CN109768237B - Lithium-sulfur battery positive electrode material, preparation method and application - Google Patents
Lithium-sulfur battery positive electrode material, preparation method and application Download PDFInfo
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- CN109768237B CN109768237B CN201811582991.3A CN201811582991A CN109768237B CN 109768237 B CN109768237 B CN 109768237B CN 201811582991 A CN201811582991 A CN 201811582991A CN 109768237 B CN109768237 B CN 109768237B
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Abstract
The invention relates to the technical field of lithium-sulfur secondary battery materials, in particular to a novel lithium-sulfur battery positive electrode material, a preparation method and application, and particularly relates to a novel MOF material compounded by metal selenides and metal oxides, a preparation method and application of the MOF material as the lithium-sulfur battery positive electrode material. The novel lithium-sulfur battery positive electrode material is an MOF material compounded by metal selenides and metal oxides, the material is composed of four parts, namely ZIF67, CoSe, CoO and S, the mass fraction of ZIF67 is 20-40%, the mass fraction of CoSe is 10-20%, the mass fraction of CoO is 10-20%, the mass fraction of S is 50-80%, the material has a rich pore channel structure, and meanwhile, the compound synergistic effect of the metal selenides and the metal oxides can better improve the adsorption effect on lithium polysulfide and improve the utilization rate of the positive electrode material.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur secondary battery materials, in particular to a lithium-sulfur battery positive electrode material, a preparation method and application thereof, and especially relates to a metal selenide and metal oxide composite MOF material, a preparation method and application thereof as a lithium-sulfur battery positive electrode material.
Background
The traditional lithium battery anode material is limited to 200-250Wh kg-1The energy density of the battery can not meet the requirements of industries such as electric automobiles, large-scale energy storage equipment and the like on the energy density of the battery. However, it is limited to 200-250Wh kg-1The energy density of the battery can not meet the requirements of industries such as electric automobiles, large-scale energy storage equipment and the like on the energy density of the battery. Therefore, related research make internal disorder or usurp on high energy density batteries in academic circles is promoted, and lithium sulfur batteries belong to a research hotspot of high energy batteries. In fact, as early as 60 s in the 20 th century, elemental sulfur was proposed as a positive electrode material for lithium ion batteries, and then research on lithium sulfur batteries was started. The elemental sulfur has higher theoretical ratioCapacity (167mAh g)-1) And is considered to be the most potential positive electrode material of the next-generation lithium ion secondary battery. The theoretical specific energy and the theoretical energy density of the lithium-sulfur battery system can reach considerable 2600Wh kg-1And 2800Wh L-1Is far higher than the specific energy of the prior transition metal oxide material lithium ion battery. In addition, sulfur has the advantages of abundant reserves, low price, environmental friendliness and the like, and most probably provides a light power source and support for the current electric automobiles, so that the lithium sulfur battery is considered to be one of the secondary batteries with the most research and high specific energy and low cost.
The lithium-sulfur battery has the problems of low utilization rate of positive active materials, short cycle life, poor rate performance, serious self-discharge and the like, and the industrial practical application of the lithium-sulfur battery is restricted. The reasons for these problems are mainly:
(1) the positive active substance sulfur has extremely low electronic conductivity and ionic conductivity at room temperature, and the elementary sulfur and the reaction intermediate product organic sulfide have poor electronic conductivity and ionic conductivity, which causes the relatively poor heavy-current charging and discharging and rate capability of the battery.
(2) Polysulfide (LisSx, 4) intermediate of sulfur in electrochemical redox reaction<x<8) Is easy to dissolve in organic electrolyte, so that the utilization rate of active substances is not high; polysulfide ions generated in the charging and discharging process can be dissolved in an organic solvent to generate shuttle effect between the two electrodes, so that the utilization rate, specific capacity and cycle performance of sulfur are reduced; it also causes an increase in the viscosity of the electrolyte and a decrease in Li+The diffusion rate of (c).
(3) Polysulfide dissolved in the electrolyte generates shuttle between the anode and the cathode of the battery, so that irreversible loss of active substances is caused, and the charge-discharge efficiency is obviously reduced.
(4) Polysulfide diffuses into the negative electrode, reacts with the lithium negative electrode, causes self-discharge of the battery, and reacts to form solid-state insulated Li2S and Li2S2Causing deterioration of the surface of the lithium negative electrode and irreversible loss of the active material.
(5) Final product of electrochemical reduction of sulfur (Li)2S and Li2S2) Is insoluble insulating material and is easy to be dissolvedBlocking the electron and ion transport channels of the sulfur anode.
In summary, the main problems to be solved in the lithium-sulfur battery are poor conductivity of the positive electrode material and dissolution and diffusion of polysulfide. The carbon material adopted as the sulfur-based composite electrode material of the lithium-sulfur battery mainly has two functions, namely providing electrical conductivity for insulating elemental sulfur and providing a pore structure for loaded sulfur, so that the electrical conductivity and the pore structure of the selected carbon material are required to be key factors.
As a novel porous framework, a Metal Organic Framework (MOF) has good electrochemical activity, good pore characteristics and large specific surface area and stable chemical properties, the structure, porosity and specific surface area of a metal organic framework material are controlled and selected, the pore channel of the formed composite material not only adsorbs active substance sulfur, but also has rich functional groups on the surface of the pore channel, more active substance sulfur materials can be adsorbed and loaded through bonds, and the porous structure of the MOF helps to inhibit the dissolution of elemental sulfur and polysulfide in electrolyte, so that the cycle performance of a lithium sulfur battery is fully improved, and the utilization rate of active substances of a positive electrode material is kept high. Active substance sulfur is infiltrated into the pores and pore channels of the microporous carbon polyhedron, and the unique porous structure of the microporous carbon polyhedron limits the dissolution of sulfur and polysulfide. Thus, Metal Organic Framework (MOF) is a new porous framework with great practical promise in lithium sulfur batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel MOF material compounded by metal selenides and metal oxides, the material has rich pore channel structures, and meanwhile, the compound synergistic effect of the metal selenides and the metal oxides can better improve the adsorption effect on lithium polysulfide and improve the utilization rate of a positive electrode material.
The technical scheme of the invention is as follows:
the novel positive electrode material for the lithium-sulfur battery is an MOF material compounded by metal selenides and metal oxides, and is characterized by comprising 20-40% of ZIF67, 10-20% of CoSe, 10-20% of CoO and 50-80% of S, wherein the mass fraction of ZIF67 is ZIF, and the mass fraction of CoSe, CoO and S is ZIF.
The invention also provides a preparation method of the novel lithium-sulfur battery positive electrode material, which comprises the following specific steps:
the first step is as follows: preparation of ZIF67 powder (zeolitic imidazolate framework)
Step one, liquid A: 5-10mmol of cobalt nitrate hexahydrate dispersed in 125-250ml of methanol;
and B, liquid B: 20-40mmol of 2-methylimidazole, and dispersing in 125-250ml of methanol;
and step two, pouring the solution B into the solution A under magnetic stirring, and stirring for 3-5 minutes until the solution A is uniform to obtain the ZIF67 precursor solution.
Step three, sealing the obtained ZIF67 precursor liquid, standing and aging for 24 hours to obtain a ZIF67 solution;
step four, carrying out centrifugal washing on the ZIF67 solution for 3 times by using methanol and 3 times by using ethanol; drying at 60-80 deg.C overnight to obtain ZIF67 powder;
the second step is that: synthesizing ZIF67@ CoSe @ CoO (ZIF67 composite cobalt selenide composite cobalt oxide material),
mixing ZIF67 powder and selenium powder in the first step, wherein the mass ratio of ZIF67 to selenium powder is 1: 1; then, the mixture is subjected to heat preservation for 1-3 hours at the temperature of 250-500 ℃, then heated to the temperature of 500-850 ℃ and subjected to heat preservation for 1-3 hours, and the whole process is heated in a nitrogen atmosphere at the speed of 1-2 ℃/min to obtain ZIF67@ CoSe @ CoO, namely a ZIF67 composite cobalt selenide composite cobalt oxide material;
the third step: preparation of S/ZIF67@ CoSe @ CoO material
Mixing the ZIF67@ CoSe @ CoO material with pure-phase nano sulfur powder, putting the mixture into a tubular furnace under the protection of nitrogen, and carrying out heat treatment at 150 ℃ for 24 hours to obtain the S/ZIF67@ CoSe @ CoO material.
Preferably, in the third step, the mass ratio of the ZIF67@ CoSe @ CoO material to the pure-phase nano sulfur powder is 2: 3.
The stirring is magnetic stirring, and the rotating speed is 100-300 r/min.
Another object of the present invention is to provide the use of the obtained S/ZIF67@ CoSe @ CoO material as a positive electrode material or active material for lithium sulfur batteries.
The preparation method of the novel lithium-sulfur battery cathode material is characterized in that the raw materials are all obtained from commercial sources.
The invention has the beneficial effects that:
the novel lithium-sulfur battery positive electrode material is an MOF material compounded by metal selenides and metal oxides, has rich pore channel structures, and can improve the adsorption effect on lithium polysulfide and the utilization rate of the positive electrode material by the compound synergistic effect of the metal selenides and the metal oxides.
The S/ZIF67@ CoSe @ CoO material is innovatively prepared, CoSe and CoO are cooperatively used for carrying sulfur, the utilization rate of sulfur is improved, and meanwhile, the volume expansion in the charging and discharging processes is reduced by combining the hollow structure of ZIF67, so that the electrochemical performance is stable.
Drawings
FIG. 1 first turn charge and discharge curves at 0.2C for the S/ZIF67@ CoSe @ CoO material of example 1 of the present invention as a positive electrode material for a lithium sulfur battery.
FIG. 2 the cycling profile for the first 50 cycles at 0.2C for the example 2S/ZIF67@ CoSe @ CoO material of the present invention as the positive electrode material for a lithium sulfur battery.
Detailed Description
The technical solutions of the present invention will be described more clearly and completely with reference to the following embodiments of the present invention. The described embodiments are merely exemplary embodiments of the invention, rather than limiting the invention in any way, and any variations, equivalents, modifications, etc. which fall within the spirit and scope of the invention are intended to be embraced therein.
Example 1 a method for preparing a novel positive electrode material for a lithium-sulfur battery,
the first step is as follows: preparation of ZIF67 powder (zeolitic imidazolate framework)
Step one, liquid A: 5mmol of cobalt nitrate hexahydrate dispersed in 125ml of methanol;
and B, liquid B: 20mmol of 2-methylimidazole dispersed in 125ml of methanol;
and step two, pouring the solution B into the solution A under magnetic stirring, and stirring for 3 minutes until the solution A is uniform to obtain the ZIF67 precursor solution.
And step three, sealing the ZIF67 precursor solution, standing and aging for 24 hours to obtain a ZIF67 solution.
Step four, carrying out centrifugal washing on the ZIF67 solution for 3 times by using methanol and 3 times by using ethanol; drying at 60 deg.C overnight to obtain ZIF67 powder.
The second step is that: synthesis of ZIF67@ CoSe @ CoO ZIF67 composite cobalt selenide composite cobalt oxide material)
Mixing 1g of ZIF67 powder and 1g of selenium powder in the first step, wherein the mass ratio of ZIF67 to selenium powder is 1: 1. and then preserving the heat of the mixture for 2 hours at 350 ℃, then heating to 750 ℃ and preserving the heat for 2 hours, and heating in a nitrogen atmosphere at the speed of 1 ℃/min to obtain ZIF67@ CoSe @ CoO, namely the ZIF67 composite cobalt selenide composite cobalt oxide material.
The third step: 1g of ZIF67@ CoSe @ CoO material and 1.5g of pure-phase nano sulfur powder are mixed and put into a tubular furnace under the protection of nitrogen, and the mixture is thermally treated at 150 ℃ for 24 hours to obtain the S/ZIF67@ CoSe @ CoO material.
Taking the prepared S/ZIF67@ CoSe @ CoO as an active material, carbon powder as a conductive agent, polyvinylidene fluoride (PVDF) as an adhesive, adding the S/ZIF67@ CoSe @ CoO: C: 8:1:1 by weight into a mortar for mixing and grinding uniformly, then dropping N-methyl pyrrolidone (NMP) for grinding into slurry, uniformly coating the slurry on an aluminum foil, wherein the loading capacity is 2mg, then putting the slurry into a constant-temperature drying box at 60 ℃ for drying for 12h, drying the slurry to constant weight, and pressing the slurry into a sheet by using a tablet press under the pressure of 5MPa, thereby preparing the S/ZIF67@ CoSe CoO lithium sulfur battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
FIG. 1 first turn charge and discharge curves at 0.2C for the S/ZIF67@ CoSe @ CoO material of example 1 of the present invention as a positive electrode material for a lithium sulfur battery. The specific capacity of the first circle of the material as the positive electrode material of the lithium-sulfur battery is 1500mAh/mg, the charging and discharging platform is obvious, the discharging voltage is 2.4V and 2.1V, and the coulomb efficiency is increased by 100% as is obvious from the graph 1.
Example 2 a method for preparing a novel positive electrode material for a lithium-sulfur battery,
the first step is as follows: preparation of ZIF67 powder (zeolitic imidazolate framework)
Step one, liquid A: 10mmol of cobalt nitrate hexahydrate dispersed in 250ml of methanol (pink);
and B, liquid B: 40mmol of 2-methylimidazole dispersed in 250ml of methanol (clear color);
and step two, pouring the solution B into the solution A under magnetic stirring, and stirring for 5 minutes until the solution A is uniform. (purple, turbid with stirring)
Step three, sealing the obtained ZIF67 precursor liquid, standing and aging for 24 hours to obtain a ZIF67 solution;
step four, carrying out centrifugal washing on the ZIF67 solution for 3 times by using methanol and 3 times by using ethanol; drying at 80 deg.C overnight to obtain ZIF67 powder.
The second step is that: synthesizing ZIF67@ CoSe @ CoO (ZIF67 composite cobalt selenide composite cobalt oxide material),
mixing 2g of ZIF67 powder and 2g of selenium powder in the first step, wherein the mass ratio of ZIF67 to selenium powder is 1: 1. then the mixture is kept at 350 ℃ for 2 hours, then is heated to 750 ℃ and kept at the temperature for 2 hours, and is heated in a nitrogen atmosphere in the whole process at the speed of 1 ℃/min.
Obtaining ZIF67@ CoSe @ CoO, namely a ZIF67 composite cobalt selenide composite cobalt oxide material;
the third step: preparation of S/ZIF67@ CoSe @ CoO material
2g of ZIF67@ CoSe @ CoO material and 3g of pure-phase nano sulfur powder are mixed and put into a tubular furnace under the protection of nitrogen, and the mixture is thermally treated at 150 ℃ for 24 hours to obtain the S/ZIF67@ CoSe @ CoO material.
Taking the prepared S/ZIF67@ CoSe @ CoO as an active material, carbon powder as a conductive agent, polyvinylidene fluoride (PVDF) as an adhesive, adding the S/ZIF67@ CoSe @ CoO: C: 8:1:1 by weight into a mortar for mixing and grinding uniformly, then dropping N-methyl pyrrolidone (NMP) for grinding into slurry, uniformly coating the slurry on an aluminum foil, wherein the loading capacity is 2mg, then putting the slurry into a constant-temperature drying box at 60 ℃ for drying for 12h, drying the slurry to constant weight, and pressing the slurry into a sheet by using a tablet press under the pressure of 5MPa, thereby preparing the S/ZIF67@ CoSe CoO lithium sulfur battery positive plate; the metal lithium is used as a counter electrode and a reference electrode, the lithium-sulfur electrolyte is used as an electrolyte, the porous polypropylene is used as a diaphragm, and the CR2025 button cell is assembled in a glove box filled with argon.
FIG. 2 is a plot of the first 50 cycles at 0.2C for the S/ZIF67@ CoSe @ CoO material of example 2 of the present invention as a positive electrode material for a lithium sulfur battery. As can be seen from FIG. 2, the material has good cycling stability, and after 50 cycles, the material still retains a specific discharge capacity of about 1000mAh/mg, which represents that S/ZIF67@ CoSe @ CoO material can improve the energy density of the active substance sulfur, and simultaneously, the electrochemical performance of the battery is improved.
Claims (4)
1. A preparation method of a lithium-sulfur battery anode material is characterized in that,
the positive electrode material of the lithium-sulfur battery is a MOF material compounded by metal selenides and metal oxides, and consists of four parts, namely ZIF67, CoSe, CoO and S, wherein the mass fraction of ZIF67 is 20-40%, the mass fraction of CoSe is 10-20%, the mass fraction of CoO is 10-20%, and the mass fraction of S is 50-80%;
the preparation method of the lithium-sulfur battery positive electrode material comprises the following specific steps:
the first step is as follows: preparation of ZIF67 powder
Step one, liquid A: 5-10mmol of cobalt nitrate hexahydrate dispersed in 125-250ml of methanol;
and B, liquid B: 20-40mmol of 2-methylimidazole, and dispersing in 125-250ml of methanol;
step two, pouring the solution B into the solution A under magnetic stirring, and stirring for 3-5 minutes until the solution A is uniform to obtain a ZIF67 precursor solution;
step three, sealing the obtained ZIF67 precursor liquid, standing and aging for 24 hours to obtain a ZIF67 solution;
step four, carrying out centrifugal washing on the ZIF67 solution for 3 times by using methanol and 3 times by using ethanol; drying at 60-80 deg.C overnight to obtain ZIF67 powder;
the second step is that: synthesis of ZIF67@ CoSe @ CoO,
mixing ZIF67 powder and selenium powder in the first step, wherein the mass ratio of ZIF67 to selenium powder is 1: 1; then, the mixture is subjected to heat preservation for 1-3 hours at the temperature of 250-500 ℃, then heated to the temperature of 500-850 ℃ and subjected to heat preservation for 1-3 hours, and the whole process is heated in a nitrogen atmosphere at the speed of 1-2 ℃/min to obtain ZIF67@ CoSe @ CoO, namely a ZIF67 composite cobalt selenide composite cobalt oxide material;
the third step: preparation of S/ZIF67@ CoSe @ CoO material
Mixing the ZIF67@ CoSe @ CoO material with pure-phase nano sulfur powder, putting the mixture into a tubular furnace under the protection of nitrogen, and carrying out heat treatment at 150 ℃ for 24 hours to obtain the S/ZIF67@ CoSe @ CoO material.
2. The method for preparing the positive electrode material of the lithium-sulfur battery as claimed in claim 1, wherein in the third step, the mass ratio of the ZIF67@ CoSe @ CoO material to the pure-phase nano sulfur powder is 2: 3.
3. The method of claim 1, wherein the stirring is magnetic stirring at a speed of 100 to 300 r/min.
4. Use of the positive electrode material obtained by the method for preparing a positive electrode material for a lithium-sulfur battery according to any one of claims 1 to 3 as a positive electrode material or an active material for a lithium-sulfur battery.
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| CN110492088B (en) * | 2019-09-16 | 2021-02-09 | 安徽师范大学 | ZIF-8@ reduced graphene oxide loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN110611099A (en) * | 2019-09-16 | 2019-12-24 | 肇庆市华师大光电产业研究院 | Preparation method of 3D-ZIF8@ ZIF67 for lithium-sulfur battery cathode material |
| CN110707309B (en) * | 2019-10-29 | 2022-06-03 | 肇庆市华师大光电产业研究院 | Preparation method of ZIF8 lithium-sulfur battery cathode material with 3DOM structure |
| CN111969187A (en) * | 2020-07-30 | 2020-11-20 | 广东格林赛福能源科技有限公司 | Preparation method, material and application of high-performance CoSe/C-NS composite material |
| CN112156185A (en) * | 2020-09-14 | 2021-01-01 | 湖北大学 | Preparation method of copper selenide nanocomposite with excellent photo-thermal effect |
| CN112436158B (en) * | 2020-11-06 | 2022-09-13 | 扬州大学 | Anode catalyst of alcohol fuel cell |
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| WO2023082219A1 (en) * | 2021-11-13 | 2023-05-19 | 广东暨创硒源纳米研究院有限公司 | Method for efficiently preparing nano-composite material in which metal-organic framework is loaded with selenium atoms and use thereof |
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