CN111293291A - Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents

Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof Download PDF

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CN111293291A
CN111293291A CN202010100841.5A CN202010100841A CN111293291A CN 111293291 A CN111293291 A CN 111293291A CN 202010100841 A CN202010100841 A CN 202010100841A CN 111293291 A CN111293291 A CN 111293291A
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王新
李超杰
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a novel efficient lithium-sulfur battery positive electrode material and a preparation method thereof. The positive electrode material is a CNT-ZnCo-LDH composite material. The positive electrode material has high conductivity, has physical adsorption and chemical adsorption on polysulfide, also has an electrocatalysis effect, promotes the transformation of the polysulfide, effectively inhibits a shuttle effect, and integrates multiple effects.

Description

Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a novel efficient lithium-sulfur battery positive electrode material and a preparation method thereof.
Background
With the rapid development of society and the rapid increase of economic level, the demand of people on energy sources is steadily increased. The lithium ion battery is the most widely applied battery type at present, and has the advantages of high energy density, low self-discharge rate, long service life and the like, so the lithium ion battery has wide application prospect. Although the specific capacity of the lithium ion battery is close to the theoretical specific capacity of 300mAh ∙ g-1But still remainThe increasing energy demand of human production and life cannot be met, and particularly, with the popularization of portable electronic devices, mobile power sources and new energy automobiles, the relatively low energy density of lithium ion batteries increasingly cannot meet the demand of large energy storage devices. It has become one of the hot spots of recent research to find an energy storage material with higher energy density, lighter weight, smaller volume and longer cycle life. In recent years, researchers at home and abroad have attracted attention to lithium-sulfur batteries using elemental sulfur as a battery positive electrode and metal lithium as a battery negative electrode material, wherein the elemental sulfur has 1675mAh ∙ g as the lithium-sulfur battery positive electrode-1The high theoretical specific capacity shows great potential as energy storage material.
Despite the advantages of lithium sulfur batteries, there are some disadvantages: firstly, elemental sulfur and its discharge product Li2S2And Li2The conductivity of S is poor; secondly, the volume expansion effect is caused by the change of the density of the substance in the reaction process; again, the shuttling effect is due to the dissolution of lithium polysulphides. The above problems of the present lithium-sulfur battery severely limit the improvement of the specific capacity, cycle life and cycle stability. In order to solve these problems, it is important to develop a novel positive electrode material for a lithium-sulfur battery and to improve the utilization rate of active materials in the electrode material.
Disclosure of Invention
The invention aims to provide a novel high-efficiency lithium-sulfur battery positive electrode material and a preparation method thereof aiming at the defects of low utilization rate of active substances, poor conductivity of the positive electrode material and shuttle effect of the lithium-sulfur battery positive electrode material prepared in the prior art.
The technical scheme of the invention is as follows: a novel high-efficiency positive electrode material of a lithium-sulfur battery is a CNT-ZnCo-LDH composite material.
The CNT-ZnCo-LDH composite material is composed of a layered zinc-cobalt double hydroxide ZnCo-LDH which is uniformly attached to a multi-walled carbon nanotube CNT.
The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material comprises the following steps of firstly preparing zinc oxide nano-particles CNT-ZnO attached to a multi-walled carbon nano-tube; then, zinc oxide nano particles are converted into a metal imidazole type molecular sieve framework ZIF8 by a hydrothermal method, so that a metal imidazole type molecular sieve framework CNT-ZIF8 attached to the multi-walled carbon nano tube is obtained; finally, the zinc-cobalt double hydroxide CNT-ZnCo-LDH attached to the multi-walled carbon nano-tube is obtained by hydrothermal replacement.
The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) preparation of CNT-ZnO: firstly, dissolving zinc acetate in absolute methanol, stirring at 40-60 ℃ until the zinc acetate is completely dissolved to obtain a zinc acetate solution, adding the zinc acetate solution into a round-bottom flask for oil bath, and keeping the temperature at 65-75 ℃; then adding CNT into absolute methanol, performing ultrasonic treatment until the CNT is completely dissolved, adding the dissolved CNT solution into the round-bottom flask, and stirring for 20-30 min at 65-75 ℃; finally, adding potassium hydroxide into absolute methanol, stirring and heating at 65-75 ℃, dropwise adding the heated potassium hydroxide solution into the round-bottom flask, stirring at 65-75 ℃ for 1-3 hours, centrifuging, washing and drying to obtain CNT-ZnO;
(2) preparation of CNT-ZIF 8: firstly, dissolving the CNT-ZnO obtained in the step (1) in absolute methanol, and marking as solution A; dissolving dimethyloxazole in absolute methanol to obtain solution B; adding the solution B into a round-bottom flask with the temperature of 50-60 ℃ for preheating, adding the solution A into the round-bottom flask, reacting at the temperature of 50-60 ℃ for 0.5-1 h, centrifuging, washing and drying to obtain CNT-ZIF 8;
(3) preparation of CNT-ZnCo-LDH: firstly, adding cobalt nitrate hexahydrate and absolute ethyl alcohol into a round-bottom flask, and heating and stirring at 78-84 ℃; and (3) adding the CNT-ZIF8 obtained in the step (2) into absolute ethyl alcohol, performing ultrasonic treatment until the CNT-ZIF8 is dissolved, adding the dissolved CNT-ZIF8 into the round-bottom flask, reacting for 1-2 hours at 78-84 ℃, centrifuging, washing and drying to obtain the CNT-ZnCo-LDH.
0.2-0.4 g of zinc acetate in the step (1) is dissolved in 50-60 mL of anhydrous methanol; 0.1-0.3 g of CNT is dissolved in 30-40 mL of anhydrous methanol; 0.2-0.3 g of potassium hydroxide is dissolved in 40-50 mL of anhydrous methanol.
Dissolving 50-60 mg of CNT-ZnO obtained in the step (1) in 5-10 mL of anhydrous methanol in the step (2); 4.1-4.5 g of dimethyloxazole is dissolved in 50-60 mL of anhydrous methanol; the volume of the round-bottom flask in the step is 250-350 mL.
264-272 mg of cobalt nitrate hexahydrate and 67-73 mL of absolute ethyl alcohol are added into the round-bottom flask in the step (3); and (3) dissolving 811-22 mg of the CNT-ZIF obtained in the step (2) in 10-20 mL of absolute ethanol.
Washing precipitates obtained by centrifugation in the step (1) and the step (2) with anhydrous methanol for three times; and (4) washing the precipitate obtained by centrifugation in the step (3) with absolute ethyl alcohol for three times.
And (3) drying for 12-14 h at the temperature of 60-70 ℃.
The invention has the beneficial effects that: the invention adopts CNT-ZnCo-LDH composite material as the modification of the anode material of the lithium-sulfur battery
Lithium-sulfur battery, having the following advantages:
(1) the ZnCo double hydroxide ZnCo-LDH has a polar surface, a single layer of the ZnCo-LDH has electropositivity, the polar surface of the ZnCo-LDH can have strong interaction with polysulfide, and meanwhile, the electropositivity of the ZnCo-LDH can also adsorb polysulfide ions with electronegativity.
(2) The electrocatalysis of ZnCo-LDH also greatly enhances the polysulfide redox reaction kinetics, and can improve the transfer capacity and the rate capability of the lithium battery.
(3) In the design process of the invention, the conductive network constructed by the multi-wall carbon nano tubes is used as the support frame attached with the double hydroxide, so that the conductivity of the anode can be obviously improved. The current density that the multi-wall carbon nano-tube can bear is 109A ∙ cm-2This number is 1000 times that of metallic copper. So that the multi-walled carbon nanotube is used for the lithium-sulfur batteryIn the positive electrode material, the discharge specific capacity, the rate capability and the cycling stability of the lithium-sulfur battery can be obviously improved.
(4) The prepared CNT-ZnCo-LDH composite material is used as a positive electrode material of a lithium-sulfur battery to be applied to the lithium-sulfur battery, and the first charge-discharge specific capacity of the battery reaches 1465mAh ∙ g under 0.1C-1The lithium-sulfur battery has high discharge capacity and excellent cycling stability, and the electrochemical performance of the lithium-sulfur battery is obviously superior to that of a lithium-sulfur battery prepared by the prior art.
(5) The preparation method comprises the steps of firstly preparing zinc oxide particles CNT-ZnO attached to the multi-walled carbon nano-tube, then converting the zinc oxide nano-particles into ZIF8 by a hydrothermal method, thus obtaining a metal imidazole type molecular sieve framework CNT-ZIF8 attached to the multi-walled carbon nano-tube, and finally obtaining a zinc-cobalt double hydroxide CNT-ZnCo-LDH attached to the multi-walled carbon nano-tube by hydrothermal replacement. The conductivity can be improved by introducing the CNT, but the CNT is provided with few active sites, so that the in-situ growth of the ZnCo-LDH is not facilitated, and the preparation method disclosed by the invention has the advantages that the LDH is uniformly dispersed on the CNT by taking the CNT-ZIF8 as intermediate conversion, so that the agglomeration of the ZnCo-LDH is avoided. The preparation method is a preparation method of the lithium-sulfur battery positive electrode material with the characteristics of high yield and industrial feasibility.
In conclusion, the invention obtains uniformly distributed ZnCo-LDH on the CNT for the first time, and the introduction of the CNT improves the conductivity of the anode material; the obtained composite material has physical adsorption and chemical adsorption on polysulfide, simultaneously has catalytic action, promotes the transformation of polysulfide and effectively inhibits shuttle effect.
Drawings
FIG. 1 is a scanning electron micrograph of the CNT-ZnCo-LDH composite prepared in example 1.
FIG. 2 is the electrochemical charge-discharge curve of the CNT-ZnCo-LDH composite materials respectively prepared in examples 1-3 as the positive electrode material of a lithium-sulfur battery for the lithium-sulfur battery.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The raw materials involved are all obtained commercially: industrial grade multi-walled carbon nanotubes, IM6, high tech. of new materials, inc; zinc acetate, analytically pure, mcelin; potassium hydroxide, analytically pure, mcelin; 98% of dimethylimidazole and alatin; cobalt nitrate hexahydrate, analytically pure, alatin.
Example 1
The novel efficient positive electrode material of the lithium-sulfur battery is a CNT-ZnCo-LDH composite material. The CNT-ZnCo-LDH composite material is composed of a lamellar zinc-cobalt double hydroxide ZnCo-LDH which is uniformly attached to a multi-wall carbon nano-tube CNT.
The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) preparation of CNT-ZnO: firstly, dissolving 0.3g of zinc acetate in 55mL of anhydrous methanol, stirring at 50 ℃ until the zinc acetate is completely dissolved to obtain a zinc acetate solution, adding the zinc acetate solution into a round-bottom flask for oil bath, and keeping the temperature at 70 ℃; then adding 0.2g of CNT into 35mL of anhydrous methanol, carrying out ultrasonic treatment until the CNT is completely dissolved, adding the dissolved CNT solution into the round-bottom flask, and stirring for 25min at 70 ℃; finally, adding 0.25g of potassium hydroxide into 45mL of anhydrous methanol, stirring and heating on a heating plate at 70 ℃, dropwise adding the heated potassium hydroxide solution into the round-bottom flask, stirring for 2 hours at 70 ℃, centrifugally collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying for 12 hours at 65 ℃ to obtain CNT-ZnO;
(2) preparation of CNT-ZIF 8: firstly, dissolving 55mg of CNT-ZnO obtained in the step (1) in 7.5mL of anhydrous methanol, and marking as solution A; dissolving 4.3g of dimethyloxazole in 55mL of anhydrous methanol to obtain solution B; adding the solution B into a 300mL round-bottom flask with the temperature of 55 ℃ for preheating, adding the solution A into the round-bottom flask, reacting at 55 ℃ for 0.7h, centrifuging, collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying at 65 ℃ for 12h to obtain CNT-ZIF 8;
(3) preparation of CNT-ZnCo-LDH: firstly, 268mg of cobalt nitrate hexahydrate and 70mL of absolute ethyl alcohol are added into a round-bottom flask, and the mixture is heated and stirred at 82 ℃; and (3) adding 16mg of CNT-ZIF8 obtained in the step (2) into 15mL of absolute ethanol, performing ultrasonic treatment until the CNT-ZIF8 is dissolved, adding the dissolved CNT-ZIF8 into the round-bottom flask, reacting at 81 ℃ for 1.5h, centrifuging, collecting precipitates, washing the precipitates with absolute ethanol for three times, and drying at 65 ℃ for 12h to obtain the CNT-ZnCo-LDH.
As can be seen in fig. 1, the resulting zinc-cobalt double hydroxide CNT-ZnCo-LDH attached to the multi-walled carbon nanotubes is a lamellar structure. The lamellar structure of the ZnCo-LDH can generate physical constraint on polysulfide, and the hydrophilic groups and hydroxyl groups rich on the surfaces of the ZnCo-LDH particles can generate chemical constraint on polysulfide, so that the polysulfide is effectively inhibited from being dissolved in an organic electrolyte solution through the physical constraint and the chemical constraint, the utilization rate of active substances is improved, and the circulation stability is improved. In addition, the electrocatalysis of ZnCo-LDH greatly enhances the polysulfide redox reaction kinetics, and can improve the transfer capacity and the rate capability of the lithium battery.
As can be seen from the black solid line in FIG. 2, the material has a first discharge capacity of up to 1465mAh ∙ g as a positive electrode material for a lithium-sulfur battery at a current density of 0.1C-1。
Example 2
The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) preparation of CNT-ZnO: firstly, dissolving 0.2g of zinc acetate in 50mL of anhydrous methanol, stirring at 40 ℃ until the zinc acetate is completely dissolved to obtain a zinc acetate solution, adding the zinc acetate solution into a round-bottom flask for oil bath, and keeping the temperature at 65 ℃; then adding 0.1g of CNT into 30mL of anhydrous methanol, carrying out ultrasonic treatment until the CNT is completely dissolved, adding the dissolved CNT solution into the round-bottom flask, and stirring for 20min at 65 ℃; finally, adding 0.2g of potassium hydroxide into 40mL of anhydrous methanol, stirring and heating on a 65 ℃ heating plate, dropwise adding the heated potassium hydroxide solution into the round-bottom flask, stirring for 1h at 65 ℃, centrifuging, collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying for 13h at 60 ℃ to obtain CNT-ZnO;
(2) preparation of CNT-ZIF 8: firstly, 50mg of CNT-ZnO obtained in the step (1) is dissolved in 5mL of anhydrous methanol and is marked as solution A; dissolving 4.1g of dimethyloxazole in 50mL of anhydrous methanol, and marking as solution B; adding the solution B into a 250mL round-bottom flask with the temperature of 50 ℃ for preheating, adding the solution A into the round-bottom flask, reacting at 50 ℃ for 0.5h, centrifuging, collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying at 60 ℃ for 13h to obtain CNT-ZIF 8;
(3) preparation of CNT-ZnCo-LDH: firstly, 264mg of cobalt nitrate hexahydrate and 67mL of absolute ethyl alcohol are added into a round-bottom flask, and the mixture is heated and stirred at 78 ℃; and (3) adding 11mg of CNT-ZIF8 obtained in the step (2) into 10mL of absolute ethyl alcohol, performing ultrasonic treatment until the CNT-ZIF8 is dissolved, adding the dissolved CNT-ZIF8 into the round-bottom flask, reacting at 78 ℃ for 1h, centrifuging, collecting precipitate, washing the precipitate with absolute ethyl alcohol for three times, and drying at 60 ℃ for 13h to obtain the CNT-ZnCo-LDH.
As can be seen from the black dotted line in FIG. 2, the material has the first discharge capacity of 1439mAh ∙ g for the lithium-sulfur battery as the positive electrode material under the current density of 0.1C-1. The capacity was slightly lower than in example 1.
Example 3
The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) preparation of CNT-ZnO: firstly, 0.4g of zinc acetate is dissolved in 60mL of anhydrous methanol, the mixture is stirred at the temperature of 60 ℃ until the zinc acetate is completely dissolved to obtain a zinc acetate solution, the zinc acetate solution is added into a round bottom flask for oil bath, and the temperature is kept at 75 ℃; then adding 0.3g of CNT into 40mL of anhydrous methanol, carrying out ultrasonic treatment until the CNT is completely dissolved, adding the dissolved CNT solution into the round-bottom flask, and stirring for 30min at 75 ℃; finally, adding 0.3g of potassium hydroxide into 50mL of anhydrous methanol, stirring and heating on a heating plate at 75 ℃, dropwise adding the heated potassium hydroxide solution into the round-bottom flask, stirring for 3 hours at 75 ℃, centrifuging, collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying for 14 hours at 70 ℃ to obtain CNT-ZnO;
(2) preparation of CNT-ZIF 8: firstly, 60mg of CNT-ZnO obtained in the step (1) is dissolved in 10mL of anhydrous methanol and is marked as solution A; dissolving 4.5g of dimethyloxazole in 60mL of anhydrous methanol, and marking as solution B; adding the solution B into a 350mL round-bottom flask with the temperature of 60 ℃ for preheating, adding the solution A into the round-bottom flask, reacting at 60 ℃ for 1h, centrifuging, collecting precipitate, washing the precipitate with anhydrous methanol for three times, and drying at 70 ℃ for 14h to obtain CNT-ZIF 8;
(3) preparation of CNT-ZnCo-LDH: 272mg of cobalt nitrate hexahydrate and 73mL of absolute ethanol are added into a round-bottom flask, and the mixture is heated and stirred at 84 ℃; and (3) adding 22mg of CNT-ZIF8 obtained in the step (2) into 20mL of absolute ethyl alcohol, performing ultrasonic treatment until the CNT-ZIF8 is dissolved, adding the dissolved CNT-ZIF8 into the round-bottom flask, reacting for 2 hours at 84 ℃, centrifuging, collecting precipitates, washing the precipitates with the absolute ethyl alcohol for three times, and drying for 14 hours at 70 ℃ to obtain the CNT-ZnCo-LDH.
As can be seen from the black chain line in FIG. 2, the material has the first discharge capacity of 1348mAh ∙ g for the lithium-sulfur battery as the positive electrode material at the current density of 0.1C-1. The capacity is significantly lower than in example 1.

Claims (9)

1. A novel high-efficiency positive electrode material of a lithium-sulfur battery is characterized in that the positive electrode material is a CNT-ZnCo-LDH composite material.
2. The novel high-efficiency positive electrode material for lithium-sulfur batteries as claimed in claim 1, wherein said CNT-ZnCo-LDH composite material is composed of a layer of sheet-like zinc-cobalt double hydroxide ZnCo-LDH uniformly attached to multi-walled carbon nanotubes CNTs.
3. The preparation method of the novel high-efficiency positive electrode material for the lithium-sulfur battery as claimed in claim 1, is characterized by firstly preparing zinc oxide nanoparticles CNT-ZnO attached to multi-walled carbon nanotubes; then, zinc oxide nano particles are converted into a metal imidazole type molecular sieve framework ZIF8 by a hydrothermal method, so that a metal imidazole type molecular sieve framework CNT-ZIF8 attached to the multi-walled carbon nano tube is obtained; finally, the zinc-cobalt double hydroxide CNT-ZnCo-LDH attached to the multi-walled carbon nano-tube is obtained by hydrothermal replacement.
4. The preparation method of the novel high-efficiency lithium-sulfur battery positive electrode material as claimed in claim 3, is characterized by comprising the following steps:
(1) preparation of CNT-ZnO: firstly, dissolving zinc acetate in absolute methanol, stirring at 40-60 ℃ until the zinc acetate is completely dissolved to obtain a zinc acetate solution, adding the zinc acetate solution into a round-bottom flask for oil bath, and keeping the temperature at 65-75 ℃; then adding CNT into absolute methanol, performing ultrasonic treatment until the CNT is completely dissolved, adding the dissolved CNT solution into the round-bottom flask, and stirring for 20-30 min at 65-75 ℃; finally, adding potassium hydroxide into absolute methanol, stirring and heating at 65-75 ℃, dropwise adding the heated potassium hydroxide solution into the round-bottom flask, stirring at 65-75 ℃ for 1-3 hours, centrifuging, washing and drying to obtain CNT-ZnO;
(2) preparation of CNT-ZIF 8: firstly, dissolving the CNT-ZnO obtained in the step (1) in absolute methanol, and marking as solution A; dissolving dimethyloxazole in absolute methanol to obtain solution B; adding the solution B into a round-bottom flask with the temperature of 50-60 ℃ for preheating, adding the solution A into the round-bottom flask, reacting at the temperature of 50-60 ℃ for 0.5-1 h, centrifuging, washing and drying to obtain CNT-ZIF 8;
(3) preparation of CNT-ZnCo-LDH: firstly, adding cobalt nitrate hexahydrate and absolute ethyl alcohol into a round-bottom flask, and heating and stirring at 78-84 ℃; and (3) adding the CNT-ZIF8 obtained in the step (2) into absolute ethyl alcohol, performing ultrasonic treatment until the CNT-ZIF8 is dissolved, adding the dissolved CNT-ZIF8 into the round-bottom flask, reacting for 1-2 hours at 78-84 ℃, centrifuging, washing and drying to obtain the CNT-ZnCo-LDH.
5. The preparation method of the novel high-efficiency lithium-sulfur battery cathode material according to claim 4, wherein in the step (1), 0.2-0.4 g of zinc acetate is dissolved in 50-60 mL of anhydrous methanol; 0.1-0.3 g of CNT is dissolved in 30-40 mL of anhydrous methanol; 0.2-0.3 g of potassium hydroxide is dissolved in 40-50 mL of anhydrous methanol.
6. The preparation method of the novel high-efficiency positive electrode material for the lithium-sulfur battery according to claim 5, wherein 50-60 mg of the CNT-ZnO obtained in the step (1) is dissolved in 5-10 mL of anhydrous methanol in the step (2); 4.1-4.5 g of dimethyloxazole is dissolved in 50-60 mL of anhydrous methanol; the volume of the round-bottom flask in the step is 250-350 mL.
7. The preparation method of the novel high-efficiency lithium-sulfur battery cathode material as claimed in claim 6, wherein 264-272 mg of cobalt nitrate hexahydrate and 67-73 mL of absolute ethyl alcohol are added into the round-bottom flask in the step (3); and (3) dissolving 811-22 mg of the CNT-ZIF obtained in the step (2) in 10-20 mL of absolute ethanol.
8. The method for preparing the novel high-efficiency lithium-sulfur battery cathode material as claimed in claim 4, wherein the precipitates obtained by the centrifugation in the steps (1) and (2) are washed with anhydrous methanol three times; and (4) washing the precipitate obtained by centrifugation in the step (3) with absolute ethyl alcohol for three times.
9. The preparation method of the novel high-efficiency lithium-sulfur battery cathode material according to claim 4, wherein the drying in the steps (1), (2) and (3) is carried out at the temperature of 60-70 ℃ for 12-14 h.
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Cited By (1)

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CN111668503A (en) * 2020-07-20 2020-09-15 山东大学 Bimetal sulfide lithium-air battery positive electrode material and preparation method and application thereof

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