CN109560271B - Lithium-sulfur battery positive electrode material, and preparation method and application thereof - Google Patents
Lithium-sulfur battery positive electrode material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode preparation, and particularly relates to a lithium-sulfur battery positive electrode material, and a preparation method and application thereof. In consideration of the high specific surface area and the high electronic conductivity of the one-dimensional electrode material and the advantages of the one-dimensional electrode material in the aspects of constructing a conductive network and buffering the volume expansion of the electrode, the Zn-Al double hydroxide anode material with the layered porous structure is prepared by a simple coprecipitation method, and the preparation method is a preparation method of the Zn-Al double hydroxide anode material with the characteristics of high yield, industrial feasibility and the like. The coprecipitation method adopted in the Zn-Al double-hydroxide anode material is easy and effective, and the large-scale and low-cost industrialization of the preparation of the Zn-Al double-hydroxide anode material is easy to realize.
Description
Technical Field
The invention belongs to the technical field of electrode preparation, and particularly relates to a lithium-sulfur battery positive electrode material, and a preparation method and application thereof.
Background
In recent years, due to rapid development of advanced portable electronic products, electric vehicles, and energy storage power stations, development of a secondary battery system having high energy density, long life, and low cost is urgently required. The lithium-sulfur battery not only has theoretical specific energy as high as 2600Wh/kg, but also has the advantages of low price, rich resources, environmental friendliness and the like of elemental sulfur as a positive electrode material, so that the lithium-sulfur battery is the key point for developing the next-generation secondary battery.
However, the development of applications for lithium-sulfur batteries has encountered a number of problems: first, elemental sulfur (5X 10)-30S·cm-1) And its discharge product Li2S is an electronic and ionic insulator, and the electrochemical activity of the sulfur electrode is extremely low; secondly, lithium polysulfide which is an intermediate product of sulfur electrode discharge is easily dissolved in organic electrolyte, so that active substance loss and shuttle effect are caused, and the rapid decline of battery capacity and the reduction of charging and discharging storage efficiency are caused; in addition, the sulfur electrode has a large volume during charging and dischargingThe change also leads to the destruction of the mechanical properties of the electrode, accelerating the degradation of the battery performance. The above problems severely restrict the development of lithium sulfur secondary batteries.
Disclosure of Invention
The invention provides a preparation method of a positive electrode material of a lithium-sulfur battery, which aims at the problems of the lithium-sulfur battery, and the preparation method of the positive electrode material of the lithium-sulfur battery is characterized in that the Zn-Al double hydroxide positive electrode material with a layered porous structure is prepared by a simple coprecipitation method in consideration of the advantages of a one-dimensional electrode material in high specific surface area and high electronic conductivity and in the aspects of constructing a conductive network and buffering the volume expansion of an electrode. The coprecipitation method adopted in the Zn-Al double-hydroxide anode material is easy and effective, and the large-scale and low-cost industrialization of the preparation of the Zn-Al double-hydroxide anode material is easy to realize.
The technical scheme of the invention is as follows:
a positive electrode material for a lithium-sulfur battery, characterized in that: the positive electrode material consists of Zn-Al double hydroxide; the Zn-Al double hydroxide anode material is formed by mutually connecting and stacking nano sheets and has a layered porous structure; the Zn-Al double hydroxide anode material directly grows into a film on a carbon-containing aluminum foil by a coprecipitation method.
The invention also aims to provide a preparation method of the positive electrode material of the lithium-sulfur battery, which is used for preparing the Zn-Al double hydroxide positive electrode material with the layered porous structure by using a simple coprecipitation method and comprises the following specific steps:
the first step is as follows: preparing a precursor solution:
dissolving sodium carbonate in deionized water, stirring for 30min until the sodium carbonate is completely dissolved to obtain a sodium carbonate aqueous solution, mixing the sodium carbonate aqueous solution with ammonia water with the concentration of 1-20moL/L, and stirring for 30-120min until the sodium carbonate aqueous solution and the ammonia water are fully mixed to form a uniform mixed solution A;
the second step is that: preparing layered porous structure Zn-Al double hydroxide:
and (2) putting the zinc foil with the size of 30mm multiplied by 0.25mm and the carbon-containing aluminum foil with the size of 30mm multiplied by 0.15mm into the uniform mixed solution A, standing for 2-6 days at room temperature, taking out the carbon-containing aluminum foil from the mixed solution after full reaction, washing the carbon-containing aluminum foil for 2-10 times by deionized water, and finally drying in a drying oven at 50-80 ℃ to obtain the layered porous structure Zn-Al double hydroxide.
The zinc foil of the present invention functions to provide a zinc source and the product is formed on a carbon-containing aluminum foil.
The invention is also characterized in that:
preferably, in the first step, the mass concentration of the sodium carbonate solution is in the range of 5 to 20g/L, preferably 15 to 20g/L, and more preferably 17.8 g/L.
Preferably, in the first step, the volume ratio of the sodium carbonate solution to the ammonia water is 1: 1.
in the lithium-sulfur battery positive electrode material, the preparation method and the like, the related raw materials are all obtained by commercial purchase.
The invention relates to application of a lithium-sulfur battery cathode material in a lithium-sulfur battery, and application of the cathode material obtained by the preparation method of the lithium-sulfur battery cathode material in the lithium-sulfur battery.
The invention has the following beneficial effects:
(1) compared with the prior art, the method has the following prominent substantive characteristics: in the design process of the invention, the structural problem of the sulfur-based composite material in the lithium-sulfur battery anode material is fully considered, and the method for preparing the Zn-Al double hydroxide with the layered porous structure by using the simple coprecipitation method is innovatively provided. The Zn-Al-containing double hydroxide directly grows as a film on the carbon-containing aluminum foil, so that the use of a binder is avoided, active substances are directly contacted with a substrate to reduce the internal resistance of an electrode, the content of the active substances is improved, and a complete conductive network is constructed by a one-dimensional layered structure of the Zn-Al double hydroxide, so that the specific surface area is improved, the transmission rate of electrons and ions is improved, the conductivity is enhanced, and the capacity of a battery is improved.
(2) In the design process of the invention, the porous structure of the Zn-Al double hydroxide can effectively coat sulfur, thereby avoiding the shuttle effect generated in the charge and discharge process, relieving the volume expansion in the charge and discharge process and further improving the overall performance of the lithium-sulfur battery. Therefore, the overall performance of the lithium-sulfur battery is greatly improved.
(3) The layered porous structure Zn-Al double hydroxide anode material prepared by the method is used as a lithium-sulfur battery consisting of the anode working electrode, the first charge-discharge specific capacity of the battery reaches 1250mAh/g at 0.1 ℃, the discharge capacity is high, the cycling stability is excellent, and the electrochemical performance of the layered porous structure Zn-Al double hydroxide anode material is obviously superior to that of the lithium-sulfur battery prepared by the prior art.
(4) 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
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a scanning electron micrograph of a Zn-Al double hydroxide positive electrode material having a layered porous structure obtained in example 1.
Fig. 2 is an electrochemical charge-discharge curve of a lithium-sulfur battery fabricated from the multi-layered porous structure Zn — Al double hydroxide positive electrode material obtained in example 1.
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 positive electrode material of a lithium-sulfur battery,
the first step is as follows: preparing a precursor solution:
dissolving 1.78g of sodium carbonate in 100mL of deionized water, stirring for 30min until the sodium carbonate is completely dissolved to obtain a sodium carbonate aqueous solution, mixing the sodium carbonate aqueous solution with 100mL of ammonia water with the concentration of 5moL/L, and stirring for 30min until the sodium carbonate aqueous solution and the ammonia water are fully mixed to form a uniform mixed solution A.
The second step is that: preparing layered porous structure Zn-Al double hydroxide:
and (2) putting a zinc foil with the size of 30mm multiplied by 0.25mm and a carbon-containing aluminum foil with the size of 30mm multiplied by 0.15mm into the uniform mixed solution A, standing for 2 days at room temperature, taking out the carbon-containing aluminum foil from the mixed solution after full reaction, washing the carbon-containing aluminum foil for 4 times by using deionized water, and finally drying in a 60 ℃ oven to obtain the layered porous structure Zn-Al double hydroxide.
FIG. 1 is a scanning electron microscope photograph of the layered porous Zn-Al double hydroxide cathode material prepared in this example. In a scanning picture, the porous structure of the Zn-Al double hydroxide with rich pores designed by the invention is more visually displayed.
Fig. 2 is an electrochemical charge-discharge curve of a lithium-sulfur battery fabricated from the multi-layered porous Zn — Al double hydroxide positive electrode material fabricated in this example. It can be seen from this fig. 2 that at a current density of 0.1C the first discharge capacity of the material is up to 1250 mAh/g.
The method for manufacturing the lithium-sulfur battery is realized by taking a Zn-Al double hydroxide positive electrode material with a multi-layer porous structure as a positive electrode of the lithium-sulfur battery and adopting an industry conventional technology.
Example 2: preparation method of lithium-sulfur battery positive electrode material
The first step is as follows: preparing a precursor solution:
dissolving 1.78g of sodium carbonate in 100mL of deionized water, stirring for 30min until the sodium carbonate is completely dissolved to obtain a sodium carbonate aqueous solution, mixing the sodium carbonate aqueous solution with 100mL of ammonia water with the concentration of 10moL/L, and stirring for 60min until the sodium carbonate aqueous solution and the ammonia water are fully mixed to form a uniform mixed solution A.
The second step is that: preparing layered porous structure Zn-Al double hydroxide:
and (2) putting a zinc foil with the size of 30mm multiplied by 0.25mm and a carbon-containing aluminum foil with the size of 30mm multiplied by 0.15mm into the uniform mixed solution A, standing for 4 days at room temperature, taking out the carbon-containing aluminum foil from the mixed solution after full reaction, washing the carbon-containing aluminum foil for 6 times by using deionized water, and finally drying in an oven at 80 ℃ to obtain the layered porous structure Zn-Al double hydroxide.
Claims (6)
1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps: the positive electrode material consists of Zn-Al double hydroxide; the Zn-Al double hydroxide anode material is formed by mutually connecting and stacking nano sheets and has a layered porous structure; the Zn-Al double hydroxide anode material directly grows into a film on a carbon-containing aluminum foil by a coprecipitation method;
the preparation method utilizes a coprecipitation method to prepare the Zn-Al double hydroxide anode material with the layered porous structure, and comprises the following specific steps:
the first step is as follows: preparing a precursor solution:
dissolving sodium carbonate in deionized water, stirring for 30min until the sodium carbonate is completely dissolved to obtain a sodium carbonate aqueous solution, mixing the sodium carbonate aqueous solution with ammonia water with the concentration of 1-20moL/L, and stirring for 30-120min until the sodium carbonate aqueous solution and the ammonia water are fully mixed to form a uniform mixed solution A;
the second step is that: preparing layered porous structure Zn-Al double hydroxide:
and (2) putting the zinc foil with the size of 30mm multiplied by 0.25mm and the carbon-containing aluminum foil with the size of 30mm multiplied by 0.15mm into the uniform mixed solution A, standing for 2-6 days at room temperature, taking out the carbon-containing aluminum foil from the mixed solution after full reaction, washing the carbon-containing aluminum foil for 2-10 times by deionized water, and finally drying in a drying oven at 50-80 ℃ to obtain the layered porous structure Zn-Al double hydroxide.
2. The method of claim 1, wherein the sodium carbonate solution has a mass concentration of 5-20g/L in the first step.
3. The method of claim 2, wherein the sodium carbonate solution has a mass concentration of 15-20 g/L.
4. The method according to claim 3, wherein the sodium carbonate solution has a mass concentration of 17.8 g/L.
5. The method of claim 1, wherein the volume ratio of the sodium carbonate solution to the ammonia water in the first step is 1: 1.
6. 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 5 in a lithium-sulfur battery.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198925A (en) * | 2013-04-28 | 2013-07-10 | 广西贺州市桂东电子科技有限责任公司 | Method for controlling distribution of mesohigh electronic aluminum foil etching holes |
| CN105655152A (en) * | 2015-12-31 | 2016-06-08 | 上海应用技术学院 | Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof |
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| JP6001198B2 (en) * | 2014-10-01 | 2016-10-05 | 日本碍子株式会社 | Batteries using layered double hydroxides |
| EP3284722B1 (en) * | 2015-04-14 | 2021-04-28 | NGK Insulators, Ltd. | Layered double hydroxide, layered double hydroxide dense film, and composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103198925A (en) * | 2013-04-28 | 2013-07-10 | 广西贺州市桂东电子科技有限责任公司 | Method for controlling distribution of mesohigh electronic aluminum foil etching holes |
| CN105655152A (en) * | 2015-12-31 | 2016-06-08 | 上海应用技术学院 | Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Ionic conductivity of Zn-Al layered double hydroxide films grown on aluminum substrate;R.Pizzoferrato等;《Solid State Ionics》;20171122;第314卷;第30-35页 * |
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