CN112002874A - Lithium-sulfur battery positive plate and preparation method thereof - Google Patents

Lithium-sulfur battery positive plate and preparation method thereof Download PDF

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Publication number
CN112002874A
CN112002874A CN202010908952.9A CN202010908952A CN112002874A CN 112002874 A CN112002874 A CN 112002874A CN 202010908952 A CN202010908952 A CN 202010908952A CN 112002874 A CN112002874 A CN 112002874A
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lithium
sulfur battery
positive plate
polyvinyl alcohol
sulfur
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CN202010908952.9A
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周成冈
胡俊
韩波
吴金平
夏开胜
高强
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China University of Geosciences
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China University of Geosciences
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium-sulfur battery positive plate and a preparation method thereof. A preparation method of a lithium-sulfur battery positive plate comprises the steps of grinding active substance sulfur and a conductive agent in a certain mass ratio uniformly, adding the ground active substance sulfur and the conductive agent into a phosphorylated polyvinyl alcohol aqueous solution, and carrying out coating, drying and slicing to obtain the lithium-sulfur battery positive plate; on the other hand, the phosphoric acid group rich in the phosphorylated polyvinyl alcohol can anchor the polysulfide in the positive electrode by forming a coordinate bond with the polysulfide, thereby inhibiting the shuttling of the polysulfide between the positive electrode and the negative electrode, i.e., inhibiting the "shuttling effect", and greatly improving the cycle stability of the lithium-sulfur battery. The positive plate of the lithium-sulfur battery has good dispersibility of the conductive agent and the active substance sulfur, strong binding power and good cycling stability of the lithium-sulfur battery; the preparation method of the lithium-sulfur battery positive plate is simple in process, environment-friendly and capable of being prepared in a large scale.

Description

Lithium-sulfur battery positive plate and preparation method thereof
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery positive plate and a preparation method thereof.
Background
Lithium sulfur batteries have received much attention due to their high specific capacity and specific energy, and are considered to be one of the most promising next-generation energy storage systems. However, the development of lithium-sulfur batteries also faces challenges such as poor conductivity of the active material, large volume changes in the sulfur positive electrode, and notorious "shuttle effects". An intermediate product polysulfide formed in the charging and discharging processes of the lithium-sulfur battery is easily dissolved in electrolyte and shuttles back and forth between a positive electrode and a negative electrode under the action of concentration gradient or electric field force, and the process is the shuttle effect. Polysulfide diffuses to the negative electrode and reacts with the lithium sheet to generate insoluble lithium sulfide to cover the surface of the negative electrode, so that the negative electrode is passivated, the insoluble lithium sulfide is consumed, active substances are reduced, the coulombic efficiency is low, the cycle stability is poor, and the problem that the influence on the electrochemical performance of the lithium-sulfur battery is the most serious is solved.
In order to solve the above problems, researchers have introduced carbon nanotubes with porous structures, graphene, and heterogeneous element-doped carbon materials, and have attempted to improve the electrochemical performance of lithium-sulfur batteries, but these materials are complicated in preparation process and difficult to prepare on a large scale. The binder, as one of the important components of the electrode, has been proven to have an important role in the electrochemical performance of the electrode. Polyvinylidene fluoride (PVDF) is used as a conventional binder and has good binding power and electrochemical stability, so that it is widely used for preparing the positive electrode of a lithium-sulfur battery. However, PVDF is easily swelled in the electrolyte, so that the electrode structure is damaged during the cycle process, the electrical contact performance between the carbon material and the active material is deteriorated, and the electrochemical performance of the battery is seriously affected; in addition, PVDF and polysulfide have weak intermolecular forces, and it is difficult to effectively anchor the polysulfide, and thus it is difficult to suppress the progress of the "shuttle effect".
For this reason, researchers have been working on developing binders having various functions for the preparation of positive electrodes of lithium sulfur batteries. From the viewpoint of improving electrochemical performance, the binder should have strong binding power, maintain a stable structure in the electrolyte, and have a certain inhibition effect on the "shuttle effect". From the viewpoint of environmental protection, the binder should have water solubility with water as a solvent. In the prior art, gelatin is adopted as a binder of the positive electrode of the lithium-sulfur battery; the gelatin is rich in carboxyl and amino, and has excellent dispersing capacity and binding power; however, the gelatin molecule itself has weak intermolecular interaction with polysulfides, and it is difficult to effectively anchor the polysulfides and to suppress the "shuttle effect", and thus it is difficult to effectively improve the cycle stability of the lithium-sulfur battery.
Therefore, some modifications need to be performed on the positive electrode of the lithium-sulfur battery, so that the active substances, namely sulfur and carbon materials, in the positive electrode of the lithium-sulfur battery have good dispersing ability and strong binding power, and the shuttle effect can be inhibited, so that the cycle stability and the electrochemical performance of the lithium-sulfur battery are greatly improved.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery positive plate with good battery cycle stability, excellent electrochemical performance, good positive material dispersibility and strong binding power and a preparation method thereof, aiming at the defects in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a lithium-sulfur battery positive plate comprises the steps of grinding active substance sulfur and a conductive agent according to a certain mass ratio uniformly, adding the ground active substance sulfur and the conductive agent into a phosphorylated polyvinyl alcohol aqueous solution, coating, drying and slicing to obtain the lithium-sulfur battery positive plate.
Preferably, the conductive agent includes a carbon material.
Preferably, the carbon material is 30-50 parts by mass; the active substance sulfur accounts for 40-65 parts by weight; the phosphorylated polyvinyl alcohol is 5-10 parts by mass.
Preferably, the phosphorylated polyvinyl alcohol is prepared into a phosphorylated polyvinyl alcohol aqueous solution with a mass concentration of 2-3 wt.%, then the carbon material and the active substance sulfur are added into the phosphorylated polyvinyl alcohol aqueous solution in parts by mass, and are uniformly stirred to prepare a mixed slurry, the mixed slurry is coated on a current collector through a scraper, and the lithium-sulfur battery positive electrode is prepared after drying.
Preferably, the carbon material includes one or more of Super P, acetylene black, carbon nanotube, and graphene.
Preferably, the specific preparation process of the phosphorylated polyvinyl alcohol is as follows: mixing polyvinyl alcohol, urea, phosphoric acid and deionized water, and then heating for reaction; and cooling after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate in the mixed solution, purifying the precipitate, and drying in vacuum to obtain the phosphorylated polyvinyl alcohol.
Preferably, the mass part of the polyvinyl alcohol is 1.5 parts; the mass portion of the urea is 2 portions; 1.5-6 parts of phosphoric acid; the mass portion of the deionized water is 60 portions.
Preferably, the temperature of the heating reaction is 95 ℃, and the time of the heating reaction is 1 h; the temperature of the vacuum drying is 50 ℃, and the time of the vacuum drying is 24 h.
Preferably, the purification process is as follows: dissolving the precipitate with deionized water, adding absolute ethyl alcohol to separate out the precipitate, and performing suction filtration to obtain a separated precipitate; the whole process is repeated three times to obtain the phosphorylated polyvinyl alcohol.
A lithium-sulfur battery positive plate is prepared by the method.
The invention relates to a lithium-sulfur battery positive plate and a preparation method thereof. The preparation process of the lithium-sulfur battery positive plate comprises the steps of grinding active substance sulfur and a conductive agent according to a certain mass ratio uniformly, adding the ground active substance sulfur and the conductive agent into a phosphorylated polyvinyl alcohol aqueous solution, and carrying out coating, drying and slicing to obtain the lithium-sulfur battery positive plate; the lithium-sulfur battery positive plate uses the phosphorylated polyvinyl alcohol as a binder, so that the active substance sulfur and the conductive agent have good dispersibility and strong binding power; because an intermediate product polysulfide which is easily formed in the charging and discharging processes of the lithium-sulfur battery shuttles back and forth between the positive electrode and the negative electrode, the cycle stability of the lithium-sulfur battery is poor; in the invention, the phosphorylated polyvinyl alcohol is used as a binder, the phosphorylated polyvinyl alcohol is rich in phosphate groups, and the phosphate groups can form coordinate bonds with polysulfide to anchor the polysulfide in the positive electrode, so that the shuttle of the polysulfide between the positive electrode and the negative electrode, namely the shuttle effect is inhibited, and the cycle stability of the lithium-sulfur battery can be greatly improved.
Drawings
FIG. 1 is a scanning electron microscope image of a positive plate of a lithium-sulfur battery prepared in example 1 of the present invention magnified 3.5 ten thousand times;
FIG. 2 is a scanning electron microscope image of a positive plate of a lithium-sulfur battery prepared in example 1 of the present invention, magnified 1 thousand times;
fig. 3 is a graph comparing the cycle performance curves at 0.5C discharge rate of the assembled batteries of the positive electrode sheets of the lithium sulfur batteries prepared in example 1, example 2, example 3 and comparative example 1.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
1. Selecting the material with the specific surface area of 60m2 g-1The Super P as carbon material is marked as C; selecting sublimed sulfur as active substance sulfur, and marking as S; and respectively weighing 1 part of S and 1 part of C in parts by mass in an agate mortar, and grinding for 30min to obtain the carbon/sulfur positive electrode material (marked as C/S).
2. Preparing a binder: adding 1.5 parts of polyvinyl alcohol, 2 parts of urea, 3 parts of phosphoric acid and 60 parts of deionized water into a three-neck flask according to the parts by weight, and reacting for 1 hour in an oil bath at 95 ℃; cooling after the reaction is finished, and adding absolute ethyl alcohol to separate out precipitates in the mixed solution; dissolving the obtained precipitate with deionized water, adding anhydrous ethanol to separate out the precipitate, and performing suction filtration to obtain the separated precipitate; the whole process is repeated three times, and the process is repeated three times to wash out phosphoric acid and urea in the precipitate to obtain high-purity phosphorylated polyvinyl alcohol, and finally, the phosphorylated polyvinyl alcohol is obtained by vacuum drying at 50 ℃ for 24 hours.
3. Dissolving 1 part of phosphorylated polyvinyl alcohol in deionized water to prepare a phosphorylated polyvinyl alcohol aqueous solution with the mass fraction of 3 wt.%, namely a binder solution; dispersing 9 parts of the carbon/sulfur anode material prepared in the step 1 in a prepared phosphorylated polyvinyl alcohol aqueous solution, and magnetically stirring for 12 hours to prepare anode slurry; coating the obtained anode slurry on a current collector aluminum foil to prepare a sheet, and drying, rolling and slicing to obtain the required anode sheet, wherein the thickness of the anode sheet can be 100 mu m.
The positive plate prepared in the embodiment 1 of the invention is assembled into a lithium-sulfur battery, and the specific method comprises the following steps:
the positive electrode of the lithium-sulfur battery adopts the positive plate prepared in the embodiment 1 of the invention, the negative electrode adopts a lithium plate with the thickness of 60 μm, the diaphragm adopts a Celgard2400 type polypropylene film, the electrolyte is a mixed solution of bis (trifluoromethyl) sulfimide lithium dissolved in dimethyl ether and 1, 3-dioxolane, wherein the volume ratio of the dimethyl ether to the 1, 3-dioxolane is 1: 1; lithium bis (trifluoromethylsulfonyl) imide was used in a concentration of 1mol/L, and lithium nitrate (LiNO) was used in a mass concentration of 1%3) As an electrolyte additive; the components are assembled into a button cell in a positive electrode/diaphragm/negative electrode structure, and the whole cell assembly process is completed in an argon glove box.
As shown in fig. 1 and 2, which are scanning electron micrographs of the positive plate prepared in example 1 of the present invention, it can be seen from fig. 1 and 2 that the sublimed sulfur and the carbon material are uniformly dispersed and the electrode surface is dense, indicating that the phosphorylated polyvinyl alcohol binder has good dispersing and binding abilities.
As shown in fig. 3, the lithium-sulfur battery prepared in example 1 of the present invention was tested at a rate of 0.5C for constant current charging and discharging, and the battery was tested at room temperature, and the test results showed that: the first discharge specific capacity of the battery is 815.9mAh/g, the discharge specific capacity after 100 cycles is 601.7mAh/g, and the capacity retention rate is 73.75%.
Example 2
The preparation process of the lithium sulfur battery positive electrode and the lithium sulfur battery assembly process of example 2 are substantially the same as those of example 1, except that in step 2, the mass fraction of the polyvinyl alcohol is 1.5 parts; and 6 parts of phosphoric acid.
As shown in fig. 3, the battery assembled in this example 2 was tested at room temperature for constant current charge and discharge at a rate of 0.5C, and the test results showed that: the first discharge specific capacity of the battery is 675mAh/g, the discharge specific capacity after 100 cycles is 553mAh/g, and the capacity retention rate is 81.9%.
Example 3
The preparation process of the lithium sulfur battery positive electrode and the lithium sulfur battery assembly process of example 3 are substantially the same as those of example 1, except that in step 2, the mass fraction of the polyvinyl alcohol is 1.5 parts; 1.5 parts of phosphoric acid.
As shown in fig. 3, the battery assembled in this example 3 was tested at room temperature by constant current charge and discharge test at 0.5C rate, and the test results showed that: the first discharge specific capacity of the battery is 761mAh/g, the discharge specific capacity after 100 cycles is 569mAh/g, and the capacity retention rate is 74.8%.
Comparative example
The preparation process in the comparative example was substantially the same as that of example 1 except that in step 2, the binder used was different, and the binder used in the comparative example was PVDF; and (3) dissolving 1 part of PVDF in N-methylpyrrolidone to prepare a binder solution with the mass concentration of 2% of PVDF, and dispersing 9 parts of the carbon/sulfur cathode material prepared in the step (1) in the prepared binder solution.
As shown in fig. 3, the battery assembled in the comparative example was subjected to a constant current charge and discharge test at a rate of 0.5C, and the battery was tested at room temperature, and the test results showed that: the first discharge specific capacity of the battery is 840mAh/g, the discharge specific capacity after 100 times of circulation is 371.2mAh/g, and the capacity retention rate is only 44.19%.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.

Claims (10)

1. A preparation method of a lithium-sulfur battery positive plate is characterized by grinding active substance sulfur and a conductive agent uniformly according to a certain mass ratio, adding the ground active substance sulfur and the conductive agent into a phosphorylated polyvinyl alcohol aqueous solution, and carrying out coating, drying and slicing to obtain the lithium-sulfur battery positive plate.
2. The method of claim 1, wherein the conductive agent comprises a carbon material.
3. The method for preparing the positive plate of the lithium-sulfur battery according to claim 2, wherein the carbon material is used in an amount of 30 to 50 parts by mass; the active substance sulfur accounts for 40-65 parts by weight; the phosphorylated polyvinyl alcohol is 5-10 parts by mass.
4. The method for preparing the positive plate of the lithium-sulfur battery according to claim 3, wherein the phosphorylated polyvinyl alcohol is prepared into a phosphorylated polyvinyl alcohol aqueous solution with a mass concentration of 2-3 wt.%, then the carbon material and the active substance sulfur are added into the phosphorylated polyvinyl alcohol aqueous solution in parts by mass, and are uniformly stirred to prepare a mixed slurry, the mixed slurry is coated on a current collector through a scraper, and the positive plate of the lithium-sulfur battery is obtained by drying and slicing.
5. The method of claim 2, wherein the carbon material comprises one or more of Super P, acetylene black, carbon nanotubes, and graphene.
6. The method for preparing a positive plate of a lithium-sulfur battery according to any one of claims 1 to 5, wherein the phosphorylated polyvinyl alcohol is prepared by the following specific process: mixing polyvinyl alcohol, urea, phosphoric acid and deionized water, and then heating for reaction; and cooling after the reaction is finished, adding absolute ethyl alcohol to separate out a precipitate in the mixed solution, purifying the precipitate, and drying in vacuum to obtain the phosphorylated polyvinyl alcohol.
7. The method for preparing the positive plate of the lithium-sulfur battery according to claim 6, wherein the polyvinyl alcohol is 1.5 parts by mass; the mass portion of the urea is 2 portions; 1.5-6 parts of phosphoric acid; the mass portion of the deionized water is 60 portions.
8. The method for preparing the positive plate of the lithium-sulfur battery according to claim 6, wherein the temperature of the heating reaction is 95 ℃, and the time of the heating reaction is 1 h; the temperature of the vacuum drying is 50 ℃, and the time of the vacuum drying is 24 h.
9. The method for preparing the positive plate of the lithium-sulfur battery according to claim 6, wherein the purification process is as follows: dissolving the precipitate with deionized water, adding absolute ethyl alcohol to separate out the precipitate, and performing suction filtration to obtain a separated precipitate; the whole process is repeated three times to obtain the phosphorylated polyvinyl alcohol.
10. A positive electrode sheet for a lithium-sulfur battery, characterized by being produced by the method according to any one of claims 1 to 9.
CN202010908952.9A 2020-09-02 2020-09-02 Lithium-sulfur battery positive plate and preparation method thereof Pending CN112002874A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101608002A (en) * 2008-06-19 2009-12-23 天津市化学试剂研究所 The preparation method of ammonium alcohol polyvinyl phosphate
CN109411570A (en) * 2018-12-10 2019-03-01 华东理工大学 A kind of polyvinyl alcohol phosphate phosphorous diffusion source and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101608002A (en) * 2008-06-19 2009-12-23 天津市化学试剂研究所 The preparation method of ammonium alcohol polyvinyl phosphate
CN109411570A (en) * 2018-12-10 2019-03-01 华东理工大学 A kind of polyvinyl alcohol phosphate phosphorous diffusion source and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李琦旸: "碳纳米管/硫复合正极材料微观反应界面的构筑与调控", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 *

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Application publication date: 20201127