CN108336307A - A kind of copper metal organic frame load sulfur materials and its preparation method and application - Google Patents
A kind of copper metal organic frame load sulfur materials and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of copper metal organic frames to load sulfur materials and its preparation method and application, and the preparation method of copper metal organic frame load sulfur materials carries out as steps described below：Dimethylformamide and absolute ethyl alcohol are added in mantoquita and the mixture of Trimesic acid, from room temperature to 80~90 DEG C, keeps the temperature at least 20 hours, filters, it is dry, obtain copper metal organic frame；Copper metal organic frame is uniformly mixed with sulphur, obtains solid powder, under inert gas conditions, solid powder is warming up to 150~160 DEG C and keeps the temperature 10~12 hours, is down to room temperature naturally.The preparation side of the present invention through simple chemical synthesis, filter, be dried to obtain copper metal organic frame, which can effectively limit the dissolving migration of polysulfide.CR2032 button lithium-sulfur cells are formed using copper metal organic frame load sulfur materials as anode, cyclical stability and charging and discharging capacity can be improved.
Description
Technical field
The invention belongs to lithium sulphur pond technical field of material, relate in particular to a kind of copper metal organic frame sulfur loaded
Material and its preparation method and application.
Background technology
With the growth of world population, to the increase of energy demand, the nowadays sustainable new energy of the living necessities of the mankind
The support in source, such as solar energy, wind energy.However the intermittence of these regenerative resources causes their use to need advanced energy
Stocking system is measured, energy could be stored when it has excessive in this way, and supply that is on-demand when needed and keeping constant is got home
On front yard and industrial power.The one kind of lithium-sulfur cell as novel energy stocking system, because it has more compared with lithium ion battery
High energy density causes the vast concern in global range.It is 2.15V that lithium-sulfur cell, which has average voltage, this can
Metric density can be up to 2500W h kg-1Or 2800W h L-1Left and right.In addition, sulphur simple substance is cheap, earth's crust rich content, this
So that lithium-sulfur cell is especially attractive as a kind of energy storage vehicle of low cost.Another advantage of sulphur is its nothing
Toxicity.Unquestionably, all these advantages make lithium-sulfur cell become the energy storage unit of outstanding substitutability, and to subtract
Environmental problem and global warming caused by the burning of few fossil fuel are made contributions.Although current lithium-sulfur cell technology has considerable
Progress, but the industrialization of lithium-sulfur cell is still difficult to realize, the main reason is that due to living existing for lithium-sulphur cell positive electrode
Property material utilization is low, sulphur conductivity is extremely low, polysulfide dissolving migration, the problems such as cycle life is short.Therefore, in order to enhance
The conductivity of positive sulphur, the dissolving migration for reducing polysulfide, the capacity and cyclical stability for improving lithium-sulfur cell, research and development are novel
Lithium sulfur battery anode material is most important.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of copper metal organic frames to load sulfur materials,
Copper metal organic frame load sulfur materials synthesize copper metal organic frame, copper metal organic frame using simple hydro-thermal method
By compound with elemental sulfur, copper metal organic frame load sulfur materials are obtained.
Another object of the present invention is to provide a kind of copper metal organic frames to load sulfur materials in improving specific capacity
Application, by adjusting load capacity of the elemental sulfur in copper metal organic frame, can obtain having compared with high charge-discharge specific capacity and
The electrode material of preferable cyclical stability.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of preparation method of copper metal organic frame load sulfur materials, carries out as steps described below：
Step 1, dimethylformamide (DMF) and anhydrous second are sequentially added in mantoquita and the mixture of Trimesic acid
Alcohol is warming up to 80~90 DEG C for 20~25 DEG C from room temperature, under agitation, keeps the temperature at least 20 hours, obtains blue turbid；By institute
Blue turbid filtering is stated, it is dry, obtain copper metal organic frame；Wherein, the amount of the mantoquita and the substance of Trimesic acid
Than being 3：The ratio of the parts by volume of (2~3), the mass parts of the Trimesic acid and the dimethylformamide be (1.5~
1.8)：(130~160)；The ratio of the mass parts of the Trimesic acid and the parts by volume of the absolute ethyl alcohol is (1.5~1.8)：
(130~160)；
In the step 1, soaking time is 20~24 hours.
In the step 1, the mantoquita is copper chloride or copper nitrate.
In the step 1, the unit of the mass parts is g, and the unit of the parts by volume is mL.
In the step 1, the drying is vacuum drying, and dry temperature is 40~50 DEG C, drying time at least 12
Hour.
Step 2, step 1 gained copper metal organic frame is uniformly mixed with sulphur, solid powder is obtained, in inert gas item
Under part, the solid powder is warming up to 150~160 DEG C and keeps the temperature 10~12 hours, is down to room temperature naturally, wherein institute
The mass ratio for stating copper metal organic frame and sulphur is 1：(1~3).
In the step 2, the heating rate that the solid powder is warming up to 150~160 DEG C is 4~8 DEG C/min.
In the step 2, the inert gas is argon gas.
In the step 2, the copper metal organic frame is with the mixed uniformly mode of sulphur：The copper metal is organic
Frame is ground at least 30 minutes with sulphur.
It in the step 2, is cooled to room temperature naturally, it is negative to obtain copper metal organic frame for ground 180~200 mesh sieve
Carry sulfur materials.
The copper metal organic frame that above-mentioned preparation method obtains loads sulfur materials.
In the above-mentioned technical solutions, the copper metal organic frame load sulfur materials include：Copper metal organic frame and sulphur,
Wherein, the copper metal organic frame has rough surface, hole is formed on the rough surface, in the rough surface
Uniform fold has the sulphur in the upper and hole.
In the above-mentioned technical solutions, the load capacity of the sulphur is 20~65wt%.
A kind of application of above-mentioned copper metal organic frame load sulfur materials in improving lithium-sulfur cell specific capacity.
In the above-mentioned technical solutions, the copper metal organic frame is loaded into sulfur materials, acetylene black and binder polytetrafluoro
Ethylene is uniformly mixed, and absolute ethyl alcohol is added dropwise, allows it to roll into smooth thin slice, wherein the copper metal organic frame load
The mass parts ratio of sulfur materials, acetylene black and polyfluortetraethylene of binding element is 5:(2.5~3.5):(1.8~2.2)；It will be described smooth
Thin slice is cut into the disk of diameter 1cm, 3~4mg of weight, as anode.
In the above-mentioned technical solutions, double trifluoromethanesulfonimide lithium solution of 1M are as electrolyte, metal lithium sheet conduct
To electrode, microporous polypropylene membrane is as diaphragm, the anode, electrolyte, diaphragm and to electrode composition CR2032 button lithiums sulphur electricity
Pond；The CR2032 buttons lithium-sulfur cell can alleviate lithium-sulfur cell special capacity fade and raising lithium-sulfur cell stable circulation
Property：For the CR2032 buttons lithium-sulfur cell in the current density of 200mA/g, first discharge specific capacity is 1460~1770mA h/
g；After 10 weeks after charge and discharge cycles, specific capacity is 900~1100mA h/g；After 20 weeks after charge and discharge cycles, specific capacity is
750~950mA h/g；After 40 weeks after charge and discharge cycles, specific capacity is 600~700mA h/g.
Compared with the prior art, of the invention preparation method is simple, through simple chemical synthesis, filters, is dried to obtain
Copper metal organic frame, the copper metal organic frame can effectively limit the dissolving migration of polysulfide, sulphur made to be filled in
The surface of copper metal organic frame.Using copper metal organic frame load sulfur materials as anode composition CR2032 button lithiums sulphur electricity
Cyclical stability and charging and discharging capacity can be improved in pond.
Description of the drawings
Fig. 1 is the XRD diagram picture of original Cu-MOF, S, CuMOF1S1, CuMOF1S2 and CuMOF1S3；
Fig. 2 is scanning electron microscope image (SEM) and mapping images, wherein Fig. 2 (a) and Fig. 2 (b) is original Cu-MOF
Scanning electron microscope image (SEM), Fig. 2 (c) and Fig. 2 (d) are the SEM image of CuMOF1S2 composite materials, Fig. 2 (e), Fig. 2 (f),
Fig. 2 (g), Fig. 2 (h) and Fig. 2 (i) are the mapping images of CuMOF1S2 composite materials；
Fig. 3 is thermogravimetric analysis (TGA) image of CuMOF1S1, CuMOF1S2, CuMOF1S3 and S；
Fig. 4 is the charge and discharge cycles song that CuMOF1S1, CuMOF1S2 and CuMOF1S3 electrode are 200mA/g in current density
Line；
Fig. 5 is the first charge-discharge curve of CuMOF1S1, CuMOF1S2 and CuMOF1S3 under 200mA/g current densities；
Fig. 6 is 1st, 5,10,20,50 and 100 week charging and discharging curves of the CuMOF1S2 under 200mA/g current densities.
Specific implementation mode
In the specific implementation mode of the present invention, copper nitrate (Cu (NO3)2·3H2O) purchase is tried from Tianjin good fortune morning chemistry
Agent factory, analysis are pure；Trimesic acid (C9H6O6) buy from the Tianjin sky over the river and unify Science and Technology Ltd., analysis is pure；Dimethyl methyl
Amide (C3H7NO) from Tianjin Fengchuan Chemical Reagent Science ＆ Technology Co., Ltd., analysis is pure for purchase；Absolute ethyl alcohol (C2H6O it) buys certainly
The Tianjin sky over the river unifies Science and Technology Ltd., and analysis is pure.Sulphur uses sublimed sulfur (AR), purchase to unify the limited public affairs of science and technology from the sky over the river
Department.In Tianjin Fengchuan Chemical Reagent Science ＆ Technology Co., Ltd., analysis is pure for copper chloride purchase.
In the specific implementation mode of the present invention, copper metal organic frame load sulfur materials can be expressed as CuMOF S,
The preparation of CuMOF@S and electrochemical property test are as follows：Copper metal organic frame load sulfur materials are pulverized and acetylene black
With polyfluortetraethylene of binding element (PTFE) in mass ratio 5:3:2 ratio makes electrode slice.Film-making process is as follows：It will weigh respectively
Good copper metal organic frame load sulfur materials, acetylene black and polyfluortetraethylene of binding element (PTFE) mixing, is added dropwise 3~4 drop nothings
Water-ethanol rolls into smooth thin slice using stainless steel bar on stainless steel, and the disk of diameter 1cm or so is cut into scissors, control
The quality of each disk is between 3~4mg, as anode.Double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M (mol/L) are molten
Liquid (lark prestige Science and Technology Ltd.) is used as electrolyte, wherein is containing volume ratio in double trifluoromethanesulfonimide lithium solution
1:The LiNO of 1 1,3- dioxolanes and glycol dimethyl ether and 1% (mass volume ratio)3.(polypropylene is micro- by Cegard2300
Pore membrane) it is used as diaphragm, metal lithium sheet to be used as to electrode and reference electrode, CR2032 buttons are formed in the glove box full of argon gas
Lithium-sulfur cell.The LAND CT2001A battery test system copper test metal organic frame sulfur loadeds that Jin Nuo companies produce in Wuhan
The charge-discharge performance of material, constant current charge-discharge current density are 200mA/g, voltage range 1.5-2.5V.This experiment charge and discharge
Environment temperature be 25 DEG C of constant temperatures.
In the specific implementation mode of the present invention, Rigaku D/MAX2500V/PC type X-ray diffractometers is selected to analyze material
Material phase composition (use Cu/K alpha rays,)；Material is swept using FEI Nova Nano SEM 2300
Retouch Electronic Speculum test (accelerating potential 15.0kV) (for testing SEM and mapping images)；Use the TGA Q500 of TA companies of the U.S.
Type synchronous solving carries out thermogravimetric analysis (Thermo Gravimetric Analyzer, TGA) to material.
The technical solution further illustrated the present invention in the following with reference to the drawings and specific embodiments.
Embodiment 1
A kind of preparation method of copper metal organic frame load sulfur materials, carries out as steps described below：
Step 1, the ratio for weighing the amount of substance is 3:2 copper chloride and Trimesic acid, sets in 250ml round-bottomed flasks,
150mL dimethylformamides (DMF) and 150mL absolute ethyl alcohols are sequentially added in copper chloride and the mixture of Trimesic acid,
It is warming up to 85 DEG C for 20~25 DEG C from room temperature, under agitation, keeps the temperature 20 hours, obtain blue turbid；Blue turbid is filtered,
It is dried in vacuum overnight (12 hours) at 40 DEG C, obtains the copper metal organic frame of blue powder shape.
Step 2, step 1 gained copper metal organic frame is mixed with sublimed sulfur, is ground 30 minutes in mortar, consolidate
Solid powder is transferred to corundum boat by body powder, wherein the mass ratio of copper metal organic frame and biochemical sulphur is 1：1.By corundum
Boat is placed in tube furnace, and under the conditions of inert gas (Ar), solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min
And 10 hours are kept the temperature, being down to room temperature naturally can (whole process keep Ar atmosphere).Naturally it is cooled to room temperature, ground 200 mesh sieve obtains
To copper metal organic frame load sulfur materials (CuMOF1S1).
Embodiment 2
A kind of preparation method of copper metal organic frame load sulfur materials, carries out as steps described below：
Step 1, the ratio for weighing the amount of substance is 3:2 copper nitrate and Trimesic acid, sets in 250ml round-bottomed flasks,
150mL dimethylformamides (DMF) and 150mL absolute ethyl alcohols are sequentially added in copper chloride and the mixture of Trimesic acid,
It is warming up to 85 DEG C for 20~25 DEG C from room temperature, under agitation, keeps the temperature 20 hours, obtain blue turbid；Blue turbid is filtered,
It is dried in vacuum overnight (12 hours) at 40 DEG C, obtains the copper metal organic frame of blue powder shape.
Step 2, step 1 gained copper metal organic frame is mixed with sublimed sulfur, is ground 30 minutes in mortar, consolidate
Solid powder is transferred to corundum boat by body powder, wherein the mass ratio of copper metal organic frame and biochemical sulphur is 1：2.By corundum
Boat is placed in tube furnace, and under the conditions of inert gas (Ar), solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min
And 10 hours are kept the temperature, being down to room temperature naturally can (whole process keep Ar atmosphere).Naturally it is cooled to room temperature, ground 200 mesh sieve obtains
To copper metal organic frame load sulfur materials (CuMOF1S2).
Embodiment 3
A kind of preparation method of copper metal organic frame load sulfur materials, carries out as steps described below：
Step 1, the ratio for weighing the amount of substance is 3:2 copper nitrate and Trimesic acid, sets in 250ml round-bottomed flasks,
150mL dimethylformamides (DMF) and 150mL absolute ethyl alcohols are sequentially added in copper chloride and the mixture of Trimesic acid,
It is warming up to 85 DEG C for 20~25 DEG C from room temperature, under agitation, keeps the temperature 20 hours, obtain blue turbid；Blue turbid is filtered,
It is dried in vacuum overnight (12 hours) at 40 DEG C, obtains the copper metal organic frame (Cu-MOF) of blue powder shape.
Step 2, step 1 gained copper metal organic frame is mixed with sublimed sulfur, is ground 30 minutes in mortar, consolidate
Solid powder is transferred to corundum boat by body powder, wherein the mass ratio of copper metal organic frame and biochemical sulphur is 1：3.By corundum
Boat is placed in tube furnace, and under the conditions of inert gas (Ar), solid powder is warming up to 155 DEG C with the heating rate of 4 DEG C/min
And 10 hours are kept the temperature, being down to room temperature naturally can (whole process keep Ar atmosphere).Naturally it is cooled to room temperature, ground 200 mesh sieve obtains
To copper metal organic frame load sulfur materials (CuMOF1S3).
Embodiment 4
A kind of preparation method of copper metal organic frame, carries out as steps described below：
Step 1, the ratio for weighing the amount of substance is 3:2 copper chloride and Trimesic acid, sets in 250ml round-bottomed flasks,
150mL dimethylformamides (DMF) and 150mL absolute ethyl alcohols are sequentially added in copper chloride and the mixture of Trimesic acid,
It is warming up to 85 DEG C for 20~25 DEG C from room temperature, under agitation, keeps the temperature 20 hours, obtain blue turbid；Blue turbid is filtered,
It is dried in vacuum overnight (12 hours) at 40 DEG C, obtains the copper metal organic frame of blue powder shape.
Step 2, after step 1 gained copper metal organic frame being ground 30 minutes in mortar, it is transferred to corundum boat,
In.Corundum boat is placed in tube furnace, under the conditions of inert gas (Ar), by solid powder with the heating rate liter of 4 DEG C/min
Temperature is to 155 DEG C and keeps the temperature 10 hours, and being down to room temperature naturally can (whole process keep Ar atmosphere).Naturally it is cooled to room temperature, it is ground
200 mesh sieve, and obtain original Cu-MOF.
(1) polycrystalline X-ray powder diffraction (XRD) analysis of sample
Fig. 1 is the XRD diagram picture of original Cu-MOF, S, CuMOF1S1, CuMOF1S2 and CuMOF1S3.As seen from the figure, former
Cu-MOF, CuMOF1S1, CuMOF1S2 and CuMOF1S3 of beginning is crystalline state, and Cu-MOF is remaining it with compound rear remain unchanged of sulphur
The crystalline structure of script, and in Cu-MOF and sulphur new crystalline phase is not occurred with different quality after compound, and can find out very bright
The characteristic peak of aobvious sulphur.
(2) morphology analysis of sample
Fig. 2 (a) and Fig. 2 (b) is the scanning electron microscope image (SEM) of original Cu-MOF, and Fig. 2 (c) and Fig. 2 (d) are
The SEM image of CuMOF1S2 composite materials, Fig. 2 (e), Fig. 2 (f), Fig. 2 (g), Fig. 2 (h) and Fig. 2 (i) are CuMOF1S2 composite woods
The mapping images of material.By Fig. 2 (a) and 2 (b) it is found that Cu-MOF itself has rough surface and pore structure, in hole and
Its rough surface can be used for fixing sulphur；In Fig. 2 (c) and 2 (d), it is thick clearly can to see that sulphur has been filled in Cu-MOF itself
Rough surface, and the surfaces Cu-MOF is made to cover a thick layer sulphur, and CuMOF1S2 is maintained and the material of original Cu-MOF
Almost the same structure.Fig. 2 (e), 2 (f), 2 (g), 2 (h) and the mapping images that 2 (i) is MOF1S2 composite materials, from figure
In we clearer can see that sulphur is equably covered in the surface of Cu-MOF very much.
(3) thermogravimetric analysis of sample
Fig. 3 is thermogravimetric analysis (TGA) image of CuMOF1S1, CuMOF1S2, CuMOF1S3 and S.Bright sulfur is at 290 DEG C or so
Complete agravity, CuMOF1S1, CuMOF1S2 and CuMOF1S3 lose the sulphur of load at 270 DEG C or so completely, and CuMOF1S1,
The weight-loss curve of weight-loss curves and bright sulfur of the CuMOF1S2 and CuMOF1S3 before 290 DEG C almost coincide, this is preferably demonstrate,proved
It is illustrated before 290 DEG C, the weight that composite material is lost is entirely the quality of its sulphur loaded.It is analyzed by TGA, Wo Menke
To calculate the practical sulfur content of each sample, the sulphur load capacity of CuMOF1S1, CuMOF1S2 and CuMOF1S3 are respectively
30.48w t%, 55.94w t%, 64.7w t%.
(4) electrochemical property test of sample
CR2032 button lithium-sulfur cells are respectively prepared in CuMOF1S1, CuMOF1S2 and CuMOF1S3 according to the method described above,
Fig. 4 is CuMOF1S1, CuMOF1S2 and CuMOF1S3 electrode of CR2032 button lithium-sulfur cells when current density is 200mA/g
Charge and discharge cycles curve.As shown in Figure 4, the 1st week capacity C uMOF1S2 is slightly above CuMOFS1 and is higher than CuMOF1S3.Cycle
After 20 weeks, the reversible discharge capacity of CuMOFS2 composite electrodes can reach 942.7mA h/g, be 1.26 times of CuMOFS1
(750.3mA h/g) is 1.05 times (the 895.2mA h/g) of CuMOF1S3.After cycle 55 weeks, CuMOF1S3 composite materials
Capacity sharp-decay, and the capacity of CuMOF1S1, CuMOF1S2 composite material gradually tends to balance, and CuMOF1S2 composite materials
Specific capacity a little higher than CuMOF1S1 always, there is higher sulfur nutrient to have certain pass for this and CuMOF1S2 materials itself
System.The rapid attenuation of CuMOF1S3 capacity may be to be circulated throughout since its composite material surface has accumulated excessive sulphur
The frame structure of CuMOF1S3 materials has capacity rapid attenuation caused by a degree of cave in journey.Compared with CuMOF1S1,
There is CuMOF1S2 composite materials itself higher sulfur content, frame structure can be kept well in cyclic process,
So CuMOF1S2 materials can not only prevent the dissolving of polysulfide, but also have enough sulphur loads, so CuMOF1S2 materials
Capacity is relatively high, although and CuMOF1S1 material capacity is not ideal enough, its cyclical stability is relatively preferable, also with
The sulphur that it is loaded is relatively fewer, and material volume variation is smaller in cyclic process, and then can preferably keep its material former
There is structure to have certain relationship.
Table 1 is that CR2032 button lithium-sulfur cells are made in current density in CuMOF1S, CuMOF1S2 and CuMOF1S3 in Fig. 4
For the measurement result of 200mA/g
Fig. 5 is the first charge-discharge curve of CuMOF1S1, CuMOF1S2 and CuMOF1S3 under 200mA/g current densities.
It is to lose electronics from polysulfide and become elemental sulfur to cause in the charging platform of 2.2V or so it can be seen that in the charging stage
's.Two typical discharge platforms 2.35 and 2.1V in discharge curve are due to S8To the polysulfide of long-chain transformation and
Long-chain polysulphides become short and small sulfide and change to be formed.The charging platform of CuMOF1S2 composite materials and CuMOF1S1 phases
Like, than the platform of CuMOF1S3 compared to long, what the conclusion of this and constant current charge-discharge curve was consistent with, CuMOF1S2 materials
Specific capacity is far above the specific capacity of CuMOF1S3 materials, bigger with CuMOF1S1 materials, but is not much different.
Fig. 6 is CuMOF1S2 the 1st under 200mA/g current densities, 5,10,20,50,100 weeks charging and discharging curves.By scheming
It is found that CuMOF1S2 composite samples are hindered with the increasing of circulating cycle number, specific capacity gradually decreases, this is recycled with constant current charge-discharge
The conclusion of Fig. 4 is consistent.The charge and discharge platform voltage of CuMOFS2 composite materials is almost not much different in the 1-100 weeks, this says
It is bright in 100 weeks cycle periods, the material of charge and discharge is all identical, and only with the increase of circulating cycle number, specific capacity has
The charging/discharging voltage platform for causing to recycle corresponding to week in later stage number of decaying is shorter and shorter.
A series of composite materials works are obtained by the way that the sulphur of the synthesis of simple chemical method, filtering, drying and different quality is compound
For lithium sulfur battery anode material.Be assembled into button lithium-sulfur cell, to some row composite samples under the current density of 200mA/g into
Row charge-discharge performance is tested, and a series of comparisons are carried out.The result shows that CuMOF1S2 composite electrode first charge-discharge specific capacities
CuMOF1S1, CuMOF1S3 composite material are compared with stable circulation all to increase.After recycling 20 weeks, CuMOF1S2 composite materials
The reversible discharge capacity of electrode can reach 942.7mA h/g, be 1.26 times (the 750.3mA h/g) of CuMOF1S1, be
1.05 times (895.2mA h/g) of CuMOF1S3.The raising of CuMOF1S2 composite materials specific discharge capacity and cyclical stability is
Due to having suitable sulphur in CuMOF1S2 composite materials, and organic frame can be kept not cave in charge and discharge process,
And then play the role of limiting polysulfide dissolving well, and the capacity attenuation of electrode material is alleviated to a certain extent
And bulk effect.
In the inventive solutions, the parameters such as time, temperature, and the selection of different mantoquitas, equal energy are adjusted
Reach the property consistent with above-described embodiment.
This research promotes plan (No.52XC1502) to provide scientific research warp by Tianjin Normal University's Middl-age and youth faculty Academic innovations
Take support.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of preparation method of copper metal organic frame load sulfur materials, which is characterized in that carry out as steps described below：
Step 1, dimethylformamide and absolute ethyl alcohol are sequentially added in mantoquita and the mixture of Trimesic acid, from room temperature 20
~25 DEG C are warming up to 80~90 DEG C, under agitation, keep the temperature at least 20 hours, obtain blue turbid；By the blue turbid
Filtering, it is dry, obtain copper metal organic frame；Wherein, the ratio of the amount of the mantoquita and the substance of Trimesic acid is 3：(2~
3), the ratio of the mass parts of the Trimesic acid and the parts by volume of the dimethylformamide is (1.5~1.8)：(130~
160)；The ratio of the mass parts of the Trimesic acid and the parts by volume of the absolute ethyl alcohol is (1.5~1.8)：(130~160)；
Step 2, step 1 gained copper metal organic frame is uniformly mixed with sulphur, solid powder is obtained, in inert gas conditions
Under, the solid powder is warming up to 150~160 DEG C and keeps the temperature 10~12 hours, is down to room temperature naturally, wherein described
The mass ratio of copper metal organic frame and sulphur is 1：(1~3).
2. preparation method according to claim 1, which is characterized in that in the step 1, soaking time is 20~24 small
When；The mantoquita is copper chloride or copper nitrate；In the step 1, the unit of the mass parts is g, the list of the parts by volume
Position is mL；In the step 1, the drying is vacuum drying, and dry temperature is 40~50 DEG C, and drying time at least 12 is small
When.
3. preparation method according to claim 1, which is characterized in that in the step 2, the solid powder is warming up to
150~160 DEG C of heating rate is 4~8 DEG C/min；The inert gas is argon gas.
4. preparation method according to claim 1, which is characterized in that in the step 2, the copper metal organic frame
It is with the mixed uniformly mode of sulphur：The copper metal organic frame and sulphur are ground at least 30 minutes；In the step 2, from
It is so cooled to room temperature, ground 180~200 mesh sieve obtains copper metal organic frame load sulfur materials.
5. the copper metal organic frame that the preparation method as described in any one of Claims 1 to 4 obtains loads sulfur materials.
6. copper metal organic frame according to claim 5 loads sulfur materials, which is characterized in that the copper metal has machine frame
Frame loads sulfur materials：Copper metal organic frame and sulphur, wherein the copper metal organic frame has rough surface, in institute
It states and is formed with hole on rough surface, uniform fold has the sulphur on the rough surface and in the hole.
7. copper metal organic frame according to claim 5 loads sulfur materials, which is characterized in that the load capacity of the sulphur is
20~65wt%.
8. copper metal organic frame load sulfur materials are improving lithium-sulfur cell specific capacity as described in claim 5~7 any one
In application.
9. application according to claim 8, which is characterized in that the copper metal organic frame is loaded sulfur materials, acetylene
Black and polyfluortetraethylene of binding element is uniformly mixed, and absolute ethyl alcohol is added dropwise, allows it to roll into smooth thin slice, wherein the copper
The mass parts ratio that metal organic frame loads sulfur materials, acetylene black and polyfluortetraethylene of binding element is 5:(2.5~3.5):(1.8
~2.2)；The smooth thin slice is cut into the disk of diameter 1cm, 3~4mg of weight, as anode.
10. application according to claim 9, which is characterized in that double trifluoromethanesulfonimide lithium solution of 1M are as electricity
Liquid is solved, metal lithium sheet is used as to electrode, and microporous polypropylene membrane is used as diaphragm, the anode, electrolyte, diaphragm and to electrode composition
CR2032 button lithium-sulfur cells；The CR2032 buttons lithium-sulfur cell can alleviate lithium-sulfur cell special capacity fade and raising lithium
Sulphur circulating battery stability：In the current density of 200mA/g, first discharge specific capacity is the CR2032 buttons lithium-sulfur cell
1460~1770mA h/g；After 10 weeks after charge and discharge cycles, specific capacity is 900~1100mA h/g；The charge and discharge after 20 weeks
After cycle, specific capacity is 750~950mA h/g；After 40 weeks after charge and discharge cycles, specific capacity is 600~700mA h/g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360974A (en) * | 2018-11-29 | 2019-02-19 | 郑州大学 | A kind of Lithium-sulphur battery anode material and its preparation method and application based on manganese cluster base MOF |
| CN112516306A (en) * | 2019-09-02 | 2021-03-19 | 天津大学 | Copper ion doped metal organic material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151524A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Positive pole material for high-performance lithium-sulfur battery and preparation method thereof |
| CN103236542A (en) * | 2013-04-17 | 2013-08-07 | 浙江大学 | Preparation method for lithium-sulfur battery positive electrode material adopting metal-organic framework material as sulfur carrier |
-
2017
- 2017-01-19 CN CN201710038813.3A patent/CN108336307A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103151524A (en) * | 2013-03-04 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Positive pole material for high-performance lithium-sulfur battery and preparation method thereof |
| CN103236542A (en) * | 2013-04-17 | 2013-08-07 | 浙江大学 | Preparation method for lithium-sulfur battery positive electrode material adopting metal-organic framework material as sulfur carrier |
Non-Patent Citations (1)
| Title |
|---|
| ZIQI WANG等: ""A Metal-Organic Framework with Open Metal Sites for Enhanced Confinement of Sulfur and Lithium-Sulfur Battery of Long Cycling Life"", 《CRYST. GROWTH DES.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360974A (en) * | 2018-11-29 | 2019-02-19 | 郑州大学 | A kind of Lithium-sulphur battery anode material and its preparation method and application based on manganese cluster base MOF |
| CN109360974B (en) * | 2018-11-29 | 2021-06-11 | 郑州大学 | Lithium-sulfur battery positive electrode material based on manganese cluster MOF and preparation method and application thereof |
| CN112516306A (en) * | 2019-09-02 | 2021-03-19 | 天津大学 | Copper ion doped metal organic material, preparation method and application thereof |
| CN112516306B (en) * | 2019-09-02 | 2022-07-01 | 天津大学 | Copper ion doped metal organic material, preparation method and application thereof |
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