CN109755503B - 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 - Google Patents
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 Download PDFInfo
- Publication number
- CN109755503B CN109755503B CN201811521713.7A CN201811521713A CN109755503B CN 109755503 B CN109755503 B CN 109755503B CN 201811521713 A CN201811521713 A CN 201811521713A CN 109755503 B CN109755503 B CN 109755503B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- carbon tube
- composite material
- lithium
- manganese compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of a manganese compound/carbon tube sulfur-carrying composite material and application thereof in a lithium-sulfur battery, wherein the preparation method comprises the following steps: mixing and grinding carbon tube and sulfur, adding CS2Fully stirring and drying to obtain the carbon tube sulfur-carrying composite material; mixing the carbon tube sulfur-carrying composite material with carbon black and polyvinylidene fluoride according to a certain mass ratio, adding N-methyl pyrrolidone and a manganese compound, stirring and ultrasonically dispersing uniformly, uniformly coating the obtained slurry on a current collector aluminum foil, and transferring the aluminum foil into an oven to be dried to obtain the manganese compound and carbon tube sulfur-carrying composite positive electrode material; the preparation method provided by the invention is simple to operate, mild in condition and easy for large-scale production; the prepared manganese compound and carbon tube sulfur-loaded composite cathode material is used in the lithium-sulfur battery, can solve the problem that polysulfide ions are dissolved in liquid electrolyte in the charging and discharging processes of the lithium-sulfur battery, effectively inhibits the shuttle effect, and improves the coulombic efficiency and the cycle stability of the lithium-sulfur battery.
Description
Technical Field
The invention belongs to the field of nano composite material research, and particularly relates to a preparation method of a manganese compound/carbon tube composite positive electrode material for a lithium-sulfur battery in the aspects of improving the electrochemical performance of the lithium-sulfur battery, inhibiting polysulfide shuttling effect and the like.
Background
With the rapid development of economy and the improvement of life style of people, the demand of people on energy is increasing day by day, however, the environmental pollution and the exhaustion of reserves thereof caused by fossil fuel make the demand of people on novel alternative energy more and more urgent. The new energy, especially the chemical energy, has the characteristics of cleanness, environmental protection, safety, high efficiency and the like, and is favored by meeting the requirements of the strategy of sustainable development of human beings. Solar panels and wind farms are currently being installed worldwide, but to take full advantage of these intermittent energy sources, rechargeable battery systems are a vital part. Since the commercialization of lithium ion batteries in 1991, through the development of more than 20 years, the performances of the anode and cathode materials of the traditional lithium ion batteries are close to the theoretical limit, but the lithium ion batteries still have unsatisfactory effects in terms of increasingly large energy storage systems. The theoretical specific capacity of the lithium-sulfur battery is 1675 mAh.g-1The lithium ion battery is 10 times of the traditional lithium ion battery, and has the advantages of rich sulfur storage, low price, low toxicity, no public nuisance and the like, thereby bringing wide attention to people. However, the shuttling effect of the lithium-sulfur battery is easy to generate during the charging and discharging process, and the problems of volume expansion, lithium corrosion and the like during the charging and discharging process cause the problems of low utilization rate of active materials, low coulombic efficiency, poor cycle performance and the like of the lithium-sulfur battery, so that the shuttling effect becomes an obstacle in the commercial application process of the lithium-sulfur battery.
In order to solve the problems and realize large-scale use of the lithium sulfur battery, a novel electrode structure needs to be designed and developed, and a simple and convenient preparation method with low cost is developed to improve the electrochemical performance of the lithium sulfur battery, so that the practical application prospect of the lithium sulfur battery is improved.
Disclosure of Invention
The technical problem to be solved by the embodiments of the present invention is to provide a preparation method of a manganese compound/carbon tube sulfur-loaded composite material and an application thereof in a lithium-sulfur battery. The manganese compound/carbon tube sulfur-carrying composite material provided by the invention improves the problems of conductivity of the positive electrode of the lithium sulfur battery, shuttle effect of polysulfide and the like, shows excellent cycle stability and has the advantage of large-scale production.
To achieve the above object, a first object of the present invention is to provide a method comprising the steps of:
(1) preparing a carbon tube sulfur-carrying composite material: mixing a carbon tube and elemental sulfur according to a mass ratio of 1: 1-2, uniformly grinding, and mixing the materials in a feed liquid mass ratio of 1: 10-15 addition of CS2Stirring, and standing at room temperature to CS2After complete volatilization, preserving the heat of the residual substances in an oven at 120-160 ℃ for 8-12 h, and then cooling to room temperature to obtain the carbon tube sulfur-carrying composite material;
(2) preparation of manganese compound/carbon tube sulfur-carrying composite material: mixing the carbon tube sulfur-carrying composite material obtained in the step (1) with conductive additive carbon black and binder polyvinylidene fluoride, adding solvent N-methyl pyrrolidone and manganese compound, stirring and ultrasonically dispersing uniformly, controlling the viscosity to be 1000-10000 cps, obtaining composite material slurry, drying the obtained composite material slurry, and obtaining the manganese compound/carbon tube sulfur-carrying composite material, wherein the manganese compound has catalytic conversion capability on redox reaction in a lithium sulfur battery, and the mass ratio of the carbon tube sulfur-carrying composite material, the carbon black, the polyvinylidene fluoride and the manganese compound is (300-400): (15-50): (15-50): (3-5).
Further setting, uniformly coating the composite material slurry on a current collector aluminum foil with the thickness of 150-400 microns by using a scraper, and then transferring the current collector aluminum foil into an oven at 40-60 ℃ for drying to obtain the manganese compound and carbon tube negative sulfur composite cathode material in a sheet shape.
The current collector aluminum foil is 30um in thickness, and is cleaned by N-methyl pyrrolidone and alcohol before use to remove a surface oxide layer and impurities, and the current collector aluminum foil is naturally dried for later use.
The manganese compound is manganese tetraphenylporphyrin, manganese (III) acetylacetonate, (1S,2S) - (+) - [1, 2-cyclohexanediaminazon-N, N' -bis (3, 5-di-tert-butylsalicylidene) ] manganese (III) chloride or manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid).
The second purpose of the invention is to provide a manganese compound/carbon tube sulfur-carrying composite material prepared by the preparation method.
The invention also provides an application of the composite material in a positive electrode material of a lithium-sulfur battery.
The influence of the manganese compound/carbon tube composite positive material on the performance of the lithium-sulfur battery is tested as follows:
(1) assembling the battery: cutting the manganese compound and the carbon tube sulfur-loaded composite anode material into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum sheets to prepare an anode piece for later use; as a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without the manganese compound is also prepared into a contrast positive electrode piece for standby by the same method;
the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm: using commercial lithium metal sheets as reference electrode and counter electrode, adopting lithium bistrifluoromethanesulfonylimide/1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME) LiTFSI/DOL. DMC (1: 1) and dissolving 1% LiNO3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(2) carrying out battery charge and discharge tests under different multiplying powers by adopting a blue/Xinwei battery test system under the test conditions of room temperature environment and 1.5-3.0V of window voltage;
the room temperature in the invention is 10-30 ℃.
The invention has the beneficial effects that:
(1) manganese compounds can catalyze the oxidation-reduction reaction in the battery;
(2) the prepared manganese compound and carbon tube sulfur-loaded composite anode material can additionally provide an electron/ion conduction path, reduce the internal resistance of the battery and greatly improve the discharge capacity and the cycle stability of the battery;
(3) the composite positive electrode material containing the manganese compound can enhance the reactivity with polysulfide and accelerate the chemical reaction kinetics, thereby inhibiting the shuttle effect and improving the performance of the lithium-sulfur battery;
(4) the carrier porous carbon provides a sulfur storage space and can limit the diffusion and transportation of polysulfide and lithium sulfide;
in summary, on the one hand, the invention provides a preparation method of a manganese compound/carbon tube sulfur-carrying composite anode material, which is simple to operate, does not involve high temperature and high pressure, can be completed at room temperature, and is easy for large-scale production; on the other hand, when the prepared composite cathode material is used in a lithium-sulfur battery, the problem that polysulfide ions are dissolved in liquid electrolyte in the charging and discharging processes of the lithium-sulfur battery can be solved, the shuttle effect is effectively inhibited, and the coulomb efficiency and the cycling stability of the lithium-sulfur battery are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4The multiplying power performance of the carbon tube sulfur-carried composite anode material used for the lithium sulfur battery and the lithium sulfur battery without the manganese compound material is compared;
FIG. 2: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4Carbon tube-carried sulfur composite positive electrode material for lithium-sulfur battery and manganese C without tetraphenylporphyrin44H30ClMnN4A charge-discharge platform contrast diagram of a lithium-sulfur battery of the material at 1C;
FIG. 3: manganese tetraphenylporphyrin C prepared in example 1 of the present invention44H30ClMnN4Use of carbon tube graphite composite anode material in lithium sulfur electricityCycling performance plot for the pool.
FIG. 4: four manganese compounds (manganese tetraphenylporphyrin C) prepared in examples 1,2, 3 and 4 of the present invention44H30ClMnN4(1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Manganese (C) tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3Manganese (III) acetylacetonate C15H21MnO6) The multiplying power performance of the carbon tube sulfur-carried composite anode material used for the lithium sulfur battery and the lithium sulfur battery without the manganese compound material is compared.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1: manganese tetraphenylporphyrin C44H30ClMnN4Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: putting 200mg of carbon tube and 200mg of elemental sulfur into a mortar, fully and uniformly grinding porous carbon and sulfur, transferring the obtained mixture into a 25mL weighing bottle, and adding 3.2mL of CS2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 120 ℃ oven, preserving the temperature for 12h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese tetraphenylporphyrin C44H30ClMnN4Preparing a carbon tube sulfur-carrying composite anode material: 300mg of carbon tube sulfur-carrying composite material, 15mg of conductive additive carbon black, 15mg of adhesive polyvinylidene fluoride and 3-4 mg of tetraphenylporphyrinmanganese C44H30ClMnN4Mixing, adding 2.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry to 10000cps, and coating on a current collector aluminum foil with a scraper at a thickness of 150 μm (the aluminum foil is washed twice with NMP and alcohol to remove surface oxide layer and impurities, and air-dried naturally, the aluminum foil thickness is 30 μm). Then the aluminum foil is rotatedMoving the anode material into a drying oven at 40 ℃ and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a control experiment, manganese C tetraphenylporphyrin was absent44H30ClMnN4The carbon tube sulfur-carrying composite anode material is also prepared into a comparison anode pole piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 1 shows manganese tetraphenylporphyrin C prepared in this example44H30ClMnN4Carbon tube sulfur-carried composite positive electrode material for lithium sulfur battery and manganese C without adding tetraphenylporphyrin44H30ClMnN4The rate performance of the lithium-sulfur battery is compared, and the manganese C tetraphenylporphyrin is shown in the figure44H30ClMnN4The capacity of the lithium-sulfur battery of the carbon tube-carried sulfur composite material is obviously better than that of the lithium-sulfur battery without adding tetraphenylporphyrin manganese C44H30ClMnN4The battery of (1).
FIG. 2 shows manganese tetraphenylporphyrin C44H30ClMnN4Carbon tube sulfur-carried composite positive electrode material for lithium sulfur battery and manganese C without tetraphenylporphyrin44H30ClMnN4The charge-discharge platform contrast diagram of the lithium-sulfur battery under 1C is obvious from the figure, and the lithium-sulfur battery contains tetraphenylporphyrinmanganese C44H30ClMnN4The lithium-sulfur battery of the positive electrode material has higher discharge capacity.
FIG. 3 shows manganese tetraphenylporphyrin C44H30ClMnN4The carbon tube sulfur-carried composite positive material is used for lithium-sulfur battery and does not contain tetraphenylporphyrin manganese C44H30ClMnN4The lithium-sulfur batteries were compared, and a cycle stability test was carried out, from which it can be seen that manganese C, a tetraphenylporphyrin, was contained44H30ClMnN4The battery has good stability and capacity.
Example 2: (1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) (1S,2S) - (+) - [1, 2-cyclohexanediaminazine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube-carried sulfur composite material, 50mg of conductive additive carbon black, 50mg of adhesive polyvinylidene fluoride, 4-5 mg of (1S,2S) - (+) - [1, 2-cyclohexanediamine nitrogen-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deductingAnd (5) preparing the blank aluminum sheet into a positive pole piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without containing various manganese compounds is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 contains (1S,2S) - (+) - [1, 2-cyclohexanediaminazepine-N, N' -bis (3, 5-di-tert-butylsalicylidene)]Manganese (III) chloride C36H52ClMnN2O2The carbon tube sulfur-loaded composite cathode material is used for a comparison graph of the rate performance of a lithium sulfur battery and a lithium sulfur battery without a manganese compound material, and the graph shows that the lithium sulfur battery containing the cathode material of the manganese compound has higher discharge capacity under various rates.
Example 3: manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
(1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube sulfur-carrying composite material, 50mg of conductive additive carbon black and adhesive50mg of polyvinylidene fluoride and 4-5 mg of manganese (Mn) (C) tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without the manganese compound is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 contains manganese tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) Mn (C)11H19O2)3The graph for comparing the rate performance of the carbon tube sulfur-loaded composite cathode material used for the lithium sulfur battery with that of the lithium sulfur battery without the manganese compound material shows that the carbon tube sulfur-loaded composite cathode material contains manganese Mn (C) which is tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid)11H19O2)3The lithium-sulfur battery of the cathode material has higher discharge capacity under various multiplying powers.
Example 4: manganese (III) acetylacetonate C15H21MnO6Preparation of carbon tube-carried sulfur composite anode material and application of anode material in lithium-sulfur battery
（1) Preparing a carbon tube sulfur-carrying composite material: 200mg of the carbon tube composite material obtained above and 400mg of elemental sulfur are put into a mortar, porous carbon and sulfur are fully and uniformly ground, the obtained mixture is transferred into a 25mL weighing bottle, and 6mL of CS is added2Stirring thoroughly until CS is obtained2Completely volatilizing, transferring the mixture to a 150 ℃ oven, preserving the temperature for 10h, then cooling to room temperature, and collecting the obtained product to obtain the carbon tube sulfur-carrying composite material;
(2) manganese (III) acetylacetonate C15H21MnO6Preparing a carbon tube sulfur-carrying composite anode material: 400mg of carbon tube sulfur-carrying composite material, 50mg of conductive additive carbon black, 50mg of adhesive polyvinylidene fluoride and 4-5 mg of acetylacetone manganese (III) C15H21MnO6Mixing, adding 3.5mL NMP, ultrasonic dispersing, stirring thoroughly, controlling the viscosity of the slurry at 6000cps, and coating on the current collector aluminum foil with a scraper at 150 μm thickness (the aluminum foil is cleaned with NMP and alcohol twice to remove surface oxide layer and impurities, air drying naturally, the aluminum foil thickness is 30 μm). Then transferring the aluminum foil into a 50 ℃ oven, and drying to obtain the required anode material;
(3) assembling the battery: and (3) cutting the composite electrode material prepared in the step (2) into round pieces with the diameter of 14mm, weighing in a dry environment, and deducting the mass of blank aluminum pieces to prepare a positive electrode piece for later use. As a contrast experiment, the carbon tube sulfur-carrying composite positive electrode material without containing various manganese compounds is also prepared into a contrast positive electrode piece for standby by the same method; the cell assembly was carried out in a glove box filled with argon, water and oxygen, each less than lpm. Commercial lithium metal sheets were used as reference and counter electrodes, and LiTFSI/DOL.DMC (1: 1) was used with 1% LiNO dissolved3After a diaphragm of the liquid electrolyte is assembled into a CR2025 button cell by adopting Celgard2400, standing for 24 hours, and then carrying out charge and discharge tests;
(4) the Xinwei battery testing system performs battery charge and discharge tests under different multiplying powers, the testing conditions are room temperature environment, the window initial voltage is 1.5V, and the termination voltage is 3.0V;
FIG. 4 shows manganese (III) acetylacetonate C15H21MnO6The carbon tube sulfur-carried composite positive electrode material is respectively used for the rate performance comparison graph of a lithium sulfur battery and a lithium sulfur battery without manganese compound materials, and the graph obviously shows that the carbon tube sulfur-carried composite positive electrode material contains manganese (III) acetylacetonate C15H21MnO6The lithium-sulfur battery of the cathode material has higher discharge capacity under various multiplying powers.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (3)
1. A positive electrode material for a lithium-sulfur battery, characterized in that: the preparation method comprises the following steps:
(1) preparing a carbon tube sulfur-carrying composite material: mixing a carbon tube and elemental sulfur according to a mass ratio of 1: 1-2, uniformly grinding, and mixing the materials in a feed liquid mass ratio of 1: 10-15 addition of CS2Stirring, and standing at room temperature to CS2After complete volatilization, preserving the heat of the residual substances in an oven at 120-160 ℃ for 8-12 h, and then cooling to room temperature to obtain the carbon tube sulfur-carrying composite material;
(2) preparation of manganese compound/carbon tube sulfur-carrying composite material: mixing the carbon tube sulfur-carrying composite material obtained in the step (1) with conductive additive carbon black and binder polyvinylidene fluoride, adding solvent N-methyl pyrrolidone and manganese compound, stirring and ultrasonically dispersing uniformly, controlling the viscosity to be 1000-10000 cps, obtaining composite material slurry, drying the obtained composite material slurry, and obtaining the manganese compound/carbon tube sulfur-carrying composite material, wherein the manganese compound has catalytic conversion capability on redox reaction in a lithium sulfur battery, and the mass ratio of the carbon tube sulfur-carrying composite material, the carbon black, the polyvinylidene fluoride and the manganese compound is (300-400): (15-50): (15-50): (3-5);
the manganese compound is (1S,2S) - (+) - [1, 2-cyclohexanediamine nitrogen-N, N' -bis (3, 5-di-tert-butylsalicylidene) ] manganese chloride (III) or tris (2,2,6, 6-tetramethyl-3, 5-heptenoic acid) manganese.
2. The positive electrode material for a lithium-sulfur battery according to claim 1, characterized in that: and uniformly coating the composite material slurry on a current collector aluminum foil by using a scraper with the thickness of 150-400 mu m, and then transferring the current collector aluminum foil into a drying oven at 40-60 ℃ for drying to obtain the manganese compound and carbon tube negative sulfur composite cathode material in a sheet shape.
3. The lithium sulfur battery positive electrode material according to claim 2, characterized in that: the thickness of the current collector aluminum foil is 30 micrometers, the current collector aluminum foil is cleaned by N-methyl pyrrolidone and alcohol before use to remove a surface oxide layer and impurities, and the current collector aluminum foil is naturally dried for later use.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109755503A CN109755503A (en) | 2019-05-14 |
| CN109755503B true CN109755503B (en) | 2021-09-07 |
Family
ID=66402618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811521713.7A Active 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109755503B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368567A (en) * | 2022-09-30 | 2022-11-22 | 上海屹锂新能源科技有限公司 | Reverse vulcanized copolymer positive active material and all-solid-state battery thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8183030B2 (en) * | 2006-10-13 | 2012-05-22 | Archer Daniels Midland Company | Use of cell surface displays in yeast cell catalyst supports |
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN105609707A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation method of manganese dioxide hollow sphere cathode material for lithium-sulfur battery |
| CN106129384A (en) * | 2016-09-07 | 2016-11-16 | 中南大学 | The complex of carbon/sulfur of a kind of manganese dioxide nano-plates cladding, preparation method and applications |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303708C (en) * | 2002-07-31 | 2007-03-07 | 曹喜峰 | Air electride |
| US8907133B2 (en) * | 2008-07-14 | 2014-12-09 | Esionic Es, Inc. | Electrolyte compositions and electrochemical double layer capacitors formed there from |
| US20110165497A1 (en) * | 2010-01-06 | 2011-07-07 | Gm Global Technology Operations, Inc. | Method for Mitigating Fuel Cell Chemical Degradation |
| CN104393259B (en) * | 2014-10-13 | 2017-01-25 | 同济大学 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
| JP6390582B2 (en) * | 2015-10-21 | 2018-09-19 | トヨタ自動車株式会社 | Flow battery |
| CN108269978B (en) * | 2017-12-27 | 2020-12-08 | 温州大学 | Quantum dot/carbon tube sulfur-carrying composite cathode material and preparation method and application thereof |
-
2018
- 2018-12-13 CN CN201811521713.7A patent/CN109755503B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8183030B2 (en) * | 2006-10-13 | 2012-05-22 | Archer Daniels Midland Company | Use of cell surface displays in yeast cell catalyst supports |
| CN102683659A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院物理研究所 | Lithium-sulphur battery anode material and preparation method thereof |
| CN105609707A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation method of manganese dioxide hollow sphere cathode material for lithium-sulfur battery |
| CN106129384A (en) * | 2016-09-07 | 2016-11-16 | 中南大学 | The complex of carbon/sulfur of a kind of manganese dioxide nano-plates cladding, preparation method and applications |
Non-Patent Citations (1)
| Title |
|---|
| Coating of sulfur particles with manganese oxide nanowires as a cathode material in lithium-sulfur batteries;Jeongyeon Lee et al;《Materials Letters》;20151130;第158卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109755503A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107221716B (en) | Rechargeable aqueous zinc ion battery | |
| CN108269978B (en) | Quantum dot/carbon tube sulfur-carrying composite cathode material and preparation method and application thereof | |
| CN108448168B (en) | Electrolyte for water-based zinc ion secondary battery and preparation method and application thereof | |
| CN104201323B (en) | The preparation method of alumina-coated lithium cobaltate cathode material | |
| CN108539171B (en) | Preparation method of zinc sulfide and graphene oxide compound and application of compound in positive electrode material of lithium-sulfur battery | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN105280949A (en) | Lithium sulfur battery using manganese dioxide/graphene as cathode barrier layer | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN109755504B (en) | Preparation method of ferriporphyrin/carbon nanotube composite positive electrode material and application of ferriporphyrin/carbon nanotube composite positive electrode material in positive electrode of lithium-sulfur battery | |
| CN104934579A (en) | Preparation method for porous graphite doped and carbon coated graphite anode material | |
| CN107359372B (en) | Aqueous electrolyte and aqueous metal ion battery | |
| CN110148787A (en) | A kind of electrolyte and lithium-sulfur cell improving lithium-sulfur cell capacity | |
| CN103427068B (en) | A kind of positive electrode and preparation method thereof for lithium-sulfur cell | |
| CN104795555A (en) | Aqueous-solution sodium-ion battery and cathode material, preparation method and application thereof | |
| CN107342412A (en) | A kind of preparation method of nanoparticle phosphotungstate/sulphur positive electrode | |
| CN107978736B (en) | Metal alloy/carbon tube/graphene sulfur-loaded composite cathode material and preparation method and application thereof | |
| CN109742439A (en) | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application | |
| CN112259722A (en) | Water system mixed ion secondary battery and preparation method and application thereof | |
| CN103855373A (en) | Vanadium pentoxide / graphene composite material and its preparation method and application | |
| CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
| CN113871611B (en) | Preparation method of high-entropy oxide material composite ternary material | |
| CN113054197B (en) | Hard carbon binder, negative plate containing hard carbon binder and sodium ion battery | |
| CN101399120A (en) | Novel hybrid supercapacitor | |
| CN109728297A (en) | Metal phthalocyanine/carbon pipe composite material preparation method and its application in lithium-sulphur cell positive electrode | |
| CN113193240A (en) | Aqueous all-manganese secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |