thickness of porous nano carbon thin slice is 30nm.
(2) transmission electron microscope test:
As in figure 2 it is shown, as shown in Figure 2, the nano-sulfur spot diameter in lithium sulfur battery anode material is 1nm～10nm to test result, and the hole of porous nano carbon thin slice is micropore and mesoporous, and porous nano carbon thin slice is three-dimensional communication network structure.
(3) thermogravimetric analysis test:
Test result as it is shown on figure 3, from the figure 3, it may be seen that in described lithium sulfur battery anode material sulfur at 150 DEG C～320 DEG C decomposition, porous nano carbon thin slice and redox graphene 500 DEG C～650 DEG C decomposition；Being calculated the weight/mass percentage composition of sulfur in lithium sulfur battery anode material by Thermogravimetric Data is 70%, illustrates that the activity substance content in described positive electrode is high.
(4) cycle performance test:
Test result is as shown in Figure 4, as shown in Figure 4, described lithium-sulfur cell is 0.1% weekly in room temperature (30 DEG C) capacity attenuation rate, and after the circulation 200 weeks of 0.1C, capacity also has 892.3mAh/g, illustrates that described positive electrode has good cyclical stability.
Embodiment 2
(1) by 1.15g magnesium and 3.9g sucrose mixing and ball milling, ratio of grinding media to material is 10:1, rotating speed 300rpm, ball milling 6h, and gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas, subsequently described autoclave is evacuated to below 0.1MPa；Described autoclave electric furnace is heated to 550 DEG C, room temperature is naturally cooled to after reaction 8h, obtain product, take part ball milling 6h under the rotating speed of 300rpm that product upper strata is loose, the material obtained after ball milling first cleans to bubble-free generation with the dilute hydrochloric acid that concentration is 0.1M, it is neutral for cleaning to pH with deionized water again, is dried 10h, obtains porous nano carbon thin slice at 100 DEG C；By porous nano carbon thin slice and the sulfur simple substance mixing and ball milling of 1:4 in mass ratio; ratio of grinding media to material is 10:1; rotating speed is 300rpm; ball milling 6h; gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas; it is heated to 180 DEG C with electric furnace, under argon shield, reacts 24h, obtain porous nano carbon thin slice/nano-sulfur complex.
(2) the porous nano carbon thin slice/nano-sulfur complex of 0.5g is dissolved in 100mL ethanol solution, ultrasonic 30min, adding concentration is the graphene oxide of 3mg/mL, the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:10, dropping ammonia regulation pH value is 10.1, ultrasonic 60min, obtains the mixed solution of black；Mixed solution is put into there is teflon-lined water heating kettle, it is heated to 95 DEG C of hydro-thermal reactions 48h in an oven and obtains product, the product microporous filter membrane vacuum in 22 μm apertures is filtered, be washed with deionized to pH value be 7,24h it is dried in 60 DEG C of baking ovens, obtain porous nano carbon thin slice/nano-sulfur/redox graphene composite, for lithium sulfur battery anode material of the present invention.Described lithium sulfur battery anode material tabletting is obtained lithium-sulphur cell positive electrode, it is not necessary to use binding agent and collector.
Dripping 0.1mL electrolyte on the lithium-sulphur cell positive electrode that the present embodiment prepares makes it absorb, and after infiltration 48h, described lithium-sulphur cell positive electrode, the barrier film of Celgard2325 model and metal lithium sheet is assembled into lithium-sulfur cell；Described electrolyte is the LiNO of 0.2M by double trifluoromethanesulfonimide lithiums (LiTFSI) that concentration is 1M and concentration3Being dissolved in the mixed solution of DOX (DOL) and glycol dimethyl ether (DME) formation, the volume ratio of DOX and glycol dimethyl ether is 1:1.
The porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell that prepare the present embodiment are tested, and result is as follows:
(1) atomic force microscope test:
Test result is similar with Fig. 1 result, it is known that the thickness of porous nano carbon thin slice is 32nm.
(2) transmission electron microscope test:
Test result is similar with Fig. 2 result, it is known that, the nano-sulfur spot diameter of lithium sulfur battery anode material is 1nm～20nm, and the hole of porous nano carbon thin slice is micropore and mesoporous, in three-dimensional communication network structure.
(3) thermogravimetric analysis test:
Test result is similar with Fig. 3, it is known that in lithium sulfur battery anode material sulfur at 150 DEG C～320 DEG C decomposition, porous nano carbon thin slice and redox graphene 500 DEG C～650 DEG C decomposition；Being calculated the weight/mass percentage composition of sulfur in lithium sulfur battery anode material by Thermogravimetric Data is 68%, illustrates that the activity substance content in described positive electrode is high.
(4) cycle performance test:
Test result is similar with Fig. 4, it is known that described lithium-sulfur cell is 0.1% weekly in room temperature (30 DEG C) capacity attenuation rate, and after the circulation 200 weeks of 0.1C, capacity also has 800.3mAh/g, illustrates that described positive electrode has good cyclical stability.
Embodiment 3
(1) by 1.15g zinc and 3.9g glucose mixing and ball milling, ratio of grinding media to material is 10:1, and rotating speed is 300rpm, ball milling 6h, gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas, subsequently described autoclave is evacuated to below 0.1MPa；Described autoclave electric furnace is heated to 550 DEG C, room temperature is naturally cooled to after reaction 8h, obtain product, take part ball milling 6h under the rotating speed of 300rpm that product upper strata is loose, the material obtained after ball milling first cleans to bubble-free generation with the dilute hydrochloric acid that concentration is 0.1M, it is neutral for cleaning to pH with deionized water again, is dried 10h, obtains porous nano carbon thin slice at 100 DEG C；By porous nano carbon thin slice and the sulfur simple substance mixing and ball milling of 1:4 in mass ratio; ratio of grinding media to material is 10:1; rotating speed is 300rpm; ball milling 6h; gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas; it is heated to 180 DEG C with electric furnace, under argon shield, reacts 24h, obtain porous nano carbon thin slice/nano-sulfur complex.
(2) the porous nano carbon thin slice/nano-sulfur complex of 0.5g is dissolved in 100mL ethanol solution, ultrasonic 30min, adding concentration is the graphene oxide of 3mg/mL, the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:10, dropping ammonia regulation pH value is 10.1, ultrasonic 60min, obtains the mixed solution of black；Mixed solution is put into there is teflon-lined water heating kettle, it is heated to 95 DEG C of hydro-thermal reactions 48h in an oven and obtains product, the product microporous filter membrane vacuum in 22 μm apertures is filtered, be washed with deionized to pH value be 7,24h it is dried in 60 DEG C of baking ovens, obtain porous nano carbon thin slice/nano-sulfur/redox graphene composite, for lithium sulfur battery anode material of the present invention.Described lithium sulfur battery anode material tabletting is obtained lithium-sulphur cell positive electrode, it is not necessary to use binding agent and collector.
Dripping 0.1mL electrolyte on the lithium-sulphur cell positive electrode that the present embodiment prepares makes it absorb, and after infiltration 48h, described lithium-sulphur cell positive electrode, the barrier film of Celgard2325 model and metal lithium sheet is assembled into lithium-sulfur cell；Described electrolyte is the LiNO of 0.2M by double trifluoromethanesulfonimide lithiums (LiTFSI) that concentration is 1M and concentration3Being dissolved in the mixed solution of DOX (DOL) and glycol dimethyl ether (DME) formation, the volume ratio of DOX and glycol dimethyl ether is 1:1.
The porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell that prepare the present embodiment are tested, and result is as follows:
(1) atomic force microscope test:
Test result is similar with Fig. 1, it is known that the thickness of porous nano carbon thin slice is 30nm.
(2) transmission electron microscope test:
Test result is similar with Fig. 2, it is known that the nano-sulfur spot diameter of lithium sulfur battery anode material is 1nm～20nm, and the hole of porous nano carbon thin slice is micropore and mesoporous, the network structure in three-dimensional communication.
(3) thermogravimetric analysis test:
Test result is similar with Fig. 3, it is known that in lithium sulfur battery anode material sulfur at 150 DEG C～320 DEG C decomposition, porous nano carbon thin slice and redox graphene 500 DEG C～650 DEG C decomposition；Being calculated the weight/mass percentage composition of sulfur in lithium sulfur battery anode material by Thermogravimetric Data is 71%, illustrates that the activity substance content in described positive electrode is high.
(4) cycle performance test:
Test result is similar with Fig. 4, it is known that described lithium-sulfur cell is 0.1% weekly in room temperature (30 DEG C) capacity attenuation rate, and after the circulation 200 weeks of 0.1C, capacity also has 780.7mAh/g, illustrates that described positive electrode has good cyclical stability.
Embodiment 4
(1) by 1.15g zinc and 1.15g sucrose mixing and ball milling, ratio of grinding media to material is 15:1, and rotating speed is 200rpm, ball milling 2h, gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas, subsequently described autoclave is evacuated to below 0.1MPa；Described autoclave electric furnace is heated to 450 DEG C, room temperature is naturally cooled to after reaction 4h, obtain product, take part ball milling 2h under the rotating speed of 200rpm that product upper strata is loose, the material obtained after ball milling first cleans to bubble-free generation with the dilute hydrochloric acid that concentration is 0.01M, it is neutral for cleaning to pH with deionized water again, is dried 6h, obtains porous nano carbon thin slice at 80 DEG C；By porous nano carbon thin slice and the sulfur simple substance mixing and ball milling of 1:1 in mass ratio; ratio of grinding media to material is 15:1; rotating speed is 200rpm; ball milling 2h; gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas; it is heated to 180 DEG C with electric furnace, under argon shield, reacts 12h, obtain porous nano carbon thin slice/nano-sulfur complex.
(2) the porous nano carbon thin slice/nano-sulfur complex of 0.5g is dissolved in 100mL ethanol solution, ultrasonic 30min, adding concentration is the graphene oxide of 3mg/mL, the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:7, dropping ammonia regulation pH value is 10.1, ultrasonic 30min, obtains the mixed solution of black；Mixed solution is put into there is teflon-lined water heating kettle, it is heated to 80 DEG C of hydro-thermal reactions 24h in an oven and obtains product, the product microporous filter membrane vacuum in 22 μm apertures is filtered, be washed with deionized to pH value be 7,12h it is dried in 40 DEG C of baking ovens, obtain porous nano carbon thin slice/nano-sulfur/redox graphene composite, for lithium sulfur battery anode material of the present invention.Described lithium sulfur battery anode material tabletting is obtained lithium-sulphur cell positive electrode, it is not necessary to use binding agent and collector.
Dripping 0.1mL electrolyte on the lithium-sulphur cell positive electrode that the present embodiment prepares makes it absorb, and after infiltration 48h, described lithium-sulphur cell positive electrode, the barrier film of Celgard2325 model and metal lithium sheet is assembled into lithium-sulfur cell；Described electrolyte is the LiNO of 0.2M by double trifluoromethanesulfonimide lithiums (LiTFSI) that concentration is 1M and concentration3Being dissolved in the mixed solution of DOX (DOL) and glycol dimethyl ether (DME) formation, the volume ratio of DOX and glycol dimethyl ether is 1:1.
The porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell that prepare the present embodiment are tested, and result is as follows:
(1) atomic force microscope test:
Test result is similar with Fig. 1, it is known that the thickness of porous nano carbon thin slice is 40nm.
(2) transmission electron microscope test:
Test result is similar with Fig. 2, it is known that the nano-sulfur spot diameter of described lithium sulfur battery anode material is 0.5nm～50nm, and the hole of porous nano carbon thin slice is micropore and mesoporous, in three-dimensional communication network structure.
(3) thermogravimetric analysis test:
Test result is similar with Fig. 3, it is known that, in described lithium sulfur battery anode material sulfur at 150 DEG C～320 DEG C decomposition, porous nano carbon thin slice and redox graphene 500 DEG C～650 DEG C decomposition；Being calculated the weight/mass percentage composition of sulfur in lithium sulfur battery anode material by Thermogravimetric Data is 40%.
(4) cycle performance test:
Test result is similar with Fig. 4, it is known that, described lithium-sulfur cell is 0.1% weekly in room temperature (30 DEG C) capacity attenuation rate, and after the circulation 200 weeks of 0.1C, capacity also has 850.5mAh/g, illustrates that described positive electrode has good cyclical stability.
Embodiment 5
(1) by 1.15g zinc and 1.15g sucrose mixing and ball milling, ratio of grinding media to material is 5:1, and rotating speed is 600rpm, ball milling 2h, and gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas, subsequently described autoclave is evacuated to below 0.1MPa；Described autoclave electric furnace is heated to 600 DEG C, room temperature is naturally cooled to after reaction 24h, obtain product, take part ball milling 8h under the rotating speed of 600rpm that product upper strata is loose, the material obtained after ball milling first cleans to bubble-free generation with the dilute hydrochloric acid that concentration is 0.2M, it is neutral for cleaning to pH with deionized water again, is dried 6h, obtains porous nano carbon thin slice at 120 DEG C；By porous nano carbon thin slice and the sulfur simple substance mixing and ball milling of 1:9 in mass ratio; ratio of grinding media to material is 5:1; rotating speed is 600rpm; ball milling 8h; gained mixture is sealed in stainless steel autoclave in the glove box of full noble gas; it is heated to 200 DEG C with electric furnace, under argon shield, reacts 36h, obtain porous nano carbon thin slice/nano-sulfur complex.
(2) the porous nano carbon thin slice/nano-sulfur complex of 0.5g is dissolved in 100mL ethanol solution, ultrasonic 30min, adding concentration is the graphene oxide of 3mg/mL, the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:13, dropping ammonia regulation pH value is 10.1, ultrasonic 90min, obtains the mixed solution of black；Mixed solution is put into there is teflon-lined water heating kettle, it is heated to 100 DEG C of hydro-thermal reactions 72h in an oven and obtains product, the product microporous filter membrane vacuum in 22 μm apertures is filtered, be washed with deionized to pH value be 7,12h it is dried in 80 DEG C of baking ovens, obtain porous nano carbon thin slice/nano-sulfur/redox graphene composite, for lithium sulfur battery anode material of the present invention.Described lithium sulfur battery anode material tabletting is obtained lithium-sulphur cell positive electrode, it is not necessary to use binding agent and collector.
Dripping 0.1mL electrolyte on the lithium-sulphur cell positive electrode that the present embodiment prepares makes it absorb, and after infiltration 48h, described lithium-sulphur cell positive electrode, the barrier film of Celgard2325 model and metal lithium sheet is assembled into lithium-sulfur cell；Described electrolyte is the LiNO of 0.2M by double trifluoromethanesulfonimide lithiums (LiTFSI) that concentration is 1M and concentration3Being dissolved in the mixed solution of DOX (DOL) and glycol dimethyl ether (DME) formation, the volume ratio of DOX and glycol dimethyl ether is 1:1.
The porous nano carbon thin slice, lithium sulfur battery anode material and the lithium-sulfur cell that prepare the present embodiment are tested, and result is as follows:
(1) atomic force microscope test:
Test result is similar with Fig. 1, it is known that the thickness of described porous nano carbon thin slice is 35nm.
(2) transmission electron microscope test:
Test result is similar with Fig. 2, it is known that the nano-sulfur spot diameter of described lithium sulfur battery anode material is 0.5nm～15nm, and the hole that nano-sized carbon thin slice has is micropore and mesoporous, in three-dimensional communication network structure.
(3) thermogravimetric analysis test:
Test result and Fig. 3 institute is similar, from the figure 3, it may be seen that in described lithium sulfur battery anode material sulfur at 150 DEG C～320 DEG C decomposition, porous nano carbon thin slice and redox graphene 500 DEG C～650 DEG C decomposition；Being calculated the weight/mass percentage composition of sulfur in lithium sulfur battery anode material by Thermogravimetric Data is 71.3%, illustrates that the activity substance content in described positive electrode is high.
(4) cycle performance test:
Test result is similar with Fig. 4, it is known that described lithium-sulfur cell is 0.1% weekly in room temperature (30 DEG C) capacity attenuation rate, and after the circulation 200 weeks of 0.1C, capacity also has 685.7mAh/g, illustrates that described positive electrode has good cyclical stability.
Claims (9)
1. a lithium sulfur battery anode material, it is characterized in that: described positive electrode is with porous nano carbon thin slice as skeleton, described carbon thin slice has abundant micropore and mesoporous, for three-dimensional communication network structure, being filled with nano-sulfur point in the hole that described network structure is formed, skeleton outer layer reduced oxygen functionalized graphene is coated with.
2. the preparation method of a lithium sulfur battery anode material as claimed in claim 1, it is characterised in that: described method step is as follows:
(1) by porous nano carbon thin slice and sulfur simple substance mixing and ball milling, gained mixture reacts 12h～36h at the anhydrous closed environment of anaerobic, inert gas shielding and 180 DEG C～200 DEG C, obtains porous nano carbon thin slice/nano-sulfur complex；
The mass ratio of porous nano carbon thin slice and sulfur simple substance is 1:1～1:9；
(2) being dissolved in ethanol solution by porous nano carbon thin slice/nano-sulfur complex, ultrasonic disperse is uniform, adds graphene oxide and with ammonia regulation pH value of solution to 10.1, and ultrasonic disperse is uniform obtains mixed solution；By mixed solution hydro-thermal reaction 24h～72h at 80 DEG C～100 DEG C, filtering, washing, to neutral, be dried more than 12h at 40 DEG C～80 DEG C, obtain described lithium sulfur battery anode material.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: in step (1), ball milling speed is 100rpm～300rpm, ball milling 2h～8h；Ratio of grinding media to material is 15:1～5:1.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: in step (1), noble gas is argon；The anhydrous closed environment of described anaerobic, by being sealed in stainless steel autoclave in the glove box of full noble gas by gained mixture, carries out evacuation realization subsequently to autoclave, and heating uses electric furnace.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: in step (2), ethanol solution is made up of the water that volume ratio is 1:1 and dehydrated alcohol.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: in step (2), the mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:7～1:13.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: step (2) ultrasonic time is 30min～90min.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: the employing of step (2) hydro-thermal reaction has teflon-lined water heating kettle and carries out, and heating uses baking oven；Filtering and use microporous filter membrane vacuum to filter, slurry is the water of more than deionization purity；More than 12h it is dried in an oven at 40 DEG C～80 DEG C.
The preparation method of a kind of lithium sulfur battery anode material the most according to claim 2, it is characterised in that: in step (1), ball milling speed is 100rpm～300rpm, ball milling 2h～8h；Ratio of grinding media to material is 15:1～5:1；Noble gas is argon；The anhydrous closed environment of described anaerobic, by being sealed in autoclave in the glove box of full noble gas by gained mixture, carries out evacuation realization subsequently to stainless steel autoclave, and heating uses electric furnace；Described in step (2), ethanol solution is made up of the water that volume ratio is 1:1 and dehydrated alcohol；The mass ratio of graphene oxide and porous nano carbon thin slice/nano-sulfur complex is 1:7～1:13；Ultrasonic time is 30min～90min；Hydro-thermal reaction employing has teflon-lined water heating kettle and carries out, and heating uses baking oven；Filtering and use microporous filter membrane vacuum to filter, slurry is the water of more than deionization purity, is dried more than 12h in an oven at 40 DEG C～80 DEG C.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328895A (en) * | 2016-09-09 | 2017-01-11 | 广西大学 | Graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material and preparation method thereof |
| CN106848232A (en) * | 2017-02-17 | 2017-06-13 | 中南大学 | A kind of preparation method and applications of three-dimensional grapheme sulphur composite |
| 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 |
| CN107959001A (en) * | 2016-10-18 | 2018-04-24 | 福建新峰二维材料科技有限公司 | The preparation method and lithium sulphur/carbon battery of a kind of sulphur/carbon composite anode material |
| CN108232163A (en) * | 2018-01-15 | 2018-06-29 | 江苏师范大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN108258208A (en) * | 2017-12-26 | 2018-07-06 | 上海交通大学 | For sulphur/carbon nanometer three-dimensional structure composite material of lithium-sulphur cell positive electrode and its preparation |
| CN108281633A (en) * | 2018-01-26 | 2018-07-13 | 南开大学 | Lithium sulfur battery anode material, preparation method and lithium-sulfur cell |
| CN109273698A (en) * | 2018-11-19 | 2019-01-25 | 河南景创新能源科技有限公司 | A kind of lithium sulfur battery anode material and its preparation method and application |
| CN109346678A (en) * | 2018-11-21 | 2019-02-15 | 长沙矿冶研究院有限责任公司 | A kind of high-sulfur load lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell |
| CN109473637A (en) * | 2018-08-13 | 2019-03-15 | 国网浙江省电力有限公司湖州供电公司 | A kind of guard method of long circulation life cathode of lithium |
| WO2020060132A1 (en) * | 2018-09-19 | 2020-03-26 | 주식회사 엘지화학 | Sulfur-carbon composite manufacturing method, sulfur-carbon composite manufactured thereby, cathode comprising same sulfur-carbon composite, and lithium secondary battery comprising same cathode |
| CN112201484A (en) * | 2020-08-24 | 2021-01-08 | 温州大学 | Two-dimensional ultrathin carbon nanosheet and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100255197A1 (en) * | 2002-01-08 | 2010-10-07 | Muradov Nazim Z | Three-Dimensional Carbon Fibers and Method and Apparatus for their Production |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
| CN104393233A (en) * | 2014-10-10 | 2015-03-04 | 南京中储新能源有限公司 | Graphene array-based carbon-sulfur composite electrode and secondary cell |
| CN105293479A (en) * | 2015-12-03 | 2016-02-03 | 青岛昊鑫新能源科技有限公司 | Preparation method of three-dimensional orderly square-hole mesoporous graphene skeleton material |
-
2016
- 2016-03-17 CN CN201610154334.3A patent/CN105826523A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100255197A1 (en) * | 2002-01-08 | 2010-10-07 | Muradov Nazim Z | Three-Dimensional Carbon Fibers and Method and Apparatus for their Production |
| CN102145888A (en) * | 2011-04-12 | 2011-08-10 | 东南大学 | Preparation method of grapheme three-dimensional entity |
| CN104393233A (en) * | 2014-10-10 | 2015-03-04 | 南京中储新能源有限公司 | Graphene array-based carbon-sulfur composite electrode and secondary cell |
| CN105293479A (en) * | 2015-12-03 | 2016-02-03 | 青岛昊鑫新能源科技有限公司 | Preparation method of three-dimensional orderly square-hole mesoporous graphene skeleton material |
Non-Patent Citations (3)
| Title |
|---|
| BING DING，CHANGZHOU YUAN等: "Encapsulating sulfur into hierarchically ordered porous carbon as a high-performance cathode for lithium-sulfur batteries", 《CHEMISTRY》 * |
| NIANWU LI，MING ZHENG等: "High-rate lithium-sulfur batteries promoted by reduced graphene oxide coating", 《CHEMICAL COMMUNICATIONS》 * |
| 李永，宋健: "《新能源车辆储能与控制技术》", 31 January 2014, 机械工业出版社 * |
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