CN106876673B - The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether - Google Patents

The method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether Download PDF

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CN106876673B
CN106876673B CN201710145000.4A CN201710145000A CN106876673B CN 106876673 B CN106876673 B CN 106876673B CN 201710145000 A CN201710145000 A CN 201710145000A CN 106876673 B CN106876673 B CN 106876673B
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titanium dioxide
graphene oxide
graphene
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nano
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CN106876673A (en
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赵力
张羽听
吴清
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Harbin Institute of Technology
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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 method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether, is related to a kind of preparation method of lithium sulfur battery anode material.The present invention is to solve the technical problem that the preparation method of graphene coated sulfur materials complexity is limited with the shuttle effect of limitation polysulfide in current lithium sulfur battery anode material.The present invention: one, graphene oxide cream is prepared；Two, mixing and ball milling, freezing reduction, vacuum drying.The present invention in electrode material by adding titanium dioxide, the diffusion dissolution of polysulfide can be effectively limited by the chemical bond of titanium dioxide and polysulfide, and the methods of general hydro-thermal method and chemical vapor deposition are unfavorable for the industrialized production of material, and the present invention uses hydrophilic nano-titanium dioxide, material is prepared by ball milling simple process, improving for industrialized production may.

Description

One-step method prepares the core-shell structure lithium sulphur electricity that titanium dioxide and graphene bilayer coat altogether The method of pond positive electrode
Technical field
The present invention relates to a kind of preparation methods of lithium sulfur battery anode material.
Background technique
Lithium-sulphur cell positive electrode sulphur possesses the theoretical specific capacity of 1675mAh/g and the theoretical energy density of 2567Wh/kg, thus It is widely studied, as most possible one of next-generation energy-storage battery, sulphur simple substance possesses at low cost, abundant raw material, environment friend The advantages that good, although possessing these excellent features, because of the poor circulation and lower specific power of sulfur electrode, resistance The development of lithium-sulfur cell is hindered, the electronic conductivity of sulphur only has 5 × 10 at room temperature-30S/cm, it reduce the utilizations of active material Rate, in charge and discharge, volume expansion 80% causes electrode structure unstable, another is exactly the shuttle effect of polysulfide, causes The rapid decay of capacity and lower coulombic efficiency.
Therefore researcher designs electrode material, is coated using different carbon materials, conducting polymer, metal oxide Active material, wherein carbon material is studied more extensive with graphene, because its good electronic conductivity and mechanical performance, biggish Specific surface area, recent studies have shown that graphene coated sulphur has a good chemical property, but complicated preparation method and The shuttle effect for limiting polysulfide is limited, limits its practical application.
Summary of the invention
The present invention is the preparation method in order to solve graphene coated sulfur materials complexity in current lithium sulfur battery anode material With the limited technical problem of shuttle effect of limitation polysulfide, and provide that a kind of one-step method prepares titanium dioxide and graphene is double The method for the core-shell structure lithium sulfur battery anode material that layer coats altogether.
One-step method of the invention prepares the core-shell structure lithium-sulphur cell positive electrode material that titanium dioxide and graphene bilayer coat altogether The method of material carries out according to the following steps:
One, it prepares graphene oxide cream: KOH being added into graphene oxide water solution, in the water-bath that temperature is 95 DEG C 2h is heated, is cooled to room temperature, 10min is centrifuged under conditions of revolving speed is 10000 revs/min, collects whole pastes, then will be whole Paste is put into ultrasonic disperse 3h~4h in distilled water, obtains graphene oxide cream；Oxygen in the graphene oxide water solution The concentration of graphite alkene is 1mg/mL；The mass ratio of graphene oxide and KOH in the graphene oxide water solution is 1: 8；The concentration of graphene oxide is 2.5mg/mL~20mg/mL in the graphene oxide cream；
Two, by graphene oxide cream mixing and ball milling 7h obtained in nano-sulfur, nano-titanium dioxide and step 1, in temperature 3h is freezed under conditions of being -18 DEG C~-20 DEG C, obtains ice block mixture, HI aqueous solution, which is poured into ice block mixture, to be made It obtains ice block mixture to be totally submerged in HI aqueous solution, impregnates 12h under conditions of temperature is 5 DEG C, then soak at room temperature 6h~for 24 hours is steeped, ethyl alcohol and deionized water filtering and washing is successively used, takes filter cake, then filter cake in temperature is in a vacuum drying oven 60 DEG C are dried under conditions of vacuum for 24 hours to get the core-shell structure lithium-sulfur cell coated altogether to titanium dioxide and graphene bilayer Positive electrode；The mass ratio of the nano-titanium dioxide and nano-sulfur is 1:(2~5)；Graphite oxide described in step 1 The mass ratio of nano-sulfur described in graphene oxide and step 2 in aqueous solution is 1:(7~9)；In the HI aqueous solution The concentration of HI is 1mol/L~5mol/L.
The present invention can pass through the chemical bond of titanium dioxide and polysulfide by adding titanium dioxide in electrode material The effectively diffusion dissolution of limitation polysulfide, and the methods of general hydro-thermal method and chemical vapor deposition are unfavorable for the industry of material Metaplasia produces, and the present invention uses hydrophilic nano-titanium dioxide, prepares material by ball milling simple process, mentions for industrialized production It is high possible.
The lithium sulfur battery anode material even particle distribution that the present invention synthesizes, titanium dioxide are uniformly coated on sulfur granules table Face, under suitable covering amount, no extra distribution titanium dioxide and uncoated sulphur surface.It is coated again in suitable graphene Under, the electronic conductivity of material is improved, the polarization of material is reduced.Charge-discharge test shows the lithium sulphur electricity that the present invention synthesizes Pond positive electrode possesses good electrochemistry under the core-shell structure that the titanium dioxide and graphene of appropriate ratio coat altogether Can, charge and discharge cycles 100 times under 0.1C multiplying power, discharge capacity 969.1mAh/g for the first time, the discharge capacity after 100 circulations 558.6mAh/g, 100 0.1C circulation coulombs are high-efficient, and up to 57.6%, there are also good high rate performances, put for the first time in 0.2C Capacitance is 640.8mAh/g, and discharge capacity is 539.1mAh/g to 0.5C for the first time, and discharge capacity is 400.1mAh/g, 2C to 1C for the first time Discharge capacity is 248.1mAh/g for the first time, and discharge capacity is 132.1mAh/g to 3C for the first time.It can be seen from first charge-discharge curve The discharge and recharge reaction of the sulphur of coated by titanium dioxide appropriate effectively is steady, and the cladding of graphene improves the utilization rate of sulphur.By Impedance spectrum, which can be seen that titanium dioxide and the cladding of graphene, can reduce polarization, and covering amount is bigger, polarize smaller.By recycling The cladding that voltammogram can be seen that titanium dioxide can improve reactivity, and graphene coated improves the cycle performance of reaction.By For EDS figure as can be seen that titanium dioxide, graphene uniform are coated on sulphur surface, Elemental redistribution is uniform.
Detailed description of the invention
Fig. 1 is XRD diagram,It is sulphur,It is titanium dioxide, curve 1 is to test an obtained mixture, and curve 2 is test two Obtained mixture, curve 3 are to test three obtained mixtures；
Fig. 2 is XRD diagram,It is sulphur,It is titanium dioxide,It is graphene oxide, curve 1 is to test four obtained titanium dioxides The core-shell structure lithium sulfur battery anode material that titanium and graphene bilayer coat altogether, curve 2 be test five obtained titanium dioxide and The core-shell structure lithium sulfur battery anode material that graphene bilayer coats altogether, curve 3 are to test six obtained titanium dioxide and graphite The core-shell structure lithium sulfur battery anode material that alkene bilayer coats altogether, curve 4 are to test the titanium dioxide and graphene pair that seven obtain The core-shell structure lithium sulfur battery anode material that layer coats altogether；
Fig. 3 is the SEM figure for testing the nano-sulfur in four steps two；
Fig. 4 is the SEM figure for testing the nano-titanium dioxide in four steps two；
Fig. 5 is to test three to obtain the SEM figure of mixture；
Fig. 6 is to test two to obtain the SEM figure of mixture；
Fig. 7 is to test one to obtain the SEM figure of mixture；
Fig. 8 is to test the titanium dioxide that four obtain and the core-shell structure lithium sulfur battery anode material that graphene bilayer coats altogether SEM figure；
Fig. 9 is to test the titanium dioxide that five obtain and the core-shell structure lithium sulfur battery anode material that graphene bilayer coats altogether SEM figure；
Figure 10 is to test the titanium dioxide that six obtain and the core-shell structure lithium-sulphur cell positive electrode material that graphene bilayer coats altogether The SEM of material schemes；
Figure 11 is cycle performance curve graph, and curve 1 is to test the button cells of the ten assembly test result under 0.1C multiplying power, Curve 2 be test nine assembly button cell under 0.1C multiplying power test result, curve 3 be test 11 assembly button cells The test result under 0.1C multiplying power, curve 4 be test eight assembly button cell under 0.1C multiplying power test result；
Figure 12 is cycle performance curve graph, and curve 1 is to test the button cell that 13 assemble to test knot under 0.1C multiplying power Fruit, curve 2 be test 15 assembly button cell under 0.1C multiplying power test result, curve 3 be test 14 assembly knobs Detain battery test result under 0.1C multiplying power, curve 4 be test 12 assembly button cell under 0.1C multiplying power test result；
Figure 13 is first charge-discharge curve graph, and curve 1 is to test the button cell that eight assemble to test knot under 0.1C multiplying power Fruit, curve 2 be test nine assembly button cell under 0.1C multiplying power test result, curve 3 be test ten assembly button electricity Pond test result under 0.1C multiplying power, curve 4 be test 11 assembly button cell under 0.1C multiplying power test result；
Figure 14 is first charge-discharge curve graph, and curve 1 is to test the button cell that 14 assemble to test under 0.1C multiplying power As a result, curve 2 be test 12 assembly button cell under 0.1C multiplying power test result, curve 3 be test 13 assembly Button cell test result under 0.1C multiplying power, curve 4 are to test the button cell that 15 assemble to test knot under 0.1C multiplying power Fruit.
Figure 15 is high rate performance figure, and ■ is the button cell for testing eight assembly, ● it is the button cell for testing 11 assembly, ▲ it is the button cell for testing ten assembly, ▼ is the button cell for testing nine assembly；
Figure 16 is high rate performance figure, and ■ is the button cell for testing 13 assembly, ● it is the button electricity for testing 12 assembly Pond, ▲ it is the button cell for testing 14 assembly, ▼ is the button cell for testing 15 assembly；
Figure 17 is impedance diagram, and curve 1 is the button cell for testing eight assembly, and curve 2 is the button cell for testing ten assembly, Curve 3 is the button cell for testing 11 assembly, and curve 4 is the button cell for testing nine assembly；
Figure 18 is impedance diagram, and curve 1 is the button cell for testing 13 assembly, and curve 2 is the button for testing 12 assembly Battery, curve 3 are the button cells for testing 15 assembly, and curve 4 is the button cell for testing 14 assembly；
Figure 19 is CV figure, and curve 1 is the button cell for testing eight assembly, and curve 2 is the button cell for testing 11 assembly, Curve 3 is the button cell for testing ten assembly, and curve 4 is the button cell for testing nine assembly；
Figure 20 is 3 figures of CV circulation for testing the button cell of 13 assembly；
EDS test is carried out to the mixture that test two obtains, Figure 21 is oxygen element, and Figure 22 is S element, and Figure 23 is titanium member Element；
The core-shell structure lithium sulfur battery anode material that the titanium dioxide and graphene bilayer obtain to test six coats altogether into Row EDS test, Figure 24 is carbon, and Figure 25 is oxygen element, and Figure 26 is element sulphur, and Figure 27 is titanium elements.
Specific embodiment
Specific embodiment 1: present embodiment is that one-step method prepares the nucleocapsid that titanium dioxide and graphene bilayer coat altogether The method of structure lithium sulfur battery anode material specifically carries out according to the following steps:
One, it prepares graphene oxide cream: KOH being added into graphene oxide water solution, in the water-bath that temperature is 95 DEG C 2h is heated, is cooled to room temperature, 10min is centrifuged under conditions of revolving speed is 10000 revs/min, collects whole pastes, then will be whole Paste is put into ultrasonic disperse 3h~4h in distilled water, obtains graphene oxide cream；Oxygen in the graphene oxide water solution The concentration of graphite alkene is 1mg/mL；The mass ratio of graphene oxide and KOH in the graphene oxide water solution is 1: 8；The concentration of graphene oxide is 2.5mg/mL~20mg/mL in the graphene oxide cream；
Two, by graphene oxide cream mixing and ball milling 7h obtained in nano-sulfur, nano-titanium dioxide and step 1, in temperature 3h is freezed under conditions of being -18 DEG C~-20 DEG C, obtains ice block mixture, HI aqueous solution, which is poured into ice block mixture, to be made It obtains ice block mixture to be totally submerged in HI aqueous solution, impregnates 12h under conditions of temperature is 5 DEG C, then soak at room temperature 6h~for 24 hours is steeped, ethyl alcohol and deionized water filtering and washing is successively used, takes filter cake, then filter cake in temperature is in a vacuum drying oven 60 DEG C are dried under conditions of vacuum for 24 hours to get the core-shell structure lithium-sulfur cell coated altogether to titanium dioxide and graphene bilayer Positive electrode；The mass ratio of the nano-titanium dioxide and nano-sulfur is 1:(2~5)；Graphite oxide described in step 1 The mass ratio of nano-sulfur described in graphene oxide and step 2 in aqueous solution is 1:(7~9)；In the HI aqueous solution The concentration of HI is 1mol/L~5mol/L.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: oxidation described in step 1 Graphene oxide in graphene aqueous solution the preparation method is as follows:
The concentrated sulfuric acid that 120mL mass fraction is 98% is added in the three-necked bottle of 250mL, is subsequently placed in 0 DEG C of ice-water bath In, add 5g graphite and 2.5g NaNO3, then magnetic agitation 30min adds the powdered KMnO of 3g every 10min4, in total plus 5 It is secondary, the reaction was continued under ice-water bath and stirring condition 2h；
Then continue to stir 2h in 35 DEG C of constant temperature oil bath, reactant is slowly added into the distilled water of 360mL, and The speed that control is added makes reaction temperature be no more than 90 DEG C, then continues isothermal reaction 1h at 75 DEG C, obtains the suspension of brown Liquid, the suspension for taking out color are placed in draught cupboard, and 40 DEG C of distilled water 1000mL is added, and the mass concentration that 50mL is then added is 30% hydrogen peroxide solution stands 12h, is filtered 3 times using the hydrochloric acid cleaning of the 5wt% of 250mL, filter cake is taken out, at 50 DEG C Drying for 24 hours, obtains graphene oxide in air dry oven.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first embodiment in that: oxidation described in step 1 The concentration of graphene oxide is 20mg/mL in graphene cream.It is other same as the specific embodiment one.
Specific embodiment 4: the present embodiment is different from the first embodiment in that: nanometer described in step 2 The mass ratio of titanium dioxide and nano-sulfur is 1:4.It is other same as the specific embodiment one.
Specific embodiment 5: the present embodiment is different from the first embodiment in that: oxidation described in step 1 The mass ratio of nano-sulfur described in graphene oxide and step 2 in graphene aqueous solution is 1:8.Other and specific embodiment party Formula one is identical.
Effect of the invention is verified by following tests:
Test one: by nano-sulfur and nano-titanium dioxide mixing and ball milling 7h, mixture is obtained；The nano-titanium dioxide Mass ratio with nano-sulfur is 3:7.
Test two: by nano-sulfur and nano-titanium dioxide mixing and ball milling 7h, mixture is obtained；The nano-titanium dioxide Mass ratio with nano-sulfur is 1:4.
Test three: by nano-sulfur and nano-titanium dioxide mixing and ball milling 7h, mixture is obtained；The nano-titanium dioxide Mass ratio with nano-sulfur is 1:9.
Test four: this test is that one-step method prepares the core-shell structure lithium-sulfur cell that titanium dioxide and graphene bilayer coat altogether The method of positive electrode specifically carries out according to the following steps:
One, it prepares graphene oxide cream: KOH being added into graphene oxide water solution, in the water-bath that temperature is 95 DEG C 2h is heated, is cooled to room temperature, 10min is centrifuged under conditions of revolving speed is 10000 revs/min, collects whole pastes, then will be whole Paste is put into ultrasonic disperse 3h in distilled water, obtains graphene oxide cream；Stone is aoxidized in the graphene oxide water solution The concentration of black alkene is 1mg/mL；The mass ratio of graphene oxide and KOH in the graphene oxide water solution is 1:8；Institute The concentration of graphene oxide is 20mg/mL in the graphene oxide cream stated；
Two, by graphene oxide cream mixing and ball milling 7h obtained in nano-sulfur, nano-titanium dioxide and step 1, in temperature 3h is freezed under conditions of being -18 DEG C, obtains ice block mixture, HI aqueous solution is poured into ice block mixture and makes ice cube shape Mixture is totally submerged in HI aqueous solution, is impregnated 12h under conditions of temperature is 5 DEG C, is then impregnated 12h at room temperature, according to It is secondary to use ethyl alcohol and deionized water filtering and washing, filter cake is taken, then filter cake in temperature is 60 DEG C and vacuum in a vacuum drying oven Under the conditions of dry for 24 hours to get the core-shell structure lithium sulfur battery anode material coated altogether to titanium dioxide and graphene bilayer；It is described Nano-titanium dioxide and nano-sulfur mass ratio be 1:4；Oxidation stone in graphene oxide water solution described in step 1 The mass ratio of nano-sulfur described in black alkene and step 2 is 1:8；The concentration of HI is 3mol/L in the HI aqueous solution.
Graphene oxide in graphene oxide water solution described in step 1 the preparation method is as follows:
The concentrated sulfuric acid that 120mL mass fraction is 98% is added in the three-necked bottle of 250mL, is subsequently placed in 0 DEG C of ice-water bath In, add 5g graphite and 2.5g NaNO3, then magnetic agitation 30min adds the powdered KMnO of 3g every 10min4, in total plus 5 It is secondary, the reaction was continued under ice-water bath and stirring condition 2h；
Then continue to stir 2h in 35 DEG C of constant temperature oil bath, reactant is slowly added into the distilled water of 360mL, and The speed that control is added makes reaction temperature be no more than 90 DEG C, then continues isothermal reaction 1h at 75 DEG C, obtains the suspension of brown Liquid, the suspension for taking out color are placed in draught cupboard, and 40 DEG C of distilled water 1000mL is added, and the mass concentration that 50mL is then added is 30% hydrogen peroxide solution stands 12h, is filtered 3 times using the hydrochloric acid cleaning of the 5wt% of 250mL, filter cake is taken out, at 50 DEG C Drying for 24 hours, obtains graphene oxide in air dry oven.
Test five: this test is unlike test four: the oxidation in graphene oxide water solution described in step 1 The mass ratio of nano-sulfur described in graphene and step 2 is 1:4, other identical as test four.
Test six: this test is unlike test four: the oxidation in graphene oxide water solution described in step 1 The mass ratio of nano-sulfur described in graphene and step 2 is 3:4, other identical as test four.
Test seven: one prepares graphene oxide cream: KOH being added into graphene oxide water solution, is 95 DEG C in temperature 2h is heated in water-bath, is cooled to room temperature, 10min is centrifuged under conditions of revolving speed is 10000 revs/min, collects whole pastes, then Whole pastes are put into ultrasonic disperse 3h in distilled water, obtain graphene oxide cream；In the graphene oxide water solution The concentration of graphene oxide is 1mg/mL；The mass ratio of graphene oxide and KOH in the graphene oxide water solution is 1:8；The concentration of graphene oxide is 20mg/mL in the graphene oxide cream；
Two, by graphene oxide cream mixing and ball milling 7h obtained in nano-sulfur and step 1, the condition for being -18 DEG C in temperature Lower freezing 3h, obtains ice block mixture, HI aqueous solution is poured into ice block mixture, ice block mixture is soaked completely It is less than in HI aqueous solution, impregnates 12h under conditions of temperature is 5 DEG C, then impregnate 12h at room temperature, successively with ethyl alcohol and going Ionized water filtering and washing takes filter cake, and then filter cake is dry under conditions of temperature is 60 DEG C and vacuum in a vacuum drying oven For 24 hours to get the core-shell structure lithium sulfur battery anode material for arriving graphene coated；Graphene oxide water solution described in step 1 In graphene oxide and step 2 described in nano-sulfur mass ratio be 1:2；The concentration of HI is in the HI aqueous solution 3mol/L。
Graphene oxide in graphene oxide water solution described in step 1 the preparation method is as follows:
The concentrated sulfuric acid that 120mL mass fraction is 98% is added in the three-necked bottle of 250mL, is subsequently placed in 0 DEG C of ice-water bath In, add 5g graphite and 2.5g NaNO3, then magnetic agitation 30min adds the powdered KMnO of 3g every 10min4, in total plus 5 It is secondary, the reaction was continued under ice-water bath and stirring condition 2h；
Then continue to stir 2h in 35 DEG C of constant temperature oil bath, reactant is slowly added into the distilled water of 360mL, and The speed that control is added makes reaction temperature be no more than 90 DEG C, then continues isothermal reaction 1h at 75 DEG C, obtains the suspension of brown Liquid, the suspension for taking out color are placed in draught cupboard, and 40 DEG C of distilled water 1000mL is added, and the mass concentration that 50mL is then added is 30% hydrogen peroxide solution stands 12h, is filtered 3 times using the hydrochloric acid cleaning of the 5wt% of 250mL, filter cake is taken out, at 50 DEG C Drying for 24 hours, obtains graphene oxide in air dry oven.
Test eight: using nano-sulfur as electrode material, conductive agent acetylene black, binder PVDF according to mass ratio 8:1:1 system Standby active material, using aluminium foil as collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) is electrolyte, dress It is made into button cell.
Test nine: mixture prepared by test one is as electrode material, conductive agent acetylene black, binder PVDF according to matter Amount prepares active material than 8:1:1, using aluminium foil as collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) For electrolyte, it is assembled into button cell.
Test ten: mixture prepared by test two is as electrode material, conductive agent acetylene black, binder PVDF according to matter Amount prepares active material than 8:1:1, using aluminium foil as collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) For electrolyte, it is assembled into button cell.
Test 11: mixture prepared by test three as electrode material, conductive agent acetylene black, binder PVDF according to Mass ratio 8:1:1 prepares active material, using aluminium foil as collector, LiTFSI (1mol/L), LiNO3The DOL/ of (0.1mol/L) DME is electrolyte, is assembled into button cell.
Test 12: just by titanium dioxide prepared by test four and the core-shell structure lithium-sulfur cell that graphene bilayer coats altogether Pole material prepares active material according to mass ratio 8:1:1 as electrode material, conductive agent acetylene black, binder PVDF, with aluminium foil For collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) is electrolyte, is assembled into button cell.
Test 13: just by titanium dioxide prepared by test five and the core-shell structure lithium-sulfur cell that graphene bilayer coats altogether Pole material prepares active material according to mass ratio 8:1:1 as electrode material, conductive agent acetylene black, binder PVDF, with aluminium foil For collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) is electrolyte, is assembled into button cell.
Test 14: just by titanium dioxide prepared by test six and the core-shell structure lithium-sulfur cell that graphene bilayer coats altogether Pole material prepares active material according to mass ratio 8:1:1 as electrode material, conductive agent acetylene black, binder PVDF, with aluminium foil For collector, LiTFSI (1mol/L), LiNO3The DOL/DME of (0.1mol/L) is electrolyte, is assembled into button cell.
Test 15: the core-shell structure lithium sulfur battery anode material of graphene coated prepared by test seven is as electrode material Material, conductive agent acetylene black, binder PVDF prepare active material according to mass ratio 8:1:1, using aluminium foil as collector, LiTFSI (1mol/L)、LiNO3The DOL/DME of (0.1mol/L) is electrolyte, is assembled into button cell.
Fig. 1 is XRD diagram,It is sulphur,It is titanium dioxide, curve 1 is to test an obtained mixture, and curve 2 is test two Obtained mixture, curve 3 are to test three obtained mixtures.
Fig. 2 is XRD diagram,It is sulphur,It is titanium dioxide,It is graphene oxide, curve 1 is to test four obtained titanium dioxides The core-shell structure lithium sulfur battery anode material that titanium and graphene bilayer coat altogether, curve 2 be test five obtained titanium dioxide and The core-shell structure lithium sulfur battery anode material that graphene bilayer coats altogether, curve 3 are to test six obtained titanium dioxide and graphite The core-shell structure lithium sulfur battery anode material that alkene bilayer coats altogether, curve 4 are to test the titanium dioxide and graphene pair that seven obtain The core-shell structure lithium sulfur battery anode material that layer coats altogether.From Fig. 1 and 2 as can be seen that the curve 1-3 in two figures is in 2 θ 27 °, 36 ° and 54 ° or so have apparent diffraction maximum, this and anatase TiO2Characteristic peak it is corresponding, the diffraction of composite material Equally there is the characteristic peak of S at peak, illustrates that titanium dioxide in material, sulphur exist with crystal form, in the ratio of titanium dioxide Rise, the feature peak intensity of sulphur weakened, illustrate that sulphur is wrapped by more close, in Fig. 2, the diffraction peak intensity of titanium dioxide compared with Fig. 1 is weakened, and as the covering amount of graphene rises, the characteristic peak of sulphur further weakens, and illustrates that sulphur is also wrapped by tighter It is close.
Fig. 3 is the SEM figure for testing the nano-sulfur in four steps two, and Fig. 4 is the nano-titanium dioxide tested in four steps two SEM figure, Fig. 5 be test three obtain mixture SEM figure, Fig. 6 be test two obtain mixture SEM figure, Fig. 7 is test one The SEM figure of mixture is obtained, Fig. 8 is to test the titanium dioxide that four obtain and the core-shell structure lithium sulphur electricity that graphene bilayer coats altogether The SEM of pond positive electrode schemes, and Fig. 9 is to test the titanium dioxide that five obtain and the core-shell structure lithium sulphur electricity that graphene bilayer coats altogether The SEM of pond positive electrode schemes, and Figure 10 is to test the titanium dioxide that six obtain and the core-shell structure lithium sulphur that graphene bilayer coats altogether The SEM of cell positive material schemes, and as can be seen from the figure material granule is evenly distributed, and titanium dioxide is uniformly coated on sulfur granules Surface, in the case where the mass ratio of nano-titanium dioxide and nano-sulfur is the covering amount of 1:4, no extra distribution titanium dioxide and uncoated Sulphur surface；It is 1:4 in the mass ratio of nano-titanium dioxide and nano-sulfur；In graphene oxide water solution described in step 1 Graphene oxide and step 2 described in nano-sulfur mass ratio be 1:4 graphene coat down again, material is evenly coated.
Figure 11 is cycle performance curve graph, and curve 1 is to test the button cells of the ten assembly test result under 0.1C multiplying power, Curve 2 be test nine assembly button cell under 0.1C multiplying power test result, curve 3 be test 11 assembly button cells The test result under 0.1C multiplying power, curve 4 be test eight assembly button cell under 0.1C multiplying power test result.
Figure 12 is cycle performance curve graph, and curve 1 is to test the button cell that 13 assemble to test knot under 0.1C multiplying power Fruit, curve 2 be test 15 assembly button cell under 0.1C multiplying power test result, curve 3 be test 14 assembly knobs Detain battery test result under 0.1C multiplying power, curve 4 be test 12 assembly button cell under 0.1C multiplying power test result.
Figure 13 is first charge-discharge curve graph, and curve 1 is to test the button cell that eight assemble to test knot under 0.1C multiplying power Fruit, curve 2 be test nine assembly button cell under 0.1C multiplying power test result, curve 3 be test ten assembly button electricity Pond test result under 0.1C multiplying power, curve 4 be test 11 assembly button cell under 0.1C multiplying power test result.
Figure 14 is first charge-discharge curve graph, and curve 1 is to test the button cell that 14 assemble to test under 0.1C multiplying power As a result, curve 2 be test 12 assembly button cell under 0.1C multiplying power test result, curve 3 be test 13 assembly Button cell test result under 0.1C multiplying power, curve 4 are to test the button cell that 15 assemble to test knot under 0.1C multiplying power Fruit.
From Figure 11-14 as can be seen that being 1:4 in the mass ratio of nano-titanium dioxide and nano-sulfur, graphene oxide is water-soluble The mass ratio of nano-sulfur described in graphene oxide and step 2 in liquid is that the titanium dioxide of 1:4 ratio and graphene coat altogether Core-shell structure under, possess good chemical property, charge and discharge cycles 100 times under 0.1C multiplying power, discharge capacity for the first time 969.1mAh/g, the discharge capacity 558.6mAh/g after 100 circulations, 100 times 0.1C circulation coulomb is high-efficient up to 57.6%, two The discharge and recharge reaction of the sulphur of titanium-oxide-coated effectively is steady, and the cladding of graphene improves the utilization rate of sulphur.
Figure 15 is high rate performance figure, and ■ is the button cell for testing eight assembly, ● it is the button cell for testing 11 assembly, ▲ it is the button cell for testing ten assembly, ▼ is the button cell for testing nine assembly.
Figure 16 is high rate performance figure, and ■ is the button cell for testing 13 assembly, ● it is the button electricity for testing 12 assembly Pond, ▲ it is the button cell for testing 14 assembly, ▼ is the button cell for testing 15 assembly.
The test condition of Figure 15 and 16 is as follows: preceding 5 cycle-indexes are tested under 0.1C multiplying power, in 6-10 cycle-index It tests under 0.2C multiplying power, is tested under 0.5C multiplying power in 11-15 cycle-index, in 16-20 cycle-index in 1C multiplying power Lower test is tested under 2C multiplying power in 21-25 cycle-index, is tested under 3C multiplying power in 26-30 cycle-index, in 31- 130 times cycle-index is tested under 0.1C multiplying power.
Material has good high rate performance it can be seen from Figure 15 and 16, and in 0.2C, discharge capacity is 640.8mAh/ for the first time Discharge capacity is 539.1mAh/g for the first time by g, 0.5C, and discharge capacity is 400.1mAh/g to 1C for the first time, and discharge capacity is 2C for the first time Discharge capacity is 132.1mAh/g for the first time by 248.1mAh/g, 3C.
Figure 17 is impedance diagram, and curve 1 is the button cell for testing eight assembly, and curve 2 is the button cell for testing ten assembly, Curve 3 is the button cell for testing 11 assembly, and curve 4 is the button cell for testing nine assembly.
Figure 18 is impedance diagram, and curve 1 is the button cell for testing 13 assembly, and curve 2 is the button for testing 12 assembly Battery, curve 3 are the button cells for testing 15 assembly, and curve 4 is the button cell for testing 14 assembly.
The cladding of titanium dioxide and graphene can reduce polarization it can be seen from Figure 17-18, and covering amount is bigger, and polarization is got over It is small.
Figure 19 is CV figure, and curve 1 is the button cell for testing eight assembly, and curve 2 is the button cell for testing 11 assembly, Curve 3 is the button cell for testing ten assembly, and curve 4 is the button cell for testing nine assembly.
Figure 20 is 3 figures of CV circulation for testing the button cell of 13 assembly.
By Figure 19-20 it can be seen that the cladding of titanium dioxide can improve reactivity, graphene coated improves following for reaction Ring performance.
EDS test is carried out to the mixture that test two obtains, Figure 21 is oxygen element, and Figure 22 is S element, and Figure 23 is titanium member Element.
The core-shell structure lithium sulfur battery anode material that the titanium dioxide and graphene bilayer obtain to test six coats altogether into Row EDS test, Figure 24 is carbon, and Figure 25 is oxygen element, and Figure 26 is element sulphur, and Figure 27 is titanium elements.
By Figure 21-27 it can be seen that titanium dioxide, graphene uniform are coated on sulphur surface, Elemental redistribution is uniform.

Claims (1)

1. the method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether, It is characterized in that the method that one-step method prepares the core-shell structure lithium sulfur battery anode material that titanium dioxide and graphene bilayer coat altogether It carries out according to the following steps:
One, it prepares graphene oxide cream: KOH being added into graphene oxide water solution, heated in the water-bath that temperature is 95 DEG C 2h is cooled to room temperature, and is centrifuged 10min under conditions of revolving speed is 10000 revs/min, collects whole pastes, then by whole pastes Object is put into ultrasonic disperse 3h in distilled water, obtains graphene oxide cream；Graphene oxide in the graphene oxide water solution Concentration be 1mg/mL；The mass ratio of graphene oxide and KOH in the graphene oxide water solution is 1:8；Described The concentration of graphene oxide is 20mg/mL in graphene oxide cream；
Two, by graphene oxide cream mixing and ball milling 7h obtained in nano-sulfur, nano-titanium dioxide and step 1, be in temperature- 3h is freezed under conditions of 18 DEG C, obtains ice block mixture, HI aqueous solution is poured into ice block mixture, ice cube shape is mixed It closes object to be totally submerged in HI aqueous solution, impregnates 12h under conditions of temperature is 5 DEG C, then impregnate 12h at room temperature, successively With ethyl alcohol and deionized water filtering and washing, take filter cake, then in a vacuum drying oven filter cake in the item that temperature is 60 DEG C and vacuum It dries under part for 24 hours to get the core-shell structure lithium sulfur battery anode material coated altogether to titanium dioxide and graphene bilayer；Described The mass ratio of nano-titanium dioxide and nano-sulfur is 1:4；Graphite oxide in graphene oxide water solution described in step 1 The mass ratio of nano-sulfur described in alkene and step 2 is 1:4；The concentration of HI is 3mol/L in the HI aqueous solution；
The core-shell structure lithium sulfur battery anode material that the titanium dioxide and graphene bilayer coats altogether is filled as electrode material It is made into button cell；Button cell charge and discharge cycles 100 times under 0.1C multiplying power, for the first time discharge capacity 969.1mAh/g, the discharge capacity 558.6mAh/g after 100 circulations, 100 times 0.1C circulation coulomb is high-efficient up to 57.6%；
In 0.2C, discharge capacity is 640.8mAh/g to the button cell for the first time, and discharge capacity is 539.1mAh/ to 0.5C for the first time Discharge capacity is 400.1mAh/g for the first time by g, 1C, and discharge capacity is 248.1mAh/g to 2C for the first time, and discharge capacity is 3C for the first time 132.1mAh/g。
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