CN110760072A - Preparation method of lithium-sulfur battery positive electrode material of composite metal organic framework - Google Patents
Preparation method of lithium-sulfur battery positive electrode material of composite metal organic framework Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
The invention relates to a preparation method of a lithium-sulfur battery anode material, which comprises two metal organic frameworks of ZIF67 and ZIF8, and is compounded with elemental sulfur to obtain the lithium-sulfur battery anode material.
Description
Technical Field
The invention relates to a preparation method of a composite metal organic framework material applied to a lithium-sulfur battery anode, and the composite material is specifically formed by compounding two metal organic frameworks ZIF67 and ZIF8, and belongs to the field of material chemistry.
Background
With the continuous emergence of new technologies, new energy products are more and more concerned by people. Higher demands are made on energy density and rapid charge and discharge capability of commercial batteries. The lithium ion battery which is commercially available at present cannot meet the requirements of people due to low energy density. However, when elemental sulfur is used as a positive electrode material, the theoretical energy density of the battery is as high as 2600Wh/kg, the theoretical specific capacity can reach 1675 mA.h/g, and the sulfur is rich in storage in nature, low in price and non-toxic, so that the lithium-sulfur battery is considered by the researchers to be a secondary energy storage system with great development prospect.
Despite the advantages of sulfur positive electrode materials, sulfur electrodes have problems in their commercial applications: (1) elemental sulfur has very poor conductivity, resulting in low utilization of sulfur. (2) Elemental sulfur and discharge end product Li2The large difference in density of S causes the sulfur electrode to undergo significant volume expansion and contraction (about 80%) during the cycling process, causing the electrode material to fall off and break during the cycling process, thereby destroying the overall structure of the electrode and causing loss of active materials. (3) The discharge intermediate product (high valence state lithium polysulfide) of the sulfur electrode has high solubility in organic electrolyte, can penetrate through a diaphragm to reach a negative electrode to further generate insoluble low valence state lithium sulfide with lithium, and is attached to a negative electrode lithium sheet to generate a shuttle effect, so that the corrosion of metal lithium, the loss of active substances, poor cycle performance of the lithium-sulfur battery and serious self-discharge phenomenon are caused.
The invention provides a simple and effective method for preparing a metal organic framework formed by compounding ZIF67 and ZIF 8. Previous studies have shown that the metal-organic framework possesses good adsorption on lithium polysulfides, and is capable of enhancing the kinetics of redox reactions, and exhibits good effects on inhibiting the "shuttle effect" of lithium polysulfides. The invention synthesizes a composite metal organic framework formed by combining two metal organic frameworks by a simple hydrothermal method, further improves the specific surface area of the material and the adsorption and conversion effect on lithium polysulfide, improves the utilization rate of active substances, and improves the cyclicity and stability of the battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a lithium-sulfur battery cathode material, which is characterized in that a material formed by compounding two metal organic frameworks ZIF67 and ZIF8 is prepared by a simple solvothermal method, can well adsorb lithium polysulfide, inhibits the shuttle effect of the lithium polysulfide, and promotes the redox reaction kinetics of the lithium-sulfur battery in the charging and discharging processes.
A preparation method of a lithium-sulfur battery positive electrode material specifically comprises the following steps:
the first step is as follows: synthesis of ZIF67 material:
a certain amount of Co (NO)3)2·6H2Dissolving O in methanol, stirring to dissolve completely to obtain Co (NO)3)2A solution; dissolving 2-methylimidazole (Hmim) in methanol, and stirring until the 2-methylimidazole is completely dissolved to obtain a 2-methylimidazole solution. The 2-methylimidazole solution was slowly poured into an equal volume of Co (NO)3)2Stirring the solution for 30min, standing and aging for 24h after the purple clear liquid turns into purple turbid liquid, and centrifuging to collect precipitate. And then centrifugally washing the mixture for 5 times by using methanol, centrifugally washing the mixture for 2 times by using ethanol, and drying the mixture in vacuum to obtain a ZIF67 material.
Further, Co (NO) in the first step3)2The molar concentration of the cobalt nitrate in the solution is 0.04 mol/L; the molar concentration of dimethyl imidazole in 2-methylimidazole is 0.16 mol/L.
Further, the vacuum drying temperature in the first step is 60 ℃, and the drying time is 24 h.
The second step is that: synthesizing ZIF67/ZnO material:
adding Zn (CH)3COO)2·H2Adding O into methanol, placing on a heating plate, stirring at 65 ℃ until the O is completely dissolved to obtain Zn (CH)3COO)2And (3) solution. Adding KOH into methanol, putting on a heating plate, and stirring until the KOH is completely dissolved to obtain a KOH solution. Adding ZIF67 into methanol, recording as ZIF solution, ultrasonic treating for 20-30min, and adding Zn (CH)3COO)2The solution was stirred at 65 ℃ for 20 min. And dropwise adding the KOH solution into the mixed solution by using a dropper, stirring for 2 hours after the dropwise adding is finished, centrifugally collecting precipitates, and drying to obtain the ZIF67/ZnO material.
Further, Zn (CH) in the second step3COO)2Zn (CH) in solution3COO)2The molar concentration of the active carbon is 0.035 mol/L; the molar concentration of KOH in the KOH solution was 0.106 mol/L.
Further, in the second step, the mass volume ratio of ZIF67 to methanol in the ZIF solution was 10:3g/L to 0.1g, and the volume of methanol required to dissolve ZIF67 was 30 ml.
Further, the Zn (CH)3COO)2The volume ratio of the solution, the KOH solution and the ZIF solution is 5: 4: 3.
The third step: preparing a ZIF67/ZIF8 composite material:
adding 2-methylimidazole into methanol, heating to 50 ℃ on a heating plate, and completely dissolving at the temperature of 50 ℃ to obtain a 2-methylimidazole solution; and adding the ZIF67/ZnO material prepared in the second step into absolute methanol, namely a ZIF67/ZnO solution, carrying out ultrasonic treatment for 30min, adding the mixture into a 2-methylimidazole solution, continuously stirring for 20min at 50 ℃, centrifuging, collecting precipitates, centrifugally washing for 5 times by using the absolute methanol, and drying at 60 ℃ overnight to obtain the ZIF67/ZIF8 composite material.
Further, the mass volume ratio of the 2-methylimidazole to the methanol in the 2-methylimidazole solution in the third step is 20-41 g/L.
Furthermore, in the ZIF67/ZnO solution, the mass-to-volume ratio of a ZIF67/ZnO material to anhydrous methanol is 10:1 g/L.
Further, the volume ratio of the 2-methylimidazole solution to the ZIF67/ZnO solution was 5: 1.
According to the preparation method of the ZIF67/ZIF8 composite material for the lithium-sulfur battery, the related raw materials are all obtained by commercial purchase.
The invention has the following beneficial effects:
(1) according to the invention, two metal organic frameworks ZIF67 and ZIF8 are combined by a simple solvothermal method to form a composite structure which has a high specific surface area and can adsorb lithium polysulfide. The ultra-high specific surface area not only can provide sufficient reaction sites for electrochemical reaction, but also can adsorb polysulfide, improve the kinetics of redox reaction, and effectively inhibit the shuttle effect of lithium polysulfide.
(2) The ZIF67/ZIF8 composite material prepared by the method is applied to the lithium-sulfur battery, the first charge-discharge specific capacity of the battery reaches 1100mAh/g at 0.1 ℃, and the battery has high discharge capacity and excellent cycling stability.
(3) The invention relates to a preparation method of a lithium-sulfur battery positive electrode material with the characteristics of high yield and industrial feasibility.
Drawings
FIG. 1 is a TEM photograph of the ZIF67 material prepared in example 1.
FIG. 2 is a graph showing the cycle performance of a button cell prepared by mixing the ZIF67/ZIF8 composite material prepared in example 1 with sulfur as a positive electrode material.
Example 1:
the first step is as follows: synthesis of ZIF67 material:
1.145g of Co (NO)3)2·6H2Dissolving O in 125ml methanol, stirring to dissolve completely to obtain Co (NO)3)2·6H2And (4) O solution. 1.640g of 2-methylimidazole (Hmim) was dissolved in 125mL of methanol, and the solution was stirred until the solution was completely dissolved to obtain a 2-methylimidazole solution. Slowly pouring the 2-methylimidazole solution into Co (NO)3)2·6H2Stirring for 30min in the solution of O until the purple clear liquid turns into purple turbid liquid, standing and aging for 24h, and centrifuging to collect precipitate. Followed by 5 washes with methanol and 2 washes with ethanol by centrifugation and vacuum drying at 60 ℃ for 24 hours to obtain ZIF67 material.
The second step is that: synthesizing ZIF67/ZnO material:
0.3864g of Zn (CH)3COO)2·H2Adding O into 50ml methanol, placing on a heating plate, stirring at 65 ℃ until Zn (CH) is completely dissolved to obtain Zn (3COO)2·H2And (4) O solution. 0.2384g of KOH was put into 40ml of methanol, and the solution was stirred on a heating plate at 65 ℃ until completely dissolved to obtain a KOH solution. Adding 0.1g ZIF67 obtained in the first step into 30ml methanol, performing ultrasonic treatment for 20-30min, and adding Zn (CH)3COO)2·H2In O solution, stirring at 65 ℃ for 20 min. And dropwise adding the KOH solution into the mixed solution by using a dropper, quickly stirring after the dropwise adding is finished, centrifugally collecting precipitates after reacting for 2 hours, and drying to obtain the ZIF67/ZnO material.
The third step: preparing a ZIF67/ZIF8 composite material:
adding 2.05g of 2-methylimidazole into 50ml of methanol, heating the mixture on a heating plate to 50 ℃ to completely dissolve the mixture to obtain a 2-methylimidazole solution, weighing 0.1g of prepared ZIF67/ZnO, adding the mixture into 10ml of methanol, carrying out ultrasonic treatment for 30min, adding the mixture into the 2-methylimidazole solution, and stirring the mixture for 20min at 50 ℃. Centrifuging to collect precipitate, centrifuging and washing with anhydrous methanol for 5 times, and drying at 60 ℃ overnight to obtain the ZIF67/ZIF8 composite material.
FIG. 1 is a TEM photograph of ZIF67 prepared in example 1. The prepared ZIF67 is in a regular 12-sided structure, and the diameters of the ZIF67 are mostly distributed between 600-700 nm.
FIG. 2 is a graph showing the cycle performance of a button cell prepared by mixing the ZIF67/ZIF8 composite material prepared in example 1 with sulfur as a positive electrode material. From the circulation diagram, the specific discharge capacity of the first circle of the battery reaches 1100mAh/g under the multiplying power of 0.1C, and after 100 circles of circulation, the specific discharge capacity still can reach 950mAh/g, so that good circulation stability is shown.
Example 2:
the first step is as follows: synthesis of ZIF67 material:
1.145g of Co (NO)3)2·6H2Dissolving O in 125ml methanol, stirring to dissolve completely to obtain Co (NO)3)2·6H2And (4) O solution. 1.640g of 2-methylimidazole (Hmim) was dissolved in 125mL of methanol, and the solution was stirred until the solution was completely dissolved to obtain a 2-methylimidazole solution. Slowly pouring the 2-methylimidazole solution into Co (NO)3)2·6H2Stirring for 30min in the solution of O until the purple clear liquid turns into purple turbid liquid, standing and aging for 24h, and centrifuging to collect precipitate. Followed by 5 washes with methanol and 2 washes with ethanol by centrifugation and vacuum drying at 60 ℃ for 24 hours to obtain ZIF67 material.
The second step is that: synthesis of ZIF 67/ZnO:
0.3864g of Zn (CH)3COO)2·H2Adding O into 50ml methanol, placing on a heating plate, stirring at 65 ℃ until Zn (CH) is completely dissolved to obtain Zn (3COO)2·H2And (4) O solution. 0.2384g of KOH were added to 40ml of methanol and placed on a hot plate at 65 ℃ with stirring until completely dissolvedA KOH solution was obtained. Adding 0.1g ZIF67 obtained in the first step into 30ml methanol, performing ultrasonic treatment for 20-30min, and adding Zn (CH)3COO)2·H2In O solution, stirring at 65 ℃ for 20 min. And dropwise adding the KOH solution into the mixed solution by using a dropper, quickly stirring after the dropwise adding is finished, centrifugally collecting precipitates after reacting for 2 hours, and drying to obtain the ZIF67/ZnO material.
The third step: preparation of ZIF67/ZIF 8:
adding 1.03g of 2-methylimidazole into 50ml of methanol, heating the mixture on a heating plate to 50 ℃ to completely dissolve the mixture to obtain a 2-methylimidazole solution, weighing 0.1g of prepared ZIF67/ZnO, adding the mixture into 10ml of methanol, carrying out ultrasonic treatment for 30min, adding the mixture into the 2-methylimidazole solution, and stirring the mixture for 20min at 50 ℃. Centrifuging to collect precipitate, centrifuging and washing with anhydrous methanol for 5 times, and drying at 60 ℃ overnight to obtain the ZIF67/ZIF8 composite material.
Claims (9)
1. A preparation method of a lithium-sulfur battery positive electrode material of a composite metal organic framework comprises the following steps:
the first step is as follows: synthesis of ZIF67 material:
a certain amount of Co (NO)3)2·6H2Dissolving O in methanol, stirring to dissolve completely to obtain Co (NO)3)2A solution; dissolving 2-methylimidazole (Hmim) in methanol, and stirring until the 2-methylimidazole is completely dissolved to obtain a 2-methylimidazole solution; the 2-methylimidazole solution was slowly poured into an equal volume of Co (NO)3)2Stirring the solution for 30min, standing and aging for 24h after the purple clear liquid is converted into purple turbid liquid, and centrifuging to collect precipitate; centrifuging and washing the mixture for 5 times by using methanol, centrifuging and washing the mixture for 2 times by using ethanol, and drying the mixture in vacuum to obtain a ZIF67 material;
the second step is that: synthesizing ZIF67/ZnO material:
adding Zn (CH)3COO)2·H2Adding O into methanol, placing on a heating plate, stirring at 65 ℃ until the O is completely dissolved to obtain Zn (CH)3COO)2A solution; adding KOH into methanol, putting on a heating plate, and stirring until the KOH is completely dissolved at 65 ℃ to obtain a KOH solution; adding ZIF67 into methanol, recording as ZIF solution, and treating with ultrasoundTreating for 20-30min, adding Zn (CH)3COO)2Stirring the solution for 20min at 65 ℃; dripping a KOH solution into the mixed solution by using a dropper, stirring for 2 hours after the dripping is finished, centrifugally collecting precipitates, and drying to obtain a ZIF67/ZnO material;
the third step: preparing a ZIF67/ZIF8 composite material:
adding 2-methylimidazole into methanol, heating the mixture on a heating plate to 50 ℃, and completely dissolving the mixture to obtain a 2-methylimidazole solution; and adding the ZIF67/ZnO material prepared in the second step into absolute methanol, namely a ZIF67/ZnO solution, carrying out ultrasonic treatment for 30min, adding the mixture into a 2-methylimidazole solution, continuously stirring for 20min at 50 ℃, centrifuging, collecting precipitates, centrifugally washing for 5 times by using the absolute methanol, and drying at 60 ℃ overnight to obtain the ZIF67/ZIF8 composite material.
2. The method of claim 1, wherein: co (NO) in the first step3)2·6H2Co (NO) in solution with O3)2The molar concentration of (A) is 0.04 mol/L; the molar concentration of 2-methylimidazole in the 2-methylimidazole solution is 0.16 mol/L.
3. The method of claim 1, wherein: in the first step, the vacuum drying temperature is 60 ℃, and the drying time is 24 hours.
4. The method of claim 1, wherein: in the second step Zn (CH)3COO)2The molar concentration of (2) was 0.035mol/L and the molar concentration of KOH was 0.106 mol/L.
5. The method of claim 1, wherein: in the second step, the mass-to-volume ratio of ZIF67 to methanol in the ZIF solution is 10:3 g/L.
6. The production method according to claim 4 or 5, characterized in that: the Zn (CH)3COO)2The volume ratio of the solution, the KOH solution and the ZIF solution is 5: 4: 3.
7. the method of claim 1, wherein: in the third step, the mass volume ratio of the 2-methylimidazole to the methanol in the 2-methylimidazole solution is 20-41 g/L.
8. The method of claim 1, wherein: in the ZIF67/ZnO solution, the mass-to-volume ratio of a ZIF67/ZnO material to anhydrous methanol is 10:1 g/L.
9. The method of claim 8, wherein: the volume ratio of the 2-methylimidazole solution to the ZIF67/ZnO solution is 5: 1.
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| CN111377427A (en) * | 2020-02-28 | 2020-07-07 | 肇庆市华师大光电产业研究院 | Sodium-sulfur battery positive electrode material and preparation method thereof |
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| CN109935813A (en) * | 2019-03-13 | 2019-06-25 | 河源广工大协同创新研究院 | A kind of preparation method and application of novel cathode material for lithium ion battery |
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| CN104549082A (en) * | 2014-12-19 | 2015-04-29 | 安徽建筑大学 | ZnO@ZIF-8 core-shell structure microsphere and preparation method thereof |
| US20180339284A1 (en) * | 2016-02-04 | 2018-11-29 | Nanjing Normal University | Synthesis and Application of MOFs/natural Polymers Composite Beads Adsorbents |
| CN106684355A (en) * | 2016-12-29 | 2017-05-17 | 中国电子科技集团公司第十八研究所 | Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111377427A (en) * | 2020-02-28 | 2020-07-07 | 肇庆市华师大光电产业研究院 | Sodium-sulfur battery positive electrode material and preparation method thereof |
| CN111377427B (en) * | 2020-02-28 | 2023-06-06 | 肇庆市华师大光电产业研究院 | Sodium-sulfur battery positive electrode material and preparation method thereof |
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