CN108598415A - A kind of composite material and preparation method for lithium-sulphur cell positive electrode - Google Patents
A kind of composite material and preparation method for lithium-sulphur cell positive electrode Download PDFInfo
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- CN108598415A CN108598415A CN201810370105.4A CN201810370105A CN108598415A CN 108598415 A CN108598415 A CN 108598415A CN 201810370105 A CN201810370105 A CN 201810370105A CN 108598415 A CN108598415 A CN 108598415A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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Abstract
The present invention relates to a kind of composite material and preparation methods for lithium-sulphur cell positive electrode, presulfurization polymerisation is carried out at high temperature using diaminomaleonitrile and sulphur, open loop forms free radical catalysis cyano trimerization formation covalent triazine frame to eight ring of sulphur at high temperature, sulphur is fixed in the form of C S keys on polymer backbone simultaneously, loads to more sulphur on covalent triazine frame followed by fusion method.Wherein the covalent triazine frame of nitrogen atom doping has good electric conductivity, can effectively improve sulphur positive conductive；Stable covalent triazine frame structure can alleviate destruction of the sulphur anode volume expansion with contraction to anode in charge and discharge process；The sulphur of material internal is fixed on chemical bond form can effectively inhibit the shuttle effect of more lithium sulfides.Excellent cycle performance and high rate performance are shown when the composite material is used for lithium-sulfur cell.
Description
Technical field
The present invention relates to field of chemical power source more particularly to a kind of composite materials and its preparation for lithium-sulphur cell positive electrode
Method.
Background technology
With the fast development of modern science and technology, lithium ion battery is also gradually applied to large size from small portable device
In device (such as electric vehicle).And traditional lithium ion battery cannot meet need of the people to high continuation of the journey chemical energy storage device
It asks.The theoretical specific capacity of elemental sulfur is 1675mAhg-1, energy density is up to 2600Whkg-1, and it is rich with reserves
Richness, it is environmental-friendly and cheap the advantages that.Therefore, lithium-sulfur cell receives the favor of researcher, is considered current commercial lithium
One of viable substitute of ion battery.
Although lithium-sulfur cell has the advantages that so many, several great technology barriers can not be ignored, such as sulphur
And its solid product (Li2S2/Li2S insulation characterisitic), the large volume expansion (79%) during lithiumation, it is often more important that dissolving
More lithium sulfide (Li2Sn, 4≤n≤8) enter in electrolyte, cause to generate shuttle effect in charge and discharge process.On the one hand, it wears
Shuttle effect cause sulphur anode capacitance loss and lithium-sulfur cell cycle life it is poor；On the other hand, it is passivated cathode of lithium, limits lithium
The high rate performance of sulphur battery and the utilization rate of active sulfur.
To solve the above-mentioned problems, it needs to select suitable sulfur-donor, which will realize three functions：First, to be exhausted
The elemental sulfur of edge provides electric conductivity, second is that stable pore structure is provided for sulfur loaded, third, can inhibit soluble more lithium sulfides
Shuttle effect.In recent years, in order to improve the chemical property of lithium-sulfur cell, researchers have been developed for many strategies.
Wherein, one of most effective way is that sulphur is fixed to carrier inside by way of physics confinement or chemical bond energy.Wherein, object
Reason confinement is that sulphur is diffused into inside the porous material with high-specific surface area and Kong Rong by fusion method, such as mesoporous carbon, oxygen
Graphite alkene, carbon nanotube, conducting polymer, metal organic framework (MOFs), covalent organic framework (COFs) and porous organic
Gather.Although these composite materials improve cycle performance to a certain extent, these materials fetter sulphur or more lithium sulfides
Active force is weaker, after longer cycle more lithium sulfides still will produce shuttle effect.Sulphur is fettered by chemical interactions
It can effectively solve the above problems.According to previous research, open loop forms the form of linear diradical, its energy to elemental sulfur at high temperature
Enough by free radical intercalation reaction and organic monomer or polymer reaction to form stable C-S keys.
In addition, conjugation organic frame is since it is with big specific surface area and Kong Rong, high electric conductivity, aperture is adjustable and
The advantages that stability is good, therefore be conjugated organic porous material and do lithium-sulfur cell sulfur-donor with outstanding advantage.
Based on the above research, the present invention is research object with positive material for lithium-sulfur battery and preparation method thereof, utilizes two
Amino Maleic nitrile and sulphur react at high temperature carries out presulfurization, and covalent triazine is catalyzed and synthesized by the free radical formed under sulphur high temperature
Frame, while sulphur is fixed in the form of C-S keys on polymer backbone, is loaded to more sulphur altogether followed by fusion method
On valence triazine frame.Prepared composite material not only has good electric conductivity, while can effectively inhibit the molten of polysulfide
Solution diffusion.It uses it for showing excellent stable circulation performance and high rate performance when lithium-sulphur cell positive electrode.
Invention content
For lithium-sulfur cell institute facing challenges, the object of the present invention is to provide a kind of for the compound of lithium-sulphur cell positive electrode
Material and preparation method thereof improves the cycle performance and high rate performance of lithium-sulfur cell with this.
The present invention is achieved through the following technical solutions：
A kind of composite material and preparation method for lithium-sulphur cell positive electrode is prepared as：It is first that 3.5g sublimed sulfurs is molten
In 7.6g CS2In, ultrasonic disperse 5min；Add 5.4g diaminomaleonitriles, ultrasonic disperse 30min；Then mixed liquor is put
Enter in autoclave, vacuumizes and sealed after mending nitrogen three times repeatedly, 12h is heated under the conditions of 400 DEG C；By products therefrom and distillation
Sulphur in mass ratio 40:It is put into glass tube, is evacuated and hermetically sealed after 60 grindings uniformly；Glass tube is put into tube furnace 155 DEG C
Then lower heating 12h is warming up to 200 DEG C of heating 30min.Finally, composite material S@CTF-S are prepared.
A kind of button-shaped lithium-sulfur cell, is assembled by above-mentioned composite material.Specifically assemble method is：By 7：2：1
Mass ratio weighs composite material, acetylene black and Kynoar (PVDF), and three is uniformly mixed to form slurry；Slurry is uniformly applied
It spreads on aluminium foil, is put into 60 DEG C of dry 12h in vacuum drying chamber；Electrode slice is cut into the circular electric pole piece of a diameter of 12mm,
It is that the button-shaped lithium-sulfur cell of CR2032 types is made in the glove box full of argon gas to electrode with lithium metal.
The present invention actual gain be：
The present invention carries out presulfurization polymerisation at high temperature using diaminomaleonitrile and sulphur, utilizes sulfur catalysis cyano three
It is poly-, while sulphur being fixed in the form of C-S keys on polymer backbone, the combined coefficient of composite material can be effectively improved, is improved
The load capacity of sulphur in composite material.The covalent triazine frame of nitrogen atom doping has good electric conductivity, passes through the mutual friendship of sulphur
Connection effect further improves its electric conductivity, so as to effectively improve sulphur positive conductive.Stable covalent triazine frame structure
Destruction of the sulphur anode volume expansion with contraction to anode in charge and discharge process can be alleviated, material internal is fixed on chemical bond form
Sulphur can effectively inhibit the shuttle effects of more lithium sulfides.
Description of the drawings
The present invention has following attached drawing：
Fig. 1 is the hot weight curve of S@CTF-S；
Fig. 2 is the X-ray diffractogram of S@CTF-S and elemental sulfur；
Fig. 3 is the x-ray photoelectron spectroscopy figure of S@CTF-S；
Capacity voltage patterns of Fig. 4 (a) S@CTF-S under 0.5C multiplying powers, (b) with CS2- CTF-S is the made lithium of positive electrode
Capacity voltage pattern of the sulphur battery under 0.5C multiplying powers is (c) the made lithium-sulfur cell of positive electrode under 0.5C multiplying powers using CTF-S
Capacity voltage pattern is (d) the made lithium-sulfur cell of positive electrode in 0.1mV s using S@CTF-S-1Cyclic voltammetric under sweep speed
Figure, (e) with CS2- CTF-S is the made lithium-sulfur cell of positive electrode in 0.1mVs-1Cyclic voltammogram under sweep speed, (f) with
CTF-S is the made lithium-sulfur cell of positive electrode in 0.1mV s-1Cyclic voltammogram under sweep speed；
Fig. 5 is respectively with S@CTF-S, CS2- CTF-S, CTF-S are the made lithium-sulfur cell of positive electrode under 0.5C multiplying powers
Stable circulation performance figure and coulombic efficiency figure；
Fig. 6 is imitated using the S@CTF-S stable circulation performance figures for being the made lithium-sulfur cell of positive electrode under 1C multiplying powers and coulomb
Rate figure；
Fig. 7 is respectively with S@CTF-S, CS2- CTF-S, CTF-S are the AC impedance figure of the made lithium-sulfur cell of positive electrode；
Fig. 8 is using S@CTF-S as the high rate performance figure of the made lithium-sulfur cell of positive electrode.
Specific implementation mode
Below in conjunction with attached drawing, invention is further described in detail.
Specific implementation
(1) 3.5g sublimed sulfurs are first dissolved in 7.6g CS2In, ultrasonic disperse 5min；5.4g diaminomaleonitriles are added,
Ultrasonic disperse 30min；Then mixed liquor is put into autoclave, vacuumizes and sealed after mending nitrogen three times repeatedly, in 400 DEG C of item
12h is heated under part；By products therefrom and sublimed sulfur in mass ratio 40:It is put into glass tube after 60 grindings uniformly, vacuumizes sealing；
Glass tube is put into tube furnace and heats 12h at 155 DEG C, is then warming up to 200 DEG C of heating 30min.Finally, composite wood is prepared
Expect [email protected] not added with sublimed sulfur presulfurization and being not added with distillation for 66% sulfur content is prepared respectively with above-mentioned identical method
Sulphur and CS2The composite material of presulfurization, is respectively labeled as CS2- CTF-S and CTF-S.
(2) 7 are pressed：2：1 mass ratio weighs composite material, acetylene black and Kynoar (PVDF), and three uniformly mixes
Form slurry；By slurry even application on aluminium foil, being put into vacuum drying chamber 60 DEG C of dry 12h to get lithium-sulphur cell positive electrode.
(3) pole piece is made in the thin slice that positive electrode is cut into a diameter of 12mm.It is to electrode, full of argon with lithium metal
CR2032 type button cells are made in the glove box of gas, diaphragm uses more microporous polypropylene membranes (Celgard2400, the U.S.),
Electrolyte is l.0mol L-1Bis- (trimethyl fluoride sulfonyl) imine lithiums be dissolved in volume ratio 1:1 1,3- dioxolanes and second two
The mixed liquor that diethylene glycol dimethyl ether is matched, additive are the anhydrous nitric acid lithium of mass fraction 1wt%.It is surveyed using LandCT2001A batteries
The charge-discharge performance of test system test sample, charge and discharge final voltage are 1.7-2.8V.Cyclic voltammetry uses Shanghai Chen Hua
CHI760E electrochemical workstations are tested, sweep speed 0.1mVs-1, voltage range 1.7-2.8V.
It is analyzed and characterized
Sample is carried out using Dutch X ' Pert PRO MPD types X-ray diffractometer (XRD, CuK α, λ=0.15406nm)
Structure, material phase analysis.Sulphur using German STA 409PC Luxx thermogravimetric analyzers (TGA) test sample in a nitrogen atmosphere contains
Amount.Contained element and functional group pass through 670 type examination of infrared spectrum instrument (FT- of U.S. Thermo Nicolet NEXUS in sample
IR it) is analyzed with Thermo Scientific ESCALab250Xi multifunctional light electronics energy disperse spectroscopies (XPS, AlK α).
As a result it and analyzes：
In order to obtain in S@CTF-S composite materials sulphur content, thermal weight loss test (such as Fig. 1) has been carried out to the sample.According to
Between Fig. 1 is it is found that the loss of sulphur occurs mainly in 200~400 DEG C, the content of sulphur is 66% in composite material.200~350
About 58% sulphur loss between DEG C, this part are mainly to melt to be diffused into sulphur in composite material, 350~400 DEG C it
Between about 8% sulphur loss, this part be mainly with chemical interactions be fixed to composite material in sulphur.
Fig. 2 is the X-ray diffractogram of S@CTF-S composite materials and sublimed sulfur.Fig. 2 (a) sulphur crystal compared with Fig. 2 (b)
Diffraction maximum obviously weakens, and illustrates that most sulphur all has enter into material internal.
In order to further verify the chemical composition of composite material, S@CTF-S composite materials XPS tests have been subjected to.Such as Fig. 3
(a) C1s shown in is segmented into 3 peaks, corresponds to C-N=C (288.6ev), C-S (286.1ev), C-C (284.6ev) respectively.
As shown in Fig. 3 (b), the peaks N1s are segmented into two peaks, correspond to pyridine type N (398.3eV) and the higher pyrrole of conjugation degree respectively
Cough up type N (399.5eV).Theoretical research shows that the hole on pyridine type N and electronic defects position are conducive to the quick biography of lithium ion
It is defeated, to improve the electric conductivity of material.The S2p as shown in Fig. 4 (c) is segmented into four kinds of peaks, corresponds to C-S (168ev), C- respectively
Sn- C (164.8ev), C-Sn- C (163.6ev), S-S (161.7ev), in composite material the formation of C-S illustrate sulphur with chemical bond
Form is fixed on CTF material internals.In summary analysis it is inferred that successfully prepared S@CTF-S composite materials herein.
Fig. 4 is S@CTF-S, CS2- CTF-S and CTF-S the 1st, 2,100 and 700 constant current under 0.5C current densities is filled
Discharge curve and in 0.1mV s-1Cyclic voltammogram under sweep speed, the S@CTF-S lithiums it can be seen from Fig. 4 (a), (b), (c)
Δ E=243mV between sulphur battery charging and discharging platform, and CS2Δ between-CTF-S and CTF-S lithium-sulfur cell charge and discharge platforms
E is respectively 317mV and 292mV.Illustrate the lower electrode polarization rate of S@CTF-S lithium-sulfur cells, makes it have smaller dynamics
React obstacle, higher invertibity.All there are two apparent reduction peak and an oxidation peaks by Fig. 4 (d), (e), (f), wherein higher
Reduction peak correspond to elemental sulfur in discharge process and be changed into soluble more lithium sulfide (LiSx, 4≤x≤8) process, relatively low reduction
Peak corresponds to soluble more lithium sulfides in discharge process and is transformed into insoluble Li2S2And Li2The process of S, an oxidation peak is to inductive charging
Li in the process2S2/Li2S is changed into S8Process.This and the charge and discharge level in the constant current charge-discharge diagram in Fig. 4 (a), (b), (c)
Platform is consistent.In addition, as can be seen that S@CTF-S are since enclosing second from cyclic voltammogram, oxidation peak and reduction peak spacing subtract
Small, after illustrating the activation by first lap, reaction resistance reduces, and invertibity and stability improve.
Fig. 5 is S@CTF-S, CS2Cycle performances and coulombic efficiency of-the CTF-S and CTF-S under the current density of 0.5C
Figure, S@CTF-S, CS2The initial capacity of-CTF-S and CTF-S is respectively 1050.8mAg-1, 681mAhg-1, 531.1mAh
g-1, after 700 cycles, capacity is kept at 544.5mAhg-1, 343.3mAhg-1, 316mAhg-1.It can be with
Find out that S@CTF-S show high specific capacity and cyclical stability.S@CTF-S composite materials can effectively inhibit wearing for more lithium sulfides
Shuttle effect carries the cyclical stability of lithium-sulfur cell, illustrates after presulfurization between sulphur and triazine frame structure in a manner of C-S keys
In conjunction with, and stronger chemical interactions prevent the dissolving of more lithium sulfides, diffusion.
Further to prove the good cyclical stability of S@CTF-S composite materials, it is tested under 1C current densities
Constant current charge-discharge curve.As shown in fig. 6, the initial capacity of S@CTF-S is 834.1mAg-1, after 700 cycles, hold
Amount conservation rate is maintained at 447.9mAg-1, coulombic efficiency is still up to 97.5%, illustrates the good cyclical stabilities of S@CTF-S.
Further to analyze the reason of S@CTF-S composite material batteries are with superperformance, respectively to three kinds of composite materials
Lithium-sulfur cell carried out ac impedance measurement.As seen from Figure 7, AC impedance curve is by the circular arc of high frequency region and low
The rectilinear(-al) in frequency area.Half circular diameter of high frequency region is smaller, and resistance is smaller.With CS2- CTF-S is compared with CTF-S composite materials,
The impedance of S@CTF-S composite materials reduces, and illustrates that the presence of sulphur promotes covalent triazine frame and formed, and pass through the mutual of sulphur
Crosslinked action improves the electric conductivity of covalent triazine frame.
To further illustrate the good chemical property of S@CTF-S composite materials, high rate performance test has been carried out to it.Figure
8 for the assembled battery of S@CTF-S composite materials institute high rate performance figure, as seen from the figure, S@CTF-S composite materials batteries 0.1C,
Specific capacity can maintain 830.9mAhg respectively when 0.2C, 0.5C, 1C, 2C-1、783.2mAh·g-1、706.3mAh·g-1、
605.3mAh·g-1, specific capacity remains to return to 531.9mAhg when returning 0.5C-1, illustrate S@CTF-S composite material electricity
Pond has good high rate performance.
It is reacted at high temperature using diaminomaleonitrile and sulphur herein and carries out presulfurization, pass through the freedom formed under sulphur high temperature
Base catalyzes and synthesizes covalent triazine frame, while sulphur is fixed in the form of C-S keys on polymer backbone, followed by fusion method
More sulphur are loaded on covalent triazine frame, to prepare S@CTF-S composite materials, which is used for lithium sulphur
Good chemical property is shown when anode：Under the current density of 1C, its specific discharge capacity is still high after recycling 700 times
Up to 447.9mAh g-1, coulombic efficiency is maintained at 97.5% or more.This, which is attributed to sulphur and is polymerized to triazine frame structure to cyano three, plays
There is the covalent triazine frame of facilitation, presulfurization large hole to have conducive to the payload of high-content sulphur；Nitrogen-atoms is mixed
Miscellaneous covalent triazine frame has good electric conductivity, and covalent triazine frame is further increased by the effect of being cross-linked with each other of sulphur
Electric conductivity, so as to effectively improve sulphur positive conductive；Stable covalent triazine frame structure can alleviate sulphur in charge and discharge process
Anode volume expands and shrinks the destruction to anode；The sulphur of material internal is fixed on chemical bond form can effectively inhibit to vulcanize more
The shuttle effect of lithium.
Claims (2)
1. a kind of composite material and preparation method for lithium-sulphur cell positive electrode, it is characterised in that：It is first that 3.5g sublimed sulfurs is molten
In 7.6g CS2In, ultrasonic disperse 5min；Add 5.4g diaminomaleonitriles, ultrasonic disperse 30min；Then mixed liquor is put
Enter in autoclave, vacuumizes and sealed after mending nitrogen three times repeatedly, 12h is heated under the conditions of 400 DEG C；By products therefrom and distillation
Sulphur in mass ratio 40:It is put into glass tube after 60 grindings uniformly, vacuumizes sealing；Glass tube is put into tube furnace at 155 DEG C
12h is heated, 200 DEG C of heating 30min are then warming up to.Finally, composite material S@CTF-S are prepared, and are applied to button
Formula lithium-sulphur cell positive electrode.
2. button-shaped lithium-sulfur cell according to claim 1, it is characterised in that：By 7：2：1 mass ratio weighs composite wood
Material, acetylene black and Kynoar (PVDF), three is uniformly mixed to form slurry；By slurry even application on aluminium foil, it is put into
60 DEG C of dry 12h in vacuum drying chamber；The circular electric pole piece that electrode slice is cut into a diameter of 12mm is to electricity with lithium metal
Pole makes the button-shaped lithium-sulfur cell of CR2032 types in the glove box full of argon gas.
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| CN109449393A (en) * | 2018-10-17 | 2019-03-08 | 深圳大学 | Porous vulcanization covalent organic framework of one kind and preparation method thereof and lithium-sulfur cell |
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| CN109950472A (en) * | 2019-03-21 | 2019-06-28 | 华中科技大学 | A kind of lithium sulfur battery anode material and preparation method thereof, electrode slice and lithium-sulfur cell |
| CN113113591A (en) * | 2021-03-22 | 2021-07-13 | 杭州电子科技大学 | Method for improving rate performance of lithium-sulfur battery |
| CN114171741A (en) * | 2020-09-11 | 2022-03-11 | 天津工业大学 | Positive active material carrier of lithium-sulfur battery and preparation method thereof |
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| CN109449393A (en) * | 2018-10-17 | 2019-03-08 | 深圳大学 | Porous vulcanization covalent organic framework of one kind and preparation method thereof and lithium-sulfur cell |
| CN109546149A (en) * | 2018-10-23 | 2019-03-29 | 北京航空航天大学 | A kind of lithium-sulphur cell positive electrode copolymerization sulfur materials and with its manufactured lithium-sulfur cell |
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| CN109950472A (en) * | 2019-03-21 | 2019-06-28 | 华中科技大学 | A kind of lithium sulfur battery anode material and preparation method thereof, electrode slice and lithium-sulfur cell |
| CN109950472B (en) * | 2019-03-21 | 2020-11-24 | 华中科技大学 | Lithium-sulfur battery positive electrode material, preparation method thereof, electrode plate and lithium-sulfur battery |
| CN114171741A (en) * | 2020-09-11 | 2022-03-11 | 天津工业大学 | Positive active material carrier of lithium-sulfur battery and preparation method thereof |
| CN113113591A (en) * | 2021-03-22 | 2021-07-13 | 杭州电子科技大学 | Method for improving rate performance of lithium-sulfur battery |
| CN114736370A (en) * | 2022-04-25 | 2022-07-12 | 吉林师范大学 | Fluorine-doped covalent triazine skeleton polymer and sulfur-containing compound thereof, and preparation method and application thereof |
| CN114784452A (en) * | 2022-05-24 | 2022-07-22 | 南京工业大学 | Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material |
| CN114784452B (en) * | 2022-05-24 | 2023-09-26 | 南京工业大学 | Method for preparing lithium-sulfur battery diaphragm material by using fluorine-containing covalent organic framework material |
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