CN106661149A - Sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite - Google Patents

Sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite Download PDF

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Publication number
CN106661149A
CN106661149A CN201580042528.8A CN201580042528A CN106661149A CN 106661149 A CN106661149 A CN 106661149A CN 201580042528 A CN201580042528 A CN 201580042528A CN 106661149 A CN106661149 A CN 106661149A
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sulphur
polyacrylonitrile
cnt
compound
weight
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赵娜红
J·蒂伦
B·许曼
陈赟华
李传玲
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Robert Bosch GmbH
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Robert Bosch GmbH
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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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a sulfur-polyacrylonitrile composite, which comprises polyacrylonitrile particles, sulfur and one or more carbon conductive additives. The present invention further relates to a method for preparing said sulfur-polyacrylonitrile composite, and an electrode and a lithium-sulfur battery comprising said sulfur-polyacrylonitrile composite.

Description

Sulphur-PAN compounds, the method for preparing the compound and comprising the compound Electrode and lithium-sulfur cell
Technical field
The present invention relates to sulphur-polyacrylonitrile compound, it includes polyacrylonitrile particle, sulphur and one or more conductive carbon and adds Plus agent.The invention further relates to prepare the method for the sulphur-polyacrylonitrile compound and comprising the sulphur-polyacrylonitrile compound Electrode and lithium-sulfur cell.
Background technology
Lithium sulphur (Li-S) battery has attracted considerable concern due to its high-energy-density and low cost.But due to sulphur Insulation characterisitic, it is impossible to reach the theoretical energy density of 2600Wh/kg.Therefore conductive additive must be added, so from theoretical value It is reduced to actual 600Wh/kg.Additionally, elementary sulfur forms polysulfide S during reducingx 2-, it dissolves in electrolyte.Therefore It is proposed that several efforts be made so that sulphur is retained in the imagination in positive electrode substrate.A kind of most promising imagination is to be embedded in sulphur In the conducting base of thermolytic polyacrylonitrile (PAN).This attractive sulphur-polyacrylonitrile (SPAN) compound is lived as positive pole Property material, shows the high rate performance of height ratio capacity, good efficiency, low self-discharge, excellent cyclical stability and improvement.Mirror In the present situation in high energy density cells application, it is necessary to inherently improve the energy density of the Li- sulphur systems.For this purpose, having People has been engaged in many research work to improve the material capacity of SPAN compounds.
The content of the invention
The present invention provides sulphur-polyacrylonitrile (SPAN) compound with high sulfur content and favourable electric conductivity.There is prospect , high positive electrode capacity and good high rate performance is provided when with high current density discharge.
According to an aspect of the present invention, there is provided sulphur-polyacrylonitrile compound, it includes polyacrylonitrile particle, sulphur and one Plant or various conductive carbonaceous additives, one or more conductive carbon additive embeds and/or be embedded in the polyacrylonitrile particle In.
According to another aspect of the present invention, there is provided the method for preparing sulphur-polyacrylonitrile compound, methods described include with Lower step：
1) polyacrylonitrile particle is prepared by polyacrylonitrile solution or dispersion by EFI or spray drying；
2) will be by step 1) obtained in product heat together with sulphur,
Characterized in that, in step 1) in, it is extra conductive by one or more during polyacrylonitrile particle is prepared Carbonaceous additive applies to the polyacrylonitrile particle.
On the other hand, the present invention relates to include the electrode of sulphur of the invention-polyacrylonitrile compound.
Another further aspect, the present invention relates to include the lithium-sulfur cell of electrode of the invention.
Description of the drawings
Various aspects of the invention are explained in more detail according to accompanying drawing, wherein：
Fig. 1 a show the schematic diagram of sulphur-polyacrylonitrile (SPAN) compound of the particle form comprising SuperP carbon blacks；
Fig. 1 b show the schematic diagram of sulphur-polyacrylonitrile (SPAN) compound of the particle form without SuperP carbon blacks； And
Fig. 2 show transmission electron microscope (TEM) photo of SuperP carbon blacks.
Specific embodiment
If without explanation in addition, by all of publication, patent application, patent and other bibliography referred in this Full content is clearly incorporated herein by reference for all purposes, as fully illustrated.
Unless otherwise defined, the implication and the technical field of the invention of all of technology as used herein and scientific terminology Those of ordinary skill it is common understand it is identical.If there is conflict, it is defined by this specification, including definition.
If quantity, concentration or other numerical value or parameter as scope, preferred scope or a series of preferred upper limits and Preferred lower limit is given, then should be understood to especially to include by any pair any range upper limit or preferred numerical value with appoint The all of scope that meaning range lower limit or preferred numerical value are formed, no matter whether these scopes are respectively disclosed.Here is referred to During the scope of numerical value, unless otherwise stated, it is meant that the scope include its end points and all of integer within the range and Fraction.
On the one hand, the present invention relates to sulphur-polyacrylonitrile compound, it includes polyacrylonitrile particle, sulphur and one or more Conductive carbonaceous additive, in one or more conductive carbon additive embedding and/or the embedded polyacrylonitrile particle.
According to an embodiment of sulphur of the invention-polyacrylonitrile compound, the sulphur-polyacrylonitrile compound Can be formed as follows so that the polyacrylonitrile particle in the case where there is sulphur dehydrogenation and cyclisation and with sulphur or many sulfurations Thing is bonded.
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, the polyacrylonitrile particle Diameter can between 100nm and 10 μm, preferably between 100nm and 2 μm, such as about 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 1.5 μm, 5 μm or 8 μm.
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, described one or more conductive Carbonaceous additive can be by a polyacrylonitrile particles bridge to another polyacrylonitrile particle, so as to bridge between the particle Electronic conduction network.Specifically, one end of the conductive carbonaceous additive can be embedded in a polyacrylonitrile particle, and same The other end of conductive carbonaceous additive can be embedded in another polyacrylonitrile particle.
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, described one or more conductive Carbonaceous additive can be selected from：CNT (CNT), graphite and carbon nano-particle, such as acetylene black, SuperP carbon blacks (Fig. 2) or section Qin (Ketjen) is black.
The diameter of CNT (CNT) that can be used in sulphur of the invention-polyacrylonitrile compound is preferably 1 To 100nm, such as about 2nm, 3nm, 5nm, 10nm, 30nm, 40nm, 60nm or 80nm.For CNT as used herein (CNT) length has no particular limits, e.g., less than 5 μm, 5 to 15 μm or more than 15 μm.Preferred CNT length can be 0.3 to 6 times of PAN particle diameters.
For the concrete form of CNT (CNT) as used herein is not limited.SWCN can be used (SWNT), double-walled carbon nano-tube (DWNT) and multi-walled carbon nano-tubes (MWNT).
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, the CNT (CNT) can To be open-ended, and the internal voids of the CNT (CNT) can fill 1 to 30 weight %, preferably 10 to 20 The sulphur of weight %, so as to form sulphur-carbon mano-tube composite (S/CNT), based on the sulphur-carbon mano-tube composite (S/CNT) Weight.
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, the polyacrylonitrile is based on The gross weight of particle and conductive carbonaceous additive, the content of described one or more conductive carbonaceous additive is less than or equal to 15 weights Amount %, particularly preferably less than or equal to preferably lower than or equal to 10 weight %, more preferably less than or equal to 8 weight %, 5 weights Amount %.
According to another embodiment of sulphur of the invention-polyacrylonitrile compound, the sulphur-polypropylene is based on The gross weight of nitrile compound, the sulphur loading capacity of the sulphur-polyacrylonitrile compound can be 20 to 55 weight %, preferably 30 to 50 weight %.
On the other hand, the present invention relates to the method for preparing sulphur-polyacrylonitrile compound, the method comprising the steps of：
1) polyacrylonitrile particle is prepared by polyacrylonitrile solution or dispersion by EFI or spray drying；
2) will be by step 1) obtained in product heat together with sulphur,
Characterized in that, in step 1) in, it is extra conductive by one or more during polyacrylonitrile particle is prepared Carbonaceous additive applies to the polyacrylonitrile particle.
1) the polyacrylonitrile particle comprising conductive carbonaceous additive is prepared
Polyacrylonitrile particle can be prepared by polyacrylonitrile solution or dispersion by EFI or spray drying.For polyacrylonitrile Concentration in the solution or dispersion has no particular limits, for example, 3 to 20 weight %, preferably 5 to 15 weight %, More preferably 6 to 10 weight %, can determine according to desired polyacrylonitrile particle diameter.
In step 1) in, can additionally by one or more conductive carbonaceous additive during polyacrylonitrile particle is prepared Apply to the polyacrylonitrile particle, such that it is able to embedding one or more conductive carbon additive and/or being embedded in described In polyacrylonitrile particle.
It is based on the gross weight of the polyacrylonitrile particle and conductive carbonaceous additive, preferably one or more conductive carbon The content of additive is less than or equal to 15 weight %, more preferably less than or equal to preferably lower than or equal to 10 weight %, 8 weights Amount %, particularly preferably less than or equal to 5 weight %.
According to another embodiment of the method according to the invention, the polyacrylonitrile solution or dispersion can be extra Comprising one or more conductive carbonaceous additive, there is conductive carbon additive to embed such that it is able to prepare by EFI or spray drying simultaneously And/or the polyacrylonitrile particle being embedded.
According to another embodiment of the method according to the invention, can simultaneously by for the EFI or spray drying Nozzle near nozzle spray the solution or dispersion of one or more conductive carbonaceous additive, such that it is able to make it is described a kind of or In the preferred embedding of various conductive carbonaceous additives and/or the embedded polyacrylonitrile particle, one or more conductive carbon addition Agent can be led by a polyacrylonitrile particles bridge to another polyacrylonitrile particle so as to bridge electronics between the particle Electric network.Specifically, one end of the conductive carbonaceous additive can be embedded in a polyacrylonitrile particle, and same conductive carbon The other end of additive can be embedded in another polyacrylonitrile particle.
According to another embodiment of the method according to the invention, described one or more conductive carbonaceous additive can be selected From：CNT (CNT), graphite and carbon nano-particle, such as acetylene black, SuperP carbon blacks (Fig. 2) or section's qin (Ketjen) are black.
Can be in the extra polyacrylonitrile solution comprising conductive carbonaceous additive or dispersion or in conductive carbonaceous additive Solution or dispersion used in the diameter of CNT (CNT) be preferably 1 to 100nm, such as about 2nm, 3nm, 5nm, 10nm, 30nm, 40nm, 60nm or 80nm.For the length of CNT (CNT) as used herein has no particular limits, example Such as less than 5 μm, 5 to 15 μm or more than 15 μm.Preferred CNT length can be 0.3 to 6 times of PAN particle diameters.
For the concrete form of CNT (CNT) as used herein is not limited.SWCN can be used (SWNT), double-walled carbon nano-tube (DWNT) and multi-walled carbon nano-tubes (MWNT).
According to another embodiment of the method according to the invention, the CNT (CNT) can be open-ended , the CNT (CNT) is in the extra polyacrylonitrile solution comprising conductive carbonaceous additive or dispersion or in conduction Before used in the solution or dispersion of carbonaceous additive, can together with sulphur in a vacuum at 550 to 700 DEG C, preferably about 600 Be calcined at DEG C about 48 hours, such that it is able to make the CNT (CNT) internal voids or hole fill 1 to 30 weight %, It is preferred that the sulphur of 10 to 20 weight %, so as to form sulphur-carbon mano-tube composite (S/CNT), is based on the sulphur-CNT multiple The weight of compound (S/CNT).
2) will be by step 1) obtained in product heat together with sulphur
According to another embodiment of the method according to the invention, in step 2) in can be by by step 1) obtained produce Product heat 0.5 in the protective atmosphere of such as argon gas together with sulphur at a temperature of 280 to 460 DEG C, preferably 390 to 460 DEG C To 6 hours, preferably 0.5 to 4 hour, more preferably 0.5 to 3 hour, so that polyacrylonitrile can take off in the case where there is sulphur Hydrogen and cyclisation are simultaneously bonded with sulphur or polysulfide.
According to another embodiment of the method according to the invention, the total of the sulphur-polyacrylonitrile compound is based on Weight, the sulphur loading capacity of the sulphur-polyacrylonitrile compound can be 20 to 55 weight %, preferably 30 to 50 weight %.
Preparation work electrode
SPAN nano particles can be mixed with carbon black and polyvinylidene fluoride (PVDF), and be coated on Al paper tinsels.Can be with Lithium paper tinsel is used as to electrode, and with barrier film and by LiPF6The carbonic ester electrolyte assembling of salt and ethylene carbonate ester solvent composition.
On the other hand, the present invention relates to include the electrode of sulphur of the invention-polyacrylonitrile compound.
On the other hand, the present invention relates to include the lithium-sulfur cell of electrode of the invention.
Compared with the conventional synthesis process of traditional rough PAN startings, due to the high surface area of PAN of the invention There is provided the big reaction interface with sulphur, it is possible to achieve higher sulfur content.With the SPAN phases for only being synthesized by traditional PAN and sulphur Than there is higher electron conduction according to the SPAN that the present invention is obtained simultaneously.CNTs on the outer surface of PAN is still remained in On the outer surface of SPAN, there is provided conductive coating.Therefore, the SPAN composite electrodes show high positive electrode capacity, low resistance, excellent Different cyclical stability and favourable high rate performance.
The present inventor have studied the chemical process of polyacrylonitrile dehydrogenation in the case where there is sulphur, disclose poly- third The chemical constitution of cyclised backbone derived from alkene nitrile.It was found that obtaining higher polymer backbone graphitization by higher synthesis temperature Degree, it is final to obtain higher C- high rate performances and higher cyclical stability.However, the compound is prepared at relatively high temperatures Shi Fasheng degrades, and causes relatively low sulfur content, ultimately results in relatively low positive electrode capacity.Meanwhile, it is obtained at relatively high temperatures SPAN compounds show larger specific surface area, and this also supports higher C- high rate performances.Although in capacity and high C- multiplying powers Weigh between performance, optimum synthesising temperature can be selected from 390 to 460 DEG C.
The potential application of compound of the invention includes lithium ion battery with high energy density, and it has the stored energy application can The high power density of acceptance, such as electric tool, photovoltaic cell and electric motor car.

Claims (17)

1. sulphur-polyacrylonitrile compound, it is characterised in that the sulphur-polyacrylonitrile compound comprising polyacrylonitrile particle, sulphur and One or more conductive carbonaceous additive, one or more conductive carbon additive embedding and/or the embedded polyacrylonitrile In grain.
2. sulphur according to claim 1-polyacrylonitrile compound, it is characterised in that polyacrylonitrile takes off in the case where there is sulphur Hydrogen and cyclisation are simultaneously bonded with sulphur or polysulfide.
3. according to the sulphur-polyacrylonitrile compound of claim 1 or 2, it is characterised in that the diameter of the polyacrylonitrile particle exists Between 100nm and 10 μm, preferably between 100nm and 2 μm.
4. according to the sulphur-polyacrylonitrile compound of one of claims 1 to 3, it is characterised in that one or more conductive carbon Additive is by a polyacrylonitrile particles bridge to another polyacrylonitrile particle.
5. according to the sulphur-polyacrylonitrile compound of one of Claims 1-4, it is characterised in that one or more conductive carbon Additive is selected from CNT (CNT), carbon nano-particle and graphite.
6. sulphur according to claim 5-polyacrylonitrile compound, it is characterised in that the CNT (CNT) is open-ended , and the internal voids of the CNT (CNT) fill 1 to 30 weight %, the sulphur of preferably 10 to 20 weight %, so as to shape Into sulphur-carbon mano-tube composite (S/CNT), the weight based on the sulphur-carbon mano-tube composite (S/CNT).
7. according to the sulphur-polyacrylonitrile compound of one of claim 1 to 6, it is characterised in that one or more conductive carbon The content of additive is less than or equal to 15 weight %, based on the polyacrylonitrile particle and the gross weight of the conductive carbonaceous additive Amount.
8. according to the sulphur-polyacrylonitrile compound of one of claim 1 to 7, it is characterised in that be based on the sulphur-polypropylene The gross weight of nitrile compound, the sulphur loading capacity of the sulphur-polyacrylonitrile compound is 20 to 55 weight %, preferably 30 to 50 weights Amount %.
9. the method for preparing sulphur-polyacrylonitrile compound, the method comprising the steps of：
1) polyacrylonitrile particle is prepared by polyacrylonitrile solution or dispersion by EFI or spray drying；
2) will be by step 1) obtained in product heat together with sulphur,
Characterized in that, in step 1) in, additionally one or more conductive carbon is added during polyacrylonitrile particle is prepared Plus agent applies to the polyacrylonitrile particle.
10. method according to claim 9, it is characterised in that the polyacrylonitrile solution or dispersion additionally comprising a kind of or Various conductive carbonaceous additives.
11. methods according to claim 9, it is characterised in that while by near the nozzle for the EFI or spray drying Nozzle spray the solution or dispersion of one or more conductive carbonaceous additive.
12. according to the method for one of claim 9 to 11, it is characterised in that described one or more conductive carbonaceous additive is selected from CNT (CNT), carbon nano-particle and graphite.
13. methods according to claim 12, it is characterised in that the CNT (CNT) is open-ended, and described The internal voids of CNT (CNT) fill 1 to 30 weight %, the sulphur of preferably 10 to 20 weight %, so as to form sulphur-carbon nanometer Pipe compound (S/CNT), the weight based on the sulphur-carbon mano-tube composite (S/CNT).
14. according to the method for one of claim 9 to 13, it is characterised in that in step 2) in will be by step 1) obtained in product Heat at a temperature of 280 to 460 DEG C, preferably 390 to 460 DEG C in protective atmosphere together with sulphur 0.5 to 6 hour, preferably 0.5 to 4 hour, more preferably 0.5 to 3 hour.
15. according to the method for one of claim 9 to 14, it is characterised in that be based on the total of the sulphur-polyacrylonitrile compound Weight, the sulphur loading capacity of the sulphur-polyacrylonitrile compound is 20 to 55 weight %, preferably 30 to 50 weight %.
16. electrodes, it is characterised in that the electrode comprising according to the sulphur-polyacrylonitrile compound of one of claim 1 to 8 or By sulphur obtained in the method according to one of claim 9 to 15-polyacrylonitrile compound.
17. lithium-sulfur cells, it is characterised in that the lithium-sulfur cell includes electrode according to claim 16.
CN201580042528.8A 2014-08-07 2015-08-07 Sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite Pending CN106661149A (en)

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PCT/CN2014/083884 WO2016019544A1 (en) 2014-08-07 2014-08-07 Sulfur-polyacrylonitrile composite, preparation and use thereof
CNPCT/CN2014/083884 2014-08-07
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

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CN113745477B (en) * 2021-08-25 2023-08-04 福建师范大学 Preparation method and application of sulfur-doped polyacrylonitrile-chlorella derived carbon composite potassium ion battery anode material
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