CN109755503A - The preparation method and its application in lithium-sulfur cell that manganese sub-group compound/carbon pipe carries sulphur composite material - Google Patents
The preparation method and its application in lithium-sulfur cell that manganese sub-group compound/carbon pipe carries sulphur composite material Download PDFInfo
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- CN109755503A CN109755503A CN201811521713.7A CN201811521713A CN109755503A CN 109755503 A CN109755503 A CN 109755503A CN 201811521713 A CN201811521713 A CN 201811521713A CN 109755503 A CN109755503 A CN 109755503A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The preparation method for carrying sulphur composite material the present invention provides manganese sub-group compound/carbon pipe and its application in lithium-sulfur cell, process are as follows: by carbon pipe and sulphur simple substance mixed grinding, CS is added2It is dried after being sufficiently stirred and carbon pipe load sulphur composite material is made；Carbon pipe is carried sulphur composite material to mix with carbon black, Kynoar by certain mass ratio, then N-Methyl pyrrolidone is added, and simultaneously ultrasonic disperse is uniform for manganese sub-group compound stirring, gained slurry is coated uniformly in current collector aluminum foil, then aluminium foil is transferred to drying in oven and carries sulphur composite positive pole to get manganese sub-group compound and carbon pipe；Preparation method provided by the invention, easy to operate, mild condition are easy to be mass produced；Manganese sub-group compound obtained and carbon pipe carry sulphur composite positive pole in lithium-sulfur cell, it can solve dissolution of more sulphions in liquid electrolyte in lithium-sulfur cell charge and discharge process, effectively inhibit shuttle effect, improves the coulombic efficiency and cyclical stability of lithium-sulfur cell.
Description
Technical field
The invention belongs to nanocomposite research fields, in particular to a kind of to improve its electrochemistry for lithium-sulfur cell
Manganese sub-group compound/carbon pipe composite positive pole preparation method of can and inhibit polysulfide shuttle effect etc..
Background technique
With the progress of rapid economic development and people life style, demand of the people to the energy is growing, however
The exhaustion increasingly of environmental pollution and its reserves caused by fossil fuel, so that demand of the people to novel alternative energy source is more and more tighter
Compel.New energy, especially chemical energy source have the characteristics that clean and environmental protection and safe and efficient, meet human kind sustainable development strategy
It is required that and gaining great popularity.Currently, installing solar panel and wind power plant in global range, but to make full use of
These intermittent energy sources, chargeable cell system are vital a part.Since lithium ion battery is commercialized since 1991,
By development in more than 20 years, the performance of the positive and negative pole material of conventional lithium ion battery had been approached its theoretical limit, but in face of more
It is still unsatisfactory to carry out huger energy-storage system.Lithium-sulfur cell is 1675mAhg due to its theoretical specific capacity-1, be traditional lithium from
10 times of sub- battery, and the rich reserves of sulphur, cheap, the low toxicity advantages such as nuisanceless cause the extensive concern of people.
However, lithium-sulfur cell is easy to produce volume expansion and lithium corrosion in shuttle effect and charge and discharge process in charge and discharge process
The problems such as make the problems such as lithium-sulfur cell active material utilization is low, coulombic efficiency is low, poor circulation, become lithium-sulfur cell
Obstruction during business application.
In order to solve these problems, its large-scale use is realized, it is necessary to design and develop novel electrode structure, develop
Easy and low-cost preparation method improves the chemical property of lithium-sulfur cell, to promote the practical application of lithium-sulfur cell
Prospect.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that providing a kind of manganese sub-group compound/carbon pipe load sulphur composite wood
The preparation method of material and its application in lithium-sulfur cell.Manganese sub-group compound of the invention/carbon pipe carries sulphur composite material and improves
The problems such as electric conductivity of sulphur lithium battery anode and the shuttle effect of polysulfide, excellent cyclical stability is shown, has been had
The advantage of large-scale production.
To achieve the above object, first goal of the invention of the invention be to provide it is a kind of the following steps are included:
(1) carbon pipe carries the preparation of sulphur composite material: carbon pipe being mixed with elemental sulfur 1:1~2 in mass ratio, after grinding uniformly
CS is added with feed liquid mass ratio 1:10~152Middle stirring is subsequently placed in room temperature down toward CS2After volatilization completely, surplus materials is in 120
8~12h is kept the temperature in~160 DEG C of baking ovens, is cooled to room temperature carries sulphur composite material to get carbon pipe later；
(2) manganese sub-group compound/carbon pipe carries the preparation of sulphur composite material: by carbon pipe obtained by step (1) carry sulphur composite material with
Conductive additive carbon black, binder Kynoar are mixed together, and solvent N-methyl pyrilidone and manganese systems are then added
It closes object stirring and ultrasonic disperse is uniform, control viscosity in 1000~10000cps, composite material sizing agent is obtained, by gained composite wood
The drying of slurry material carries sulphur composite material to get manganese sub-group compound/carbon pipe, and the manganese sub-group compound is to the oxygen in lithium-sulfur cell
Changing reduction reaction has catalyzed conversion ability, and the carbon pipe carries sulphur composite material, carbon black, Kynoar and manganese sub-group compound
Mass ratio be (300-400): (15-50): (15-50): (3-5).
Further setting is the collector aluminium for being coated uniformly on composite material sizing agent with 150~400mm thickness with scraper
On foil, current collector aluminum foil is then transferred to 40~60 DEG C of drying in oven to get the manganese sub-group compound and carbon pipe of flake shape
Negative sulphur composite positive pole.
Further setting is the current collector aluminum foil with a thickness of 30um, and N-Methyl pyrrolidone is used before use
And alcohol washes, it is spare after natural air drying to remove surface oxide layer and impurity.
It is Tetraphenyl porphyrin manganese, manganese acetylacetonate (III), (1S, 2S)-that further setting, which is the manganese sub-group compound,
(+)-[1,2- cyclohexane diamine nitrogen-N, N'- bis- (3,5- di-t-butyl salicylidenes)] manganese chloride (III) or three (2,2,6,6-
Tetramethyl -3,5- heptenoic acid) manganese.
A second object of the present invention is to provide a kind of manganese sub-group compound prepared by preparation method as mentioned/carbon pipes to carry
Sulphur composite material.
The present invention also provides a kind of composite materials as mentioned to apply in lithium sulfur battery anode material.
Influence test of the manganese sub-group compound of the present invention/carbon pipe composite positive pole to lithium-sulfur cell performance:
(1) assembling of battery: manganese sub-group compound produced by the present invention and carbon pipe are carried into sulphur composite positive pole, are cut into diameter
It for the circular piece of 14mm, weighs under dry environment, and deducts blank aluminium flake quality, it is stand-by that anode pole piece is made；As right
It according to the facts tests, it is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole without manganese sub-group compound in the same way；
It is being full of argon gas, water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm: with commercial metals
Lithium piece is for reference electrode and to electrode, using double trifluoromethanesulfonimide lithiums/1,3-dioxolane (DOL), glycol dinitrate
Ether (DME) LiTFSI/DOL.DMC (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, assembling
After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test；
(2) battery charging and discharging test is carried out under different multiplying using blue electricity/new prestige battery test system, test condition is
Room temperature environment, window voltage are 1.5~3.0V；
Heretofore described room temperature is 10~30 DEG C.
The beneficial effects of the present invention are:
(1) using the redox reaction in manganese sub-group compound energy catalytic cell；
(2) manganese sub-group compound and carbon pipe prepared carries sulphur composite positive pole, can be additionally provided electrons/ions conduction way
Diameter reduces the internal resistance of cell, greatly enhances the discharge capacity and stable circulation performance of battery；
(3) composite positive pole containing manganese sub-group compound can enhance accelerates to chemically react with the reactivity of polysulfide
Dynamics improves lithium-sulfur cell performance to inhibit shuttle effect；
(4) carrier porous carbon provide storage sulphur space, and can limit polysulfide, lithium sulfide diffusion and transport；
In summary, on the one hand, the present invention provides the preparation sides that manganese sub-group compound/carbon pipe carries sulphur composite positive pole
Method, it is easy to operate, it is not related to high temperature and pressure, can be completed at room temperature, is easy to be mass produced；On the other hand, it obtained will be somebody's turn to do
Composite positive pole is in lithium-sulfur cell, can solve in lithium-sulfur cell charge and discharge process more sulphions in liquid electrolyte
Dissolution, effectively inhibit shuttle effect, improve the coulombic efficiency and cyclical stability of lithium-sulfur cell.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
Fig. 1: Tetraphenyl porphyrin manganese C made from the embodiment of the present invention 144H30ClMnN4Sulphur composite positive pole is carried with carbon pipe to use
In lithium-sulfur cell and the lithium-sulfur cell high rate performance comparison diagram for being free of manganese sub-group compound material；
Fig. 2: Tetraphenyl porphyrin manganese C made from the embodiment of the present invention 144H30ClMnN4Sulphur composite positive pole is carried with carbon pipe to use
In lithium-sulfur cell and be free of Tetraphenyl porphyrin manganese C44H30ClMnN4Charge and discharge platform comparison diagram of the lithium-sulfur cell of material at 1C；
Fig. 3: Tetraphenyl porphyrin manganese C made from the embodiment of the present invention 144H30ClMnN4It is used with carbon pipe graphite composite positive pole
Cycle performance figure when lithium-sulfur cell.
Fig. 4: four kinds of manganese sub-group compound (Tetraphenyl porphyrin manganese C made from the embodiment of the present invention 1,2,3,444H30ClMnN4、
(1S, 2S)-(+)-[1,2- cyclohexane diamine nitrogen-N, N'- bis- (3,5- di-t-butyl salicylidenes)] manganese chloride (III)
C36H52ClMnN2O2, three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C11H19O2)3, manganese acetylacetonate (III)
C15H21MnO6) be used for lithium-sulfur cell with carbon pipe load sulphur composite positive pole and be free of the lithium-sulfur cell multiplying power of manganese sub-group compound material
Performance comparison figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
Embodiment 1: Tetraphenyl porphyrin manganese C44H30ClMnN4The preparation of sulphur composite positive pole is carried with carbon pipe and in lithium sulphur electricity
It is applied in pond
(1) carbon pipe carries the preparation of sulphur composite material: the carbon pipe and 200mg elemental sulfur for taking 200mg in mortar, by porous carbon and
Sulphur is fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 3.2mLCS is added2It is sufficiently stirred, to CS2Volatilization
Completely, mixture is transferred to 120 DEG C of baking oven heat preservation 12h, be cooled to room temperature later, it is multiple up to carbon pipe load sulphur to collect products therefrom
Condensation material；
(2) Tetraphenyl porphyrin manganese C44H30ClMnN4The preparation of carbon pipe load sulphur composite positive pole: carbon pipe is carried into sulphur composite wood
Expect 300mg and conductive additive carbon black 15mg, bonding agent Kynoar 15mg, 3~4mg Tetraphenyl porphyrin manganese C44H30ClMnN4
Then mixing is added 2.5mL NMP and ultrasonic disperse, is sufficiently stirred, control the viscosity of slurry in 10000cps, then with
The thickness of 150mm is coated in (aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer in current collector aluminum foil with scraper
And impurity, natural air drying, aluminum foil thickness 30um).Then aluminium foil is transferred in 40 DEG C of baking ovens, drying to get to it is required just
Pole material；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, tetraphenyl porphin is free of
Quinoline manganese C44H30ClMnN4Carbon pipe carry sulphur composite positive pole be also made in the same way control anode pole piece it is stand-by；It is being full of argon
Gas, water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and
To electrode, using LiTFSI/DOL.DMC (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400,
It is assembled into after CR2025 button cell, stands for 24 hours, then carry out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
Fig. 1 is Tetraphenyl porphyrin manganese C made from the present embodiment44H30ClMnN4Carbon pipe carries sulphur composite positive pole and is used for lithium sulphur
Battery and no addition Tetraphenyl porphyrin manganese C44H30ClMnN4Lithium-sulfur cell high rate performance comparison diagram, it can be seen from the figure that
With Tetraphenyl porphyrin manganese C44H30ClMnN4Carbon pipe carry the lithium-sulfur cell capacity of sulphur composite material and be substantially better than and do not add four
Phenyl Manganese Porphyrin C44H30ClMnN4Battery.
Fig. 2 is Tetraphenyl porphyrin manganese C44H30ClMnN4Carbon pipe carries sulphur composite positive pole for lithium-sulfur cell and is free of four benzene
Base Manganese Porphyrin C44H30ClMnN4Charge and discharge platform comparison diagram of the lithium-sulfur cell at 1C, from the graph, it is apparent that containing
Tetraphenyl porphyrin manganese C44H30ClMnN4The lithium-sulfur cell of positive electrode possess higher discharge capacity.
Fig. 3 is Tetraphenyl porphyrin manganese C44H30ClMnN4Carbon pipe carry sulphur composite positive pole be used for lithium-sulfur cell, be free of four
Phenyl Manganese Porphyrin C44H30ClMnN4Lithium-sulfur cell comparison, carry out cyclical stability test, it can be seen that contain tetraphenyl porphin
Quinoline manganese C44H30ClMnN4Stability test and capacity it is good.
Embodiment 2:(1S, 2S)-(+)-[1,2- cyclohexane diamine nitrogen-N, N'- bis- (3,5- di-t-butyl salicylidenes)]
Manganese chloride (III) C36H52ClMnN2O2The preparation of sulphur composite positive pole is carried with carbon pipe and is applied in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: taking the above-mentioned resulting carbon pipe composite material of 200mg and 400mg elemental sulfur
In mortar, porous carbon and sulphur are fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 6mL CS is added2
It is sufficiently stirred, to CS2Volatilization is transferred to 150 DEG C of baking oven heat preservation 10h completely, by mixture, is cooled to room temperature later, collects gained
Product carries sulphur composite material up to carbon pipe；
(2) (1S, 2S)-(+)-[1,2- cyclohexane diamine nitrogen-N, N'- bis- (3,5- di-t-butyl salicylidenes)] chlorination
Manganese (III) C36H52ClMnN2O2The preparation of carbon pipe load sulphur composite positive pole: carbon pipe is carried into sulphur composite material 400mg and is added with conduction
Adding agent carbon black 50mg, bonding agent Kynoar 50mg, 4~5mg (1S, 2S)-(+)-, [1,2- cyclohexane diamine nitrogen-N, N'- is bis-
(3,5- di-t-butyl salicylidene)] manganese chloride (III) C36H52ClMnN2O2Then 3.5mL NMP and ultrasound point is added in mixing
It dissipates, be sufficiently stirred, control the viscosity of slurry in 6000cps, current collector aluminum foil is then coated in the thickness of 150mm scraper
Upper (aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).So
Aluminium foil is transferred in 50 DEG C of baking ovens afterwards, is dried to get required positive electrode is arrived；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, each manganese systems are free of
It is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole of conjunction object in the same way；It is being full of argon gas, water and oxygen
Gas content is respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, adopt
With LiTFSI/DOL.DMC (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, be assembled into
After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
It include (1S, 2S)-(+)-[bis- (the 3,5- di-t-butyl Asia bigcatkin willows of 1,2- cyclohexane diamine nitrogen-N, N'- in Fig. 4
Base)] manganese chloride (III) C36H52ClMnN2O2Carbon pipe carries sulphur composite positive pole for lithium-sulfur cell and is free of manganese sub-group compound material
The lithium-sulfur cell high rate performance comparison diagram of material, from the graph, it is apparent that the lithium of the positive electrode containing the manganese sub-group compound
Sulphur battery possesses higher discharge capacity under each multiplying power.
Embodiment 3: three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C11H19O2)3Sulphur anode composite is carried with carbon pipe
It the preparation of material and is applied in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: taking the above-mentioned resulting carbon pipe composite material of 200mg and 400mg elemental sulfur
In mortar, porous carbon and sulphur are fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 6mL CS is added2
It is sufficiently stirred, to CS2Volatilization is transferred to 150 DEG C of baking oven heat preservation 10h completely, by mixture, is cooled to room temperature later, collects gained
Product carries sulphur composite material up to carbon pipe；
(2) three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C11H19O2)3The system of carbon pipe load sulphur composite positive pole
It is standby: carbon pipe is carried into sulphur composite material 400mg and conductive additive carbon black 50mg, bonding agent Kynoar 50mg, 4~5mg tri-
(2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C11H19O2)3Then 3.5mL NMP and ultrasonic disperse, sufficiently is added in mixing
Stirring controls the viscosity of slurry in 6000cps, is then coated in (aluminium foil in current collector aluminum foil with the thickness of 150mm scraper
With NMP and twice of alcohol washes, to remove surface oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then by aluminium
Foil is transferred in 50 DEG C of baking ovens, is dried to get required positive electrode is arrived；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, manganese systems chemical combination is free of
It is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole of object in the same way；It is being full of argon gas, water and oxygen
Content is respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, use
LiTFSI/DOL.DMC (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, be assembled into
After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
It include three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C in Fig. 411H19O2)3Carbon pipe carries sulphur anode composite material
Material, can be obviously from figure for lithium-sulfur cell and the lithium-sulfur cell high rate performance comparison diagram for being free of manganese sub-group compound material
Out, contain three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese Mn (C11H19O2)3Positive electrode lithium-sulfur cell at each times
Possess higher discharge capacity under rate.
Embodiment 4: manganese acetylacetonate (III) C15H21MnO6The preparation of sulphur composite positive pole is carried with carbon pipe and in lithium sulphur electricity
It is applied in pond
(1) carbon pipe carries the preparation of sulphur composite material: taking the above-mentioned resulting carbon pipe composite material of 200mg and 400mg elemental sulfur
In mortar, porous carbon and sulphur are fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 6mL CS is added2
It is sufficiently stirred, to CS2Volatilization is transferred to 150 DEG C of baking oven heat preservation 10h completely, by mixture, is cooled to room temperature later, collects gained
Product carries sulphur composite material up to carbon pipe；
(2) manganese acetylacetonate (III) C15H21MnO6The preparation of carbon pipe load sulphur composite positive pole: carbon pipe is carried into sulphur composite wood
Expect 400mg and conductive additive carbon black 50mg, bonding agent Kynoar 50mg, 4~5mg manganese acetylacetonate (III)
C15H21MnO6Then mixing is added 3.5mL NMP and ultrasonic disperse, is sufficiently stirred, control the viscosity of slurry in 6000cps,
(aluminium foil NMP and twice of alcohol washes, to remove surface in current collector aluminum foil are then coated in the thickness of 150mm scraper
Oxide layer and impurity, natural air drying, aluminum foil thickness 30um).Then aluminium foil is transferred in 50 DEG C of baking ovens, is dried to get arriving
Required positive electrode；
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry
It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, each manganese systems are free of
It is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole of conjunction object in the same way；It is being full of argon gas, water and oxygen
Gas content is respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, adopt
With LiTFSI/DOL.DMC (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, be assembled into
After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test；
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment,
Window starting voltage is 1.5V, final voltage 3.0V；
It include manganese acetylacetonate (III) C in Fig. 415H21MnO6Carbon pipe carries sulphur composite positive pole and is respectively used to lithium-sulfur cell
Be free of manganese sub-group compound material lithium-sulfur cell high rate performance comparison diagram, from the graph, it is apparent that containing acetylacetone,2,4-pentanedione
Manganese (III) C15H21MnO6The lithium-sulfur cell of positive electrode possess higher discharge capacity under each multiplying power.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (6)
1. the preparation method that a kind of manganese sub-group compound/carbon pipe carries sulphur composite material, it is characterised in that the following steps are included:
(1) carbon pipe carries the preparation of sulphur composite material: carbon pipe being mixed with elemental sulfur 1:1~2 in mass ratio, with material after grinding uniformly
CS is added in liquid mass ratio 1:10~152Middle stirring is subsequently placed in room temperature down toward CS2After volatilization completely, surplus materials is in 120~160
8~12h is kept the temperature in DEG C baking oven, is cooled to room temperature carries sulphur composite material to get carbon pipe later；
(2) manganese sub-group compound/carbon pipe carries the preparation of sulphur composite material: carbon pipe obtained by step (1) is carried sulphur composite material and conduction
Additive carbon black, binder Kynoar are mixed together, and solvent N-methyl pyrilidone and manganese sub-group compound is then added
It stirs and ultrasonic disperse is uniform, control viscosity in 1000~10000cps, composite material sizing agent is obtained, by gained composite wood slurry
Material drying carries sulphur composite material to get manganese sub-group compound/carbon pipe, the manganese sub-group compound be to the oxidation in lithium-sulfur cell also
Original reaction has catalyzed conversion ability, and the carbon pipe carries the matter of sulphur composite material, carbon black, Kynoar and manganese sub-group compound
Amount is than being (300-400): (15-50): (15-50): (3-5).
2. the preparation method that manganese sub-group compound according to claim 1/carbon pipe carries sulphur composite material, it is characterised in that: will
In the current collector aluminum foil that composite material sizing agent is coated uniformly on scraper with 150~400mm thickness, then current collector aluminum foil is turned
40~60 DEG C of drying in oven are moved to get the manganese sub-group compound and the negative sulphur composite positive pole of carbon pipe of flake shape.
3. the preparation method that manganese sub-group compound according to claim 1/carbon pipe carries sulphur composite material, it is characterised in that: institute
The current collector aluminum foil stated with a thickness of 30um, N-Methyl pyrrolidone and alcohol washes are being used using preceding, to remove surface
Oxide layer and impurity, it is spare after natural air drying.
4. the preparation method that manganese sub-group compound according to claim 1/carbon pipe carries sulphur composite material, it is characterised in that: institute
The manganese sub-group compound stated be Tetraphenyl porphyrin manganese, manganese acetylacetonate (III), (1S, 2S)-(+)-[1,2- cyclohexane diamine nitrogen-N,
N'- bis- (3,5- di-t-butyl salicylidenes)] manganese chloride (III) or three (2,2,6,6- tetramethyl -3,5- heptenoic acid) manganese.
5. a kind of manganese sub-group compound prepared by preparation method as described in one of claim 1-4/carbon pipe carries sulphur composite material.
6. a kind of composite material as claimed in claim 5 is applied in lithium sulfur battery anode material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811521713.7A CN109755503B (en) | 2018-12-13 | 2018-12-13 | Preparation method of manganese compound/carbon tube sulfur-carrying composite material and application of manganese compound/carbon tube sulfur-carrying composite material in lithium-sulfur battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811521713.7A CN109755503B (en) | 2018-12-13 | 2018-12-13 | Preparation method of manganese compound/carbon tube sulfur-carrying composite material and application of manganese compound/carbon tube sulfur-carrying composite material in lithium-sulfur battery |
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| CN109755503A true CN109755503A (en) | 2019-05-14 |
| CN109755503B CN109755503B (en) | 2021-09-07 |
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