CN109301191A - A kind of novel lithium sulfur battery anode material and preparation method thereof - Google Patents
A kind of novel 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 novel lithium sulfur battery anode material and preparation method thereof.The novel lithium sulfur battery anode material, raw material include Co-MOF material and redox graphene.It is low that the positive electrode overcomes existing lithium sulfur battery anode material sulphur payload amount, polysulfide " shuttle effect " is obvious, the defect that the Volumetric expansion of lithium-sulfur cell is significant and battery performance is unstable is a kind of lithium sulfur battery anode material of height ratio capacity.
Description
Technical field
The invention belongs to the technical field of lithium-sulfur cell, it is specifically related to a kind of novel lithium sulfur battery anode material and its system
Preparation Method.
Background technique
With the rapid development of society, demand of the mankind to the energy is increasing, but not with people's living standard
It is disconnected to improve, some main fossil energies, such as coal, petroleum, natural gas increasingly shortage.Some fossil energies at the same time
Burning, bring environmental pollution and destruction are unrepairables, if the excess emissions of carbon dioxide result in greenhouse effects, into
And the continuous rising on sea level being resulted in, while the continuous discharge of vehicle exhaust also leads to the worsening of haze, this will
The serious health and living environment for threatening the mankind.Compel so studying novel renewable and clean energy resource and energy storage device in eyebrow
Eyelash.Wind energy, although the new energies cleanliness without any pollution such as solar energy and tide energy, the limitation by energy sources can not
Replacing internal combustion engine is that vehicle etc. provides the stable energy.Battery is wide as a kind of novel, high energy, free of contamination electrochmical power source
It is general to be applied to the energy storage fields such as portable electronic device, electric car and hybrid-electric car, there is height ratio capacity as one kind
Enter the visual field of people with the energy storage device of long circulation life and receives extensive attention and study.The lithium having been commercialized at present from
Sub- battery is limited by itself 300 mAh/g of theoretical specific capacity, it is clear that is not able to satisfy to lithium ion battery practical application quality
It is required that and the theoretical specific capacity of novel lithium-sulfur cell is about five times of (theoretical specific capacities of commercial Li-ion batteries theoretical specific capacity
For 1675mAh/g, specific energy is 2500 Wh/kg), it is considered to be most one of the high-energy battery of development potentiality.
However but there are many obstacles in lithium-sulfur cell in practical applications.First, bright sulfur is insulator, electronics at room temperature
It is transmitted in the anode using sulphur as positive electrode with ion extremely difficult；Second, the intermediate production formed in charge and discharge process
The more lithium sulfides of object are soluble in electrolyte solution, so as to cause the electroactive material powder of detached and solution loss on anode, and
The lithium sulfide that the more lithium sulfides of dissolution in the electrolytic solution are diffused on lithium an- ode, and react generation is deposited in the table of cathode
Face causes the internal resistance of battery to increase, eventually leads to the capacity attenuation of battery；Third, sulphur and final product Li2The density of S is different,
Volume expansion can occur for sulphur anode and fragmentation (expansion ratio 76%), these can all cause lithium-sulfur cell cyclical stability to be deteriorated.
It is mostly used to start in the metal organic framework (MOFs) of gas storage, separation in the past studied applied to lithium-sulfur cell electricity
Pole material, MOFs material have big specific surface area and microcellular structure abundant, are conducive to the infiltration of electrolyte and the biography of ion
It is defeated.But the usual electric conductivity of MOFs material is poor, this makes its performance when being used as li-ion electrode materials receive certain restrictions,
It can not get a desired effect in most cases.
Summary of the invention
A kind of novel lithium sulphur is provided it is an object of the invention to the deficiency for current lithium sulfur battery anode material technology
Cell positive material and preparation method thereof, it is low which overcomes existing lithium sulfur battery anode material sulphur payload amount,
Obviously, the Volumetric expansion of lithium-sulfur cell is significant and battery performance is unstable lacks polysulfide " shuttle effect "
It falls into, is a kind of lithium sulfur battery anode material of height ratio capacity.
The technical solution of the present invention is as follows: a kind of novel lithium sulfur battery anode material, raw material includes Co-MOF material
And redox graphene.
The mass ratio of the Co-MOF material and redox graphene is (1~5): 1.
A kind of preparation method of the novel lithium sulfur battery anode material, comprising the following steps:
(1) preparation of Co-MOF material: preparing the mixed solution of n,N-Dimethylformamide and ethyl alcohol first,
Then by Co (NO3)2·6H2O and terephthalic acid (TPA) are dissolved in mixed solution；Dissolved mixed solution is placed in again
Reaction obtains purple powder flat crystal in hydrothermal reaction kettle；Crystal is finally drying to obtain Co-MOF；Wherein N, N- by volume
Dimethylformamide: ethyl alcohol is (2~4): 1；Co(NO3)2·6H2The mass ratio of O and terephthalic acid (TPA) is 40:23；
(2) preparation of Co-MOF/ redox graphene composite material: first by Co-MOF obtained by step (1) and graphite oxide
The mixing of alkene solution；Then it is spray-dried by mixed solution ultrasound and after stirring, wherein graphene oxide is reduced to oxygen reduction
Graphite alkene；Spray drying gained powder, that is, Co-MOF/ redox graphene composite material is finally collected, it is spare；
(3) Co-MOF/ redox graphene/sulphur positive electrode preparation: Co-MOF/ made from step (2) is restored first
Graphene oxide composite material is mixed with pure phase nanometer sulphur powder, wherein Co-MOF/ redox graphene is multiple in mass ratio
Condensation material: nanometer sulphur powder is 1: (3~10)；Then the mixture is placed in the tube furnace under nitrogen protection at 100~200 DEG C
Under carry out heat treatment 8~for 24 hours, obtain positive electrode.
The n,N-Dimethylformamide and alcohol mixed solution of 50~100mL are prepared in the step (1)；Co(NO3)2·
6H2O mass is 0.16~0.32 g, and terephthalic acid (TPA) quality is 0.092~0.184 g.
The reaction temperature of hydrothermal reaction kettle is 100~120 DEG C in the step (1), and the reaction time is 25~50 h；It will be brilliant
Body is placed in baking oven dry 12~24 h under the conditions of 50~65 DEG C.
1~2gCo-MOF is mixed with the graphene oxide solution that 200~500mL concentration is 2mg/mL in the step (2).
Mixed solution ultrasound 1~2 hour in the step (2), and 10~20h is stirred, is then sprayed at 250~280 DEG C
Mist is dry.
Ultrasonic wave separating apparatus is used in the step (2), and ultrasound is carried out under 300~650W power.
Nitrogen flow is 100~250mL/min in the step (3).
The invention has the benefit that novel lithium sulfur battery anode material of the present invention is by first preparing Co-MOF material
Material, then by being combined as lithium sulfur battery anode material with nano-sulfur after spray drying process composite reduction graphene oxide.
Wherein MOFs material itself has big specific surface area and microcellular structure abundant, be conducive to electrolyte infiltration and
The transmission of ion, Co-MOF are a kind of novel porous materials, combine the high hole of the high stability and MOFs in inorganic zeolite
Gap rate and organic functions；Then the composite reduction graphene oxide by way of spray drying greatly reinforces its electric conductivity.
MOF material and redox graphene material all have big specific surface area simultaneously, make it possible to as sulphur in lithium-sulfur cell
Excellent carrier.
Graphene it is conductive it is excellent, chemical stability is high, large specific surface area, mechanical performance are strong and unique
The feature of the brilliance such as two-dimentional porous network geometry, what can simply and easily be carried out forms nucleocapsid clad structure with sulphur,
Using the modified lithium-sulfur cell of graphene, the electro-chemical activity of sulphur simple substance can be improved, shorten electronics and ion transmission path, limitation
The dissolution of polysulfide, and then improve lithium-sulfur cell overall performance.Graphene oxide is a kind of carbon materials with 2D planar structure
Material, since there is excellent electric conductivity there are the big pi bond of the delocalization of long-range in its structure.Redox graphene (rGO) is recognized
Equally to have preferable electric conductivity.Meanwhile the oxidation of precursor graphene of redox graphene in its structure due to having
Oxygen-containing group (such as hydroxyl, epoxy group, carboxyl and carbonyl) abundant and there is chemical modifiability well, these oxygen-containing groups
Group can organic ligand in substituted metal organic backbone with metal center in conjunction with, thus what generation was connected to each other by chemical bond
Activated centre of the composite material metal organic framework as electrochemical reaction, and redox graphene for composite material provide compared with
Good electric conductivity.Further, since redox graphene has preferable toughness and flexible, introducing can alleviate material
The structure collapses caused by volume change in charge and discharge process, so as to improve the cyclical stability of material.
Preparation method of the present invention is simple and easy to operate, and high yield, is easy to commercially produce.The present invention by ingenious and
Meticulous design breaks through prior art difficult point, and experimental program is simple, yield is big, has IP prospecting.
Detailed description of the invention
Fig. 1 is the charge discharge curve using novel lithium sulfur battery anode material obtained by embodiment 1.
Fig. 2 is the charge discharge curve and library using novel lithium sulfur battery anode material obtained by embodiment 1
Human relations efficiency curve.
Fig. 3 is the charge discharge curve using lithium sulfur battery anode material obtained by comparative example 1.
Fig. 4 is the charge discharge curve using lithium sulfur battery anode material obtained by comparative example 2.
Specific embodiment
Below by embodiment, the present invention is described in detail.
Embodiment 1
The novel lithium sulfur battery anode material, raw material include Co-MOF material and redox graphene.Institute
The mass ratio for stating Co-MOF material and redox graphene is 2.5:1.
The preparation method of the novel lithium sulfur battery anode material, comprising the following steps:
(1) preparation of Co-MOF material: the n,N-Dimethylformamide of preparation 50mL and ethyl alcohol is mixed first
Solution is closed, then by 0.16 g Co (NO3)2·6H2O and 0.092 g terephthalic acid (TPA) are dissolved in mixed solution；Again will
It is 100 DEG C that dissolved mixed solution, which is placed in hydrothermal reaction kettle in reaction temperature, and the reaction time obtains to react under the conditions of 25h
Purple powder flat crystal；Finally crystal is placed in baking oven under the conditions of 50 DEG C and dries 12h up to Co-MOF；Wherein press volume
Than n,N-Dimethylformamide: ethyl alcohol 4:1；
(2) preparation of Co-MOF/ redox graphene composite material: first by 1gCo-MOF and 200 mL obtained by step (1)
The graphene oxide solution that concentration is 2mg/ml mixes；Then the mixed solution is used into ultrasonic wave separating apparatus, in 300~650W
Ultrasound is carried out under power 1 hour and be spray-dried at 250 DEG C after stirring 10h；Finally collect spray drying gained powder, that is, Co-
MOF/ redox graphene composite material, it is spare；
(3) Co-MOF/ redox graphene/sulphur positive electrode preparation: first also by 1gCo-MOF/ made from step (2)
Former graphene oxide composite material is mixed with 3g pure phase nanometer sulphur powder；Then the pipe mixture being placed under nitrogen protection
Heat treatment 12h is carried out in formula furnace at 100 DEG C, obtains positive electrode.
Nitrogen flow is 120mL/min in the step (3).
Using Co-MOF/ redox graphene/sulphur positive electrode powder obtained as active material, carbon dust is conduction
Agent, Kynoar (PVDF) are adhesive, and by weight Co-MOF/ redox graphene/sulphur positive electrode powder: carbon
Powder: the ratio that Kynoar is 8:1:1 is placed in mixing in mortar, grinding uniformly, then instills N-methyl pyrrolidinone solvent
(NMP) it is ground to pulpous state, slurry is uniformly applied on aluminium foil, dry 12h is then placed in 60 DEG C of thermostatic drying chamber, is dried to
Flakiness is pushed in 5MPa pressure using tablet press machine after constant weight, S/Co-MOF/rGO lithium-sulphur cell positive electrode piece is thus made；With gold
Belonging to lithium is to electrode and reference electrode, and more S/Co-MOF/rGO lithium-sulphur cell positive electrode pieces obtained are working electrode, double the three of 1M
Fluoromethane sulfimide lithium (LiTFSI) is dissolved in 1,3-dioxolane (DOL)/glycol dimethyl ether (DME)=1:1 V%, and adds
1% LiNO3 is electrolyte, and porous polypropylene is diaphragm, and CR2025 button cell is assembled in the glove box full of argon gas.
It can be seen that, use its initial capacity of the novel lithium sulfur battery anode material for 1180mAh/g by Fig. 1, and follow
After ring 50 encloses, capacity relative attenuation is less, is still maintained at 980mAh/g, even if after enclosing to 200, discharge specific volume
Amount is still up to 800mAh/g, it is sufficient to illustrate that capacity attenuation is slower in its cyclic process.
It can see by Fig. 2 curve, using its efficiency for charge-discharge of novel lithium sulfur battery anode material close to 100%, lead to
Cross preceding 200 circle volume capacity, it can be seen that its capacity attenuation is more slow, and the capacity relative securement after 100 circles.
Embodiment 2
The novel lithium sulfur battery anode material, raw material include Co-MOF material and redox graphene.Institute
The mass ratio for stating Co-MOF material and redox graphene is 2.4:1.
The preparation method of the novel lithium sulfur battery anode material, comprising the following steps:
(1) preparation of Co-MOF material: the mixed solution of the n,N-Dimethylformamide of preparation 60mL and ethyl alcohol first, then
By 0.24 g Co (NO3)2·6H2O and 0.138g terephthalic acid (TPA) is dissolved in mixed solution；Again by dissolved mixed solution
Being placed in hydrothermal reaction kettle in reaction temperature is 120 DEG C, and reaction obtains purple powder flat crystal under the conditions of the reaction time is 30h；
Finally crystal is placed in baking oven under the conditions of 60 DEG C and dries 18h up to Co-MOF；Wherein N by volume, N- dimethyl formyl
Amine: ethyl alcohol 4:1；
(2) preparation of Co-MOF/ redox graphene composite material: first will be obtained by step (1)
1.2gCo-MOF is mixed with the graphene oxide solution that 250 mL concentration are 2mg/ml；Then by the mixed solution using super
Sound wave separating apparatus carries out ultrasound 1.5 hours under 300~650W power and is spray-dried at 260 DEG C after stirring 12h；Finally
Spray drying gained powder, that is, Co-MOF/ redox graphene composite material is collected, it is spare；
(3) Co-MOF/ redox graphene/sulphur positive electrode preparation: first also by 1gCo-MOF/ made from step (2)
Former graphene oxide composite material is mixed with 4g pure phase nanometer sulphur powder；Then the pipe mixture being placed under nitrogen protection
Heat treatment 15h is carried out in formula furnace at 120 DEG C, obtains positive electrode.
Nitrogen flow is 140mL/min in the step (3).
Using Co-MOF/ redox graphene/sulphur positive electrode powder obtained as active material, carbon dust is conduction
Agent, Kynoar (PVDF) are adhesive, and by weight Co-MOF/ redox graphene/sulphur positive electrode powder: carbon
Powder: the ratio that Kynoar is 8:1:1 is placed in mixing in mortar, grinding uniformly, then instills N-methyl pyrrolidinone solvent
(NMP) it is ground to pulpous state, slurry is uniformly applied on aluminium foil, dry 12h is then placed in 60 DEG C of thermostatic drying chamber, is dried to
Flakiness is pushed in 5MPa pressure using tablet press machine after constant weight, S/Co-MOF/rGO lithium-sulphur cell positive electrode piece is thus made；With gold
Belonging to lithium is to electrode and reference electrode, and more S/Co-MOF/rGO lithium-sulphur cell positive electrode pieces obtained are working electrode, double the three of 1M
Fluoromethane sulfimide lithium (LiTFSI) is dissolved in 1,3-dioxolane (DOL)/glycol dimethyl ether (DME)=1:1 V%, and adds
1% LiNO3 is electrolyte, and porous polypropylene is diaphragm, and CR2025 button cell is assembled in the glove box full of argon gas.
Embodiment 3
The novel lithium sulfur battery anode material, raw material include Co-MOF material and redox graphene.Institute
The mass ratio for stating Co-MOF material and redox graphene is 3:1.
The preparation method of the novel lithium sulfur battery anode material, comprising the following steps:
(1) preparation of Co-MOF material: the n,N-Dimethylformamide of preparation 70mL and ethyl alcohol is mixed first
Solution is closed, then by 0.32g Co (NO3)2·6H2O and 0.184 g terephthalic acid (TPA) are dissolved in mixed solution；Again will
It is 150 DEG C that dissolved mixed solution, which is placed in hydrothermal reaction kettle in reaction temperature, and the reaction time obtains to react under the conditions of 40h
Purple powder flat crystal；Finally crystal is placed in baking oven under the conditions of 70 DEG C and dries 20h up to Co-MOF；Wherein press volume
Than n,N-Dimethylformamide: ethyl alcohol 4:1；
(2) preparation of Co-MOF/ redox graphene composite material: first by 1.5gCo-MOF and 250 obtained by step (1)
The graphene oxide solution that mL concentration is 2mg/ml mixes；Then the mixed solution is used into ultrasonic wave separating apparatus, 300~
Ultrasound is carried out under 650W power 2 hours and be spray-dried at 270 DEG C after stirring 15h；Finally collect spray drying gained powder
That is Co-MOF/ redox graphene composite material, it is spare；
(3) Co-MOF/ redox graphene/sulphur positive electrode preparation: first also by 1gCo-MOF/ made from step (2)
Former graphene oxide composite material is mixed with 5g pure phase nanometer sulphur powder；Then the pipe mixture being placed under nitrogen protection
Heat treatment 15h is carried out in formula furnace at 120 DEG C, obtains positive electrode.
Nitrogen flow is 104mL/min in the step (3).
Using Co-MOF/ redox graphene/sulphur positive electrode powder obtained as active material, carbon dust is conduction
Agent, Kynoar (PVDF) are adhesive, and by weight Co-MOF/ redox graphene/sulphur positive electrode powder: carbon
Powder: the ratio that Kynoar is 8:1:1 is placed in mixing in mortar, grinding uniformly, then instills N-methyl pyrrolidinone solvent
(NMP) it is ground to pulpous state, slurry is uniformly applied on aluminium foil, dry 12h is then placed in 60 DEG C of thermostatic drying chamber, is dried to
Flakiness is pushed in 5MPa pressure using tablet press machine after constant weight, S/Co-MOF/rGO lithium-sulphur cell positive electrode piece is thus made；With gold
Belonging to lithium is to electrode and reference electrode, and more S/Co-MOF/rGO lithium-sulphur cell positive electrode pieces obtained are working electrode, double the three of 1M
Fluoromethane sulfimide lithium (LiTFSI) is dissolved in 1,3-dioxolane (DOL)/glycol dimethyl ether (DME)=1:1 V%, and adds
1% LiNO3 is electrolyte, and porous polypropylene is diaphragm, and CR2025 button cell is assembled in the glove box full of argon gas.
In order to compare advantages of the present invention, two groups of comparative experimentss have specially been done.
Comparative example 1
The lithium sulfur battery anode material, raw material include Co-MOF material, there is no composite graphite alkene is spray-dried, by 1gCo-MOF
It is mixed with 5g pure phase nanometer sulphur powder；Then the mixture is placed in the tube furnace under nitrogen protection at 120 DEG C and is carried out
It is heat-treated 15h, obtains positive electrode.
Using Co-MOF/ sulphur positive electrode powder obtained as active material, carbon dust is conductive agent, Kynoar
(PVDF) be adhesive, and by weight Co-MOF/ sulphur positive electrode powder: carbon dust: Kynoar is that the ratio of 8:1:1 is set
Enter in mortar to mix, grind uniformly, then instills N-methyl pyrrolidinone solvent (NMP) and be ground to pulpous state, slurry is uniformly applied
The dry 12h in the thermostatic drying chamber on aluminium foil, be then placed in 60 DEG C, after drying to constant weight using tablet press machine under 5MPa pressure
It is pressed into thin slice, S/Co-MOF lithium-sulphur cell positive electrode piece is thus made；It is to electrode and reference electrode, more S/ obtained with lithium metal
Co-MOF lithium-sulphur cell positive electrode piece is working electrode, and double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M are dissolved in 1,3- dioxy penta
Ring (DOL)/glycol dimethyl ether (DME)=1:1 V%, and 1% LiNO3 is added as electrolyte, porous polypropylene is diaphragm,
CR2025 button cell is assembled in glove box full of argon gas.
By Fig. 3 it can be seen that, use in comparative example 1 its initial capacity of S/Co-MOF lithium sulfur battery anode material for
900mAh/g or so, and after recycling 50 circles, capacity attenuation is more, and in 700mAh/g, to after 200 circles, discharge ratio
Capacity is 550mAh/g, illustrates that capacity attenuation is compared with block in its cyclic process.
Comparative example 2
The lithium sulfur battery anode material, raw material include redox graphene, and there is no compound Co-MOF materials, only will oxidation
Graphene solution is spray-dried out, collects black powder (redox graphene).1g redox graphene and 5g is pure
Phase nanometer sulphur powder is mixed；Then it will be heat-treated at 120 DEG C in tube furnace that the mixture is placed under nitrogen protection
15h obtains positive electrode.
Using redox graphene obtained/sulphur positive electrode powder as active material, carbon dust is conductive agent, gathers inclined fluorine
Ethylene (PVDF) is adhesive, and by weight redox graphene/sulphur positive electrode powder: carbon dust: Kynoar is
Mixing, grinding uniformly, then instill N-methyl pyrrolidinone solvent (NMP) and are ground to pulpous state in the ratio merging mortar of 8:1:1,
Slurry is uniformly applied on aluminium foil, dry 12h is then placed in 60 DEG C of thermostatic drying chamber, uses tablet press machine after drying to constant weight
Flakiness is pushed in 5MPa pressure, S/rGO lithium-sulphur cell positive electrode piece is thus made；With lithium metal be to electrode and reference electrode,
More S/rGO lithium-sulphur cell positive electrode pieces obtained are working electrode, and double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M are dissolved in 1,
3- dioxolanes (DOL)/glycol dimethyl ether (DME)=1:1 V%, and 1% LiNO3 is added as electrolyte, porous polypropylene is
Diaphragm assembles CR2025 button cell in the glove box full of argon gas.
It can be seen that, use in comparative example 2 its initial capacity of S/rGO lithium sulfur battery anode material for 800mAh/ by Fig. 4
G or so, and after recycling 50 circles, capacity attenuation is more, and in 550mAh/g, to after 200 circles, specific discharge capacity is
450mAh/g illustrates that capacity attenuation is compared with block in its cyclic process.
Claims (9)
1. a kind of novel lithium sulfur battery anode material, which is characterized in that raw material includes Co-MOF material and reduction-oxidation
Graphene.
2. novel lithium sulfur battery anode material according to claim 1, which is characterized in that the Co-MOF material
Mass ratio with redox graphene is (1~5): 1.
3. the preparation method of novel lithium sulfur battery anode material described in a kind of claim 1, comprising the following steps:
(1) preparation of Co-MOF material: preparing the mixed solution of n,N-Dimethylformamide and ethyl alcohol first,
Then by Co (NO3)2·6H2O and terephthalic acid (TPA) are dissolved in mixed solution；Dissolved mixed solution is placed in again
Reaction obtains purple powder flat crystal in hydrothermal reaction kettle；Crystal is finally drying to obtain Co-MOF；Wherein N, N- by volume
Dimethylformamide: ethyl alcohol is (2~4): 1；Co(NO3)2·6H2The mass ratio of O and terephthalic acid (TPA) is 40:23；
(2) preparation of Co-MOF/ redox graphene composite material: first by Co-MOF obtained by step (1) and graphite oxide
The mixing of alkene solution；Then it is spray-dried by mixed solution ultrasound and after stirring, wherein graphene oxide is reduced to oxygen reduction
Graphite alkene；Spray drying gained powder, that is, Co-MOF/ redox graphene composite material is finally collected, it is spare；
(3) Co-MOF/ redox graphene/sulphur positive electrode preparation: Co-MOF/ made from step (2) is restored first
Graphene oxide composite material is mixed with pure phase nanometer sulphur powder, wherein Co-MOF/ redox graphene is multiple in mass ratio
Condensation material: nanometer sulphur powder is 1: (3~10)；Then the mixture is placed in the tube furnace under nitrogen protection at 100~200 DEG C
Under carry out heat treatment 8~for 24 hours, obtain positive electrode.
4. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that described
The n,N-Dimethylformamide and alcohol mixed solution of 50~100mL are prepared in step (1)；Co(NO3)2·6H2O mass
For 0.16~0.32 g, terephthalic acid (TPA) quality is 0.092~0.184 g.
5. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that the step (1)
The reaction temperature of middle hydrothermal reaction kettle is 100~120 DEG C, and the reaction time is 25~50 h；Crystal is placed in baking oven 50~
Dry 12~24 h under the conditions of 65 DEG C.
6. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that the step (2)
In 1~2gCo-MOF and 200~500mL concentration be 2mg/mL graphene oxide solution mix.
7. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that the step (2)
Middle mixed solution ultrasound 1~2 hour, and 10~20h is stirred, then it is spray-dried at 250~280 DEG C.
8. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that the step (2)
It is middle to use ultrasonic wave separating apparatus, ultrasound is carried out under 300~650W power.
9. the preparation method of novel lithium sulfur battery anode material according to claim 3, which is characterized in that the step (3)
Middle nitrogen flow is 100~250mL/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755542A (en) * | 2019-03-07 | 2019-05-14 | 肇庆市华师大光电产业研究院 | A kind of positive electrode of sodium-sulfur cell material and preparation method thereof |
| CN111029583A (en) * | 2019-11-26 | 2020-04-17 | 河北工业大学 | Lithium-sulfur battery positive electrode framework material and preparation method and application thereof |
| CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN112117453A (en) * | 2020-10-16 | 2020-12-22 | 肇庆市华师大光电产业研究院 | Novel lithium-sulfur battery positive electrode composite material and preparation method thereof |
| CN113394388A (en) * | 2021-06-10 | 2021-09-14 | 肇庆市华师大光电产业研究院 | Preparation method of high-specific-capacity sodium-sulfur battery positive electrode material |
| CN113410461A (en) * | 2021-02-20 | 2021-09-17 | 西安理工大学 | Preparation method and application of self-supporting electrode MOFs/carbon paper composite material of lithium-sulfur battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035893A (en) * | 2012-12-12 | 2013-04-10 | 中南大学 | Preparation method of lithiumsulphur battery positive pole material |
| CN106684355A (en) * | 2016-12-29 | 2017-05-17 | 中国电子科技集团公司第十八研究所 | Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof |
| CN107958999A (en) * | 2016-10-15 | 2018-04-24 | 宁波丰羽新材料科技有限公司 | A kind of manufacture method of flexible self-supporting lithium sulfur battery anode material |
-
2018
- 2018-09-12 CN CN201811063572.9A patent/CN109301191A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035893A (en) * | 2012-12-12 | 2013-04-10 | 中南大学 | Preparation method of lithiumsulphur battery positive pole material |
| CN107958999A (en) * | 2016-10-15 | 2018-04-24 | 宁波丰羽新材料科技有限公司 | A kind of manufacture method of flexible self-supporting lithium sulfur battery anode material |
| CN106684355A (en) * | 2016-12-29 | 2017-05-17 | 中国电子科技集团公司第十八研究所 | Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755542A (en) * | 2019-03-07 | 2019-05-14 | 肇庆市华师大光电产业研究院 | A kind of positive electrode of sodium-sulfur cell material and preparation method thereof |
| CN111029583A (en) * | 2019-11-26 | 2020-04-17 | 河北工业大学 | Lithium-sulfur battery positive electrode framework material and preparation method and application thereof |
| CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN112117453A (en) * | 2020-10-16 | 2020-12-22 | 肇庆市华师大光电产业研究院 | Novel lithium-sulfur battery positive electrode composite material and preparation method thereof |
| CN113410461A (en) * | 2021-02-20 | 2021-09-17 | 西安理工大学 | Preparation method and application of self-supporting electrode MOFs/carbon paper composite material of lithium-sulfur battery |
| CN113410461B (en) * | 2021-02-20 | 2022-11-04 | 西安理工大学 | Preparation method and application of self-supporting electrode MOFs/carbon paper composite material of lithium-sulfur battery |
| CN113394388A (en) * | 2021-06-10 | 2021-09-14 | 肇庆市华师大光电产业研究院 | Preparation method of high-specific-capacity sodium-sulfur battery positive electrode material |
| WO2024180256A1 (en) | 2023-03-02 | 2024-09-06 | Norwegian University Of Science And Technology (Ntnu) | Cathode for li-s battery |
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