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WO2016019544A1 - Sulfur-polyacrylonitrile composite, preparation and use thereof - Google Patents

Sulfur-polyacrylonitrile composite, preparation and use thereof Download PDF

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Publication number
WO2016019544A1
WO2016019544A1 PCT/CN2014/083884 CN2014083884W WO2016019544A1 WO 2016019544 A1 WO2016019544 A1 WO 2016019544A1 CN 2014083884 W CN2014083884 W CN 2014083884W WO 2016019544 A1 WO2016019544 A1 WO 2016019544A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
polyacrylonitrile
composite
cnt
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2014/083884
Other languages
French (fr)
Inventor
Nahong ZHAO
Joerg Thielen
Bernd Schumann
Yunhua Chen
Chuanling LI
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Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Priority to PCT/CN2014/083884 priority Critical patent/WO2016019544A1/en
Priority to PCT/CN2015/086370 priority patent/WO2016019901A1/en
Priority to CN201580042528.8A priority patent/CN106661149A/en
Priority to DE112015003654.7T priority patent/DE112015003654T5/en
Priority to PCT/CN2015/086358 priority patent/WO2016019897A1/en
Priority to CN201580042511.2A priority patent/CN106575750A/en
Publication of WO2016019544A1 publication Critical patent/WO2016019544A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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

Definitions

  • the present invention relates to a sulfur-polyacrylonitrile composite, wherein said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles.
  • the present invention further relates to a method for preparing said sulfur-polyacrylonitrile composite, an electrode and a lithium-sulfur battery comprising said sulfur-polyacrylonitrile composite.
  • Li-S batteries have attracted considerable attention for their high energy density and low cost.
  • the theoretical energy density of 2600 Wh/kg cannot be reached because of sulfur 's insulating nature.
  • conductive additives have to be added and consequently the theoretical value is reduced to a realistic 600 Wh/kg.
  • elemental sulfur forms polysulfides, S x 2" , during reduction, which is soluble in the electrolyte. Therefore, several concepts have been elaborated upon that focus on retaining sulfur in the cathode matrix.
  • One of the most promising concepts is to embed sulfur into a conductive matrix of pyrolized polyacrylonitrile (PAN).
  • the present invention provides a sulfur-polyacrylonitrile (SPAN) composite, which provides a high sulfur content and a favorable electrical conductivity. It is promising to a delivery high cathode capacity and a good rate capability when discharging under a large current density.
  • SPN sulfur-polyacrylonitrile
  • sulfur-polyacrylonitrile (SPAN) composite characterized in that said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles.
  • a method for preparing a sulfur-polyacrylonitrile composite including the following steps:
  • the present invention relates to an electrode and a lithium- sulfur battery containing said composite.
  • Figure la is a schematic diagram of the sulfur cathode containing the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers and particles;
  • SPAN sulfur-polyacrylonitrile
  • Figure lb is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers with coaxial oriented CNTs;
  • SPAN sulfur-polyacrylonitrile
  • Figure lc is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers with randomly oriented CNTs;
  • SPAN sulfur-polyacrylonitrile
  • Figure Id is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers without CNTs;
  • SPAN sulfur-polyacrylonitrile
  • FIG. 2a is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of particles with SuperP carbon black;
  • SPAN sulfur-polyacrylonitrile
  • FIG. 2b is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of particles without SuperP carbon black;
  • SPAN sulfur-polyacrylonitrile
  • Figure 3 is a transmission electron microscope (TEM) image of SuperP carbon black.
  • the present invention relates to a sulfur-polyacrylonitrile composite, characterized in that said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles.
  • said sulfur-polyacrylonitrile composite can be formed in such a way that polyacrylonitrile in a form of fibers and/or particles is dehydrogenated and cyclized in the presence of sulfur and bonded with sulfur or polysulfide.
  • the fibers have a diameter of ⁇ 1 ⁇ , preferably between 50 and 500 nm.
  • a preferred average distance from fiber to fiber can be from 0.1 to 2 fiber diameters.
  • the length of the fibers is not particularly limited.
  • the particles have a diameter of between 10 nm and 10 ⁇ , preferably between 10 nm and 500 nm.
  • carbon conductive additives can be adopted and embedded in the fibers and/or the particles.
  • carbon conductive additives bridging from a fiber to another fiber and/or from a fiber to a particle and/or from a particle to another particle can be placed in the empty space of said sulfur-polyacrylonitrile composite, so as to attach the carbon conductive additives onto the outer surface of the fibers and/or the particles and to bridge the electron conductive network in-between the fibers and/or the particles.
  • the carbon conductive additives can be selected from carbon nanotube (CNT) and carbon nanoparticle, such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
  • CNT carbon nanotube
  • carbon nanoparticle such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
  • the carbon nanotube (CNT) which can be used in the sulfur-polyacrylonitrile composite according to the present invention preferably has a diameter of 1 - 100 nm, for example about 2 nm, 3 nm, 5 nm, 10 nm, 30 nm, 40 nm, 60 nm, or 80 nm.
  • the length of the carbon nanotube (CNT) used here is not particularly limited, for example less than 5 ⁇ , 5 - 15 ⁇ , or more than 15 ⁇ .
  • a preferable length of the CNT can be from 0.3 to 6 fiber diameters.
  • CNT carbon nanotube
  • SWNT Single-walled carbon nanotube
  • DWNT double-walled carbon nanotube
  • MWNT multi-walled carbon nanotube
  • the carbon nanotube (CNT) can be open-ended, and the inner voids or cavities of the carbon nanotube (CNT) can be filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), in each case based on the weight of the sulfur-carbon nanotube composite (S/CNT).
  • said sulfur-polyacrylonitrile composite has a sulfur load amount of 20 - 55 wt.%, preferably 30 - 50 wt.%, in each case based on the total weight of the sulfur-polyacrylonitrile composite.
  • the present invention relates to a method for preparing a sulfur-polyacrylonitrile composite, said method including the following steps: 1) preparation of polyacrylonitrile in a form of fibers and/or particles from a polyacrylonitrile solution or dispersion;
  • the polyacrylonitrile precursor in a form of fibers can be prepared by electrospinning.
  • the polyacrylonitrile precursor in a form of particles can be prepared by electrospraying.
  • the polyacrylonitrile precursor in a combination form of fibers and particles can be prepared sequentially by electrospinning and electrospraying.
  • the polyacrylonitrile solution or dispersion can be loaded into a syringe attached to a high-voltage power supply of an electrospinning and/or electrospraying equipment.
  • prepared polyacrylonitrile in a form of fibers and/or particles has a high surface area of 10 - 1000 m 2 /g, preferentially 10 - 500 m 2 /g.
  • the polyacrylonitrile solution or dispersion can additionally contain carbon conductive additives, in order to obtain the polyacrylonitrile in a form of fibers and/or particles with carbon conductive additives adopted and embedded in the fibers (Figs, lb - lc) and/or in the particles (Fig. 2a).
  • a solution or dispersion of carbon conductive additives can be sprayed at the same time through a nozzle close to the nozzle for said electrospinning and/or said electrospraying, so that the carbon conductive additives bridging from a fiber to another fiber and/or from a fiber to a particle and/or from a particle to another particle can be placed in the empty space of said sulfur-polyacrylonitrile composite, so as to attach the carbon conductive additives onto the outer surface of the fibers and/or the particles and to bridge the electron conductive network in-between the fibers and/or the particles.
  • the carbon conductive additives can be selected from carbon nanotube (CNT) and carbon nanoparticle, such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
  • CNT carbon nanotube
  • carbon nanoparticle such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
  • the carbon nanotube (CNT) which can be used in the polyacrylonitrile solution or dispersion additionally containing carbon conductive additives or in the solution or dispersion of carbon conductive additives preferably has a diameter of 1 - 100 nm, for example about 2 nm, 3 nm, 5 nm, 10 nm, 30 nm, 40 nm, 60 nm, or 80 nm.
  • the length of the carbon nanotube (CNT) used here is not particularly limited, for example less than 5 ⁇ , 5 - 15 ⁇ , or more than 15 ⁇ .
  • a preferable length of the CNT can be from 0.3 to 6 fiber diameters.
  • Single-walled carbon nanotube (SWNT), double-walled carbon nanotube (DWNT) and multi-walled carbon nanotube (MWNT) can be used.
  • the carbon nanotube (CNT) can be open-ended, and before the carbon nanotube (CNT) is used in the polyacrylonitrile solution or dispersion additionally containing carbon conductive additives or in the solution or dispersion of carbon conductive additives, it can be calcined together with sulfur in vacuo at 550 - 700°C, preferably at about 600°C, for about 48 hours, so that the inner voids or cavities of the carbon nanotube (CNT) can be filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), in each case based on the weight of the sulfur-carbon nanotube composite (S/CNT).
  • S/CNT sulfur-carbon nanotube composite
  • the polyacrylonitrile prepared from 1) together with sulfur can be heated at a temperature of between 390 and 460°C for 0.5 to 3 hours, for example about 2 hours, preferably in a protective atmosphere, such as argon, so that the polyacrylonitrile is dehydrogenated and cyclized in the presence of sulfur and bonded with sulfur or polysulfide.
  • a protective atmosphere such as argon
  • Fabric shaped SPAN those of containing SPAN fiber or those of containing the combination of SPAN fiber and SPAN particle, can be used as a working electrode for charging and discharging directly in a Li-S battery.
  • the SPAN nanoparticle alone needs to be mixed with carbon black and poly-(vinyl difluoride) (PVDF) and be pasted on an Al foil.
  • PVDF poly-(vinyl difluoride)
  • Lithium foil can be used as the counter electrode, and assembled with a separator and carbonate electrolyte consisted of LiPF 6 salt and ethylene carbonate solvent.
  • the present invention further relates to an electrode, which comprises the sulfur-polyacrylonitrile composite according to the present invention.
  • the electrode can consist of the sulfur-polyacrylonitrile composite according to the present invention in a form of fibers or in a form of fibers and particles.
  • the present invention further relates to a lithium-sulfur battery, which comprises the electrode according to the present invention.
  • the SPAN obtained according to the present invention has a higher electronic conductivity compared to the SPAN synthesized from the conventional PAN and sulfur only. CNTs on the outer surface of the PAN still remain on the outer surface of the SPAN, providing a conductive coating.
  • This SPAN composite electrode thus shows a high cathode capacity, a low resistance, an excellent cycling stability, and a favorable rate performance.
  • the inventors have investigated the chemical process of the dehydrogenation of polyacrylonitrile in the presence of sulfur, and revealed the chemical structure of the polyacrylonitrile-derived cyclized backbone. It has been found that a higher synthesis temperature results in a higher degree of graphitization of the polymer backbone and eventually in a higher C-rate capability and a higher cycling stability. However, the composite degrades when prepared at a higher temperature which results in a lower sulfur content and eventually in a lower cathode capacity. At the same time, the SPAN composite prepared at a higher temperature displays a larger specific surface area, which also supports the higher C-rate performance. Despite of this trade off in between the capacity and the high C-rate capability, an optimum synthesis temperature can be selected from 390 to 460°C.
  • Potential applications of the composite according to the present invention include high-energy-density lithium ion batteries with acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.

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Abstract

Sulfur-polyacrylonitrile composite, preparation and use thereof are provided, the sulfur-polyacrylonitrile composite comprising sulfur and polyacrylonitrile in a form of fibers and/or particles is used in electrode of lithium-sulfur battery.

Description

SULFUR-POLYACRYLONITRILE COMPOSITE, PREPARATION AND USE THEREOF
Technical Field
The present invention relates to a sulfur-polyacrylonitrile composite, wherein said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles. The present invention further relates to a method for preparing said sulfur-polyacrylonitrile composite, an electrode and a lithium-sulfur battery comprising said sulfur-polyacrylonitrile composite.
Background Art
Lithium- Sulfur (Li-S) batteries have attracted considerable attention for their high energy density and low cost. However, the theoretical energy density of 2600 Wh/kg cannot be reached because of sulfur 's insulating nature. Thus, conductive additives have to be added and consequently the theoretical value is reduced to a realistic 600 Wh/kg. Additionally, elemental sulfur forms polysulfides, Sx 2", during reduction, which is soluble in the electrolyte. Therefore, several concepts have been elaborated upon that focus on retaining sulfur in the cathode matrix. One of the most promising concepts is to embed sulfur into a conductive matrix of pyrolized polyacrylonitrile (PAN). This appealing sulfur-polyacrylonitrile (SPAN) composite has been used as an active cathode material showing a high specific capacity, a good efficiency, a low self-discharge, an excellent cycling stability and an improved rate performance. In view of the status quo in high energy density battery applications, the energy density of this Li-sulfur system has to be improved essentially. To do so, many researches have been conducted to improve the material capacity of SPAN composite.
Summary of Invention
The present invention provides a sulfur-polyacrylonitrile (SPAN) composite, which provides a high sulfur content and a favorable electrical conductivity. It is promising to a delivery high cathode capacity and a good rate capability when discharging under a large current density.
According to one aspect of the present invention, sulfur-polyacrylonitrile (SPAN) composite is provided, characterized in that said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles.
According to another aspect of the present invention, a method for preparing a sulfur-polyacrylonitrile composite is provided, said method including the following steps:
1) preparation of polyacrylonitrile in a form of fibers and/or particles from a polyacrylonitrile solution or dispersion;
2) heating the polyacrylonitrile prepared from 1) together with sulfur. According to a further aspect, the present invention relates to an electrode and a lithium- sulfur battery containing said composite.
Brief Description of Drawings
Each aspect of the present invention will be illustrated in more detail in conjunction with the accompanying drawings, wherein :
Figure la is a schematic diagram of the sulfur cathode containing the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers and particles;
Figure lb is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers with coaxial oriented CNTs;
Figure lc is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers with randomly oriented CNTs;
Figure Id is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of fibers without CNTs;
Figure 2a is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of particles with SuperP carbon black;
Figure 2b is a schematic diagram of the sulfur-polyacrylonitrile (SPAN) composite in a form of particles without SuperP carbon black;
Figure 3 is a transmission electron microscope (TEM) image of SuperP carbon black.
Detailed Description of Preferred Embodiments
All publications, patent applications, patents and other references mentioned herein, if not otherwise indicated, are explicitly incorporated by reference herein in their entirety for all purposes as if fully set forth.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
The present invention, according to one aspect, relates to a sulfur-polyacrylonitrile composite, characterized in that said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles. In accordance with an embodiment of the present invention, said sulfur-polyacrylonitrile composite can be formed in such a way that polyacrylonitrile in a form of fibers and/or particles is dehydrogenated and cyclized in the presence of sulfur and bonded with sulfur or polysulfide.
In accordance with another embodiment of the present invention, the fibers have a diameter of < 1 μπι, preferably between 50 and 500 nm. A preferred average distance from fiber to fiber can be from 0.1 to 2 fiber diameters. The length of the fibers is not particularly limited.
In accordance with another embodiment of the present invention, the particles have a diameter of between 10 nm and 10 μπι, preferably between 10 nm and 500 nm.
In accordance with another embodiment of the present invention, carbon conductive additives can be adopted and embedded in the fibers and/or the particles.
In accordance with another embodiment of the present invention, carbon conductive additives bridging from a fiber to another fiber and/or from a fiber to a particle and/or from a particle to another particle can be placed in the empty space of said sulfur-polyacrylonitrile composite, so as to attach the carbon conductive additives onto the outer surface of the fibers and/or the particles and to bridge the electron conductive network in-between the fibers and/or the particles.
In accordance with another embodiment of the present invention, the carbon conductive additives can be selected from carbon nanotube (CNT) and carbon nanoparticle, such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
The carbon nanotube (CNT) which can be used in the sulfur-polyacrylonitrile composite according to the present invention preferably has a diameter of 1 - 100 nm, for example about 2 nm, 3 nm, 5 nm, 10 nm, 30 nm, 40 nm, 60 nm, or 80 nm. The length of the carbon nanotube (CNT) used here is not particularly limited, for example less than 5 μπι, 5 - 15 μπι, or more than 15 μπι. A preferable length of the CNT can be from 0.3 to 6 fiber diameters.
There is no limit to the specific form of the carbon nanotube (CNT) used here. Single-walled carbon nanotube (SWNT), double-walled carbon nanotube (DWNT) and multi-walled carbon nanotube (MWNT) can be used.
In accordance with another embodiment of the present invention, the carbon nanotube (CNT) can be open-ended, and the inner voids or cavities of the carbon nanotube (CNT) can be filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), in each case based on the weight of the sulfur-carbon nanotube composite (S/CNT).
In accordance with another embodiment of the present invention, said sulfur-polyacrylonitrile composite has a sulfur load amount of 20 - 55 wt.%, preferably 30 - 50 wt.%, in each case based on the total weight of the sulfur-polyacrylonitrile composite.
The present invention, according to another aspect, relates to a method for preparing a sulfur-polyacrylonitrile composite, said method including the following steps: 1) preparation of polyacrylonitrile in a form of fibers and/or particles from a polyacrylonitrile solution or dispersion;
2) heating the polyacrylonitrile prepared from 1) together with sulfur.
1) Preparation of polyacrylonitrile
In accordance with an embodiment of the present invention, the polyacrylonitrile precursor in a form of fibers (similar as Figs, lb - Id) can be prepared by electrospinning.
In accordance with another embodiment of the present invention, the polyacrylonitrile precursor in a form of particles (similar as Fig. 2) can be prepared by electrospraying.
In accordance with another embodiment of the present invention, the polyacrylonitrile precursor in a combination form of fibers and particles (similar as Fig. la) can be prepared sequentially by electrospinning and electrospraying.
In electrospinning and/or electrospraying, the polyacrylonitrile solution or dispersion can be loaded into a syringe attached to a high-voltage power supply of an electrospinning and/or electrospraying equipment.
Thus prepared polyacrylonitrile in a form of fibers and/or particles has a high surface area of 10 - 1000 m2/g, preferentially 10 - 500 m2/g.
In accordance with another embodiment of the present invention, the polyacrylonitrile solution or dispersion can additionally contain carbon conductive additives, in order to obtain the polyacrylonitrile in a form of fibers and/or particles with carbon conductive additives adopted and embedded in the fibers (Figs, lb - lc) and/or in the particles (Fig. 2a).
In accordance with another embodiment of the present invention, a solution or dispersion of carbon conductive additives can be sprayed at the same time through a nozzle close to the nozzle for said electrospinning and/or said electrospraying, so that the carbon conductive additives bridging from a fiber to another fiber and/or from a fiber to a particle and/or from a particle to another particle can be placed in the empty space of said sulfur-polyacrylonitrile composite, so as to attach the carbon conductive additives onto the outer surface of the fibers and/or the particles and to bridge the electron conductive network in-between the fibers and/or the particles.
In accordance with another embodiment of the present invention, the carbon conductive additives can be selected from carbon nanotube (CNT) and carbon nanoparticle, such as acetylene black, SuperP carbon black (Fig. 3) or ketjen black.
The carbon nanotube (CNT) which can be used in the polyacrylonitrile solution or dispersion additionally containing carbon conductive additives or in the solution or dispersion of carbon conductive additives preferably has a diameter of 1 - 100 nm, for example about 2 nm, 3 nm, 5 nm, 10 nm, 30 nm, 40 nm, 60 nm, or 80 nm. The length of the carbon nanotube (CNT) used here is not particularly limited, for example less than 5 μπι, 5 - 15 μπι, or more than 15 μπι. A preferable length of the CNT can be from 0.3 to 6 fiber diameters. There is no limit to the specific form of the carbon nanotube (CNT) used here. Single-walled carbon nanotube (SWNT), double-walled carbon nanotube (DWNT) and multi-walled carbon nanotube (MWNT) can be used.
In accordance with another embodiment of the present invention, the carbon nanotube (CNT) can be open-ended, and before the carbon nanotube (CNT) is used in the polyacrylonitrile solution or dispersion additionally containing carbon conductive additives or in the solution or dispersion of carbon conductive additives, it can be calcined together with sulfur in vacuo at 550 - 700°C, preferably at about 600°C, for about 48 hours, so that the inner voids or cavities of the carbon nanotube (CNT) can be filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), in each case based on the weight of the sulfur-carbon nanotube composite (S/CNT).
2) Heating the polyacrylonitrile prepared from 1) together with sulfur
In accordance with another embodiment of the present invention, the polyacrylonitrile prepared from 1) together with sulfur can be heated at a temperature of between 390 and 460°C for 0.5 to 3 hours, for example about 2 hours, preferably in a protective atmosphere, such as argon, so that the polyacrylonitrile is dehydrogenated and cyclized in the presence of sulfur and bonded with sulfur or polysulfide.
Preparation of working electrode
Fabric shaped SPAN, those of containing SPAN fiber or those of containing the combination of SPAN fiber and SPAN particle, can be used as a working electrode for charging and discharging directly in a Li-S battery. The SPAN nanoparticle alone needs to be mixed with carbon black and poly-(vinyl difluoride) (PVDF) and be pasted on an Al foil. Lithium foil can be used as the counter electrode, and assembled with a separator and carbonate electrolyte consisted of LiPF6 salt and ethylene carbonate solvent.
The present invention further relates to an electrode, which comprises the sulfur-polyacrylonitrile composite according to the present invention.
In accordance with an embodiment of the present invention, the electrode can consist of the sulfur-polyacrylonitrile composite according to the present invention in a form of fibers or in a form of fibers and particles.
The present invention further relates to a lithium-sulfur battery, which comprises the electrode according to the present invention.
Due to the high surface area of the PAN according to the present invention which provides a huge reaction interphase to sulfur, a higher sulfur content can be achieved compared to the conventional synthesis procedure starting with conventional crude PAN. At the same time, the SPAN obtained according to the present invention has a higher electronic conductivity compared to the SPAN synthesized from the conventional PAN and sulfur only. CNTs on the outer surface of the PAN still remain on the outer surface of the SPAN, providing a conductive coating. This SPAN composite electrode thus shows a high cathode capacity, a low resistance, an excellent cycling stability, and a favorable rate performance.
The inventors have investigated the chemical process of the dehydrogenation of polyacrylonitrile in the presence of sulfur, and revealed the chemical structure of the polyacrylonitrile-derived cyclized backbone. It has been found that a higher synthesis temperature results in a higher degree of graphitization of the polymer backbone and eventually in a higher C-rate capability and a higher cycling stability. However, the composite degrades when prepared at a higher temperature which results in a lower sulfur content and eventually in a lower cathode capacity. At the same time, the SPAN composite prepared at a higher temperature displays a larger specific surface area, which also supports the higher C-rate performance. Despite of this trade off in between the capacity and the high C-rate capability, an optimum synthesis temperature can be selected from 390 to 460°C.
Potential applications of the composite according to the present invention include high-energy-density lithium ion batteries with acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.

Claims

1. A sulfur-polyacrylonitrile composite, characterized in that said sulfur-polyacrylonitrile composite comprises sulfur and polyacrylonitrile in a form of fibers and/or particles.
2. The sulfur-polyacrylonitrile composite of claim 1, characterized in that said sulfur-polyacrylonitrile composite is formed in such a way that polyacrylonitrile in a form of fibers and/or particles is dehydrogenated and cyclized in the presence of sulfur and bonded with sulfur or polysulfide.
3. The sulfur-polyacrylonitrile composite of claim 1, characterized in that the fibers have a diameter of < 1 μπι, preferably between 50 and 500 nm.
4. The sulfur-polyacrylonitrile composite of claim 1, characterized in that the particles have a diameter of between 10 nm and 10 μπι, preferably between 10 nm and 500 nm.
5. The sulfur-polyacrylonitrile composite of any one of claims 1 to 4, characterized in that carbon conductive additives are adopted and embedded in the fibers and/or the particles.
6. The sulfur-polyacrylonitrile composite of any one of claims 1 to 5, characterized in that carbon conductive additives bridging from a fiber to another fiber and/or from a fiber to a particle and/or from a particle to another particle are placed in the empty space of said sulfur-polyacrylonitrile composite.
7. The sulfur-polyacrylonitrile composite of claim 5 or 6, characterized in that the carbon conductive additives are selected from carbon nanotube (CNT) and carbon nanoparticle, such as SuperP carbon black or ketjen black.
8. The sulfur-polyacrylonitrile composite of claim 7, characterized in that the carbon nanotube (CNT) is open-ended, and the inner voids of the carbon nanotube (CNT) are filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), based on the weight of the sulfur-carbon nanotube composite (S/CNT).
9. The sulfur-polyacrylonitrile composite of any one of claims 1 to 8, characterized in that said sulfur-polyacrylonitrile composite has a sulfur load amount of 20 - 55 wt.% based on the total weight of the sulfur-polyacrylonitrile composite.
10. A method for preparing a sulfur-polyacrylonitrile composite, said method including the following steps:
1) preparation of polyacrylonitrile in a form of fibers and/or particles from a polyacrylonitrile solution or dispersion; 2) heating the polyacrylonitrile prepared from 1) together with sulfur.
11. The method of claim 10, characterized in that during 1), the polyacrylonitrile in a form of fibers is prepared by electrospinning.
12. The method of claim 10, characterized in that during 1), the polyacrylonitrile in a form of particles is prepared by electrospraying.
13. The method of claim 10, characterized in that during 1), the polyacrylonitrile in a form of fibers and particles is prepared sequentially by electrospinning and electrospraying.
14. The method of any one of claims 10 to 13, characterized in that the polyacrylonitrile solution or dispersion additionally contains carbon conductive additives.
15. The method of any one of claims 10 to 14, characterized in that during 1), a solution or dispersion of carbon conductive additives is sprayed at the same time through a nozzle close to the nozzle for said electrospinning and/or said electrospraying.
16. The method of claim 14 or 15, characterized in that the carbon conductive additives are selected from carbon nanotube (CNT) and carbon nanoparticle, such as acetylene black, SuperP carbon black or ketjen black.
17. The method of claim 16, characterized in that the carbon nanotube (CNT) is open-ended, and the inner voids of the carbon nanotube (CNT) are filled with 1 - 30 wt.%, preferably 10 - 20 wt.% of sulfur to form a sulfur-carbon nanotube composite (S/CNT), based on the weight of the sulfur-carbon nanotube composite (S/CNT).
18. The method of any one of claims 10 to 17, characterized in that during 2), the polyacrylonitrile prepared from 1) together with sulfur is heated at a temperature of between 390 and 460°C for 0.5 to 3 hours in a protective atmosphere.
19. An electrode, characterized in that the electrode comprises the sulfur-polyacrylonitrile composite of any one of claims 1 to 9 or the sulfur-polyacrylonitrile composite prepared by the method of any one of claims 10 to 18.
20. The electrode of claim 19, characterized in that said sulfur-polyacrylonitrile composite is present in a form of fibers or in a form of fibers and particles.
21. The electrode of claim 20, characterized in that the electrode consists of said sulfur-polyacrylonitrile composite.
22. The electrode of claim 19, characterized in that said sulfur-polyacrylonitrile composite is present in a form of particles.
23. A lithium-sulfur battery, characterized in that the lithium-sulfur battery comprises the electrode of any one of claims 19 to 22.
PCT/CN2014/083884 2014-08-07 2014-08-07 Sulfur-polyacrylonitrile composite, preparation and use thereof Ceased WO2016019544A1 (en)

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PCT/CN2015/086370 WO2016019901A1 (en) 2014-08-07 2015-08-07 A sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite
CN201580042528.8A CN106661149A (en) 2014-08-07 2015-08-07 Sulfur-PAN composite, method for preparing said composite, and electrodes and lithium-sulfur batteries comprising said composite
DE112015003654.7T DE112015003654T5 (en) 2014-08-07 2015-08-07 SWEEP PAN COMPOSITE MATERIAL, METHOD FOR PRODUCING THE COMPOSIT MATERIAL, AND ELECTRODE AND LITHIUM SULFUR BATTERY CONTAINING THE COMPOSITE MATERIAL
PCT/CN2015/086358 WO2016019897A1 (en) 2014-08-07 2015-08-07 A sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite
CN201580042511.2A CN106575750A (en) 2014-08-07 2015-08-07 Sulfur-PAN composite, method for preparing said composite, and electrodes and lithium-sulfur batteries comprising said composite

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