CN106575750A - A sulfur-pan composite, a method for preparing said composite, and an electrode and a lithium-sulfur battery comprising said composite - Google Patents

A 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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CN106575750A
CN106575750A CN201580042511.2A CN201580042511A CN106575750A CN 106575750 A CN106575750 A CN 106575750A CN 201580042511 A CN201580042511 A CN 201580042511A CN 106575750 A CN106575750 A CN 106575750A
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sulfur
polyacrylonitrile
complex
cnt
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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  • Polymers & Plastics (AREA)
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Abstract

Provided is a sulfur-polyacrylonitrile composite comprising sulfur as well as polyacrylonitrile fibers. Further provided are a method for preparing the sulfur-polyacrylonitrile composite, and an electrode and a lithium-sulfur battery comprising the sulfur-polyacrylonitrile composite.

Description

Sulfur-PAN complex, the method for preparing the complex and comprising the complex Electrode and lithium-sulfur cell
Technical field
The present invention relates to sulfur-polyacrylonitrile complex, it includes sulfur and polyacrylonitrile fibre.The invention further relates to prepare institute State method, the electrode comprising the sulfur-polyacrylonitrile complex and the lithium-sulfur cell of sulfur-polyacrylonitrile complex.
Background technology
Lithium sulfur (Li-S) battery has attracted considerable concern due to its high-energy-density and low cost.But due to sulfur 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 sulfur is retained in the imagination in positive electrode substrate.A kind of most promising imagination is to be embedded in sulfur In the conducting base of thermolytic polyacrylonitrile (PAN).This attractive sulfur-polyacrylonitrile (SPAN) complex 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- sulfur systems.For this purpose, having People has been engaged in many research work to improve the material capacity of SPAN complex.
The content of the invention
The present invention provides sulfur-polyacrylonitrile (SPAN) complex 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 sulfur-polyacrylonitrile complex, it includes sulfur and polyacrylonitrile fibre.
According to another aspect of the present invention, there is provided the method for preparing sulfur-polyacrylonitrile complex, methods described include with Lower step：
1) polyacrylonitrile fibre is prepared by polyacrylonitrile solution or dispersion by electrospinning；
2) will be by step 1) obtained in product heat together with sulfur.
On the other hand, the present invention relates to include the electrode of sulfur of the invention-polyacrylonitrile complex.
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 show the schematic diagram of PAN fiber；
Fig. 2 show (a) without conductive carbonaceous additive, the CNTs with embedded co-axial orientation or random orientation (b) and the schematic diagram of (c) PAN fiber with embedded white carbon black；
Fig. 3 show the schematic diagram of the electrospinning processes of pure PAN fiber；
Fig. 4 show the PAN that the obtained diameter in embodiment 1 (E1) is for about 300nm, 500nm, 800nm and 1000nm Scanning electron microscope (SEM) photo of fiber；
Fig. 5 show the fibers form that the obtained diameter in embodiment 1 (E1) is for about 300nm, 500nm and 1000nm The SEM photograph of sulfur-polyacrylonitrile complex (SPAN fibre composites)；
Fig. 6 show the sulfur of the SPAN fibre composites by embodiment 1 (E1) and the particle form by comparative example 1 (CE1)- The charge-discharge performance of positive pole obtained in polyacrylonitrile complex (SPAN particle composites)；
Fig. 7 show the schematic diagram of the electrospinning processes of the PAN fiber comprising embedded conductive carbonaceous additive；
It is 1 weight % (a), 2 weight % (b), 4 weight % that Fig. 8 show the obtained CNT contents in embodiment 2 (E2) The SEM photograph of the PAN fiber of (c) and 8 weight % (d)；
Fig. 9 show the SEM photograph in the section of the obtained PAN fiber with embedded CNTs in embodiment 2 (E2)；
Figure 10 show the SEM of the obtained SPAN fibre composites with embedded CNTs in embodiment 2 (E2) and shines Piece；
Figure 11 show the SEM photograph of the obtained short PAN fiber with embedded CNTs in embodiment 2a (E2a)；
Figure 12 show the optical photograph of the obtained short PAN fiber with embedded CNTs in embodiment 2a (E2a)；
It is 1 weight % (a), 2 weight % (b), 4 weights that Figure 13 show the obtained content of carbon black in embodiment 3 (E3) The SEM photograph of the PAN fiber of amount % (c) and 8 weight % (d)；
Figure 14 show the schematic diagram of the PAN of fiber and particle form；
Figure 15 show the SEM photograph of the PAN of obtained fiber and particle form in embodiment 4 (E4)；
Figure 16 a are shown and are synthesized comprising conductive carbonaceous additive by sulfur-loaded first and then the conductive carbonaceous additive of applying The schematic diagram in one path of SPAN complex；
Figure 16 b show and are synthesized by applying conductive carbonaceous additive and then sulfur-loaded first comprising conductive carbonaceous additive The schematic diagram in another path of SPAN complex；
Figure 17 show SPAN fiber of the obtained hollow space in complex comprising white carbon black in embodiment 5 (E5) and answers The SEM photograph of compound；
Figure 18 show it is obtained in embodiment 5 (E5, solid line) and in comparative example 2 (CE2, dotted line) obtained positive pole The 4th charge-discharge performance；And
Figure 19 show the 4th charge-discharge performance of the obtained positive pole in embodiment 6 (E6).
Specific embodiment
If without explanation in addition, by all of publication, patent application, patent and other lists of references 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 sulfur-polyacrylonitrile complex, it includes sulfur and polyacrylonitrile fibre.
Generally receive in correlative technology field or define in scope of the invention, term " fiber " should be managed Solution is have substantially uniform diameter in its whole length and with smooth surface.Substantially uniform diameter and light Sliding surface desirably prevents tangle up and to guarantee stable product quality in dispersion.
It is preferred that polyacrylonitrile fibre of the invention can be prepared by electrospinning.
For the molal weight of polyacrylonitrile as used herein has no particular limits, for example, can be 50 000 to 800 000g/mol, 100 000 to 500 000g/mol (Mn).
According to an embodiment of sulfur of the invention-polyacrylonitrile complex, the sulfur-polyacrylonitrile complex Polyacrylonitrile granule can further be included.The diameter of the polyacrylonitrile granule can preferably exist between 100nm and 10 μm Between 100nm and 2 μm.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, the sulfur-polyacrylonitrile is combined Thing can be formed as follows so that the polyacrylonitrile fibre and/or granule in the case where there is sulfur dehydrogenation and cyclisation simultaneously It is bonded with sulfur or polysulfide.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, the polyacrylonitrile fibre Diameter can be 50nm to 2 μm, preferably 100nm to 1.5 μm, such as about 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm or 1.2 μm.Can by the preferred average distance of fiber to fiber Think fibre diameter 0.1 to 2 times.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, the polyacrylonitrile fibre Draw ratio can be 10 to 1,000,000, preferably 10 to 500, more preferably 10 to 100.In scope of the invention, fiber Draw ratio be defined as the length-to-diameter of fiber.Fig. 1 b show the schematic diagram of the smaller PAN fiber of draw ratio. The draw ratio of PAN fiber is smaller to mean that PAN fiber is shorter.It is preferred that shorter PAN fiber can prevent from being twined in dispersion Together, monodispersed mixture is obtained, the contact with sulfur can be improved during synthesis SPAN.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, the sulfur-polyacrylonitrile is combined Thing can further include one or more conductive carbonaceous additive, as shown in figs. 2 b and 2 c.Be based on the PAN fiber and/or The gross weight of granule and conductive carbonaceous additive, the content of preferably described one or more conductive carbonaceous additive is less than or equal to 15 Weight %, preferably lower than or equal to 10 weight %, more preferably less than or equal to 8 weight %, particularly preferably less than or equal to 5 weights Amount %.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, described one or more conductive Carbonaceous additive can preferably be embedded and is embedded in the polyacrylonitrile fibre and/or granule.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, described one or more conductive Carbonaceous additive can be by a polyacrylonitrile fibre or particles bridge to another polyacrylonitrile fibre or granule, so as to described Electronic conduction network is bridged between polyacrylonitrile fibre and/or granule, shown in such as Figure 16 a (iii) and 16b (iii).Described one kind Or various conductive carbonaceous additives may be located at the hollow space of the sulfur-polyacrylonitrile complex, so that the conductive carbon adds Plus agent is attached on the outer surface of polyacrylonitrile fibre and/or granule.Alternatively or additionally, described one or more it is conductive Carbonaceous additive can preferably be embedded and is embedded in the polyacrylonitrile fibre and/or granule.Specifically, the conductive carbon addition One end of agent can be embedded in a polyacrylonitrile fibre or granule, and the other end of same conductive carbonaceous additive can be embedded in separately In one polyacrylonitrile fibre or granule.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, described one or more conductive Carbonaceous additive can be selected from：CNT (CNT), graphite and carbon nano-particle, such as acetylene black, SuperP white carbon blacks or section's qin (Ketjen) it is black.
The diameter of CNT (CNT) that can be used in sulfur of the invention-polyacrylonitrile complex 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 fiber diameter.
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 sulfur of the invention-polyacrylonitrile complex, 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 sulfur of weight %, so as to form sulfur-carbon mano-tube composite (S/CNT), based on the sulfur-carbon mano-tube composite (S/CNT) Weight.
According to another embodiment of sulfur of the invention-polyacrylonitrile complex, the sulfur-polypropylene is based on The gross weight of nitrile complex, the sulfur loading capacity of the sulfur-polyacrylonitrile complex can be 20 to 55 weight %, preferably 30 to 50 weight %.
On the other hand, the present invention relates to the method for preparing sulfur-polyacrylonitrile complex, the method comprising the steps of：
1) polyacrylonitrile fibre is prepared by polyacrylonitrile solution or dispersion by electrospinning；
2) will be by step 1) obtained in product heat together with sulfur.
1) polyacrylonitrile fibre is prepared
Polyacrylonitrile fibre can be prepared by polyacrylonitrile solution or dispersion by electrospinning, as shown in Figure 3.For poly- third Concentration of the alkene nitrile in the solution or dispersion has no particular limits, for example, 3 to 20 weight %, preferably 5 to 15 weights Amount %, more preferably 6 to 10 weight % can determine according to desired polyacrylonitrile fibre diameter.For for described poly- The solvent of acrylonitrile solution or dispersion has no particular limits, for example DMF.For mole weight of polyacrylonitrile as used herein Amount has no particular limits, for example, can be 50 000 to 800 000g/mol, 100 000 to 500 000g/mol (Mn).
According to an embodiment of the method according to the invention, in step 1) in, it is also possible to by EFI by polypropylene Nitrile solution or dispersion prepare polyacrylonitrile granule.
In the case where the sulfur-polyacrylonitrile complex further includes polyacrylonitrile granule, can be by mixing PAN The polyacrylonitrile of the combining form of fiber and PAN particle preparations fiber and granule.Alternatively it is possible to while by electrospinning and EFI prepares the polyacrylonitrile of the combining form of fiber and granule.Specifically, can simultaneously by for electrospinning PAN fiber Nozzle near nozzle by EFI prepare PAN granules.
According to another embodiment of the method according to the invention, in step 1) in additionally one or more can be led Electrical carbon additive applies to the polyacrylonitrile fibre and/or granule.It is based on the PAN fiber and/or granule and conduction The gross weight of carbonaceous additive, the content of preferably described one or more conductive carbonaceous additive is less than or equal to 15 weight %, preferably Less than or equal to 10 weight %, particularly preferably less than or equal to more preferably less than or equal to 8 weight %, 5 weight %.
Specifically, described one or more conductive carbonaceous additive can be applied in step 1) in formed it is poly- Dralon and/or granule, as shown in fig 16b.Alternatively it is possible to prepare polyacrylonitrile fibre and/or granule During described one or more conductive carbonaceous additive is applied to polyacrylonitrile fibre and/or granule, as shown in Figure 7.
According to another embodiment of the method according to the invention, by electrospinning, spraying, grinding and/or can be coated with Apply described one or more conductive carbonaceous additive.
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, as shown in fig. 7, having conduction such that it is able to prepare by electrospinning and/or EFI simultaneously Carbonaceous additive embedding and the polyacrylonitrile fibre being embedded and/or granule.
According to another embodiment of the method according to the invention, can simultaneously by for the fiber electrospinning And/or the nozzle near the nozzle of the EFI sprays the solution or dispersion of one or more conductive carbonaceous additive, so as to institute Stating one or more conductive carbonaceous additive can be by a polyacrylonitrile fibre or particles bridge to another polyacrylonitrile fibre Or granule, so as to bridge electronic conduction network, such as Figure 16 a (iii) and 16b between the polyacrylonitrile fibre and/or granule (iii) shown in.For for the solution of described one or more conductive carbonaceous additive or the no special limit of the solvent of dispersion System.Described one or more conductive carbonaceous additive may be located at the hollow space of the sulfur-polyacrylonitrile complex, so that institute State conductive carbonaceous additive to be attached on the outer surface of polyacrylonitrile fibre and/or granule.Alternatively or additionally, described one kind Or various conductive carbonaceous additives can preferably be embedded and are embedded in the polyacrylonitrile fibre and/or granule.Specifically, it is described One end of conductive carbonaceous additive can be embedded in a polyacrylonitrile fibre or granule, and the other end of same conductive carbonaceous additive During another polyacrylonitrile fibre or granule can be embedded in.
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 white carbon blacks 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 fiber diameter.
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 sulfur 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 sulfur of 10 to 20 weight %, so as to form sulfur-carbon mano-tube composite (S/CNT), is based on the sulfur-CNT multiple The weight of compound (S/CNT).
According to another embodiment of the method according to the invention, in step 1) after and in step 2) before, for example Can by cryogrinding or by ultrasonic Treatment cut the polyacrylonitrile fibre to draw ratio be 10 to 1,000, 000, preferably 10 to 500, more preferably 10 to 100.Specifically, low temperature can be implemented by ball milling or hand lapping to grind Mill, wherein liquid nitrogen can be used as into dispersant.Fig. 1 b show the schematic diagram of the smaller PAN fiber of draw ratio.PAN fiber Draw ratio is smaller to mean that PAN fiber is shorter.It is preferred that shorter PAN fiber can prevent the tangle up in dispersion, obtain Monodispersed mixture is obtained, the contact with sulfur can be improved during synthesis SPAN.
2) will be by step 1) obtained in product heat together with sulfur
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 together with sulfur 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 sulfur Hydrogen and cyclisation are simultaneously bonded with sulfur or polysulfide.
According to another embodiment of the method according to the invention, in step 2) after, for example by spraying, can grind Mill and/or be coated with extraly applies one or more conductive carbonaceous additive to by step 2) obtained in product, such as Figure 16 a institutes Show.The gross weight of the PAN fiber and/or granule and conductive carbonaceous additive is based on, preferably described one or more conductive The content of carbonaceous 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, described one or more conductive carbonaceous additive can be selected From：CNT (CNT), graphite and carbon nano-particle, such as acetylene black, SuperP white carbon blacks or section's qin (Ketjen) are black.Here Can use in step 1) used in CNT (CNT).
According to another embodiment of the method according to the invention, the total of the sulfur-polyacrylonitrile complex is based on Weight, the sulfur loading capacity of the sulfur-polyacrylonitrile complex can be 20 to 55 weight %, preferably 30 to 50 weight %.
Synthesis path embodiment 1
Figure 16 a are shown and are synthesized comprising conductive carbonaceous additive by sulfur-loaded first and then the conductive carbonaceous additive of applying The schematic diagram in one path of SPAN complex.
Specifically, PAN fiber and sulfur are heated 2 hours at 450 DEG C, to obtain SPAN fibers.By carbon nano-particle (C*) spray to SPAN fibers, to obtain the sulfur-polyacrylonitrile complex (SPAN/C) comprising carbon.Alternatively or additionally, SPAN fibers are ground together with carbon nano-particle (C*), to obtain the sulfur-polyacrylonitrile complex (SPAN/C) comprising carbon.Replace For property ground or extraly, the dispersion or slurry of graphite (C**) are coated to SPAN fibers, be then dried, to obtain carbon is included Sulfur-polyacrylonitrile complex (SPAN/C).
Synthesis path embodiment 2
Figure 16 b show and are synthesized by applying conductive carbonaceous additive and then sulfur-loaded first comprising conductive carbonaceous additive The schematic diagram in another path of SPAN complex.
Specifically, carbon nano-particle (C*) is sprayed to PAN fiber, to obtain the PAN fiber (PAN/C) comprising carbon. Alternatively or additionally, PAN fiber is ground together with carbon nano-particle (C*), to obtain the PAN fiber (PAN/ comprising carbon C).The PAN fiber (PAN/C) comprising carbon is heated 2 hours with sulfur at 450 DEG C, to obtain the sulfur-polyacrylonitrile comprising carbon Complex (SPAN/C).Alternatively or additionally, by the dispersion or slurry of graphite (C**) coat to this comprising carbon sulfur- Polyacrylonitrile complex (SPAN/C), is then dried.
Preparation work electrode
Fabric shape SPAN, it includes SPAN fibers, or the combination comprising SPAN fibers with conductive carbonaceous additive, or Combination of the person comprising SPAN fibers and SPAN granules, can directly in Li-S batteries as working electrode for charging and put Electricity.Individually SPAN nano-particle needs to mix with white carbon black and polyvinylidene fluoride (PVDF), and is coated on Al paper tinsels.Can be by 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 sulfur of the invention-polyacrylonitrile complex.
According to an embodiment of electrode of the invention, the electrode can be by sulfur of the invention-poly- third Alkene nitrile complex is constituted.Because PAN fiber can form fiber membrane, as shown in fig. 16 a and 16b, so according to the present invention by PAN fiber or the sulfur-polyacrylonitrile complex obtained by PAN fiber and granule can be directly used as electrode, especially in institute In the case of sulfur-polyacrylonitrile complex is stated comprising one or more conductive carbonaceous additive.
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 sulfur, it is possible to achieve higher sulfur content.With only by traditional PAN and it is thio into SPAN phases Than there is higher electron conduction according to the SPAN that the present invention is obtained simultaneously.The carbonaceous additive being embedded in the fiber can be with Improve inner conductive, the carbonaceous additive being attached on the outer surface of PAN can provide conductive coating.Therefore, the SPAN is combined Thing electrode shows high positive electrode capacity, low resistance, excellent cyclical stability and favourable high rate performance.
The present inventor have studied the chemical process of polyacrylonitrile dehydrogenation in the case where there is sulfur, 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 complex 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 complex shows 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.
Embodiment 1 (E1)：
1) polyacrylonitrile fibre is prepared
Polyacrylonitrile granule (being purchased from Polysciences, Mn=200 000g/mol, particle diameter is for about 30 μm) is dissolved in In N, N-dimethylformamide (DMF, purchased from Aldrich), be obtained concentration be respectively 6 weight %, 7 weight %, 8 weight % and The PAN solution of 10 weight %.As shown in figure 3, using capillary tube EFI PAN solution (1) of a diameter of 0.5mm, wherein outer power-up It is 200mm to press as the distance between 25kV, sample collection device and spinning head.At room temperature with the speed rate rotation of 50rpm PAN fiber (2) is collected on the cylinder of a diameter of 160mm.It is for about 300nm, 500nm, 800nm and 1000nm to obtain diameter respectively The PAN fiber of (corresponding to the PAN concentration of 6 weight %, 7 weight %, 8 weight % and 10 weight %).
2) will be by step 1) obtained in product heat together with sulfur
It is for about the PAN fiber and sulphur powder (Aldrich, purity of 500nm by diameter>99.995%) with 1:10(mPAN:mS) Mass ratio grinds, and heats 2 hours at 450 DEG C in the tube furnace with Ar atmosphere, so as to obtain SPAN fibre composites.Unit Plain analysis shows, based on the gross weight of the SPAN fibre composites, the sulfur loading capacity of the SPAN fibre composites of gained is 45 Weight %.
Fig. 1 and 2 a show the schematic diagram of PAN fiber.
Structural appraisal：
The size and structure of product are characterized using scanning electron microscope (SEM).
Fig. 4 show the PAN that the obtained diameter in embodiment 1 (E1) is for about 300nm, 500nm, 800nm and 1000nm The SEM photograph of fiber.Fig. 5 show the SPAN that the obtained diameter in embodiment 1 (E1) is for about 300nm, 500nm and 1000nm The SEM photograph of fibre composites.
Battery is assembled and electrochemistry assessment：
Using the chemical property of the so obtained complex of bipolar electrode button cell assessment.By coating active material (diameter is for about the SPAN fibre composites of 500nm), Super P conductive blacks (40nm, Timical) and gathering as binding agent The weight ratio of vinylidene (Solef) is 70:15:15 mixture preparation work electrode.The mixture is being coated on into Al paper tinsels After upper, by the pole drying, Ф 12mm disks are cut into, be finally dried in a vacuum at 80 DEG C 4 hours.In applying argon gas Assembling CR2016 button cells in glove box (MB-10compact, MBraun), wherein using in dimethyl carbonate (DMC), carbon The volume ratio of diethyl phthalate (DEC) and ethylene carbonate ester (EC) is 1:1:1M LiPF in 1 mixed solvent6, use Celgard 2400 as barrier film, and using lithium metal as to electrode.With perseverance at 25 DEG C on Arbin battery test systems Determine electric current density assessments performance.Blanking voltage is when (embedding Li) is discharged relative to Li+/ Li is 0.9V, is charging (de- Li) When relative to Li+/ Li is 3.1V.
Fig. 6 show the charge and discharge of positive pole obtained in the SPAN fibre composites for being for about 500nm by the diameter of embodiment 1 (E1) Electrical property.
Comparative example 1 (CE1)：
By polyacrylonitrile granule (being purchased from Polysciences, Mn=200 000g/mol, particle diameter is for about 30 μm) and sulphur powder (Aldrich, purity>99.995%) with 1:5(mPAN:mS) mass ratio grinding, 450 in the tube furnace with Ar atmosphere Heat 2 hours at DEG C, so as to obtain SPAN particle composites.Elementary analysiss show, based on the total of the SPAN particle composites Weight, the sulfur loading capacity of the SPAN particle composites of gained is 40 weight %.
Battery assembling and electrochemistry assessment are implemented in mode similar to Example 1.Fig. 6 is shown by comparative example 1 (CE1) Particle form sulfur-polyacrylonitrile (SPAN) complex (SPAN particle composites) obtained in positive pole charge-discharge performance.
Embodiment 2 (E2)：
Embodiment 2 is implemented in mode similar to Example 1, and difference is, in step 1) in, additionally will before electrospinning CNT is dispersed in PAN solution as conductive carbonaceous additive (3), so as to obtain the PAN fiber (2) with CNTs, such as Fig. 7 It is shown.
Specifically, by CNT (MWCNTs, Nanometer Port Co., Ltd., Shenzhen, China, a diameter of 20 to 40nm, Length is<2 μm) with 98 weight %H2SO4With 65 weight %HNO3H2SO4:HNO3Volume ratio=1:It is little that 2 mixture processes 12 When.Before electrospinning, based on PAN fiber and the gross weight of CNTs, by 1 weight %, 2 weight %, 4 weight % and 8 weight % The CNTs of Jing process disperses respectively to be that obtained PAN concentration is in the PAN solution (1) of 10 weight %, so as to obtain in embodiment 1 There must be the PAN fiber of CNTs, as shown in Figure 7.
Fig. 2 b show the schematic diagram of the PAN fiber of the CNTs with embedded co-axial orientation or random orientation.
It is 1 weight % (a), 2 weight % (b), 4 weight % that Fig. 8 show the obtained CNT contents in embodiment 2 (E2) The SEM photograph of the PAN fiber of (c) and 8 weight % (d).It is 8 weights that Fig. 9 show the obtained CNT contents in embodiment 2 (E2) The SEM photograph in the section of the PAN fiber of amount %.Figure 10 show in embodiment 2 (E2) it is obtained based on the PAN fiber and The CNT contents of the gross weight of CNTs are the SEM photograph of the SPAN fibre composites of 8 weight %.
Embodiment 2a (E2a)：
The PAN fiber ultrasonic cutting that obtained CNT contents in example 2 are 8 weight % is processed 1 hour (Branson S-450D, 40% amplitude).
Figure 11 show the SEM photograph of the obtained short PAN fiber with embedded CNTs in embodiment 2a (E2a). Figure 12 show the optical photograph of the obtained short PAN fiber with embedded CNTs in embodiment 2a (E2a).
Embodiment 3 (E3)：
Embodiment 3 is implemented in mode similar to Example 1, and difference is, in step 1) in, additionally will before electrospinning White carbon black is dispersed in PAN solution as conductive carbonaceous additive (3), so as to obtain the PAN fiber (2) with white carbon black, such as Fig. 7 institutes Show.
Specifically, before electrospinning, based on PAN fiber and the gross weight of white carbon black, by 1 weight %, 2 weight %, 4 weights Amount % and 8 weight % white carbon black (ECP-600JD, LionCorporation, Japan) respectively dispersion be Obtained PAN concentration is in the PAN solution (1) of 10 weight %, so as to obtain the PAN fiber with white carbon black, such as to scheme in embodiment 1 Shown in 7.
Fig. 2 c show the schematic diagram of the PAN fiber with embedded white carbon black.Figure 13 show the system in embodiment 3 (E3) The content of carbon black for obtaining is the SEM photograph of the PAN fiber of 1 weight % (a), 2 weight % (b), 4 weight % (c) and 8 weight % (d).
Embodiment 4 (E4)：
Embodiment 4 is implemented in mode similar to Example 1, and difference is, in step 2) will make in embodiment 1 before The PAN fiber for obtaining mixes with PAN granules.
Specifically, grain is prepared by the PAN solution that obtained PAN concentration in embodiment 1 is 10 weight % by EFI Footpath is for about 1 μm of polyacrylonitrile granule.In step 2) before, by the PAN granules of gained with it is obtained a diameter of in embodiment 1 The PAN fiber of about 1000nm is with 30:70 weight is than mixing.
Figure 14 show the schematic diagram of the PAN of fiber and particle form.Figure 15 show obtained in embodiment 4 (E4) The SEM photograph of the PAN of fiber and particle form.
Embodiment 5 (E5)：
By ball milling by obtained diameter in embodiment 1 be for about 300nm SPAN fibre composites and white carbon black (ECP-600JD, Lion Corporation, Japan) with 85:15 weight ratio mixing, so as to obtain multiple SPAN fibre composites of the hollow space of compound comprising white carbon black, as illustrated in fig 16 a.Elementary analysiss show, based on gained The gross weight of SPAN fibre composites, sulfur loading capacity is 44 weight %.
Battery assembling and electrochemistry assessment are implemented in mode similar to Example 1, difference is, by the active material of coating Expect (the SPAN fibre composites comprising white carbon black obtained in embodiment 5) and as the Kynoar (Solef) of binding agent Weight ratio be 95:5 mixture preparation work electrode.
Figure 17 show SPAN fiber of the obtained hollow space in complex comprising white carbon black in embodiment 5 (E5) and answers The SEM photograph of compound.Figure 18 show the 4th charge-discharge performance of the obtained positive pole in embodiment 5 (E5, solid line).
Comparative example 2 (CE2)：
Comparative example 2 is implemented in mode similar to Example 5, and difference is, using obtained SPAN in comparative example 1 Grain complex replaces obtained SPAN fibre composites in embodiment 1.
Specifically, by ball milling will in comparative example 1 obtained SPAN particle composites and white carbon black (ECP-600JD, Lion Corporation, Japan) with 80:10 weight ratio mixing, so as to obtain multiple SPAN particle composites of the hollow space of compound comprising white carbon black.Elementary analysiss show, the SPAN particle composites based on gained Gross weight, sulfur loading capacity be 40 weight %.
Battery assembling and electrochemistry assessment are implemented in mode similar to Example 1, difference is, by the active material of coating Expect (the SPAN particle composites comprising white carbon black obtained in comparative example 2) and as the Kynoar (Solef) of binding agent Weight ratio be 90:10 mixture preparation work electrode.
Figure 18 show the 4th charge-discharge performance of the obtained positive pole in comparative example 2 (CE2, dotted line).
Embodiment 6 (E6)：
Embodiment 6 is implemented in mode similar to Example 5, and difference is, during battery assembling and electrochemistry are assessed Binding agent is not used, the obtained SPAN fibre composites comprising white carbon black in embodiment 5 are directly used as into working electrode, and pressed System is on Ni foams.
Figure 19 show the 4th charge-discharge performance of the obtained positive pole in embodiment 6 (E6).
The potential application of complex 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 (30)

1. sulfur-polyacrylonitrile complex, it is characterised in that the sulfur-polyacrylonitrile complex includes sulfur and polyacrylonitrile fibre.
2. sulfur according to claim 1-polyacrylonitrile complex, it is characterised in that polyacrylonitrile takes off in the case where there is sulfur Hydrogen and cyclisation are simultaneously bonded with sulfur or polysulfide.
3. according to the sulfur-polyacrylonitrile complex of claim 1 or 2, it is characterised in that the polyacrylonitrile fibre it is a diameter of 50nm to 2 μm, preferably 100nm to 1.5 μm.
4. according to the sulfur-polyacrylonitrile complex of one of claims 1 to 3, it is characterised in that the length of the polyacrylonitrile fibre Footpath ratio is 10 to 1,000,000, preferably 10 to 500, more preferably 10 to 100.
5. according to the sulfur-polyacrylonitrile complex of one of Claims 1-4, it is characterised in that the sulfur-polyacrylonitrile is combined Thing further includes polyacrylonitrile granule.
6. sulfur according to claim 5-polyacrylonitrile complex, it is characterised in that the diameter of the polyacrylonitrile granule exists Between 100nm and 10 μm, preferably between 100nm and 2 μm.
7. according to the sulfur-polyacrylonitrile complex of one of claim 1 to 6, it is characterised in that the sulfur-polyacrylonitrile is combined Thing is further comprising one or more conductive carbonaceous additive.
8. sulfur according to claim 7-polyacrylonitrile complex, it is characterised in that described one or more conductive carbonaceous additive In embedding and the embedded polyacrylonitrile fibre.
9. according to the sulfur-polyacrylonitrile complex of claim 7 or 8, it is characterised in that one or more conductive carbon addition Agent bridges to another root polypropylene nitrile fiber by a root polypropylene nitrile fiber.
10. according to the sulfur-polyacrylonitrile complex of one of claim 7 to 9, it is characterised in that described one or more conductive Carbonaceous additive is selected from CNT (CNT), carbon nano-particle and graphite.
11. sulfur according to claim 10-polyacrylonitrile complex, it is characterised in that the CNT (CNT) is that end is opened Put, and the internal voids of the CNT (CNT) fill 1 to 30 weight %, the sulfur of preferably 10 to 20 weight %, so as to Form sulfur-carbon mano-tube composite (S/CNT), the weight based on the sulfur-carbon mano-tube composite (S/CNT).
12. according to the sulfur-polyacrylonitrile complex of one of claim 1 to 11, it is characterised in that be based on the sulfur-poly- third The gross weight of alkene nitrile complex, the sulfur loading capacity of the sulfur-polyacrylonitrile complex is 20 to 55 weight %, preferably 30 to 50 Weight %.
13. methods for preparing sulfur-polyacrylonitrile complex, the method comprising the steps of：
1) polyacrylonitrile fibre is prepared by polyacrylonitrile solution or dispersion by electrospinning；
2) will be by step 1) obtained in product heat together with sulfur.
14. methods according to claim 13, it is characterised in that in step 1) in, also by EFI by polyacrylonitrile solution or Dispersion prepares polyacrylonitrile granule.
15. methods according to claim 14, it is characterised in that while by the nozzle near for the nozzle of the electrospinning Polyacrylonitrile granule is prepared by EFI.
16. according to the method for one of claim 13 to 15, it is characterised in that in step 1) in it is extra conductive by one or more Carbonaceous additive applies to the polyacrylonitrile fibre.
17. methods according to claim 16, it is characterised in that apply described a kind of or many by spraying, grinding and/or coating Plant conductive carbonaceous additive.
18. methods according to claim 16, it is characterised in that the polyacrylonitrile solution or dispersion additionally comprising a kind of or Various conductive carbonaceous additives.
19. methods according to claim 16, it is characterised in that while by the nozzle near for the nozzle of the electrospinning The solution or dispersion of one or more conductive carbonaceous additive of injection.
20. according to the method for one of claim 16 to 19, it is characterised in that described one or more conductive carbonaceous additive is selected from CNT (CNT), carbon nano-particle and graphite.
21. methods according to claim 20, 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 sulfur of preferably 10 to 20 weight %, so as to form sulfur-carbon nanometer Pipe complex (S/CNT), the weight based on the sulfur-carbon mano-tube composite (S/CNT).
22. according to the method for one of claim 13 to 21, it is characterised in that in step 1) after and in step 2) before, cut It is 10 to 1,000,000, preferably 10 to 500, more preferably 10 to 100 to cut the polyacrylonitrile fibre to draw ratio.
23. according to the method for one of claim 13 to 22, 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 sulfur 0.5 to 6 hour, preferably 0.5 to 4 hour, more preferably 0.5 to 3 hour.
24. according to the method for one of claim 13 to 23, it is characterised in that in step 2) after, additionally by one or more Conductive carbonaceous additive applies to by step 2) obtained in product.
25. methods according to claim 24, it is characterised in that apply described a kind of or many by spraying, grinding and/or coating Plant conductive carbonaceous additive.
26. according to the method for claim 24 or 25, it is characterised in that described one or more conductive carbonaceous additive is received selected from carbon Mitron (CNT), carbon nano-particle and graphite.
27. according to the method for one of claim 13 to 26, it is characterised in that be based on the sulfur-polyacrylonitrile complex Gross weight, the sulfur loading capacity of the sulfur-polyacrylonitrile complex is 20 to 55 weight %, preferably 30 to 50 weight %.
28. electrodes, it is characterised in that the electrode package containing according to the sulfur-polyacrylonitrile complex of one of claim 1 to 12 or By sulfur obtained in the method according to one of claim 13 to 27-polyacrylonitrile complex.
29. electrodes according to claim 28, it is characterised in that the electrode is made up of the sulfur-polyacrylonitrile complex.
30. lithium-sulfur cells, it is characterised in that the lithium-sulfur cell includes the electrode according to claim 28 or 29.
CN201580042511.2A 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 Pending CN106575750A (en)

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