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WO2016192389A1 - Matériau d'électrode positive composite pour batterie au lithium-soufre et son procédé de préparation - Google Patents

Matériau d'électrode positive composite pour batterie au lithium-soufre et son procédé de préparation Download PDF

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Publication number
WO2016192389A1
WO2016192389A1 PCT/CN2015/099570 CN2015099570W WO2016192389A1 WO 2016192389 A1 WO2016192389 A1 WO 2016192389A1 CN 2015099570 W CN2015099570 W CN 2015099570W WO 2016192389 A1 WO2016192389 A1 WO 2016192389A1
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sulfur
lithium
conductive agent
sulfur battery
positive electrode
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Chinese (zh)
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周成冈
周吟
闫允潘
韩波
吴金平
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China University of Geosciences Wuhan
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China University of Geosciences Wuhan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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

Definitions

  • the invention relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery composite cathode material and a preparation method thereof.
  • the monosulfide cathode material is electrochemically reacted with S 8 +16Li ⁇ 8Li 2 S, and its specific capacity is as high as 1675 mAh ⁇ g -1 . It is the highest energy density in the known solid cathode material, and the sulfur is abundant in reserves, low in price and safe. Low toxicity, so it has a very broad application prospects.
  • the sulfur element is an electronic insulator (5 ⁇ 10 -30 S ⁇ cm -1 , 25 ° C)
  • the high-valent lithium polysulfide formed during the discharge process the lithium-sulfur battery is at different discharge voltages, lithium reacts with sulfur to form Lithium polysulfide with different valence sulfur
  • the products formed from high valence state to low valence state are Li 2 S 8 , Li 2 S 6 , Li 2 S 4 , Li 2 S 3 , Li 2 S 2 , Li 2 S ) Soluble in the electrolyte, forming a so-called "shuttle effect" which seriously affects the battery life and affects the application of lithium-sulfur batteries in actual production.
  • the shuttle effect caused by the dissolution of polysulfide significantly reduces sulfur utilization, specific capacity and cycle performance, while increasing the viscosity of the electrolyte and the migration resistance of ions; as the discharge progresses, the final product of the poor conductivity discharge Li 2 S and Li 2 S 2 may cover the surface of the positive electrode active material in the form of a solid film, thereby hindering the electrochemical reaction between the electrolyte and the electrode active material. Therefore, how to suppress the diffusion of polysulfide and improve the conductivity during the sulfur cathode cycle is the research focus of lithium-sulfur battery cathode materials.
  • the technical problem to be solved by the present invention is to provide a lithium-sulfur battery composite positive electrode material having a high initial capacity and good cycle performance at a high discharge rate and a preparation method thereof, in view of the above-mentioned deficiencies in the prior art.
  • the technical solution provided by the present invention is:
  • a lithium-sulfur battery composite cathode material comprising a conductive agent having a mesoporous structure, sulfur and a modifier dispersed in a pore of a conductive agent, wherein the modifier is chemically bonded and electrically conductive
  • the pores of the agent are connected, and the mass ratio of each component is 30 to 59.4% of the conductive agent, 40 to 60% of the sulfur, and 0.1 to 10% of the modifier.
  • the conductive agent is a mesoporous carbon material having a pore size distribution of 2-10 nm, a specific surface area of 500-800 m 2 /g, and a hydrophilic functional group at the opening of the cell;
  • the modifier is glucose, galactose One of deoxyribose.
  • the mesoporous carbon material is obtained by activation of a carbon material by preparing a solid KOH and a carbon material uniformly mixed at a mass ratio of 1-5:1, and then placing it in a tube furnace with hydrogen gas and The mixed gas of nitrogen is a protective atmosphere in which the volume ratio of hydrogen is 1-5%, calcined at 650-850 ° C for 0.5-1.5 h, and then the calcined product is washed successively with dilute hydrochloric acid and deionized water until neutral, and finally dried to obtain a medium. Hole carbon material.
  • the carbon material is a multi-walled carbon nanotube, a carbon nanofiber or a carbon nanosphere.
  • the hydrophilic functional group is a hydroxyl group or a carboxyl group.
  • the invention also provides a preparation method of the above lithium-sulfur battery composite cathode material, the steps of which are as follows:
  • the conductive agent in the step 1) is a mesoporous carbon material having a pore diameter of 2-10 nm, a specific surface area of 500-800 m 2 /g, and a hydrophilic functional group at the opening of the pore.
  • the modifying agent is a polyhydroxy sugar.
  • the modifying agent is selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, or a combination thereof.
  • the modifying agent is one of glucose, galactose, and deoxyribose.
  • the mesoporous carbon material is obtained by activation of a carbon material by preparing a solid KOH and a carbon material uniformly mixed at a mass ratio of 1-5:1, and then placing it in a tube furnace with hydrogen gas and The mixed gas of nitrogen is a protective atmosphere in which the volume ratio of hydrogen is 1-5%, calcined at 650-850 ° C for 0.5-1.5 h, and then the calcined product is washed successively with dilute hydrochloric acid and deionized water until neutral, and finally dried to obtain a medium. Hole carbon material.
  • the carbon material is a multi-walled carbon nanotube, a carbon nanofiber or a carbon nanosphere.
  • the hydrophilic functional group is a hydroxyl group and a carboxyl group.
  • the sonication time of step 2) is 30-60 min, and the ultrasonic frequency is 20-25 kHz.
  • the principle of the invention is that the conductive agent of the invention is a mesoporous structure, the electrochemically active substance sulfur is dispersed in the pores of the conductive agent, and the modifying agent (sugar) is chemically bonded to the active part of the orifice of the conductive agent. Connect to adjust the performance of the orifice.
  • the modification of the composite by the saccharide radical generated by the hydrothermal reaction of glucose and the like ensures that the lithium-sulfur cathode material selectively allows passage of lithium ions and inhibits the passage of polysulfide ions.
  • the sugar radicals at the pores have a certain adsorption effect on the lithium polysulfide, which prevents the polysulfide from overflowing from the pores and dissolves;
  • the hydrophilic radicals of the carbohydrate radicals and the mesoporous carbon pores The chemical bonding has a shrinkage effect, and the size of the orifice is adjusted to some extent, and the passage of polysulfide is inhibited to some extent without affecting the free passage of lithium ions having a small radius, thereby hindering the dissolution of lithium polysulfide.
  • the present invention mainly has the following advantages: First, the modifier (saccharide) used in the experiment can be achieved when the content is very low (the mass ratio in the composite positive electrode material is 0.6%). Very good cycle stability effect, which greatly reduces the loss of energy density of the positive electrode material; second, hydrothermal decomposition of sugars into hydrophilic radicals of mesoporous carbon material orifices for orientation Chemical bonding can ensure the uniform dispersion and distribution of carbohydrate radicals on the positive electrode material. Third, the chemical bonding of the carbohydrate free radicals with the hydrophilic functional groups of mesoporous carbon pores can ensure the efficiency of carbohydrate free radicals. The use of the channel selectively allows lithium ions to be efficiently embedded and removed to inhibit the passage of polysulfide ions, thereby improving the cycle performance of the lithium-sulfur battery.
  • the beneficial effects of the invention are as follows: 1.
  • the preparation method of the invention is simple, and the prepared lithium-sulfur battery composite cathode material is chemically bonded with a hydrophilic radical generated by a saccharide decomposition reaction such as glucose and a hydrophilic functional group at a mesoporous carbon hole. Effectively inhibiting the dissolution of polysulfide under the premise of free passage of lithium ions; 2.
  • the invention greatly increases the transmission channel of lithium ions by activating carbon materials (carbon nanotubes, carbon nanofibers or carbon nanospheres).
  • the lithium ion can be quickly embedded and removed, so that the material can be quickly charged and discharged, and has high rate performance, and the use of the modifier makes the lithium-sulfur battery using the composite positive electrode material prepared by the invention have high rate stability performance and can effectively reduce the capacity.
  • the loss and the "shuttle effect” caused by the “shuttle effect” caused by the dissolution of lithium polysulfide caused the corrosion of the lithium negative electrode and the rapid decay of the capacity, thereby significantly improving the cycle performance of the lithium-sulfur battery (the capacity retention rate was increased from 48.64% to 64.01-92.26%).
  • Example 1 is a discharge cycle test chart of a battery assembled with a lithium-sulfur battery composite positive electrode material prepared in Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 2;
  • Example 2 is a cycle test diagram of a battery assembled with a composite positive electrode material of a high-rate performance lithium-sulfur battery prepared in Example 1, Example 2, Example 3, and Example 4;
  • Example 3 is a battery discharge cycle test chart of a composite positive electrode material of a high-rate performance lithium-sulfur battery prepared in Example 5;
  • FIG. 4 is a graph showing the discharge rate of a battery assembled with a composite positive electrode material of a high-rate performance lithium-sulfur battery prepared in Example 6.
  • FIG. 4 is a graph showing the discharge rate of a battery assembled with a composite positive electrode material of a high-rate performance lithium-sulfur battery prepared in Example 6.
  • a conductive agent/sulfur composite cathode material is prepared as follows:
  • the conductive agent and sulfur are ground and mixed uniformly, they are placed in a tube furnace, with N 2 as the shielding gas, the gas flow rate is set to 50 mL/min, and the temperature is raised to 155 ° C at a rate of 10 ° C/min at room temperature. 10h, then heated to 190 ° C at a rate of 10 ° C / min for 3h, then naturally cooled to obtain a conductive agent / sulfur composite (o-CNT / S);
  • the above conductive agent/sulfur composite material is prepared into a positive electrode sheet by the following method:
  • the above conductive agent/sulfur composite material (o-CNT/S) and binder (polyvinylidene fluoride) were uniformly mixed at a mass ratio of 9:1, and then dispersed in N-methylpyrrolidone for magnetic stirring for 12 hours to obtain a positive electrode.
  • the slurry; the obtained positive electrode slurry was coated on an aluminum foil to form a sheet, dried, rolled, and sliced to obtain a desired positive electrode sheet, and the thickness of the positive electrode sheet was 100 ⁇ m.
  • the above positive electrode sheet is assembled into a battery as follows:
  • the positive electrode is made of the above positive electrode sheet
  • the negative electrode is made of a lithium foil having a thickness of about 50 ⁇ m
  • the separator is a Celegard 2400 polypropylene film
  • the electrolyte is dissolved in lithium bistrifluoromethanesulfonate (LiN(CF 3 SO 2 ) 2 ).
  • the battery assembled in this comparative example was subjected to constant current charge and discharge test at a current density of 1 C.
  • the battery test temperature was around room temperature 25 ° C.
  • the test results showed that the first discharge specific capacity of the battery was 712 mAh/g, and the discharge was performed after 200 cycles.
  • the specific capacity was 291 mAh/g, and the results are shown in Fig. 1.
  • a conductive agent/sulfur/glucose composite positive electrode material using glucose as a modifier wherein the components are used in an amount of 59.4% by weight of a conductive agent, 40% by weight of sulfur, and 0.6% by weight of a modifier.
  • the conductive agent and sulfur are ground and mixed uniformly, they are placed in a tube furnace, with N 2 as the shielding gas, the gas flow rate is set to 50 mL/min, and the temperature is raised to 155 ° C at a rate of 10 ° C/min at room temperature. 10h, then heated to 190 ° C at a rate of 10 ° C / min for 3h, then naturally cooled to obtain a conductive agent / sulfur composite (o-CNT / S);
  • the methods for preparing the positive electrode sheet, assembling the battery, and testing the battery in this example were the same as in Comparative Example 1.
  • the battery charge and discharge test results show that the first charge-discharge specific capacity of the battery is 664 mAh/g at 1 C discharge rate, and the specific capacity is 471 mAh/g after 200 cycles.
  • the results are shown in Fig. 1.
  • the cycle performance is greatly improved, and the electrochemical performance of the battery is also improved. It indicates that the hydrophilic functional group at the pore opening of the multi-walled carbon nanotubes is bonded to the glucose radical to improve the cycle performance of the battery.
  • a lithium-sulfur battery composite cathode material is prepared as follows:
  • the above porous multi-walled carbon nanotubes are prepared by using solid potassium hydroxide and multi-walled carbon nanotubes (pore size 2-5 nm, specific surface area 324 m 2 /g, pore volume 0.40 cm 3 /g) to 5
  • the mass ratio of 1: is uniformly mixed, and then placed in a tube furnace, with a mixed gas of hydrogen and nitrogen as a protective atmosphere, wherein the volume ratio of hydrogen is 5%, calcined at 850 ° C for 1.5 h, and then the calcined product is taken out, After washing with 1 mol/L of dilute hydrochloric acid, it is washed with deionized water until neutral.
  • porous multi-walled carbon nanotubes which is a mesoporous carbon material (pore size is 2-10 nm).
  • the specific surface area was 800 m 2 /g, and the pore volume was 1.06 cm 3 /g).
  • the conductive agent and sulfur are ground and mixed uniformly, they are placed in a tube furnace, with N 2 as the shielding gas, the gas flow rate is set to 50 mL/min, and the temperature is raised to 155 ° C at a rate of 10 ° C/min at room temperature. After 10 h, the temperature was raised to 190 ° C for 3 h at a rate of 10 ° C / min, and then naturally cooled to obtain a conductive agent / sulfur composite material (h-CNT / S).
  • the methods for preparing the positive electrode sheet, assembling the battery, and testing the battery were the same as in Comparative Example 1. It can be seen from Fig. 1 that the first charge-discharge specific capacity of the battery prepared in this example is 1184 mAh/g at a 1 C rate, and the specific capacity after 510 cycles is 576 mAh/g. Compared with Comparative Example 1, the initial capacity of discharge is greatly improved. This is because the carbon material multi-walled carbon nanotubes have a rich pore structure after activation, which accelerates the efficient migration and removal of lithium ions.
  • the above porous multi-walled carbon nanotubes are prepared by solid potassium hydroxide and multi-walled carbon nanotubes (pore size 2-5 nm, specific surface area 324 m 2 /g, pore volume 0.40 cm 3 /g, Nanjing Xian
  • the product is uniformly mixed at a mass ratio of 5:1, and then placed in a tube furnace with a mixture of hydrogen and nitrogen as a protective atmosphere, wherein the volume ratio of hydrogen is 5% and calcined at 850 °C. After 1.5 h, the calcined product was taken out, washed with 1 mol/L of dilute hydrochloric acid, and then washed with deionized water until neutral.
  • porous multi-walled carbon nanotubes That is, a mesoporous carbon material (having a pore diameter of 2 to 10 nm, a specific surface area of 800 m 2 /g, and a pore volume of 1.06 cm 3 /g).
  • the specific preparation method is as follows:
  • step 2) The conductive agent and sulfur weighed in step 1) are ground and uniformly mixed, and then placed in a tube furnace, with N 2 as a shielding gas, the gas flow rate is set to 50 mL/min, and the temperature is 10 ° C/min at room temperature. Heating to 155 ° C, holding for 10 h, then heating at a rate of 10 ° C / min to 190 ° C for 3 h, then naturally cooled to obtain a conductive agent / sulfur composite (o-CNT / S);
  • porous multi-walled carbon nanotube/sulfur composite prepared by dissolving glucose in 100 mL of ultrapure water to obtain 2.22 ⁇ 10 -5 mol/L aqueous glucose solution and adding to glucose aqueous solution in step 2)
  • Ultrasonic cleaning with ultrasonic cleaning device to uniformly disperse in aqueous glucose solution, sonication time is 30min, frequency is 20-25kHz; after ultrasonic completion, the solution is transferred to the reaction kettle, reacted at 140 ° C for 24h, the preparation will be The product is filtered and dried to give a mesoporous carbon/sulfur/glucose composite.
  • the methods for preparing the positive electrode sheet, assembling the battery, and testing the battery in this example were the same as in Comparative Example 1.
  • the battery charge and discharge test results show that the first charge-discharge specific capacity of the battery is 1088 mAh/g at 1 C discharge rate, and the specific capacity is 697 mAh/g after 200 cycles.
  • the results are shown in Fig. 2.
  • the first charge-discharge specific capacity is slightly smaller, but the cycle performance is greatly improved. This is because the modification of porous multi-walled carbon nanotubes/sulfur composites hinders the insertion and removal of lithium ions.
  • the effect because the modifier content is low, the inhibition effect on lithium ion insertion and removal is relatively weak, and the initial capacity is slightly decreased from 1184 mAh/g to 1088 mAh/g.
  • a porous multi-walled carbon nanotube/sulfur/glucose composite positive electrode material prepared by using glucose as a modifier, wherein the amount of each component is as follows: conductive agent porous multi-walled carbon nanotubes 59.4 wt%, electrochemically active substance Sulfur 40% by weight, modifier glucose 0.6% by weight.
  • the above porous multi-walled carbon nanotubes are prepared by solid potassium hydroxide and multi-walled carbon nanotubes (pore size 2-5 nm, specific surface area 324 m 2 /g, pore volume 0.40 cm 3 /g, Nanjing Xian
  • the product is uniformly mixed at a mass ratio of 5:1, and then placed in a tube furnace with a mixture of hydrogen and nitrogen as a protective atmosphere, wherein the volume ratio of hydrogen is 5% and calcined at 650 °C. After 1.5 h, the calcined product was taken out, washed with 1 mol/L of dilute hydrochloric acid, and then washed with deionized water until neutral.
  • porous multi-walled carbon nanotubes h-CNT
  • infrared test shows that a large number of hydrophilic functional group hydroxyl groups are formed around the surface pores of the mesoporous carbon material.
  • the specific preparation method is as follows:
  • step 2) The conductive agent and sulfur weighed in step 1) are ground and uniformly mixed, and then placed in a tube furnace with N 2 as a shielding gas, the gas flow rate is set to 50 mL/min, and the temperature is 5 ° C/min at room temperature. Heating to 160 ° C, holding for 5 h, then heating at a rate of 5 ° C / min to 210 ° C for 5 h, then naturally cooled to obtain a conductive agent / sulfur composite (o-CNT / S);
  • porous multi-walled carbon nanotube/sulfur composite material prepared by dissolving glucose in 60 mL of ultrapure water to obtain 2.22 ⁇ 10 -3 mol/L aqueous glucose solution and adding to glucose aqueous solution in step 2) (h-CNT/ S), ultrasonically ultrasonically sprayed to uniformly disperse in the aqueous glucose solution, the ultrasonic treatment time is 30 min, the frequency is 20-25 kHz; after the completion of the ultrasonication, the solution is transferred to the reaction kettle, and reacted at 100 ° C for 4 h, The prepared product is filtered and dried to finally obtain a mesoporous carbon/sulfur/glucose composite.
  • the methods for preparing the positive electrode sheet, assembling the battery, and testing the battery in this example were the same as in Comparative Example 1.
  • the battery charge and discharge test results show that the first charge-discharge specific capacity of the battery prepared in this example is 1005mAh/g at 1C rate, and the specific capacity is 793mAh/g after 200 cycles.
  • the cycle test chart of the battery is shown in Figure 2. . Compared with Example 1, a suitable amount of glucose free radicals further enhances its stability.
  • a porous multi-walled carbon nanotube/sulfur/glucose composite cathode material prepared by using glucose as a modifier is similar to that of Example 1, except that the amount of each component is determined by mass percentage: conductive porous multi-wall carbon nanometer
  • the tube was 50% by weight, the electrochemically active substance sulfur was 49.2% by weight, and the modifier glucose was 0.8% by weight.
  • the preparation method of the composite positive electrode material, the preparation of the positive electrode sheet, the assembly battery and the battery test method in this embodiment are the same as those in the first embodiment.
  • the battery charge and discharge test results show that the first charge and discharge of the battery prepared in this embodiment is at 1 C rate.
  • the specific capacity is 754mAh/g, and the specific capacity is 561mAh/g after 200 cycles.
  • the cycle test chart of the battery is shown in Figure 2. The increase in the glucose content compared to Example 2 resulted in a significant decrease in the initial capacity of the battery system, but the cycle performance was substantially unchanged, and the specific capacity reduction ratio was similar after 200 cycles.
  • a porous multi-walled carbon nanotube/sulfur/glucose composite cathode material prepared by using glucose as a modifier is similar to that of Example 1, except that the amount of each component is determined by mass percentage: conductive porous multi-wall carbon nanometer
  • the tube is 30% by weight, the electrochemically active substance sulfur is 60% by weight, and the modifier glucose is 10% by weight.
  • the preparation method of the composite positive electrode material, the preparation of the positive electrode sheet, the assembly battery and the battery test method in this embodiment are the same as those in the first embodiment.
  • the battery charge and discharge test results show that the first charge and discharge of the battery prepared in this embodiment is at 1 C rate.
  • the specific capacity is 363 mAh/g, and the specific capacity is 284 mAh/g after 200 cycles.
  • the cycle test chart of the battery is shown in Fig. 2.
  • a porous carbon nanofiber/sulfur/galactose composite cathode material prepared by using galactose as a modifier is similar to that of Example 1, except that the carbon material is carbon nanofiber, the sugar is galactose, and the solid potassium hydroxide is used.
  • carbon nanofibers pore size 2-5 nm, specific surface area 300 m 2 /g, pore volume 0.30 cm 3 /g
  • a mixed atmosphere of hydrogen and nitrogen is used as a protective atmosphere, wherein
  • the volume ratio of hydrogen is 1%, calcined at 650 ° C for 0.5 h to obtain porous carbon nanofibers (pore size 2-10 nm, specific surface area 500 m 2 /g, pore volume 0.74 cm 3 /g), the amount of each component
  • the conductive agent porous carbon nanofibers are 40% by weight
  • the electrochemically active substance sulfur is 59.4% by weight
  • the modifier galactose is 0.6% by weight.
  • the preparation of the composite positive electrode material, the preparation of the positive electrode sheet, the assembled battery, and the battery test method are the same as in the first embodiment, and the constant current charge and discharge test is performed at a current density of 3 C, and the test temperature is 25 ° C at room temperature.
  • the first discharge specific capacity of the battery prepared in this example was 931 mAh/g, and the discharge specific capacity was 859 mAh/g after 200 cycles, and the battery discharge cycle test chart is shown in FIG. Discharge at 3C rate, battery capacity attenuation is small, battery cycle performance is very good.
  • a porous carbon nanosphere/sulfur/deoxyribose composite cathode material prepared by using deoxyribose as a modifier is similar to that of Example 1, except that the carbon material is carbon nanosphere (pore size 2-6 nm, specific surface area 280 m 2 ) /g, pore volume is 0.44 cm 3 /g), the sugar is deoxyribose, and porous carbon nanospheres are obtained by activation (pore size is 2-8 nm, specific surface area is 580 m 2 /g, pore volume is 0.78 cm 3 /g) The amount of each component is determined by mass percentage: 50 wt% of conductive agent porous carbon nanospheres, 49.4 wt% of electrochemically active substance sulfur, and 0.6 wt% of modifier deoxyribose.
  • the preparation of the composite positive electrode material, the preparation of the positive electrode sheet, the assembly battery and the battery test method in this embodiment are the same as those in the first embodiment, respectively, at 0.5C, 1C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, 9C.
  • the corresponding capacity is 1084mAh / g, 1010mAh / g, 973mAh / g, 928mAh / g, 812mAh / g, 751mAh / g, 683mAh/g, 644mAh/g, 587mAh/g, 539mAh/g, 511mAh/g, it can be seen that the magnification is reduced from 10C to 0.5C, the capacity is 870mAh/g, the capacity retention rate is 80.25%, and the high rate performance of the battery. Good, the discharge rate diagram of the battery is shown in Figure 4.

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Abstract

La présente invention concerne un matériau d'électrode positive composite pour batterie au lithium-soufre et son procédé de préparation. Le matériau d'électrode positive composite pour batterie au lithium-soufre est préparé en utilisant un agent conducteur ayant une structure mésoporeuse, du soufre et un agent de modification. Le soufre est dispersé dans des trous de l'agent conducteur, l'agent de modification est relié à des orifices de l'agent conducteur en utilisant une liaison chimique et les rapports de masse des composants sont : 30 % à 59,4 % de l'agent conducteur, 40 % à 60 % de soufre et de 0,1 % à 10 % de l'agent de modification. Le procédé de préparation associé comprend : le versement du soufre dans un agent conducteur en adoptant un procédé d'aspiration en fusion, afin d'obtenir un matériau composite agent conducteur/soufre ; puis la modification du matériau composite agent conducteur/soufre pour obtenir un matériau d'électrode positive composite pour batterie au lithium-soufre. Le matériau d'électrode positive composite peut non seulement permettre d'excellentes performances de stabilité à haut rendement, mais peut également réduire efficacement la perte de substances actives et des effets tels que la corrosion de l'électrode négative au lithium et l'atténuation rapide de la capacité provoquée par un « effet navette » en raison de la dissolution du polysulfure de lithium, permettant ainsi d'augmenter considérablement les performances de cycle d'une batterie au lithium-soufre.
PCT/CN2015/099570 2015-06-03 2015-12-29 Matériau d'électrode positive composite pour batterie au lithium-soufre et son procédé de préparation Ceased WO2016192389A1 (fr)

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CN109678132A (zh) * 2018-12-29 2019-04-26 深圳市比克动力电池有限公司 多孔碳材料及其制备和应用
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324507A (zh) * 2011-09-10 2012-01-18 中南大学 一种锂硫电池复合正极材料制备方法
CN103500847A (zh) * 2013-10-02 2014-01-08 中国地质大学（武汉） 锂硫电池添加剂、含有该添加剂的正极材料及其制备方法
CN103515614A (zh) * 2013-10-02 2014-01-15 中国地质大学（武汉） 一种电池添加剂、含有该添加剂的正极材料及其制备方法
CN104900880A (zh) * 2015-06-03 2015-09-09 中国地质大学（武汉） 一种锂硫电池复合正极材料及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100484642B1 (ko) * 2002-09-23 2005-04-20 삼성에스디아이 주식회사 리튬-설퍼 전지용 양극 활물질 및 그 제조방법
WO2012100301A1 (fr) * 2011-01-27 2012-08-02 The University Of Queensland Matériau soufre-carbone et utilisation en tant que cathodes pour batteries à haute énergie
CN103199250B (zh) * 2013-04-24 2015-08-05 中国科学院苏州纳米技术与纳米仿生研究所 一种有机硅化物修饰的锂硫电池正极材料的制备方法
CN103515613B (zh) * 2013-10-02 2017-06-30 中国地质大学（武汉） 一种锂硫电池添加剂、含有该添加剂的正极材料
CN104466138B (zh) * 2014-12-24 2017-02-22 华南师范大学 一种锂硫电池球形复合正极材料及其制备方法与应用
CN104577080B (zh) * 2014-12-29 2017-02-22 中国地质大学（武汉） 一种高倍率性能锂硫电池的复合正极材料及制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102324507A (zh) * 2011-09-10 2012-01-18 中南大学 一种锂硫电池复合正极材料制备方法
CN103500847A (zh) * 2013-10-02 2014-01-08 中国地质大学（武汉） 锂硫电池添加剂、含有该添加剂的正极材料及其制备方法
CN103515614A (zh) * 2013-10-02 2014-01-15 中国地质大学（武汉） 一种电池添加剂、含有该添加剂的正极材料及其制备方法
CN104900880A (zh) * 2015-06-03 2015-09-09 中国地质大学（武汉） 一种锂硫电池复合正极材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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