CN106941161B - A kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material - Google Patents
A kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material, comprises the following steps: step (1): sulphur powder being added to stirring and dissolving in carbon disulfide and forms uniform solution；Step (2): passing through high energy ball mill ball milling for high-purity nickel powder, be added in above-mentioned solution after ball milling, and stirring forms uniform suspension, and mechanical stirring forms the spheric granules of sulphur cladding after spray drying；Step (3): spheric granules is added to and is added in ferric chloride solution, is stirred to react, is washed, filters.Step (4): filtered sediment is added in chloride containing manganese and liquor potassic permanganate, stirs into uniform suspension, heating stirring reaction, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding.Hollow structure is designed as volume expansion reserved space of the sulfur materials in charge and discharge process in the composite material, can effectively improve chemical property.
Description
Technical field
The present invention relates to nano material synthesis, in particular to a kind of preparation method of lithium sulfur battery anode material.
Background technique
Lithium-sulfur cell is using lithium metal as cathode, and elemental sulfur is the battery system of anode.There are two put the tool of lithium-sulfur cell
Level platform (about 2.4 V and 2.1 V), but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high
(2600 Wh/kg), specific capacity height (1675 mAh/g), it is at low cost the advantages that, it is considered to be very promising a new generation's electricity
Pond.But there is the problems such as active material utilization is low, cycle life is low and safety is poor at present, this seriously restricts lithium
The development of sulphur battery.The main reason for causing the above problem has the following aspects: (1) elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity low (5 × 10-30S·cm-1), since the sulphur of not no ionic state exists, thus it is tired as positive electrode activation
It is difficult；(2) the poly- more lithium sulfide Li of state of height generated in electrode process2Sn(8 n >=4 >) are soluble in electrolyte, positive and negative
Concentration difference is formed between pole, cathode is moved under the action of concentration gradient, and the high poly- more lithium sulfides of state are reduced into low by lithium metal
The poly- more lithium sulfides of state.With the progress reacted above, the oligomeric more lithium sulfides of state are assembled in cathode, are finally formed between electrodes
Concentration difference, and move to anode and be oxidized to the high poly- more lithium sulfides of state.This phenomenon is referred to as shuttle effect, reduces sulphur activity
The utilization rate of substance.Insoluble Li simultaneously2S and Li2S2It is deposited on cathode of lithium surface, is further degrading lithium-sulfur cell
Performance；(3) final product Li is reacted2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state
Migration velocity is slow in lithium, keeps electrochemical reaction kinetic rate slack-off；(4) sulphur and final product Li2The density of S is different, works as sulphur
It is lithiated rear volume expansion about 79%, easily leads to Li2The dusting of S causes the safety problem of lithium-sulfur cell.Above-mentioned insufficient restriction
The development of lithium-sulfur cell, this is also the Important Problems that the research of current lithium-sulfur cell needs to solve.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material,
The composite material is made of the graphene network of the sulphur of hollow structure, the manganese bioxide material of sulphur external sheath and N doping, is led
Electrically good to provide conductive network in outer layer graphene, the sulfenyl material of hollow structure provides the space of expansion, sulphur outer layer packet
The manganese dioxide covered can adsorb the dissolution of discharging product polysulfide, improve the chemical property of material.
The preparation method process that the present invention provides a kind of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material is as follows:
(1) sulphur powder is added to stirring and dissolving in carbon disulfide and forms uniform solution；
(2) high-purity nickel powder is passed through into high energy ball mill ball milling, is added in above-mentioned solution after ball milling, stirring forms uniform
Suspension, mechanical stirring, after spray drying formed sulphur cladding spheric granules；
(3) spheric granules is added to and is added in ferric chloride solution, be stirred to react, wash, filter.
(4) filtered sediment is added in chloride containing manganese and liquor potassic permanganate, stirs into uniform suspension, adds
Thermal agitation reaction, centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by nitrogen-doped graphene be added to the water ultrasonic disperse formed unit for uniform suspension, then by manganese dioxide cladding
Sulfur granules are added, and stir, and filter, obtain composite material after washing.
The carbon disulfide solution concentration of sulphur is 1-5g/mL in step (1);
Nickel powder in step (2): the mass ratio of sulphur powder is 0.05-0.2:1, and Ball-milling Time is 0.5-2 hours, when mechanical stirring
Between be 0.5-1 hours;
The concentration of ferric chloride solution is 1-2mol/L in step (3), and being stirred to react the time is 1-5 hours；
Manganese chloride in step (4): potassium permanganate: the mass ratio of sulphur is 1-2:1-1.5:10, and the temperature for heating reaction is 50-
70 DEG C, the reaction time is 5-30 minutes;
In step (5) concentration of nitrogen-doped graphene suspension be 0.5-2g/L, nitrogen-doped graphene nitrogen-doped graphene:
The mass ratio of sulphur is 1-2:10, and the reaction time being stirred to react is 5-30 minutes.
The invention has the following beneficial effects: the conductivity that (1) nitrogen-doped graphene has superelevation, are prepared by this method
Nitrogen-doped graphene/manganese dioxide out/hollow sulphur composite material can effectively improve the electronics of lithium sulfur battery anode material
Conductivity and ionic conductivity, while the nitrogen on graphene can carry out chemisorption to polysulfide, reduce sulphur when charge and discharge
Loss；(2) cladding of manganese dioxide can carry out physical protection to sulfenyl material in the composite material, while manganese dioxide also can be right
Polysulfide carries out chemisorption, reduces shuttle effect；(3) hollow structure is designed as sulfur materials in charge and discharge in the composite material
Volume expansion reserved space in electric process, can effectively improve chemical property.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is the charge-discharge performance figure of composite material of the present invention.
Specific embodiment
With reference to the accompanying drawing, preferably embodiment of the invention is described in further detail:
Embodiment 1
(1) 100g sulphur powder is added to the solution that stirring and dissolving in carbon disulfide forms 1g/mL；
(2) 5g high-purity nickel powder is passed through into high energy ball mill, ball milling 0.5 hour, is added in above-mentioned solution, stirs after ball milling
It mixes to form uniform suspension, mechanical stirring 0.5 hour, forms the spheric granules of sulphur cladding after spray drying；
(3) spheric granules is added to and is added in 1mol/L ferric chloride solution, is stirred to react 5 hours, washing, filtering.
(4) filtered sediment is added in manganese chloride containing 10g and 10g liquor potassic permanganate, is stirred into uniform outstanding
Supernatant liquid is heated to 50 DEG C and is stirred to react 30 minutes, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by 10g nitrogen-doped graphene be added to the water ultrasonic disperse formed uniform concentration be 0.5g/L suspension, then
The sulfur granules of manganese dioxide cladding are added, are stirred, filters, obtains composite material after washing.
Embodiment 2
(1) 100g sulphur powder is added to the solution that stirring and dissolving in carbon disulfide forms 5g/mL；
(2) 20g high-purity nickel powder is passed through into high energy ball mill, ball milling 2 hours, is added in above-mentioned solution, stirs after ball milling
It mixes to form uniform suspension, mechanical stirring 1 hour, forms the spheric granules of sulphur cladding after spray drying；
(3) spheric granules is added to and is added in 2mol/L ferric chloride solution, is stirred to react 1 hour, washing, filtering.
(4) filtered sediment is added in manganese chloride containing 20g and 15g liquor potassic permanganate, is stirred into uniform outstanding
Supernatant liquid is heated to 70 DEG C and is stirred to react 5 minutes, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by 20g nitrogen-doped graphene be added to the water ultrasonic disperse formed uniform concentration be 2g/L suspension, then will
The sulfur granules of manganese dioxide cladding are added, and stir, and filter, obtain composite material after washing.
Embodiment 3
(1) 100g sulphur powder is added to the solution that stirring and dissolving in carbon disulfide forms 2g/mL；
(2) 10g high-purity nickel powder is passed through into high energy ball mill, ball milling 1 hour, is added in above-mentioned solution, stirs after ball milling
It mixes to form uniform suspension, mechanical stirring 0.6 hour, forms the spheric granules of sulphur cladding after spray drying；
(3) spheric granules is added to and is added in 1.5mol/L ferric chloride solution, is stirred to react 3 hours, washing, filtering.
(4) filtered sediment is added in manganese chloride containing 15g and 12g liquor potassic permanganate, is stirred into uniform outstanding
Supernatant liquid is heated to 60 DEG C and is stirred to react 15 minutes, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by 15g nitrogen-doped graphene be added to the water ultrasonic disperse formed uniform concentration be 1g/L suspension, then will
The sulfur granules of manganese dioxide cladding are added, and stir, and filter, obtain composite material after washing.
Embodiment 4
(1) 100g sulphur powder is added to the solution that stirring and dissolving in carbon disulfide forms 3g/mL；
(2) 15g high-purity nickel powder is passed through into high energy ball mill, ball milling 1.5 hours, is added to after ball milling in above-mentioned solution,
Stirring forms uniform suspension, and mechanical stirring 0.7 hour, the spheric granules of sulphur cladding is formed after spray drying；
(3) spheric granules is added to and is added in 1.2mol/L ferric chloride solution, is stirred to react 4 hours, washing, filtering.
(4) filtered sediment is added in manganese chloride containing 12g and 11g liquor potassic permanganate, is stirred into uniform outstanding
Supernatant liquid is heated to 65 DEG C and is stirred to react 10 minutes, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by 12g nitrogen-doped graphene be added to the water ultrasonic disperse formed uniform concentration be 1.5g/L suspension, then
The sulfur granules of manganese dioxide cladding are added, are stirred, filters, obtains composite material after washing.
Embodiment 5
(1) 100g sulphur powder is added to the solution that stirring and dissolving in carbon disulfide forms 4g/mL；
(2) 18g high-purity nickel powder is passed through into high energy ball mill, ball milling 1.6 hours, is added to after ball milling in above-mentioned solution,
Stirring forms uniform suspension, and mechanical stirring 0.8 hour, the spheric granules of sulphur cladding is formed after spray drying；
(3) spheric granules is added to and is added in 1.8mol/L ferric chloride solution, is stirred to react 2 hours, washing, filtering.
(4) filtered sediment is added in manganese chloride containing 18g and 14g liquor potassic permanganate, is stirred into uniform outstanding
Supernatant liquid is heated to 55 DEG C and is stirred to react 25 minutes, and centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
(5) by 18g nitrogen-doped graphene be added to the water ultrasonic disperse formed uniform concentration be 1.8g/L suspension, then
The sulfur granules of manganese dioxide cladding are added, are stirred, filters, obtains composite material after washing.
The preparation and performance test of electrode；By composite material, acetylene black and PVDF 80:10:10 in mass ratio in NMP
Mixing, being coated in is electrode film on aluminium foil, and metal lithium sheet is to electrode, and CELGARD 2400 is diaphragm, the LiTFSI/ of 1mol/L
DOL-DME (volume ratio 1:1) is electrolyte, and the LiNO3 of 1mol/L is additive, electric full of button is assembled into Ar glove box
Pond carries out constant current charge-discharge test using Land battery test system.Charging/discharging voltage range is 1-3V, and current density is
0.5C, performance are as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| First discharge specific capacity (mAh/g) | 1030 | 1050 | 1070 | 1040 | 1040 |
Fig. 2 is the charge-discharge performance figure that 1 composite material of the embodiment of the present invention is prepared into lithium-sulfur cell.As can be seen from the figure
Efficiency for charge-discharge can achieve 99% or more, and first charge-discharge capacity is 1030 mAh/g, efficiency for charge-discharge 86.5%, and second
Charge/discharge capacity is 1210 mAh/g, and after 200 charge and discharge cycles, capacity still possesses 89% relative to second of discharge capacity
More than, illustrate that the structure of the composite material can effectively inhibit shuttle effect, improves the service life of sulphur battery.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, In
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (6)
1. a kind of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material preparation method, which is characterized in that including as follows
Several steps:
Step (1): sulphur powder is added to stirring and dissolving in carbon disulfide and forms uniform solution；
Step (2): high-purity nickel powder is passed through into high energy ball mill ball milling, is added in above-mentioned solution after ball milling, stirring forms equal
One suspension, mechanical stirring form the spheric granules of sulphur cladding after spray drying；
Step (3): spheric granules being added in ferric chloride solution, is stirred to react, and is washed, is filtered；
Step (4): filtered sediment is added in chloride containing manganese and liquor potassic permanganate, stirs into uniform suspension,
Heating stirring reaction, centrifugation, washing obtain the sulfur granules of manganese dioxide cladding；
Step (5): by nitrogen-doped graphene be added to the water ultrasonic disperse formed unit for uniform suspension, then by manganese dioxide cladding
Sulfur granules are added, and stir, and filter, obtain composite material after washing.
2. preparation method as described in claim 1, which is characterized in that the carbon disulfide solution concentration of sulphur in the step (1)
For 1-5g/mL.
3. preparation method as described in claim 1, which is characterized in that nickel powder in the step (2): the mass ratio of sulphur powder is
0.05-0.2:1, Ball-milling Time are 0.5-2 hours, and the mechanical stirring time is 0.5-1 hours.
4. preparation method as described in claim 1, which is characterized in that the concentration of ferric chloride solution is 1- in the step (3)
2mol/L, being stirred to react the time is 1-5 hours.
5. preparation method as described in claim 1, which is characterized in that manganese chloride in the step (4): potassium permanganate: sulphur
Mass ratio is 1-2:1-1.5:10, and the temperature for heating reaction is 50-70 DEG C, and the reaction time is 5-30 minutes.
6. preparation method as described in claim 1, which is characterized in that nitrogen-doped graphene suspension in the step (5)
Concentration is 0.5-2g/L, and nitrogen-doped graphene nitrogen-doped graphene: the mass ratio of sulphur is 1-2:10, the reaction time being stirred to react
It is 5-30 minutes.
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| CN109841805A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The hollow carbon sulphur anode composite material of sheet manganese dioxide cladding and preparation and application |
| CN109148861A (en) * | 2018-08-30 | 2019-01-04 | 广东工业大学 | Sulphur/iron oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell |
| CN109119616A (en) * | 2018-08-30 | 2019-01-01 | 广东工业大学 | Sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell |
| CN111261873A (en) * | 2020-02-12 | 2020-06-09 | 西京学院 | N-MnO2Preparation and application of/S composite material |
| CN111668469A (en) * | 2020-05-21 | 2020-09-15 | 合肥国轩高科动力能源有限公司 | Positive electrode composite material, preparation method thereof and lithium-sulfur battery |
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| CN105280949A (en) * | 2015-11-13 | 2016-01-27 | 北京理工大学 | Lithium sulfur battery using manganese dioxide/graphene as cathode barrier layer |
| CN105609707B (en) * | 2016-02-21 | 2019-03-05 | 钟玲珑 | A kind of preparation method of manganese dioxide hollow sphere lithium sulfur battery anode material |
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