CN110504426A - A kind of layered porous copper sulfide/sulphur nanocomposite based on MOFs and preparation method thereof and lithium-sulphur cell positive electrode and battery - Google Patents
A kind of layered porous copper sulfide/sulphur nanocomposite based on MOFs and preparation method thereof and lithium-sulphur cell positive electrode and battery Download PDFInfo
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Abstract
Layered porous copper sulfide/sulphur nanocomposite that the invention discloses a kind of based on MOFs and preparation method thereof and lithium-sulphur cell positive electrode and battery, three-layer laminated porous copper-based MOFs is prepared by solvent-thermal method, and carrying out vulcanization to it using sulphur powder at high temperature by tube furnace makes it generate copper sulfide, sulphuring, which is carried out, using the method for vapor deposition adheres to one layer of elemental sulfur on the surface of obtained porous laminated copper sulfide, form the unique three-dimensional copper sulfide/sulphur composite material of pattern, it is with big specific surface area, solve the problems, such as that sulphur poorly conductive and charge and discharge process volume change are big, to promote the performance of battery significantly, the material is applied to lithium sulfur battery anode material, there is good cycle, the advantages that energy density is high.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of layered porous sulphur based on MOFs
Change copper/sulphur nanocomposite and preparation method thereof and lithium-sulphur cell positive electrode and battery.
Background technique
It since fossil fuel is limited, and burns and can bring a series of environmental problem, solar energy, water energy, nuclear energy etc. are clear
The clean energy has obtained unprecedented development as alternative energy source.
Lithium-sulfur cell is as extremely promising next-generation energy-storage battery, using sulphur as active positive electrode material, with cathode of lithium material
Material forms polysulfide in anode to generate electric current, and theoretical capacity is about 1675mAh g-1, and have benefited from sulphur in the earth's crust
In richness, will further decrease battery cost.But sulphur is very poor as a kind of its electric conductivity of insulator, and in charge and discharge
Cheng Zhongqi volume change is very big, and the polysulfide generated is dissolved in electrolyte leads to the loss of active material, and then because of its electricity
Pond performance sharply declines.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of, layered porous copper sulfide/sulphur nanometer based on MOFs is multiple
Cu base is prepared using cheap raw material in condensation material and preparation method thereof and lithium-sulphur cell positive electrode and battery, the present invention
MOFs obtains copper sulfide and sulphur composite nano materials by vulcanizing, depositing.The present invention is for copper sulfide as electrode material
The technical problems such as cyclical stability difference provide a kind of novel, yield height, composite material and preparation method thereof at low cost.
The technical solution adopted by the present invention is that:
A kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, the preparation method packet
Include following steps:
(1) mantoquita and terephthalic acid (TPA) are dissolved in organic solvent, carry out solvent thermal reaction, be centrifuged after reaction,
It washs, be dried to obtain three-layer laminated copper-based MOFs；
(2) three-layer laminated copper-based MOFs and sulphur powder are respectively placed in the both ends of magnetic boat, capping, which is placed in tube furnace, to be carried out
It calcines, the layered porous copper sulfide based on MOFs can be obtained after natural cooling；
(3) the layered porous copper sulfide based on MOFs for obtaining step (2) carries out sulphuring, can be obtained based on MOFs's
Layered porous copper sulfide/sulphur nanocomposite.
Further, in step (1), the mantoquita is Gerhardite；The organic solvent is N, N- dimethyl methyl
Amide.
In step (1), the ratio between the mantoquita, amount of substance of phthalic acid are 2:1；The mantoquita is in organic solvent
Concentration is 0.03~0.27mol L-1, preferably 0.09mol L-1。
In step (1), the condition of the solvent thermal reaction is 90~130 DEG C and reacts 0.5~20 hour.
In step (2), the mass ratio of layered copper-based MOFs and sulphur powder is 2:1；The condition of the calcining be 400~
600 DEG C are calcined 1~4 hour, preferably 1 hour；It can be by three-layer laminated copper-based MOFs obtained in step (1) under this calcination temperature
In MOFs decompose and then slough the wherein p-phthalic bridge ligand in conjunction with copper, and further react with sulphur powder to be formed it is porous
Stratiform copper sulfide.
In step (3), the layered porous copper sulfide based on MOFs that step (2) is obtained is sealed in distillation sulphur powder to be full of
In the polytetrafluoroethylene (PTFE) bottle of argon gas, is kept for 20~26 hours at 150~160 DEG C, sulphuring can be completed.
Alternatively, by distillation sulphur powder ultrasonic dissolution in carbon disulfide, addition step (2) is obtained thereto in step (3)
Layered porous copper sulfide based on MOFs carries out ultrasonic disperse, is then dried to powder, is sealed in the polytetrafluoroethyl-ne full of argon gas
In alkene bottle, is kept for 20~26 hours at 150~160 DEG C, sulphuring can be completed.It can guarantee that elemental sulfur is attached on copper sulfide surface in this way
Uniformity.The drying is dry 6~8h in 35~50 DEG C of baking oven；The quality of the distillation sulphur powder and carbon disulfide
Volume ratio is 0.05~0.2g/10mL, preferably 0.1g/10mL.
In step (3), the mass ratio of the layered porous copper sulfide based on MOFs and distillation sulphur powder is 1:1~3, excellent
It is selected as 1:2.
Layered porous copper sulfide/sulphur nanocomposite based on MOFs that the preparation method is prepared is
Layered porous copper sulfide area load sulfur granules are formed.
The present invention also provides a kind of lithium-sulphur cell positive electrodes, are received by the layered porous copper sulfide/sulphur based on MOFs
Nano composite material is prepared as active material.
The present invention also provides a kind of lithium-sulfur cells, are prepared by the lithium-sulphur cell positive electrode as anode.
In layered porous copper sulfide/sulphur nanocomposite preparation method provided by the invention based on MOFs, with copper
Salt is raw material, and terephthalic acid (TPA) is organic ligand, and solvent thermal reaction is carried out in DMF solvent and synthesizes three-layer laminated copper-based MOFs
Presoma；And carrying out vulcanization to it using sulphur powder at high temperature by tube furnace makes its generate copper sulfide, due to right in this step
Combination of the phthalic acid between copper is and to start to decompose in 350 DEG C or so the MOFs in conjunction with coordinate bond, at 400 DEG C
When decompose completely, therefore organic ligand p-phthalic bridge will be sloughed, and pattern is still stratiform and porous sulphur occurs
Change copper；Sulphuring, which is carried out, using the method for vapor deposition adheres to one layer of elemental sulfur on the surface of obtained porous laminated copper sulfide,
The unique three-dimensional copper sulfide/sulphur composite material of pattern is formed, this solves the problems, such as elemental sulfur poorly conductive, and three-dimensional porous
Structure will accommodate more elemental sulfurs, solve the problems, such as volume expansion of the sulphur in charge and discharge process, there is battery more preferable
Stability, the material be applied to lithium-sulfur cell have the advantages that good cycle, specific energy density is high.
The present invention and prior art phase, have the advantage that
(1) copper sulfide obtained by can keep the porous laminated structure of MOFs well, can provide big specific surface area；
(2) copper sulfide obtained by/sulphur composite property is stablized, in air not mutability, is easy storage；
(3) copper sulfide obtained by/sulphur composite material is used as lithium sulfur battery anode material, with biggish specific capacity and preferably
Cycle performance；
(4) low in raw material price, synthesis process is simple, can be produced in batches.
Detailed description of the invention
Fig. 1 is the SEM figure of copper-based MOFs composite material prepared by comparative example 1；
Fig. 2 is the SEM figure of copper sulfide prepared by comparative example 1；
Fig. 3 is the XRD diagram of comparative example 1, embodiment 1, the copper sulfide prepared in embodiment 2；
Fig. 4 is copper sulfide/sulphur composite material SEM figure prepared by comparative example 1；
Fig. 5 is the SEM figure of copper sulfide prepared by embodiment 1；
Fig. 6 is copper sulfide/sulphur composite material SEM figure prepared by embodiment 1.
Fig. 7 is copper sulfide/sulphur composite material XRD diagram prepared by embodiment 1；
Fig. 8 is the SEM figure of copper sulfide prepared by embodiment 2；
Fig. 9 is copper sulfide/sulphur composite material SEM figure prepared by embodiment 2；
Figure 10 is copper sulfide/sulphur composite material SEM figure prepared by embodiment 3.
Figure 11 is that copper sulfide/sulphur composite material prepared by embodiment 1 is close in 0.1C electric current as lithium sulfur battery anode material
Cyclical stability test chart under degree.
Figure 12 is that copper sulfide/sulphur composite material prepared by embodiment 1 is close in 0.1C electric current as lithium sulfur battery anode material
Charging and discharging curve figure under degree.
Specific embodiment
Below in conjunction with embodiment and Figure of description, the present invention is described in detail.
Comparative example 1
A kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, comprising the following steps:
(1) preparation of copper-based MOFs: 2.7mmol Cu (NO is weighed3)2·3H2O and 1.35mmol terephthalic acid (TPA) is in beaker
In, 30mL n,N-Dimethylformamide is added, is made it completely dissolved under ultrasound, acquired solution is poured into 50mL polytetrafluoroethyl-ne
In alkene reaction kettle liner, under conditions of 110 DEG C, reacts 8 hours, is centrifuged after reaction with 8000 turns of speed per minute,
And respectively cleaned three times with n,N-Dimethylformamide and dehydrated alcohol, 60 DEG C of vacuum drying 12h are to get adjustable control, stratiform
Copper-based MOFs, SEM figure is as shown in Figure 1, as can be seen from the figure it is the smooth layer structure in surface；
(2) vulcanization process: copper-based MOFs made in 0.24g step (1) is weighed, one end of magnetic boat is placed in, weighs 0.12g
Sublimed sulfur is placed in the other end of magnetic boat, and both ends should keep certain distance, and one end of sulphur powder is placed in the gas outlet side in tube furnace
To reacting 1h under conditions of 300 DEG C, can be prepared by the sample of dark green powder shape, SEM figure is as shown in Fig. 2, can be with from figure
Find out that it maintains the pattern of the stratiform of copper-based MOFs, and surface forms porous substance, but there is no divide MOFs completely
Solution, only Partial Conversion is for CuS；Shown in its XRD diagram such as Fig. 3 (a), as can be seen from the figure product obtained in this step is
CuS, but still remain with the terephthalic acid (TPA) ligand in MOFs；
(3) sulphuring process: the product in (2) after weighing 0.1g vacuum drying is in the polytetrafluoroethylene (PTFE) ampoule of sulphuring
In, then 0.2g distillation sulphur powder is weighed, it is placed in polytetrafluoroethylene (PTFE) ampoule, after mixing, by it in water≤0.01ppm, oxygen
1h or more is placed in value≤0.01ppm glove box to be made to be filled with argon gas, is placed it in baking oven after sealing, 155 DEG C of guarantors
It holds 24 hours, can be prepared by bottle-green powder, as layered porous copper sulfide/sulphur nanocomposite based on MOFs,
SEM figure after this step reaction on the surface of the layered porous structure of CuS as shown in figure 4, as can be seen from the figure further deposit
Sulfur granules.
Embodiment 1
A kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, comprising the following steps:
(1) preparation method of copper-based MOFs is the same as comparative example 1；
(2) vulcanization process: copper-based MOFs made in 0.24g step (1) is weighed, one end of magnetic boat is placed in, weighs
0.12g sublimed sulfur is placed in the other end of magnetic boat, and both ends should keep certain distance, and one end of sulphur powder is placed in going out in tube furnace
1h is reacted under conditions of 400 DEG C in port direction, can be prepared by the powdered sample of dirty-green, and SEM schemes as shown in figure 5, from figure
In it can be seen that its stratiform for maintaining copper-based MOFs pattern, but MOFs is decomposed be totally converted for porous object completely
Matter；Its XRD diagram such as Fig. 3 (b) is shown, as can be seen from the figure all Cu of product obtained in this step1.81S, without to benzene
Dioctyl phthalate ligand exists；
(3) sulphuring process: the product in (2) after weighing 0.1g vacuum drying is in the polytetrafluoroethylene (PTFE) ampoule of sulphuring
In, then 0.2g distillation sulphur powder is weighed, it is placed in polytetrafluoroethylene (PTFE) ampoule, after mixing, by it in water≤0.01ppm, oxygen
1h or more is placed in value≤0.01ppm glove box to be made to be filled with argon gas, is placed it in baking oven after sealing, 155 DEG C of guarantors
It holds 24 hours, can be prepared by bottle-green powder, as layered porous copper sulfide/sulphur nanocomposite based on MOFs.Its
SEM figure as shown in fig. 6, it can be seen from the figure that through this step reaction after, in Cu1.81The surface of the layered porous structure of S deposited
Sulfur granules, XRD diagram as shown with 7, it can be seen from the figure that the obtained product of this step is copper sulfide/sulphur composite material.
Embodiment 2
A kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, comprising the following steps:
(1) the preparation method is the same as that of Example 1 by copper-based MOFs.
(2) vulcanization process: copper-based MOFs made in 0.24g step (1) is weighed, one end of magnetic boat is placed in, weighs
0.12g sublimed sulfur is placed in the other end of magnetic boat, and both ends should keep certain distance, and one end of sulphur powder is placed in going out in tube furnace
1h is reacted under conditions of 500 DEG C in port direction, can be prepared by the sample of brown powder, and SEM schemes as shown in figure 8, from figure
It can be seen that the pattern of its stratiform for maintaining copper-based MOFs, but MOFs is decomposed be totally converted for porous substance completely；
Its XRD diagram such as Fig. 3 (c) is shown, as can be seen from the figure all Cu of product obtained in this step1.96S, without terephthaldehyde
Sour ligand exists；
(3) sulphuring process: the product in (2) after weighing 0.1g vacuum drying is in the polytetrafluoroethylene (PTFE) ampoule of sulphuring
In, then 0.2g distillation sulphur powder is weighed, it is placed in polytetrafluoroethylene (PTFE) ampoule, after mixing, by it in water number≤0.01ppm,
1h or more is placed in oxygen value≤0.01ppm glove box to be made to be filled with argon gas, is placed it in baking oven after sealing, 155 DEG C
It is kept for 24 hours, can be prepared by bottle-green powder, as layered porous copper sulfide/sulphur nanocomposite based on MOFs,
Its SEM figure as shown in figure 9, it can be seen from the figure that through this step reaction after, in Cu1.96The surface of the layered porous structure of S deposits
Sulfur granules.
Embodiment 3
A kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, comprising the following steps:
(1) the preparation method is the same as that of Example 1 by copper-based MOFs.
(2) vulcanization process: vulcanization process is the same as embodiment 2.
(3) it sulphuring process: weighs and is dissolved in 10mL carbon disulfide under 0.2g distillation sulphur powder ultrasound, 0.1g process is then added
(2) the copper sulfide ultrasound in keeps its evenly dispersed, resulting liquid is placed on after 6h is completely dried it in 40 DEG C of baking oven
Gained powder is placed in polytetrafluoroethylene (PTFE) ampoule, by it in water number≤0.01ppm, oxygen value≤0.01ppm glove box
Placing 1h or more makes to be filled with argon gas, places it in baking oven after sealing, and 155 DEG C are kept for 24 hours, can be prepared by vulcanizing
Sulphur as shown in Figure 10, has as can be seen from the figure been supported on porous laminated copper sulfide by the compound of copper and sulphur, SEM figure
Between each layer.
Embodiment 4
Layered porous copper sulfide based on MOFs/application of the sulphur nanocomposite as lithium battery positive pole active substance
Layered porous copper sulfide/sulphur nanocomposite based on MOFs that embodiment 1 is prepared is active material,
According to 7:2:1 or 6:3:1 ratio and conductive black and PVDF after mixing, magnetic agitation 8~12 hours by it uniformly
Ground is dispersed in N-Methyl pyrrolidone, and the slurries mixed up are coated on aluminium foil using spreader, place it in 60~
In 80 DEG C of vacuum oven, the electrode slice that a small circular is cut into using slitter is taken out after 8~12 hours dry.
By made electrode slice full of high-purity argon gas and water oxygen value≤glove box of 0.01ppm in be assembled into button
Battery.By the LiTFSI of 1.0M be dissolved in 1,3 dioxolanes with glycol dimethyl ether be by volume 1:1 mix be formed by it is molten
Then 1% LiNO is added in liquid3, electrolyte is prepared.The method of specific assembled battery are as follows: electricity is dripped on motor casing
Electrode slice is placed after solution liquid, places diaphragm after two drop electrolyte are then added dropwise, places lithium after a drop electrolyte is added dropwise on diaphragm
Piece is used as to electrode, then places gasket and elastic slice respectively, is compressed battery with hydraulic press and is sealed, and is placed 6~8 hours.
Then the cycle performance and charge-discharge performance that button cell is carried out under the electric current of 0.1C, as a result such as Figure 11,12 institutes
Show, as can be seen from Figure 11 after having recycled 1000 times, the capacity of battery can still maintain 300mAh/g or so, from figure
In 12 as can be seen that during electric discharge first discharge platform in 2.15V or so, second discharge platform in 1.95V or so,
Battery has stable charge and discharge platform in charge and discharge process.
Above-mentioned reference embodiment is to a kind of layered porous copper sulfide/sulphur nanocomposite based on MOFs and its preparation side
The detailed description that method and lithium-sulphur cell positive electrode and battery carry out, is illustrative without being restrictive, can be according to limited model
It encloses and enumerates several embodiments, therefore the change and modification in the case where not departing from present general inventive concept, guarantor of the invention should be belonged to
Within the scope of shield.
Claims (10)
1. a kind of layered porous copper sulfide/sulphur nanocomposite preparation method based on MOFs, which is characterized in that the system
Preparation Method the following steps are included:
(1) mantoquita and terephthalic acid (TPA) are dissolved in organic solvent, carry out solvent thermal reaction, after reaction through centrifugation, washing,
It is dried to obtain three-layer laminated copper-based MOFs；
(2) three-layer laminated copper-based MOFs and sulphur powder are respectively placed in the both ends of magnetic boat, capping, which is placed in tube furnace, is calcined,
The layered porous copper sulfide based on MOFs can be obtained after natural cooling；
(3) the layered porous copper sulfide based on MOFs for obtaining step (2) carries out sulphuring, and the stratiform based on MOFs can be obtained
Porous copper sulfide/sulphur nanocomposite.
2. preparation method according to claim 1, which is characterized in that in step (1), the mantoquita is three nitric hydrates
Copper；The organic solvent is n,N-Dimethylformamide；The ratio between amount of substance of the mantoquita, phthalic acid is 2:1；The copper
The concentration of salt in organic solvent is 0.03~0.27mol L-1。
3. preparation method according to claim 1, which is characterized in that in step (1), the condition of the solvent thermal reaction is 90~
130 DEG C are reacted 0.5~20 hour.
4. preparation method according to claim 1, which is characterized in that in step (2), layered copper-based MOFs and sulphur powder
Mass ratio be 2:1；The condition of the calcining is 400~600 DEG C and calcines 1~4 hour.
5. preparation method according to claim 1, which is characterized in that in step (3), by step (2) obtain based on
The layered porous copper sulfide and distillation sulphur powder of MOFs is sealed in the polytetrafluoroethylene (PTFE) bottle full of argon gas, is kept at 150~160 DEG C
20~26 hours, sulphuring can be completed.
6. preparation method according to claim 1, which is characterized in that in step (3), by distillation sulphur powder ultrasonic dissolution in two
In nitric sulfid, the layered porous copper sulfide based on MOFs that step (2) obtain is added thereto and carries out ultrasonic disperse, then dries
It at powder, is sealed in the polytetrafluoroethylene (PTFE) bottle full of argon gas, is kept for 20~26 hours, be can be completed smoked at 150~160 DEG C
Sulphur.
7. preparation method described according to claim 1 or 5 or 6, which is characterized in that in step (3), the layer based on MOFs
The mass ratio of the porous copper sulfide of shape and distillation sulphur powder is 1:1~3.
8. the layered porous vulcanization based on MOFs that preparation method described in -7 any one is prepared according to claim 1
Copper/sulphur nanocomposite.
9. a kind of lithium-sulphur cell positive electrode, which is characterized in that by the layered porous copper sulfide according to any one of claims 8 based on MOFs/
Sulphur nanocomposite is prepared as active material.
10. a kind of lithium-sulfur cell, which is characterized in that be prepared by lithium-sulphur cell positive electrode as claimed in claim 9 as anode.
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| CN111233049A (en) * | 2020-01-19 | 2020-06-05 | 安徽师范大学 | Sulfur-loaded composite material of zinc cobaltate microspheres with multilayer mesoporous structure and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN113509944A (en) * | 2020-03-25 | 2021-10-19 | 韩国科学技术研究院 | Cu for ammonia synthesis1.81S catalyst and ammonia synthesis method using same |
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