CN109119613B - Method for synthesizing lithium-sulfur battery positive electrode material by taking waste fly ash as raw material - Google Patents

Method for synthesizing lithium-sulfur battery positive electrode material by taking waste fly ash as raw material Download PDF

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CN109119613B
CN109119613B CN201810980855.3A CN201810980855A CN109119613B CN 109119613 B CN109119613 B CN 109119613B CN 201810980855 A CN201810980855 A CN 201810980855A CN 109119613 B CN109119613 B CN 109119613B
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fly ash
lithium
sulfur battery
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CN109119613A (en
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闵宇霖
廖柯璇
范金辰
徐群杰
时鹏辉
赵宏阳
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Shanghai University of Electric Power
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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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention relates to a method for synthesizing a lithium-sulfur battery positive electrode material by taking waste fly ash as a raw material, which comprises the following steps: (1) pickling the waste fly ash, and drying to obtain the fly ash without impurities; (2) and (2) mixing and grinding the fly ash obtained in the step (1) after impurity removal and elemental sulfur, then putting the mixture into a closed container for drying and heat preservation, and grinding to obtain the lithium-sulfur battery anode material synthesized by taking the waste fly ash as a raw material. Compared with the prior art, the raw materials of the invention are from wastes, the material cost is greatly reduced, and the obtained anode material has higher charge-discharge specific capacity and excellent cycling stability. The preparation method is simple, low in cost, excellent in performance and suitable for large-scale commercial battery production.

Description

Method for synthesizing lithium-sulfur battery positive electrode material by taking waste fly ash as raw material
Technical Field
The invention relates to a lithium-sulfur battery positive electrode material, in particular to a method for synthesizing the lithium-sulfur battery positive electrode material by taking waste fly ash as a raw material.
Background
The energy storage principle of the lithium-sulfur battery is the breaking and regeneration of a sulfur-sulfur bond, and the active substance is sulfur. Elemental sulfur is mainly S at normal temperature8The method has the characteristics of abundant reserves in the earth, low price, environmental friendliness and the like. The lithium-sulfur battery using sulfur as the anode material has higher material theoretical specific capacity and battery theoretical specific energy which respectively reach 1672 mAh.g-1And 2600 Wh.kg-1. Is considered to be one of the most promising lithium secondary battery systems currently in research and application. Although the lithium-sulfur battery has the advantages of high capacity, high specific energy and the like, the lithium-sulfur battery has the problems of low utilization rate of active substances, low cycle life, poor safety and the like, and the development of the lithium-sulfur battery is severely restricted. The main reasons for the above problems are as follows:
1) elemental sulfur is an electronic and ionic insulator, the room-temperature conductivity is low, and the elemental sulfur is difficult to activate as a positive electrode material due to the absence of ionic sulfur, so that the problem of low-rate performance of the lithium-sulfur battery is caused;
2) high polymeric lithium polysulphides Li produced during electrode reactions2Sn(8>n>4) Easily dissolved in electrolyte, forms concentration difference between the anode and the cathode, and migrates to the cathode under the action of concentration gradient, and the high polymeric lithium polysulfide is reduced into low polymeric lithium polysulfide by metallic lithium. As the above reaction proceeds, lithium polysulfide in an oligomeric state accumulates at the negative electrode, eventually forming a concentration difference between the two electrodes, and migrates to the positive electrode to be oxidized into lithium polysulfide in a polymeric state. This phenomenon is called the shuttle effect, and reduces the utilization rate of the sulfur active material. At the same time insoluble Li2S and Li2S2Deposited on the surface of the lithium negative electrode, further deteriorating the performance of the lithium-sulfur battery, resulting in the problem of low cycle performance of the lithium-sulfur battery;
3) sulphur and end product Li2The density of S is different, and the volume expansion of sulfur after lithiation is about 79 percent, which is easy to cause Li2Pulverization of S causes safety problems of the lithium sulfur battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing a lithium-sulfur battery cathode material by using waste fly ash as a raw material.
The purpose of the invention can be realized by the following technical scheme:
the invention obtains the lithium-sulfur battery anode material by taking waste fly ash generated in the production process of a thermal power plant as a raw material, loading elemental sulfur into hollow silica spheres by a melting method by utilizing the unique structure of the hollow silica spheres.
The invention aims to provide a lithium-sulfur battery cathode material which is prepared by carrying elemental sulfur in a hollow silica sphere in a melting way.
The invention also aims to provide a method for synthesizing the lithium-sulfur battery positive electrode material by using waste fly ash as a raw material, which comprises the following steps:
(1) pickling the waste fly ash, and drying to obtain the fly ash without impurities;
(2) and (2) mixing and grinding the fly ash obtained in the step (1) after impurity removal with elemental sulfur, adding carbon disulfide for continuous grinding, and then putting the mixture into a closed container for drying and heat preservation to obtain the lithium-sulfur battery anode material synthesized by using the waste fly ash as a raw material.
Preferably, in the step (1), the fly ash is pretreated before the acid washing, and the pretreatment includes grinding, water washing or alcohol washing.
Preferably, in the step (1): the waste fly ash is waste fly ash generated after coal powder is combusted in a thermal power plant.
Preferably, in the step (1): the acid cleaning adopts dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.01-0.1 mol/L.
Preferably, in the step (1): the ratio of the waste fly ash to the acid solution is 1:20-1: 200.
Preferably, in the step (1), the pickling process comprises the following steps: adding acid solution, stirring or ultrasonic treating for 1-24 hr, and washing with deionized water to neutrality.
Preferably, in the step (2): the mass ratio of the fly ash after impurity removal to the elemental sulfur is 1:1-1:10, and the grinding time is 1-6 h.
Preferably, in the step (2): the mass ratio of the mixture of the fly ash and the elemental sulfur to the carbon disulfide is 1:5-1:50, and the mixture is continuously ground for 1-5 hours until the carbon disulfide is completely evaporated.
Preferably, in the step (2): the closed container is a metal closed container or a glass closed container, and can be a clean reaction kettle or a measuring flask without impurities, the sulfurization temperature is 150-.
Mixing and grinding the prepared positive electrode material, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 for 1-5h until the materials are completely and uniformly mixed, adding 10-50mL of N-methyl pyrrolidone to obtain uniform black slurry, coating the uniform black slurry on an aluminum foil, drying at 60 ℃ to obtain a pole piece of an assembled battery, and finally assembling the lithium-sulfur battery.
Further, in the step (1), the fly ash is pretreated before acid washing, and the pretreatment mode comprises grinding, water washing or alcohol washing. Wherein grinding is a simple treatment of the sample particle size of the coal ash to prevent too large particles or too many agglomerated particles.
Further, in the step (1), dilute hydrochloric acid or dilute sulfuric acid is adopted for acid washing, and the concentration is 0.01-1 mol/L. The purpose of the acid wash is to remove trace metal impurities from the sample.
Further, in the step (2): the mass ratio of the fly ash after impurity removal to the elemental sulfur is 1:1-1:10, and the grinding time is 1-6 h. The proportion of the fly ash and the elemental sulfur is within the reasonable range, and the excessive sulfur can cause a large amount of sulfur on the appearance of a sample and is not beneficial to the cycle performance of the battery. Too little sulfur affects the capacity reduction of the battery.
Furthermore, the closed container is a metal closed container or a glass closed container, and can be a clean reaction kettle or a measuring bottle without impurities, the sulfurization temperature is 150-. The temperature of the sulfurization is lower than 150 ℃, the elemental sulfur can not permeate into the fly ash in a molten state, and the temperature of the elemental sulfur is higher than 160 ℃, so that the sulfur has overlarge viscosity and is not beneficial to permeating into the fly ash.
The invention takes waste fly ash as a raw material, and infiltrates single sulfur into hollow silica spheres by a melting method to obtain the lithium-sulfur battery anode material. The material well solves the shuttle effect of the lithium-sulfur battery, thereby obtaining the lithium-sulfur battery with high specific capacity and long cycle performance.
According to the invention, the waste coal ash generated after high-temperature burning of coal powder in the production process of a thermal power plant is used as a raw material, the structural characteristics of the hollow silica spheres are utilized, elemental sulfur is infiltrated into the hollow silica spheres to obtain the lithium-sulfur battery cathode material, the method is simple and effective, and the obtained battery material has excellent energy storage performance. Particularly, the silicon dioxide with the hollow structure can well store and fix sulfur and well protect the lithium-sulfur battery from being chargedPolysulfide generated during the discharge process is lost to the negative electrode. Therefore, the obtained cathode material has excellent energy storage performance (under the charging and discharging current density of 1C, after 600 cycles, the specific capacity can be kept at 610 mAh.g-1)。
Compared with the prior art, the invention has the following beneficial effects:
1) the hollow silicon dioxide ball cavity with the hollow structure provides a good sulfur storage space, and the problem of poor conductivity of elemental sulfur is solved;
2) many micropores, mesopores and macropores with the diameter of 1-500 nanometers are distributed in the hollow silica spheres, the existence of the pore structures is favorable for the infiltration of elemental sulfur, and simultaneously can prevent polysulfide shuttling in the charge and discharge process of the battery, thereby improving the cycle performance of the battery (under the charge and discharge current density of 1C, after 600 cycles of cycle, the specific capacity can also be kept at 610 mAh.g-1)；
3) The fly ash mainly contains silicon dioxide and part of carbon, and the silicon-carbon material has the advantages of good electron and ion transmission rate, and the reaction kinetics of the material can be greatly improved by the advantage, so that the rate capability of the battery is improved.
Drawings
FIG. 1 is a scanning electron micrograph of the hollow silica sphere structure of the fly ash of example 1;
FIG. 2 is a transmission electron micrograph of the hollow silica sphere structure of the fly ash of example 1;
FIG. 3 is an XRD spectrum of the hollow silica sphere structure of the fly ash of example 1;
FIG. 4 is a graph showing the cycle performance of the lithium-sulfur battery prepared in example 1 by synthesizing the lithium-sulfur battery cathode material from waste fly ash.
Detailed Description
The method provided by the embodiment of the invention adopts waste fly ash as a raw material, utilizes the structural characteristics of a hollow silica sphere of the waste fly ash, and takes the penetrated single sulfur as a lithium sulfur battery anode material to prepare the lithium sulfur battery, and the electrochemical performance of the lithium sulfur battery is tested by an electrochemical workstation and a blue test system; the used electrochemical workstation is Chenghua electrochemical workstation; the blue test system used LAND-CT 2001. The electrochemical performance test adopts a 2032 type button cell test, the button cell is assembled in a glove box filled with argon, and the content value of water and the content value of oxygen in the glove box are both kept below 0.1 ppm.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A method for synthesizing a lithium-sulfur battery anode material by taking waste fly ash as a raw material. The method specifically comprises the following steps:
(1) waste fly ash from a power plant is collected, 1kg of the waste fly ash is weighed, and the waste fly ash is washed by a large amount of deionized water and dried for later use.
(2) And taking the dried product out, grinding in a dry environment, pickling, drying, wherein the grinding time is 30min, and the pickling adopts hydrochloric acid with the concentration of 0.2%, and stirring for 12h until metal impurities in the carbon material are removed. And finally, centrifugally washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain the hollow silica spheres.
(3) Mixing and grinding the dried hollow silicon dioxide spheres and elemental sulfur powder for 1h according to the mass ratio of 1:3, then adding 30mL of carbon disulfide, continuing grinding until the carbon disulfide is completely evaporated to obtain a uniformly mixed product, collecting the uniformly mixed product in a closed weighing bottle, and finally putting the uniformly mixed product in an oven for heat preservation at 156 ℃ for 10 h. Finally, a sample of the sulfur/hollow silica sphere cathode material is obtained.
(4) After the sample is obtained, it is prepared into a slurry containing a conductive agent, a binder and an organic solvent. The conductive agent is acetylene black, the adhesive is polyvinylidene fluoride (PVDF), the organic solvent is N-methyl pyrrolidone (NMP), then the slurry is coated on a copper foil current collector, and then the battery is assembled in a glove box. And finally, carrying out electrochemical test on the assembled battery in a blue light test system and an electrochemical workstation, and carrying out physical characterization on other aspects of the sample.
Fig. 1 is a scanning electron micrograph of the obtained hollow silica spheres, and the external appearance of the hollow silica sphere material can be clearly seen.
Fig. 2 is a transmission electron micrograph of the obtained hollow silica sphere material, and the hollow structure of the hollow silica sphere can be clearly seen.
Fig. 3 is an XRD spectrum of the hollow silica spheres, which characterizes the hollow silica sphere material as a silicon carbon material having silica as a main component and carbon component.
FIG. 4 is a graph of the ultra-long cycle performance of the resulting sulfur/hollow silica spheres as the positive electrode material of a lithium sulfur battery assembled into a lithium sulfur battery, wherein the data show that the battery still maintains 610mAh g after 600 cycles of charge and discharge-1The specific capacity of (A).
Example 2
The method for synthesizing the lithium-sulfur battery positive electrode material by taking the waste fly ash as the raw material specifically comprises the following steps:
(1) the waste fly ash from a power plant is collected, 5kg is weighed, and the waste fly ash is washed by a large amount of deionized water and dried for later use.
(2) And taking the dried product out, grinding in a dry environment, pickling, drying, grinding for 30min with hydrochloric acid with the pickling concentration of 0.3%, and stirring for 20h until metal impurities in the carbon material are removed. And finally, centrifugally washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain the hollow silica spheres.
(3) Mixing and grinding the dried hollow silicon dioxide spheres and elemental sulfur powder for 1h according to the mass ratio of 1:6, then adding 1L of carbon disulfide, continuing grinding until the carbon disulfide is completely evaporated to obtain a uniformly mixed product, collecting the uniformly mixed product in a closed weighing bottle, and finally putting the uniformly mixed product into an oven for heat preservation at 155 ℃ for 20 h. Finally, a sample of the sulfur/hollow silica sphere cathode material is obtained.
(4) After the sample is obtained, it is prepared into a slurry containing a conductive agent, a binder and an organic solvent. The conductive agent is acetylene black, the adhesive is polyvinylidene fluoride (PVDF), the organic solvent is N-methyl pyrrolidone (NMP), then the slurry is coated on a copper foil current collector, and then the battery is assembled in a glove box. And finally, carrying out electrochemical test on the assembled battery in a blue light test system and an electrochemical workstation, and carrying out physical characterization on other aspects of the sample.
Example 3
A method for synthesizing a lithium-sulfur battery anode material by taking waste fly ash as a raw material. The method specifically comprises the following steps:
(1) the waste fly ash from a power plant is collected, 10kg of the waste fly ash is weighed, and the waste fly ash is washed by a large amount of deionized water and dried for standby.
(2) And taking the dried product out, grinding under a dry environment, pickling, drying, wherein the grinding time is 30 hours, the pickling concentration is 0.4% hydrochloric acid, and stirring for 24 hours until metal impurities in the carbon material are removed. And finally, centrifugally washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain the hollow silica spheres.
(3) Mixing and grinding the dried hollow silicon dioxide spheres and elemental sulfur powder for 1h according to the mass ratio of 1:4, then adding 2L of carbon disulfide, continuing grinding until the carbon disulfide is completely evaporated to obtain a uniformly mixed product, collecting the uniformly mixed product in a closed weighing bottle, and finally putting the uniformly mixed product into an oven for heat preservation at 155 ℃ for 20 h. Finally, a sample of the sulfur/hollow silica sphere cathode material is obtained.
(4) After the sample is obtained, it is prepared into a slurry containing a conductive agent, a binder and an organic solvent. The conductive agent is acetylene black, the adhesive is polyvinylidene fluoride (PVDF), the organic solvent is N-methyl pyrrolidone (NMP), then the slurry is coated on a copper foil current collector, and then the battery is assembled in a glove box. And finally, carrying out electrochemical test on the assembled battery in a blue light test system and an electrochemical workstation, and carrying out physical characterization on other aspects of the sample.
Example 4
A method for synthesizing a lithium-sulfur battery anode material by taking waste fly ash as a raw material. The method specifically comprises the following steps:
(1) collecting waste fly ash generated after household briquettes are burnt, weighing 5kg, washing with a large amount of ethanol, and drying for later use.
(2) And taking the dried product out, grinding in a dry environment, carrying out acid washing and drying, wherein the grinding time is 30min, the acid washing concentration is 0.6mol/L hydrochloric acid, and carrying out ultrasonic treatment and stirring for 1h until metal impurities in the carbon material are removed. And finally, centrifugally washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain the hollow silica spheres.
(3) Mixing and grinding the dried hollow silicon dioxide spheres and elemental sulfur powder according to the mass ratio of 1:1 for 3 hours, then adding 1L of carbon disulfide, continuing grinding until the carbon disulfide is completely evaporated to obtain a uniformly mixed product, collecting the uniformly mixed product in a closed weighing bottle, and finally putting the uniformly mixed product in an oven for heat preservation for 24 hours at 150 ℃. Finally, a sample of the sulfur/hollow silica sphere cathode material is obtained.
(4) After the sample is obtained, it is prepared into a slurry containing a conductive agent, a binder and an organic solvent. The conductive agent is acetylene black, the adhesive is polyvinylidene fluoride (PVDF), the organic solvent is N-methyl pyrrolidone (NMP), then the slurry is coated on a copper foil current collector, and then the battery is assembled in a glove box. And finally, carrying out electrochemical test on the assembled battery in a blue light test system and an electrochemical workstation, and carrying out physical characterization on other aspects of the sample.
Example 5
A method for synthesizing a lithium-sulfur battery anode material by taking waste fly ash as a raw material. The method specifically comprises the following steps:
(1) the waste fly ash after the household briquette is burnt is collected, 2kg of the waste fly ash is weighed, and the waste fly ash is washed by a large amount of ethanol and dried for later use.
(2) And taking the dried product out, grinding in a dry environment, acid washing, drying, grinding for 30min, washing with dilute sulfuric acid with the acid concentration of 0.7mol/L, and performing ultrasonic treatment for 10h until metal impurities in the carbon material are removed. And finally, centrifugally washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain the hollow silica spheres.
(3) Mixing and grinding the dried hollow silicon dioxide spheres and elemental sulfur powder according to the mass ratio of 1:10 for 6h, then adding 1L of carbon disulfide, continuing grinding until the carbon disulfide is completely evaporated to obtain a uniformly mixed product, collecting the uniformly mixed product in a closed weighing bottle, and finally putting the uniformly mixed product in an oven for heat preservation at 160 ℃ for 0.5 h. Finally, a sample of the sulfur/hollow silica sphere cathode material is obtained.
(4) After the sample is obtained, it is prepared into a slurry containing a conductive agent, a binder and an organic solvent. The conductive agent is acetylene black, the adhesive is polyvinylidene fluoride (PVDF), the organic solvent is N-methyl pyrrolidone (NMP), then the slurry is coated on a copper foil current collector, and then the battery is assembled in a glove box. And finally, carrying out electrochemical test on the assembled battery in a blue light test system and an electrochemical workstation, and carrying out physical characterization on other aspects of the sample.
In the above examples, the concentration of hydrochloric acid or sulfuric acid used for acid washing may be replaced with 0.01M or 1M.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. The method for synthesizing the lithium-sulfur battery anode material by taking the waste fly ash as a raw material is characterized in that the lithium-sulfur battery anode material is prepared by melting and loading elemental sulfur in a hollow silica sphere;
the preparation method comprises the following steps:
(1) pickling the waste fly ash, and drying to obtain the fly ash without impurities;
(2) and (2) mixing and grinding the fly ash obtained in the step (1) after impurity removal with elemental sulfur, adding carbon disulfide, continuously grinding until the mixture is completely evaporated, and then putting the mixture into a closed container for drying and heat preservation to obtain the lithium-sulfur battery anode material synthesized by taking waste fly ash as a raw material.
2. The method for synthesizing the lithium-sulfur battery cathode material by using the waste fly ash as the raw material according to claim 1, wherein in the step (1), the fly ash is pretreated before acid washing, and the pretreatment comprises grinding, water washing or alcohol washing.
3. The method for synthesizing the lithium-sulfur battery cathode material by using the waste fly ash as the raw material according to claim 2, wherein in the step (1): the waste fly ash is waste fly ash generated after coal powder is combusted in a thermal power plant, or fly ash left after household coal balls or coal powder are combusted at high temperature.
4. The method for synthesizing the lithium-sulfur battery cathode material by using the waste fly ash as the raw material according to claim 1, wherein in the step (1): the acid cleaning adopts dilute hydrochloric acid or dilute sulfuric acid, and the concentration is 0.01-1 mol/L.
5. The method for synthesizing the lithium-sulfur battery cathode material by using the waste fly ash as the raw material according to claim 1 or 4, wherein in the step (1): the mass ratio of the waste fly ash to the acid is 1:20-1: 200.
6. The method for synthesizing the lithium-sulfur battery cathode material by using the waste fly ash as the raw material according to claim 1, wherein the acid washing in the step (1) comprises the following steps: adding acid solution, stirring or ultrasonic treating for 1-24 hr, and washing with deionized water to neutrality.
7. The method for synthesizing the positive electrode material of the lithium-sulfur battery by using the waste fly ash as the raw material according to claim 1, wherein in the step (2): the mass ratio of the fly ash after impurity removal to the elemental sulfur is 1:1-1:10, and the grinding time is 1-6 h.
8. The method for synthesizing the positive electrode material of the lithium-sulfur battery by using the waste fly ash as the raw material according to claim 1, wherein in the step (2): the mass ratio of the mixture of the fly ash and the elemental sulfur to the carbon disulfide is 1:5-1:50, and the mixture is continuously ground for 1-5 hours until the carbon disulfide is completely evaporated.
9. The method for synthesizing the positive electrode material of the lithium-sulfur battery by using the waste fly ash as the raw material according to claim 1, wherein in the step (2): the closed container is a metal closed container or a glass closed container, the drying temperature is 150-.
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