CN106972161B - A kind of preparation method of nitrogen-doped graphene/copper sulfide/hollow sulphur composite material - Google Patents
A kind of preparation method of nitrogen-doped graphene/copper sulfide/hollow sulphur composite material Download PDFInfo
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Abstract
A kind of preparation method of nitrogen-doped graphene/copper sulfide/hollow sulphur composite material, comprise the following steps: sulphur powder is added to stirring and dissolving in carbon disulfide and forms uniform solution by step (1)；High-purity nickel powder is passed through high energy ball mill ball milling by step (2), is 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；Spheric granules is added to and is added in ferric chloride solution by step (3), is stirred to react, washes, filters；Filtered sediment is added in the solution of containing copper chloride, thioacetamide and surfactant by step (4), stirs into uniform suspension, heating stirring reaction, and centrifugation, washing obtain the sulfur granules of vulcanization copper clad.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/copper sulfide/hollow sulphur composite materials, should
Composite material is made of the graphene network of the sulphur of hollow structure, the copper sulphide material of sulphur external sheath and N doping, electric conductivity
Good to provide conductive network in outer layer graphene, the sulfenyl material of hollow structure provides the space of expansion, sulphur external sheath
Copper sulfide 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/copper sulfide/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 the solution of containing copper chloride, thioacetamide and surfactant, is stirred
At uniform suspension, heating stirring reaction, centrifugation, washing obtain the sulfur granules of vulcanization copper clad；
(5) the nitrogen-doped graphene ultrasonic disperse that is added to the water is formed into unit for uniform suspension, then the sulphur that will vulcanize copper clad
Particle is added, and stirs, and filters, obtains 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；
Copper chloride in step (4): thioacetamide: surfactant: the mass ratio of sulphur is 1-2:1-1.5:0.1-0.2:
10, heat the temperature of reaction are as follows: 60-90 DEG C, the reaction time is 5-30 minutes, and surfactant can be dodecyl benzene sulfonic acid
One or more of sodium, dioctyl succinate disulfonate acid, sodium stearyl sulfate;
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
The electronics that nitrogen-doped graphene/copper sulfide out/hollow sulphur composite material can effectively improve lithium sulfur battery anode material is led
Electric rate and ionic conductivity, while the nitrogen on graphene can carry out chemisorption to polysulfide, reduce sulphur damage when charge and discharge
It loses；(2) cladding of copper sulfide can carry out physical protection to sulfenyl material in the composite material, while copper sulfide also can be to more vulcanizations
Object carries out chemisorption, reduces shuttle effect；(3) hollow structure is designed as sulfur materials in charge and discharge process in the composite material
In volume expansion reserved space, chemical property can have been effectively improved.
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 to copper chloride containing 10g, 10g thioacetamide and 1g dodecyl benzene sulfonic acid
In the solution of sodium, uniform suspension is stirred into, 60 DEG C is heated to and is stirred to react 30 minutes, centrifugation, washing obtain vulcanization copper clad
Sulfur granules；
(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 for vulcanizing copper clad 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 to copper chloride containing 20g, 15g thioacetamide and 2g dioctyl succinate acid sulphur
In the solution of sour sodium, uniform suspension is stirred into, 90 DEG C is heated to and is stirred to react 5 minutes, centrifugation, washing obtain vulcanization copper clad
Sulfur granules；
(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 for vulcanizing copper clad 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 to copper chloride containing 15g, 12g thioacetamide and 1.5g octadecyl sulfuric acid
In the solution of sodium, uniform suspension is stirred into, 70 DEG C is heated to and is stirred to react 15 minutes, centrifugation, washing obtain vulcanization copper clad
Sulfur granules；
(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 for vulcanizing copper clad 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 to copper chloride containing 12g, 11g thioacetamide and 1.2g detergent alkylate sulphur
In acid sodium solution, uniform suspension is stirred into, 80 DEG C is heated to and is stirred to react 10 minutes, centrifugation, washing obtain vulcanization copper clad
Sulfur granules；
(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 for vulcanizing copper clad 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 to copper chloride containing 18g, 14g thioacetamide and 1.8g dioctyl succinate acid
In the solution of sodium sulfonate, uniform suspension is stirred into, 75 DEG C is heated to and is stirred to react 25 minutes, centrifugation, washing obtain copper sulfide
The sulfur granules of 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 for vulcanizing copper clad 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) | 1020 | 1010 | 970 | 980 | 1010 |
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 1020 mAh/g, efficiency for charge-discharge 84.3%, and second
Charge/discharge capacity is 1150 mAh/g, and after 200 charge and discharge cycles, capacity still possesses 85% 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/copper sulfide/hollow sulphur composite material preparation method, which is characterized in that including following several
A step:
Sulphur powder is added to stirring and dissolving in carbon disulfide and forms uniform solution by step (1)；
High-purity nickel powder is passed through high energy ball mill ball milling by step (2), is added in above-mentioned solution after ball milling, and stirring forms uniform
Suspension, mechanical stirring, after spray drying formed sulphur cladding spheric granules；
Spheric granules is added in ferric chloride solution by step (3), is stirred to react, and is washed, is filtered；
Filtered sediment is added in the solution of containing copper chloride, thioacetamide and surfactant by step (4), stirring
At uniform suspension, heating stirring reaction, centrifugation, washing obtain the sulfur granules of vulcanization copper clad；
The nitrogen-doped graphene ultrasonic disperse that is added to the water is formed unit for uniform suspension, then the sulphur that will vulcanize copper clad by step (5)
Particle is added, and stirs, and filters, obtains composite material after washing.
2. preparation method as described in claim 1, which is characterized in that the carbon disulfide solution concentration of sulphur is 1- in step (1)
5g/mL。
3. preparation method as described in claim 1, which is characterized in that nickel powder in 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 1-2mol/ in step (3)
L, being stirred to react the time is 1-5 hours.
5. preparation method as described in claim 1, which is characterized in that copper chloride in step (4): thioacetamide: surface is living
Property agent: the mass ratio of sulphur be 1-2:1-1.5:0.1-0.2:10, heat the temperature of reaction are as follows: 60-90 DEG C, reaction time 5-30
Minute, surfactant can be one in neopelex, dioctyl succinate disulfonate acid, sodium stearyl sulfate
Kind is a variety of.
6. preparation method as described in claim 1, which is characterized in that the concentration of nitrogen-doped graphene suspension in step (5)
For 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.
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| CN108899493B (en) * | 2018-06-22 | 2020-07-31 | 中南大学 | Nano sulfur/metal sulfide composite material, preparation method thereof and application of nano sulfur/metal sulfide composite material as electrode material |
| CN108831748B (en) * | 2018-06-27 | 2020-07-17 | 安徽大学 | Nitrogen-doped graphene modified heptacopper tetrasulfide/copper sulfide composite material and preparation method and application thereof |
| CN109473606B (en) * | 2018-10-30 | 2021-12-28 | 肇庆市华师大光电产业研究院 | Self-supporting functional interlayer for lithium-sulfur battery and preparation method thereof |
| CN109847784B (en) * | 2019-02-21 | 2021-11-09 | 青岛科技大学 | Cu1.81S/Ni1.03S/NG/NF composite material and preparation method thereof |
| CN112877117B (en) * | 2021-01-21 | 2022-09-09 | 徐州振峰新材料科技有限公司 | Efficient low-price nano-copper/sulfur-doped graphene modified lubricating oil |
| CN114368775A (en) * | 2021-12-20 | 2022-04-19 | 江苏大学 | Room temperature rapid preparation method of transition metal sulfide |
| CN114914442B (en) * | 2022-05-11 | 2024-05-24 | 重庆化工职业学院 | Application of copper sulfide material in battery anode material, electrode and battery |
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