CN109786690A - A kind of lithium sulfur battery anode material and preparation method thereof - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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- CN109786690A CN109786690A CN201811583002.2A CN201811583002A CN109786690A CN 109786690 A CN109786690 A CN 109786690A CN 201811583002 A CN201811583002 A CN 201811583002A CN 109786690 A CN109786690 A CN 109786690A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium-sulfur cell, it is specifically related to a kind of lithium sulfur battery anode material and preparation method thereof.The material is the composite material that graphene@covalent organic frame material and pure phase nanometer sulphur powder are formed.Graphene and covalent organic frame material are combined well by the method for spray drying in the present invention, the two synergistic effect can preferably promote the chemical property of lithium-sulfur cell.
Description
Technical field
The invention belongs to the technical field of lithium-sulfur cell, it is specifically related to a kind of lithium sulfur battery anode material and its preparation side
Method.
Background technique
With the development of portable electronic device and electric car, the energy density of commercial li-ion battery has been difficult to meet
Growing electric energy storage requirements.The secondary cell of long continuation of the journey becomes the research focus of researcher, in the electricity of a variety of candidates
In chemical energy storage system, it is significant that the lithium-sulfur cell advantage reacted is electrochemically transformed with the polyelectron of lithium based on sulphur: high theory specific volume
Measure 1675 mAhg−1；2567 Whkg of high theory specific energy−1(much higher than the 387 of commercial cobalt acid lithium graphite lithium ion battery
Wh·kg−1)；Low-work voltage (2.2V) keeps its comparatively safe；Elemental sulfur rich reserves, at low cost and environmental-friendly simultaneously, make
Lithium-sulfur cell has huge commercial applications prospect, but there are a series of problems to restrict its commercialization process for lithium-sulfur cell, such as
Elemental sulfur and its low conductivity for discharging final product lithium sulfide limit the utilization rate of active material and the high rate performance of battery；It fills
The more lithium sulfides of the intermediate product generated in discharge process are dissolvable in water electrolyte, and shuttle between positive and negative anodes, make battery
Capacity is decayed rapidly；Up to 80% volume expansion can occur during discharge for sulphur, will cause anode and dusting occurs, lead to electricity
Pond failure.
Summary of the invention
It is an object of the invention to a kind of lithium sulfur battery anode material and its preparation are provided for above-mentioned defect
Method, the material are the composite material that graphene@covalent organic frame material and pure phase nanometer sulphur powder are formed.It prepares first covalently
Organic framework materials, then by being used as sulfur-donor material after spray drying composite graphite alkene, mixed followed by ball milling and hot fusion method
The lithium sulfur battery anode material is prepared in sulphur.In the present invention by spray drying method by graphene and covalently it is organic
Frame material combines well, and the two synergistic effect can preferably promote the chemical property of lithium-sulfur cell.
The technical solution of the present invention is as follows: a kind of lithium sulfur battery anode material, which is the covalent organic frame material of graphene@
The composite material that material is formed with pure phase nanometer sulphur powder.
The mass ratio of the graphene@covalent organic frame material and pure phase nanometer sulphur powder is 1:2~5.
The main raw material for preparing of the covalent organic frame material is Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde.
Isosorbide-5-Nitrae-the phenylenediamine and 1, the mass ratio of 3,5- mesitylene formaldehyde are 1:1.
Graphene and the mass ratio of covalent organic frame material are 0.025 in the graphene covalent organic frame material
~0.2:1.
A kind of preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) prepare covalent organic frame material: by Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde are placed in reaction tube, are added 1,
4- dioxane mixes the two dissolution, and acetic acid is then added dropwise, then vacuumizes under the conditions of liquid nitrogen frozen, catches up with most bubble, seals
Pipe, is warmed to room temperature naturally, is then transferred to reaction in constant temperature oven, is centrifuged after the reaction was completed, washs, after Soxhlet extraction, very
Empty dry faint yellow solid, that is, covalent organic frame material；
(2) it prepares graphene@covalent organic frame material: taking the covalent organic frame material being prepared in step (1), be placed in
It is ultrasonic in graphene aqueous solution, graphene@covalent organic frame material is obtained by spray drying later；
(3) graphene@covalent organic frame material/sulphur is prepared: by the covalent organic frame material of graphene@obtained in step (2)
Material and pure phase nanometer sulphur powder, which are put into ball grinder, carries out mixed processing, and the mixture obtained after ball milling is put under nitrogen protection
It is heat-treated in tube furnace, obtains the lithium sulfur battery anode material.
Isosorbide-5-Nitrae-phenylenediamine dosage is 0.5~1 g in the step (1), and 1,3,5- mesitylene formaldehyde dosage is 0.5~1 g,
Isosorbide-5-Nitrae-dioxane dosage is 5~10mL, and the acetic acid dosage that mass fraction is 10~40% is 1~5mL；It is taken in the step (2)
1~2g of covalent organic frame material is placed in the graphene aqueous solution that 50~100mL concentration is 1~2mg/mL；The step
(3) mass ratio of graphene@covalent organic frame material and pure phase nanometer sulphur powder is 1:2~5 in.
Constant temperature oven temperature is 100~150 DEG C in the step (1), is reacted 24~48 hours, stops heating, to system
After being cooled to room temperature, reaction tube is opened, is centrifuged, washing；It is dried in vacuo 12~24 hours under the conditions of 60 DEG C.
Ultrasound 30~60 minutes in the step (2)；By the homogeneous solution obtained after ultrasound in 150~200 DEG C of items
It is spray-dried under part, charging rate is 5~10mL/min.
Mixed processing 3 is carried out under the conditions of revolving speed is 500~800r/min using planetary ball mill in the step (3)
~5h；Heat treatment 8~for 24 hours is carried out at 100~200 DEG C.
The invention has the benefit that the present invention provides a kind of lithium sulfur battery anode material of height ratio capacity and its preparations
Method, the material are the composite material that graphene@covalent organic frame material and pure phase nanometer sulphur powder are formed.It prepares first covalently
Organic framework materials, then by being used as sulfur-donor material after spray drying composite graphite alkene, mixed followed by ball milling and hot fusion method
The lithium sulfur battery anode material is prepared in sulphur.
Carrier of the covalent organic frame material as lithium-sulfur cell active material, covalent organic frame material are introduced in the present invention
Material is that a kind of structure is relatively stable, novel crystalline form porous material by organic monomer Covalent bonding together, it has big π-π total
Yoke system and open regular duct, are conducive to electronics and transmit in the material, be the conductive material of function admirable, when applied to lithium
When sulphur battery, open regular duct can play good load effect to sulphur, and its excellent electric conductivity is well suited for making
For electrode material.
Graphene it is conductive it is excellent, chemical stability is high, large specific surface area, mechanical performance are strong and unique two dimension is porous
The brilliance feature such as network geometry structure can be improved the electro-chemical activity of sulphur simple substance, shorten using the modified lithium-sulfur cell of graphene
Electronics and ion transmission path limit the dissolution of polysulfide, and then improve lithium-sulfur cell overall performance.
Graphene and covalent organic frame material are combined by the method for spray drying well in the present invention, sprayed
The covalent organic frame surface that is wrapped in of graphene uniform can be formed nucleocapsid clad structure by mist drying, avoid graphene
Itself accumulation, realizes more excellent nucleocapsid covered effect, and the two synergistic effect can be promoted preferably applied to lithium-sulfur cell
The chemical property of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is that positive electrode obtained by embodiment 1 is followed applied to specific discharge capacity of lithium-sulfur cell under the conditions of 0.2C
Ring figure.
Fig. 2 is the high rate performance figure that positive electrode obtained by embodiment 1 is applied to lithium-sulfur cell.
Specific embodiment
Below by embodiment, the present invention is described in detail.
Embodiment 1
The lithium sulfur battery anode material is the composite wood that graphene@covalent organic frame material and pure phase nanometer sulphur powder are formed
Material.
The mass ratio of the graphene@covalent organic frame material and pure phase nanometer sulphur powder is 1:3.
The main raw material for preparing of the covalent organic frame material is Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde.
Isosorbide-5-Nitrae-the phenylenediamine and 1, the mass ratio of 3,5- mesitylene formaldehyde are 1:1.
Graphene and the mass ratio of covalent organic frame material are 0.08 in the graphene covalent organic frame material:
1。
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) it prepares covalent organic frame material: 0.8g Isosorbide-5-Nitrae-phenylenediamine and 0.8 g, 1,3,5- mesitylene formaldehyde is placed in reaction
Guan Zhong, 8mL Isosorbide-5-Nitrae-dioxane, which is added, mixes the two dissolution, and the acetic acid 3mL that mass fraction is 30% is then slowly added dropwise, with
The instillation of acetic acid generate yellow solid immediately, reaction tube is accessed into vacuum line, is vacuumized under the conditions of liquid nitrogen frozen, most gas is caught up with
Bubble, tube sealing are warmed to room temperature naturally, are then transferred to reaction 36 hours in 130 DEG C of constant temperature ovens, are stopped heating, cooling to system
To room temperature, reaction tube is opened, is centrifuged, washing is dried in vacuo 18 hours in 60 DEG C after Soxhlet extraction, obtains faint yellow solid
That is covalent organic frame material；
(2) it prepares graphene@covalent organic frame material: taking the covalent organic frame material 1.5g being prepared in step (1),
It is placed in the graphene aqueous solution that 80mL concentration is 1.5mg/mL ultrasound 40 minutes, it is uniform molten by what is obtained after ultrasound
Liquid is spray-dried under the conditions of 180 DEG C using spray dryer, charging rate 8mL/min；Obtaining graphene@covalently has
Machine frame frame material；
(3) graphene@covalent organic frame material/sulphur is prepared: by the covalent organic frame material of graphene@obtained in step (2)
Material and pure phase nanometer sulphur powder be put into ball grinder according to mass ratio 1:3, using planetary ball mill revolving speed be 600r/min item
The mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated at 180 DEG C by mixed processing 4h under part
12h obtains the lithium sulfur battery anode material.
As seen from Figure 1, under 0.2C current density, lithium-sulfur cell specific discharge capacity in first time circulation is up to 1562
MAh/g, with the continuous progress of circulation, battery specific capacity constantly declines, and still has 1342 mAh/g after 100 circle of circulation, reacts
The positive electrode has brilliant electrochemistry cycle performance out.
From Figure 2 it can be seen that even if preparation-obtained positive electrode is applied to lithium-sulfur cell still under the high current density of 2C
The capacity of 1015 mAh/g is so shown, and when current density is down to 0.2C again, specific discharge capacity restores again to 1482
MAh/g, this shows that the positive electrode has excellent high rate performance.
Embodiment 2
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) it prepares covalent organic frame material: 1g Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde of 1g is placed in reaction tube,
10mL Isosorbide-5-Nitrae-dioxane, which is added, mixes the two dissolution, the acetic acid 5mL that mass fraction is 40% is then slowly added dropwise, with vinegar
The instillation of acid generates yellow solid immediately, and reaction tube is accessed vacuum line, is vacuumized under the conditions of liquid nitrogen frozen, most bubble is caught up with,
Tube sealing is warmed to room temperature naturally, is then transferred to reaction 48 hours in 150 DEG C of constant temperature ovens, is stopped heating, be cooled to room to system
Wen Hou opens reaction tube, is centrifuged, washing, after Soxhlet extraction, is dried in vacuo 24 hours in 60 DEG C, obtains faint yellow solid i.e. altogether
Valence organic framework materials；
(2) it prepares graphene@covalent organic frame material: taking the covalent organic frame material 2g being prepared in step (1),
It is placed in the graphene aqueous solution that 100mL concentration is 2mg/mL ultrasound 60 minutes, it is uniform molten by what is obtained after ultrasound
Liquid is spray-dried under the conditions of 150 DEG C, charging rate 5mL/min；Obtain answering for graphene@covalent organic frame material
Close microballoon；
(3) graphene@covalent organic frame material/sulphur is prepared: by the covalent organic frame material of graphene@obtained in step (2)
Material and pure phase nanometer sulphur powder be put into ball grinder according to mass ratio 1:5, using planetary ball mill revolving speed be 800r/min item
The mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated at 200 DEG C by mixed processing 5h under part
For 24 hours, the lithium sulfur battery anode material is obtained.
Embodiment 3
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) it prepares covalent organic frame material: 0.5g Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde of 0.5g is placed in reaction
Guan Zhong, 5mL Isosorbide-5-Nitrae-dioxane, which is added, mixes the two dissolution, and the acetic acid 1mL that mass fraction is 10% is then slowly added dropwise, with
The instillation of acetic acid generate yellow solid immediately, reaction tube is accessed into vacuum line, is vacuumized under the conditions of liquid nitrogen frozen, most gas is caught up with
Bubble, tube sealing are warmed to room temperature naturally, are then transferred to reaction 24 hours in 100 DEG C of constant temperature ovens, are stopped heating, cooling to system
To room temperature, reaction tube is opened, is centrifuged, washing is dried in vacuo 12 hours in 60 DEG C after Soxhlet extraction, obtains faint yellow solid
That is covalent organic frame material；
(2) it prepares graphene@covalent organic frame material: taking the covalent organic frame material 1g being prepared in step (1), set
Ultrasound 30 minutes in the graphene aqueous solution that 50mL concentration is 1mg/mL, by the homogeneous solution obtained after ultrasound 200
It is spray-dried under the conditions of DEG C, charging rate 10mL/min, obtains the compound micro- of graphene@covalent organic frame material
Ball；
(3) graphene@covalent organic frame material/sulphur is prepared: by the covalent organic frame material of graphene@obtained in step (2)
Material and pure phase nanometer sulphur powder be put into ball grinder according to mass ratio 1:2, using planetary ball mill revolving speed be 500r/min item
The mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated at 100 DEG C by mixed processing 3h under part
8h obtains the lithium sulfur battery anode material.
Claims (10)
1. a kind of lithium sulfur battery anode material, which is characterized in that the material is that graphene@covalent organic frame material is received with pure phase
The composite material that rice sulphur powder is formed.
2. lithium sulfur battery anode material according to claim 1, which is characterized in that the covalent organic frame material of graphene@
Material and the mass ratio of pure phase nanometer sulphur powder are 1:2~5.
3. lithium sulfur battery anode material according to claim 1, which is characterized in that the covalent organic frame material it is main
Preparing raw material is Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde.
4. lithium sulfur battery anode material according to claim 3, which is characterized in that the Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- equal three
The mass ratio of benzaldehyde is 1:1.
5. lithium sulfur battery anode material according to claim 1, which is characterized in that the covalent organic frame material of graphene@
Graphene and the mass ratio of covalent organic frame material are 0.025~0.2:1 in material.
6. a kind of preparation method of lithium sulfur battery anode material described in claim 1, comprising the following steps:
(1) prepare covalent organic frame material: by Isosorbide-5-Nitrae-phenylenediamine and 1,3,5- mesitylene formaldehyde are placed in reaction tube, are added 1,
4- dioxane mixes the two dissolution, and acetic acid is then added dropwise, then vacuumizes under the conditions of liquid nitrogen frozen, catches up with most bubble, seals
Pipe, is warmed to room temperature naturally, is then transferred to reaction in constant temperature oven, is centrifuged after the reaction was completed, washs, after Soxhlet extraction, very
Empty dry faint yellow solid, that is, covalent organic frame material；
(2) it prepares graphene@covalent organic frame material: taking the covalent organic frame material being prepared in step (1), be placed in
It is ultrasonic in graphene aqueous solution, graphene@covalent organic frame material is obtained by spray drying later；
(3) graphene@covalent organic frame material/sulphur is prepared: by the covalent organic frame material of graphene@obtained in step (2)
Material and pure phase nanometer sulphur powder, which are put into ball grinder, carries out mixed processing, and the mixture obtained after ball milling is put under nitrogen protection
It is heat-treated in tube furnace, obtains the lithium sulfur battery anode material.
7. the preparation method of lithium sulfur battery anode material according to claim 6, which is characterized in that 1 in the step (1),
4- phenylenediamine dosage be 0.5~1 g, 1,3,5- mesitylene formaldehyde dosage be 0.5~1 g, Isosorbide-5-Nitrae-dioxane dosage be 5~
10mL, the acetic acid dosage that mass fraction is 10~40% is 1~5mL；Taken in the step (2) covalent organic frame material 1~
2g is placed in the graphene aqueous solution that 50~100mL concentration is 1~2mg/mL；Graphene@is covalently organic in the step (3)
Mass ratio between frame material and pure phase nanometer sulphur powder is 1:2~5.
8. the preparation method of lithium sulfur battery anode material according to claim 7, which is characterized in that permanent in the step (1)
Temperature
Oven temperature is 100~150 DEG C, is reacted 24~48 hours, and heating is stopped, and after system is cooled to room temperature, opens reaction
Pipe,
Centrifugation, washing；After Soxhlet extraction, it is dried in vacuo 12~24 hours under the conditions of 60 DEG C.
9. the preparation method of lithium sulfur battery anode material according to claim 7, which is characterized in that surpass in the step (2)
Sound
30~60 minutes；The homogeneous solution obtained after ultrasound is carried out under the conditions of 150~200 DEG C using spray dryer
It is spraying
It is dried, charging rate is 5~10mL/min.
10. the preparation method of lithium sulfur battery anode material according to claim 7, which is characterized in that make in the step (3)
3~5h of mixed processing is carried out under the conditions of revolving speed is 500~800r/min with planetary ball mill；It is carried out at 100~200 DEG C
Heat treatment 8~for 24 hours.
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| CN112886134A (en) * | 2021-01-18 | 2021-06-01 | 福建师范大学 | Preparation method of diaphragm modification material for lithium-sulfur battery |
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