WO2019095355A1

WO2019095355A1 - Preparation method of composite material containing sulfur-containing conductive polymer

Info

Publication number: WO2019095355A1
Application number: PCT/CN2017/111795
Authority: WO
Inventors: 黄文弘
Original assignee: 迪吉亚节能科技股份有限公司
Priority date: 2017-11-20
Filing date: 2017-11-20
Publication date: 2019-05-23
Also published as: CN110073526A

Abstract

A method for preparing composite material of sulfur-containing conductive polymer, the preparation method comprising the following steps: step A. uniformly mixing sulfur, polymer and graphene into a mixture; step B. heating the mixture to 80-120 °C in an inert gas atmosphere, then performing drying and dehydrogenation to form a conductive polymer; and step C. maintaining the mixture of step B at a temperature ranging from 150 °C to 300 °C and a pressure range of 14.5 Psi to 725 Psi for 0.5 to 3 hours to perform dehydrogenation-sulfurization starting-smelting reaction to form a sulfur-conductive polymer, and forming a composite material of sulfur-containing conductive polymer with graphene.

Description

\¥0 2019/095355 卩(:17 \2017/111795

Method for preparing composite material containing sulfur conductive polymer

[0001] The present invention relates to a method for preparing a composite material containing a sulfur-containing conductive polymer, and more particularly to a composite material for a sulfur-containing conductive polymer on an electrode of a secondary battery.

Background technique

[0002] The application range of mobile devices has become increasingly widespread, and has been inseparable from the lives of modern people. With this development, the requirements for the capacity and life of secondary batteries are also increasing. Lithium batteries are currently the most popular mobile device power supply because of their high operating voltage and high energy density. In order to pursue higher capacitance and better battery performance, lithium batteries of various chemical compositions have been developed, among which lithium-sulfur batteries have attracted attention because of their higher capacitance than general lithium metal oxide batteries.

technical problem

[0003] However, when sulfur is heated during charging and discharging, it becomes liquid polysulfide and flows around the electrolyte or the negative electrode of the battery, reducing the amount of recyclable sulfur active material, resulting in a decrease in the charging capacity and life of the battery. Pure sulfur is difficult to apply to secondary lithium batteries. Therefore, improving the form of sulfur in lithium-sulfur batteries is an important issue in the application of lithium-sulfur batteries.

Problem solution

Technical solution

In view of the above, in order to provide a structure different from the prior art and to improve the above-mentioned drawbacks, the inventors have accumulated many years of experience and continuous development and improvement, and the present invention has been produced.

[0005] An object of the present invention is to provide a method for preparing a sulfur-containing conductive polymer, which can improve the form of sulfur in a lithium-sulfur battery, and can effectively recycle and reuse the sulfur active material to maintain the charging capacity of the battery. And improve battery life.

[0006] In order to achieve the above object, the present invention provides a method for preparing a sulfur-containing conductive polymer, which comprises the following steps:

The sulfur, the polymer and the graphene are uniformly mixed into a mixture; Step 6. The mixture is heated to 80 to 120° in an inert gas atmosphere ⁽ :, dried and dehydrogenated to form a conductive polymer) ; \¥0 2019/095355 卩(:17 \2017/111795 and steps (: . The mixture of step 6 is at 150° (: to 300° (: temperature range and 14.5? 8:1 to 725? 8:1) The pressure range is maintained at a constant temperature of 0.5 to 3 hours to dehydrogenation to initiate a sulfur melting reaction to form a sulfur-conductive polymer and form a composite of a sulfur-containing conductive polymer with graphene.

[0007] When implemented, the material ratio in the mixture in step 8 is sulfur 10-95 \¥1%, polymer 4.9-89

, graphene 0.1-85%.

[0008] When implemented, the purity of sulfur is from 99.50% to 99.99%.

[0009] When implemented, the graphene is a single crystal graphene having a particle size of 0.2-5!1111, and the number of layers is a single layer or a plurality of layers.

[0010] When implemented, the polymer is selected from one of the group consisting of: polyvinylidene fluoride

Polyvinyl fluoride ( ), polyacrylonitrile $ eight, polystyrene $3), polyethylene oxide $£0).

[0011] When implemented, the inert gas is argon or nitrogen.

[0012] When implemented, the form of the composite material of the sulfur-containing conductive polymer formed in the step (: is powder, granule, block or fiber.

Advantageous effects of the invention

Brief description of the drawing

DRAWINGS

1 is a flow chart of an embodiment of a method for preparing a sulfur-containing conductive polymer composite material of the present invention.

2 is a schematic structural view of an embodiment of a composite material of a sulfur-containing conductive polymer of the present invention.

3 is a charge and discharge graph of an embodiment of a battery using the composite material of the present invention.

4 is a charge and discharge cycle diagram of an embodiment of a battery using the composite material of the present invention.

DESCRIPTION OF REFERENCE NUMERALS

10 sulfur conductive polymer

[0020] 20 layered graphene.

BEST MODE FOR CARRYING OUT THE INVENTION

[0021] In order to further understand the present invention, the preferred embodiments are listed below, with reference to the accompanying drawings, \¥0 2019/095355 卩 (: 17 \2017/111795 The specific composition of the contents and the effects achieved are detailed below.

[0022] Please refer to FIG. 1 , which is a flow chart of a preferred embodiment of a method for preparing a sulfur-containing conductive polymer composite material, the preparation method comprising the following steps: Step 8. Sulfur, polymer And uniformly mixing the graphene into a mixture; the step of heating the mixture to 80 to 120 ° C in an inert gas atmosphere, drying and dehydrogenating to form a conductive polymer; and the step (:. The mixture of 6 is maintained at a constant temperature of 0.5 to 3 hours at a temperature range of 150° (: to 300°) and a pressure range of 14.5 to 8:1 to 725 to 8:1 to a dehydrogenation sulfur-smelting reaction to form a A sulfur conductive polymer and a composite material of a sulfur-containing conductive polymer with graphene.

[0023] In a preferred embodiment, the material ratio in the mixture in the foregoing step 8 is 10-95% of sulfur, polymerization.

The purity of sulfur is 99.50% to 99.99%; graphene is a large-area single crystal graphene having a particle size of 2.2-5!1111, and the number of layers is a single layer or a plurality of layers; the polymer is selected from the group below One of the groups: polyvinylidene fluoride. ?), Polyvinyl fluoride?), Polyacrylonitrile VIII, Polystyrene 3), Polyoxyethylene £0).

[0024] In a preferred embodiment, the inert gas in the foregoing step 8 is argon (eight) or nitrogen (N ₂ ).

[0025] In a preferred embodiment, the foregoing step (the formed sulfur-containing conductive polymer composite material has a sulfur content of 50-90 1%, and the graphene can increase the conductivity of the composite material, The composite material of the sulfur conductive polymer may be powder, granule, block or fiber, and can be normally charged and discharged at room temperature. For the structure of the composite material of the sulfur-containing conductive polymer of the present invention, please refer to the embodiment shown in FIG. 2 . It includes a stacked layered graphene 20, and a sulfur-containing conductive polymer 10 sandwiched in the layered graphene 20.

The composite material produced by the method for producing a sulfur-containing conductive polymer composite of the present invention is mainly applied to an electrode of a secondary battery such as a lithium battery. In one example, a lithium-sulfur battery cell includes a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the positive electrode structure is: a composite material of a sulfur-containing conductive polymer/solvent/adhesive/conductive agent/coagulant/foil, negative electrode The structure is: metal lithium/copper foil, the diaphragm is a wet diaphragm, and the electrolyte is a liquid or colloidal electrolyte. 3 is a charge and discharge curve of the battery in the present example, and the charge and discharge curve in the figure shows that the composite material of the present invention is used in the positive electrode of the lithium sulfur battery, and the charge and discharge rate of the battery can reach 100%.

. Fig. 4 is a charge and discharge cycle curve of the battery in the present example. The graph shows that the charge rate of the battery is less than 3% after charging and discharging cycles of 1 (: (battery capacity) 500 times, showing good stability.

Industrial applicability \¥0 2019/095355 ?€1^2017/111795

[0027] Therefore, the present invention has the following advantages:

[0028] 1. The present invention can effectively recycle the active substance of sulfur, thereby improving the charging rate of battery cycle charging.

[0029] 2. The present invention can prevent sulfur from flowing into a liquid in the charge and discharge process and flow in the battery, thereby improving the number of cycles of charging the battery, improving the stability of the battery, and prolonging the life of the battery.

[0030] In summary, according to the above disclosure, the present invention can achieve the intended purpose, and provides a method for preparing a sulfur-containing conductive polymer capable of improving the charging capacity and life of the battery, which is highly industrial. The value of the use, the invention patent application is filed according to law.

Claims

\¥0 2019/095355 卩(:17 \2017/111795 Claims

[Claim 1] A method for producing a composite material containing a sulfur-containing conductive polymer, characterized in that the preparation method comprises the following steps:

Step: uniformly mixing sulfur, polymer and graphite into a mixture;

Step of heating the mixture to 80 to 120 ° in an inert gas atmosphere (:, drying and dehydrogenation reaction to form a conductive polymer; and step (:.

The mixture of the step 8 is maintained at a constant temperature of 0.5 to 3 hours at a temperature range of 150° (: to 300°) and a pressure range of 14.5 to 8:1 to 725 to 8:1 to a dehydrogenation and sulfur-smelting reaction. A sulfur-conductive polymer is formed and forms a composite of a sulfur-containing conductive polymer with graphene.

[Claim 2] The preparation method according to claim 1, wherein the material ratio in the mixture in step VIII is sulfur

Polymer 4

Graphene 0

[Claim 3] The preparation method according to claim 1, wherein the sulfur has a purity of 99.50% to

99.99%.

[Claim 4] The preparation method according to claim 1, wherein the graphene is a single crystal graphene having a particle diameter of 0.2 to 5, 1111, and the number of layers is a single layer or a plurality of layers.

[Claim 5] The preparation method according to claim 1, wherein the polymer is selected from the group consisting of polyvinylidene fluoride, polyvinyl fluoride, polyacrylonitrile, polystyrene, Polyethylene oxide.

[Clave 6] The production method according to claim 1, wherein the inert gas is argon or nitrogen.

[Claim 7] The preparation method according to claim 1, wherein the form of the sulfur-containing conductive polymer-formed composite formed in the step ⁽ : is a powder, a granule, a block or a fiber.