CN109802104A - 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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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 nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are formed.Nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is applied to lithium-sulfur cell, gained positive electrode improves the cycle performance of lithium-sulfur cell, the more lithium sulfides of intermediate product of its high specific surface area and the reaction of porous structure adsorption electrode, play the role of solid sulphur；The electric conductivity of material is also improved simultaneously.
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
Lithium ion battery is high because having monomer battery voltage, and energy density is high, using it is safe and reliable the features such as, be considered
It is one of the battery of new century most development potentiality.What the performance of lithium ion battery was heavily dependent on battery material can
Inverse de-/embedding lithium capacity, positive electrode is the bottleneck for hindering high-capacity lithium ion cell development, and positive electrode is also to determine electricity
An important factor for pond security performance.The mainstream positive electrode of existing lithium ion secondary battery includes cobalt acid lithium, LiMn2O4 and phosphoric acid
Iron lithium etc. is widely applied although mainstream positive electrode has been achieved in many fields, they are each in performance and in price
Have advantage and disadvantage, therefore electrochemist never stops the improvement of existing positive electrode and the R&D work of novel anode material
Only.It is close to be concentrated mainly on raising specific capacity, raising energy for further R&D work to lithium ion secondary battery anode material
Degree, reduction are carried out at wood, raising cycle characteristics and raising safety etc..
Since the theoretical capacity of existing mainstream positive electrode is all in 200mAh/g hereinafter, above-mentioned target will be realized, it is necessary to seek
It looks for and is more than
The new material of 200mAh/g.For above-mentioned generation is embedded in the positive electrode of abjection reaction, it is based on " conversion reaction "
Electroactive material high specific capacity and high specific energy can be provided, in these materials, sulphur is considered most promising
One of material.Sulphur has the electrochemistry ability of polyelectron reduction reaction, and the atomic weight of sulphur is smaller, therefore elemental sulfur has up to
The theoretical specific capacity of 1675mAh/g, the theoretical cell energy density of lithium-sulfur cell are far longer than institute at this stage up to 2600W/kg
The commercialization secondary cell used, for the operating voltage of lithium-sulfur cell in 2.1 V or so, can meet current a variety of occasions applies need
It asks.In addition, Sulphur ressource is abundant and cheap, there is application advantage in the development of the following electrochmical power source.Lithium-sulfur rechargeable battery is most
Big disadvantage is that its cyclical stability is poor, research shows that the more lithium sulfides generated in battery discharge procedure are soluble in organic electrolysis
Liquid, the more lithium sulfides diffusion arrival lithium anode surface being dissolved in electrolyte occur self discharge with it and react, and accelerate lithium
Corrosion, generating unordered more lithium sulfides is part irreversible reaction, a series of this problem results in electrode active material utilization
Rate is low and cycle performance of battery is poor.
Summary of the invention
It is an object of the invention to provide a kind of lithium-sulphur cell positive electrode material of height ratio capacity for above-mentioned defect
Nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is applied to lithium-sulfur cell, gained anode by material and preparation method thereof
Material improves the cycle performance of lithium-sulfur cell, and the intermediate product that high specific surface area and porous structure adsorption electrode react is more
Lithium sulfide plays the role of solid sulphur；The electric conductivity of material is also improved simultaneously.
The technical solution of the present invention is as follows: a kind of lithium sulfur battery anode material, which is nitrogen-doped carbon nano-fiber-carbonization
Covalently
The composite material that organic framework materials and pure phase nanometer sulphur powder are formed.
The mass ratio of the nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder is 1:2
~5.
A kind of preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) prepare covalent organic frame material: by 0.5~1g1,4- phenylenediamine and 0.5~1g1,3,5- mesitylene formaldehyde are placed in
In reaction tube, 5~10mL1 is added, 4- dioxane mixes dissolution, be then added dropwise that mass fraction is 10~40% 1~
5mL acetic acid then vacuumizes under the conditions of liquid nitrogen frozen, catches up with most bubble, and tube sealing is warmed to room temperature naturally, it is then transferred to 100~
Reaction 24~48 hours in 150 DEG C of constant temperature ovens, stop heating, after system is cooled to room temperature, open reaction tube, centrifugation is washed
It washs, after Soxhlet extraction, is dried in vacuo 12~24 hours in 60 DEG C, obtains faint yellow solid；
(2) it prepares nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material: taking 1~2g polyacrylonitrile and 1~2g step
(1) covalent organic frame material prepared in is placed in 10~20mL n,N-Dimethylformamide after stirring 12~24 hours and obtains
To homogeneous solution, takes homogeneous solution that covalent organic frame material is made by electrostatic spinning and adulterates polyacrylonitrile nanofiber,
Middle 10~20kv of spinning voltage receives 10~20cm of distance, air humidity 25~50%；It will then prepare resulting covalently organic
Frame material doping polyacrylonitrile nanofiber is placed in tube furnace, and it is small to calcine 2~5 under an argon atmosphere, at 500~1000 DEG C
When, nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material composite material is obtained after furnace cooling；
(3) sulphur-nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is prepared: by nitrogen-doped carbon obtained in step (2)
Nanofiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are put into ball grinder according to mass ratio for 1:2~5, are made
With planetary ball mill revolving speed be 500~800r/min under the conditions of 3~5h of mixed processing, the mixture obtained after ball milling is put
Enter in the tube furnace under nitrogen protection, at 100~200 DEG C be heat-treated 8~for 24 hours, obtain compound lithium sulfur battery anode material.
The invention has the benefit that lithium sulfur battery anode material of the present invention is nitrogen-doped carbon nano-fiber-carbonization
Covalent organic frame material and pure phase nanometer sulphur powder are compound.The preparation method, which first passes through method of electrostatic spinning preparation, covalently machine frame
Frame adulterates polyacrylonitrile nanofiber, then carries out high-temperature calcination and handle to obtain nitrogen-doped carbon nano-fiber-carbonization covalently have machine frame
Frame, last compound pure phase nano-sulfur powder obtain the lithium sulfur battery anode material.
Introduce covalent organic frame in the composite, covalent organic frame material be a kind of structure it is relatively stable,
By the novel crystalline form porous material of organic monomer Covalent bonding together, it has the big pi-conjugated system of π-and open regular duct,
Be conducive to electronics to transmit in the material, be the conductive material of function admirable, when being applied to lithium-sulfur cell, open regular duct
Good load effect can be played to sulphur, and its excellent electric conductivity is well suited for as electrode material.
The present invention uses polyacrylonitrile for raw material when preparing carbon nano-fiber simultaneously, due to being rich in nitrogen in polyacrylonitrile
Element obtains nitrogen-doped carbon nano-fiber naturally after polyacrylonitrile is carbonized, and it is total that the incorporation of electron rich nitrogen-atoms changes C-C
The electronics distribution and charge density for gripping pi bond system, so that nitrogenous carbon-coating has polyelectron or in alkalinity, thus enhance it and lead
Electrically, be conducive to the fast transfer of electronics in battery charge and discharge process, to enhance its chemical property.Meanwhile compared to non-
Polar carbon surface, the carbon of N doping can greatly improve the adsorption energy to polysulfide, especially pyridine type nitrogen, can pass through
Lithium in lone electron pair and polysulfide interacts, to realize the fixation to polysulfide, this is for promoting lithium-sulfur cell
Cyclical stability have great importance.
And it is to use electrostatic spinning by nitrogen-doped carbon nano-fiber and covalent organic frame that the present invention is most creative
The two organically combines, and not simply superposition or replacement, stablizes the cathode material structure, but also nitrogen is mixed
Both miscellaneous carbon nano-fiber and covalent organic frame synergistic effect, become outstanding sulfur-donor.
The present invention uses method of electrostatic spinning when preparing carbon nano-fiber, and electrospun fibers are capable of Effective Regulation fiber
Fine structure, electrospun fibers also have many advantages, such as that aperture is small, porosity is high, fiber homogeneity is good in addition to diameter is small, and
Fiber dispersion is good, reduces the problem of active material is reunited in battery charge and discharge process to a certain extent.
Detailed description of the invention
Fig. 1 is that embodiment 1, embodiment 2, embodiment 3, comparative example 1 and comparative example 2 distinguish obtained lithium-sulphur cell positive electrode
Material is applied to specific discharge capacity of lithium-sulfur cell under the conditions of 0.2C and recycles figure.
Fig. 2 is that embodiment 1, embodiment 2, embodiment 3, comparative example 1 and comparative example 2 distinguish obtained lithium-sulphur cell positive electrode
Material is applied to the high rate performance figure of lithium-sulfur cell.
Specific embodiment
Below by embodiment, the present invention is described in detail.
Embodiment 1
The lithium sulfur battery anode material is nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder
The composite material of formation.
The mass ratio of the nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder is 1:3.
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) prepare covalent organic frame material: by 0.8g1,4- phenylenediamine and 0.8g1,3,5- mesitylene formaldehyde are placed in reaction tube
In, 8mL1 is added, 4- dioxane mixes the two dissolution, the 3mL acetic acid that mass fraction is 30% is then slowly added dropwise, with
The instillation of acetic acid generates yellow solid immediately, and reaction tube is accessed vacuum line, vacuumizes under the conditions of liquid nitrogen frozen, catches up with most gas
Bubble, tube sealing are warmed to room temperature naturally, are then transferred to reaction 36 hours in 120 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；
(2) it prepares nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material: taking 1.5g polyacrylonitrile and 1.5g step
(1) covalent organic frame material prepared in, be placed in 15mL n,N-Dimethylformamide after stir 18 hours obtain it is uniform molten
Liquid takes homogeneous solution that covalent organic frame material is made by electrostatic spinning and adulterates polyacrylonitrile nanofiber, wherein spinning electricity
Press 15kv；Receive distance 15cm；Air humidity 30%；Resulting covalent organic frame material doping polyacrylonitrile will then be prepared
Nanofiber is placed in tube furnace, under an argon atmosphere, is calcined 3 hours at 800 DEG C, and nitrogen-doped carbon nanometer is obtained after furnace cooling
Fiber-carbonization covalent organic frame material composite material；
(3) sulphur-nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is prepared: by nitrogen-doped carbon obtained in step (2)
Nanofiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are put into ball grinder according to mass ratio for 1:3, use row
Planetary ball mill mixed processing 4h under the conditions of revolving speed is 600r/min, the mixture obtained after ball milling is put under nitrogen protection
Tube furnace in, be heat-treated 12h at 180 DEG C, obtain compound lithium sulfur battery anode material.
As seen from Figure 1, under 0.2C current density, which is applied to lithium-sulfur cell first
Specific discharge capacity is up to 1573 mAh/g in secondary circulation, and with the continuous progress of circulation, battery specific capacity constantly declines, circulation
Still there are 1497 mAh/g after 100 circles, reflecting the positive electrode has brilliant electrochemistry cycle performance.
From Figure 2 it can be seen that even if the preparation-obtained positive electrode of embodiment 1 is applied under the high current density of 2C
Lithium-sulfur cell still shows the capacity of 1354 mAh/g, and when current density is down to 0.2C again, specific discharge capacity is again extensive
Again to 1541 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) prepare covalent organic frame material: by 0.5g1,4- phenylenediamine and 0.5g1,3,5- mesitylene formaldehyde are placed in reaction tube
In, 5mL1 is added, 4- dioxane mixes the two dissolution, the 1mL acetic acid that mass fraction is 10% is then slowly added dropwise, with
The instillation of acetic acid generates yellow solid immediately, and reaction tube is accessed vacuum line, vacuumizes under the conditions of liquid nitrogen frozen, catches up with most gas
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；
(2) it prepares nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material: taking 1g polyacrylonitrile and 1g step (1)
The covalent organic frame material of middle preparation is placed in 10mL n,N-Dimethylformamide after stirring 12 hours and obtains uniformly
Solution takes homogeneous solution that covalent organic frame material is made by electrostatic spinning and adulterates polyacrylonitrile nanofiber, wherein spinning
Voltage 10kv；Receive distance 10cm；Air humidity 25%；Resulting covalent organic frame material doping polypropylene will then be prepared
Nitrile nanofibre is placed in tube furnace, under an argon atmosphere, is calcined 2 hours at 500 DEG C, and nitrogen-doped carbon is obtained after furnace cooling and is received
Rice fiber-carbonization covalent organic frame material composite material；
(3) sulphur-nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is prepared: by nitrogen-doped carbon obtained in step (2)
Nanofiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are put into ball grinder according to mass ratio for 1:2, use row
Planetary ball mill mixed processing 3h under the conditions of revolving speed is 500r/min, the mixture obtained after ball milling is put under nitrogen protection
Tube furnace in, be heat-treated 8h at 100 DEG C, obtain compound lithium sulfur battery anode material.
As seen from Figure 1, under 0.2C current density, which is applied to lithium-sulfur cell first
Specific discharge capacity is up to 1350 mAh/g in secondary circulation, and with the continuous progress of circulation, battery specific capacity constantly declines, circulation
Still there are 1125 mAh/g after 100 circles, reflecting the positive electrode has brilliant electrochemistry cycle performance.
From Figure 2 it can be seen that even if the preparation-obtained positive electrode of embodiment 2 is applied under the high current density of 2C
Lithium-sulfur cell still shows the capacity of 867 mAh/g, and when current density is down to 0.2C again, specific discharge capacity restores again
To 1263 mAh/g, this shows that the positive electrode has excellent high rate performance.
Embodiment 3
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) prepare covalent organic frame material: by 1g1,4- phenylenediamine and 1g1,3,5- mesitylene formaldehyde are placed in reaction tube, are added
Enter 10mL1,4- dioxane mixes the two dissolution, the 5mL acetic acid that mass fraction is 40% is then added dropwise, with the drop of acetic acid
Enter and generate yellow solid immediately, reaction tube is accessed into vacuum line, vacuumized under the conditions of liquid nitrogen frozen, catches up with most bubble, tube sealing, from
It is so warmed to room temperature, is then transferred to reaction 48 hours in 150 DEG C of constant temperature ovens, stops heating, after system is cooled to room temperature, beat
Reaction tube is opened, is centrifuged, washing is dried in vacuo 24 hours in 60 DEG C after Soxhlet extraction, obtains faint yellow solid；
(2) it prepares nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material: taking 2g polyacrylonitrile and 2g step (1)
The covalent organic frame material of middle preparation is placed in 20mL n,N-Dimethylformamide after stirring 24 hours and obtains uniformly
Solution takes homogeneous solution that covalent organic frame material is made by electrostatic spinning and adulterates polyacrylonitrile nanofiber, wherein spinning
Voltage 20kv；Receive distance 20cm；Air humidity 50%；Resulting covalent organic frame material doping polypropylene will then be prepared
Nitrile nanofibre is placed in tube furnace, under an argon atmosphere, calcines 5 hours at 1000 DEG C, nitrogen-doped carbon is obtained after furnace cooling
Nanofiber-carbonization covalent organic frame material composite material；
(3) sulphur-nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is prepared: by nitrogen-doped carbon obtained in step (2)
Nanofiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are put into ball grinder according to mass ratio for 1:5, use row
Planetary ball mill mixed processing 5h under the conditions of revolving speed is 800r/min, the mixture obtained after ball milling is put under nitrogen protection
Tube furnace in, be heat-treated at 200 DEG C and obtain compound lithium sulfur battery anode material for 24 hours.
As seen from Figure 1, under 0.2C current density, which is applied to lithium-sulfur cell first
Specific discharge capacity is up to 1467 mAh/g in secondary circulation, and with the continuous progress of circulation, battery specific capacity constantly declines, circulation
Still there are 1350 mAh/g after 100 circles, reflecting the positive electrode has brilliant electrochemistry cycle performance.
From Figure 2 it can be seen that even if the preparation-obtained positive electrode of embodiment 3 is applied under the high current density of 2C
Lithium-sulfur cell still shows the capacity of 835 mAh/g, and when current density is down to 0.2C again, specific discharge capacity restores again
To 1324 mAh/g, this shows that the positive electrode has excellent high rate performance.
Comparative example 1
The lithium sulfur battery anode material is the composite material that carbonization covalent organic frame material and pure phase nanometer sulphur powder are formed.
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) prepare covalent organic frame material: by 0.5g1,4- phenylenediamine and 0.5g1,3,5- mesitylene formaldehyde are placed in reaction tube
In, 5mL1 is added, 4- dioxane mixes the two dissolution, the 1mL acetic acid that mass fraction is 10% is then slowly added dropwise, with
The instillation of acetic acid generates yellow solid immediately, and reaction tube is accessed vacuum line, vacuumizes under the conditions of liquid nitrogen frozen, catches up with most gas
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；
Resulting covalent organic frame material will then be prepared to be placed in tube furnace, under an argon atmosphere, calcined 5 hours at 1000 DEG C,
Carbonization covalent organic frame material is obtained after furnace cooling；
(2) sulphur-carbonization covalent organic frame material is prepared: by carbonization covalent organic frame material obtained in step (1) and pure
Phase nanometer sulphur powder is that 1:2 is put into ball grinder according to mass ratio, using planetary ball mill under the conditions of revolving speed is 500r/min
The mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated 8h at 100 DEG C, obtains by mixed processing 3h
To compound lithium sulfur battery anode material.
Embodiment is lower than by the chemical property that Fig. 1, Fig. 2 will become apparent from comparative example 1, this is mainly due to nitrogen in embodiment
So that anode composite material of lithium sulfur battery overall conductivity gets a promotion, electronics and lithium ion are passed for the addition of doped carbon nano-fiber
Defeated speed increases, and active material effective rate of utilization gets a promotion, simultaneously because nitrogen-doped carbon nano-fiber for more lithium sulfides into
Row effectively absorption, reduces the loss of active material in charge and discharge process, so that the chemical property of embodiment is more excellent.
Comparative example 2
The lithium sulfur battery anode material is nitrogen-doped carbon nano-fiber and the composite material that pure phase nanometer sulphur powder is formed.
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) it prepares nitrogen-doped carbon nano-fiber: taking 1g polyacrylonitrile to be placed in 10mL n,N-Dimethylformamide and stir 12 hours
After obtain homogeneous solution, take homogeneous solution pass through electrostatic spinning (spinning voltage 10kv；Receive distance 10cm；Air humidity
25%).Polyacrylonitrile nanofiber is made；Resulting polyacrylonitrile nanofiber will then be prepared to be placed in tube furnace, in argon
Under gas atmosphere, is calcined 2 hours at 500 DEG C, nitrogen-doped carbon nano-fiber is obtained after furnace cooling；
(2) it prepares sulphur-nitrogen-doped carbon nano-fiber material: nitrogen-doped carbon nano-fiber obtained in step (1) and pure phase is received
Rice sulphur powder is that 1:2 is put into ball grinder according to mass ratio, is mixed under the conditions of revolving speed is 500r/min using planetary ball mill
3h is handled, the mixture obtained after ball milling is put into the tube furnace under nitrogen protection, 8h is heat-treated at 100 DEG C, is answered
The lithium sulfur battery anode material of conjunction.
Embodiment is far below by the chemical property that Fig. 1, Fig. 2 will become apparent from comparative example 2, this is mainly due in embodiment
The addition for the covalent organic frame material that is carbonized is so that the sulphur load capacity of anode composite material of lithium sulfur battery gets a promotion, and it is higher
Specific surface area and open cellular structure there is obvious positive meaning for the transmission of lithium ion and electronics so that electrochemistry
Performance gets a promotion.
Claims (3)
1. a kind of lithium sulfur battery anode material, which is characterized in that the material is that nitrogen-doped carbon nano-fiber-carbonization covalently has machine frame
The composite material that frame material and pure phase nanometer sulphur powder are formed.
2. lithium sulfur battery anode material according to claim 1, which is characterized in that the nitrogen-doped carbon nano-fiber-carbonization
The mass ratio of covalent organic frame material and pure phase nanometer sulphur powder is 1:2~5.
3. 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 0.5~1g1,4- phenylenediamine and 0.5~1g1,3,5- mesitylene formaldehyde are placed in
In reaction tube, 5~10mL1 is added, 4- dioxane mixes dissolution, be then added dropwise that mass fraction is 10~40% 1~
5mL acetic acid then vacuumizes under the conditions of liquid nitrogen frozen, catches up with most bubble, and tube sealing is warmed to room temperature naturally, it is then transferred to 100~
Reaction 24~48 hours in 150 DEG C of constant temperature ovens, stop heating, after system is cooled to room temperature, open reaction tube, centrifugation is washed
It washs, after Soxhlet extraction, is dried in vacuo 12~24 hours in 60 DEG C, obtains faint yellow solid；
(2) it prepares nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material: taking 1~2g polyacrylonitrile and 1~2g step
(1) covalent organic frame material prepared in is placed in 10~20mL n,N-Dimethylformamide after stirring 12~24 hours and obtains
To homogeneous solution, takes homogeneous solution that covalent organic frame material is made by electrostatic spinning and adulterates polyacrylonitrile nanofiber,
Middle 10~20kv of spinning voltage receives 10~20cm of distance, air humidity 25~50%；It will then prepare resulting covalently organic
Frame material doping polyacrylonitrile nanofiber is placed in tube furnace, and it is small to calcine 2~5 under an argon atmosphere, at 500~1000 DEG C
When, nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material composite material is obtained after furnace cooling；
(3) sulphur-nitrogen-doped carbon nano-fiber-carbonization covalent organic frame material is prepared: by nitrogen-doped carbon obtained in step (2)
Nanofiber-carbonization covalent organic frame material and pure phase nanometer sulphur powder are put into ball grinder according to mass ratio for 1:2~5, are made
With planetary ball mill revolving speed be 500~800r/min under the conditions of 3~5h of mixed processing, the mixture obtained after ball milling is put
Enter in the tube furnace under nitrogen protection, at 100~200 DEG C be heat-treated 8~for 24 hours, obtain compound lithium sulfur battery anode material.
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| CN111092206A (en) * | 2019-12-19 | 2020-05-01 | 佛山科学技术学院 | CeO (CeO)2Preparation method of lithium-sulfur battery made of TpBD/S material |
| CN111682208A (en) * | 2020-05-21 | 2020-09-18 | 上海大学 | Composite organic frame nano electrode material and preparation method thereof |
| CN111900407A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112993204A (en) * | 2021-03-24 | 2021-06-18 | 肇庆市华师大光电产业研究院 | Preparation method of high-specific-surface-area positive electrode material of lithium-sulfur battery |
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| CN114436242B (en) * | 2022-02-18 | 2023-04-28 | 辽宁科技大学 | Three-dimensional heteroatom doped porous carbon material, and preparation method and application thereof |
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