WO2015101010A1 - 一种醌类化合物-石墨烯复合材料及其制备方法和柔性锂二次电池 - Google Patents

一种醌类化合物-石墨烯复合材料及其制备方法和柔性锂二次电池 Download PDF

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WO2015101010A1
WO2015101010A1 PCT/CN2014/082200 CN2014082200W WO2015101010A1 WO 2015101010 A1 WO2015101010 A1 WO 2015101010A1 CN 2014082200 W CN2014082200 W CN 2014082200W WO 2015101010 A1 WO2015101010 A1 WO 2015101010A1
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Prior art keywords
quinone compound
graphene
composite material
quinone
graphene composite
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PCT/CN2014/082200
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English (en)
French (fr)
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王平华
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华为技术有限公司
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Priority to EP14876837.7A priority Critical patent/EP3079189A4/en
Publication of WO2015101010A1 publication Critical patent/WO2015101010A1/zh
Priority to US15/195,742 priority patent/US20160308213A1/en

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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
    • C07C225/28—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of non-condensed quinone rings
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    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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
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Definitions

  • the present invention relates to the field of energy materials, and in particular to a terpene compound-graphene composite material, a preparation method thereof and a flexible lithium secondary battery. Background technique
  • flexible wearable portable electronic products have become the future development trend, such as electronic paper, windable display, electronic tags and flexible sensors; flexible energy storage devices It is composed of a flexible electrode, an electrolyte and a flexible packaging material, and the development of the flexible electrode is the key to its development.
  • the compound or polymer may also be suitable for preparing electrode materials for flexible energy storage devices.
  • Organic lithium ion batteries usually use compounds or organic polymers as cathode materials for batteries, and organic cathode materials mostly use organic conductive polymers and their composite materials (such as polyaniline, polythiophene, polypyrrole, polypyrene, etc.), organic sulfides. Or polysulfides (such as poly 2,5-dimercapto-thiadiazole, polysulfide block, polythiopolyaniline), oxygen-containing functional compounds (indoles and their polymers, carbonyl compounds represented by anhydrides, etc.) .
  • organic positive electrode material has the advantages of high theoretical capacity (400-900 mAh/g), low synthesis, recyclability, mechanical flexibility, high molecular design, etc., but organic positive electrode materials generally have low electrical conductivity and electrolyte requirements in the reaction system. Large and easily soluble in organic electrolytes, poor material stability, make electricity The cycle performance and power performance of the pool are far lower than the traditional lithium ion battery c
  • the first aspect of the embodiments of the present invention provides a bismuth compound-graphene composite material, which has high energy density, high flexibility, high electrical conductivity and high stability, and solves the organic problem in the prior art.
  • the positive electrode material has poor electrical conductivity and poor stability, and the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • an embodiment of the present invention provides a quinone compound-graphene composite material comprising a quinone compound and graphene, the quinone compound being chemically bonded to the surface of the graphene, and the quinone compound is ruthenium. a compound-like monomer or a terpenoid polymer.
  • the quinone compound-graphene composite material provided by the embodiment of the invention has high energy density, high flexibility, high electrical conductivity, and high stability.
  • terpenoids have higher specific capacity and redox potential; dicarbonyls in terpenoids have electrochemical sites, and an oxygen atom on each carbonyl group generates an electron during discharge, and lithium ions are intercalated to form lithium enolate. Salt; lithium ion extraction during charging, carbonyl reduction, reversible intercalation and deintercalation of lithium ions through conversion between carbonyl and enol structures; better structural stability during electrochemical reaction, and therefore better Cycle stability.
  • Graphene has excellent electrical conductivity and flexibility, and can significantly improve the electrical conductivity and flexibility of the composite material, making the composite material suitable for use as a positive electrode material for preparing flexible electrodes, and having high capacity.
  • the graphene surface comprises a carboxyl functional group
  • the terpenoid compound comprises an amino functional group
  • the quinone compound is bonded by an amide bond formed by the amino functional group and the carboxyl functional group.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or An isomer of any of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the terpenoid polymer is a polymer formed of any one or more of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone, or any one of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the mass of the quinone compound is 20 to 80% by mass of the quinone compound-graphene composite.
  • the bismuth compound-graphene composite material provided by the first aspect of the present invention is composed of a graphene compound with high conductivity and a ruthenium compound, which has high energy density, high flexibility, high conductivity and high stability.
  • the problem that the organic positive electrode material in the prior art has poor electrical conductivity and poor stability is solved, and the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • an embodiment of the present invention provides a method for preparing a quinone compound-graphene composite material, comprising the following steps:
  • the azide compound monomer is aminated by a nitration reduction method to obtain a mixed liquid containing an aminated quinone compound monomer;
  • the mixed solution containing the amidated quinone compound monomer is filtered, washed, and dried to obtain an aminated hydrazine compound monomer powder;
  • the graphene oxide powder is added to a mixed acid of a concentrated ratio of concentrated sulfuric acid and concentrated nitric acid, and reacted at 50 to 60 ° C for 5 to 15 hours, followed by suction filtration, washing and vacuum drying to obtain surface carboxylated graphene. Powder
  • the mixed dispersion is refluxed at 100-120 ° C for 48-72 h under nitrogen protection, and the reaction is completed. After completion, the resultant was subjected to suction filtration, washing, and drying to obtain a terpene compound monomer-graphene composite material.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or an isomer of any one of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the reaction at 50 to 60 ° C for 5 to 15 hours is carried out under stirring and ultrasonic dispersion.
  • the method for preparing the quinone compound-graphene composite further comprises: weighing the quinone compound-graphene composite material, perchloric acid, and the like according to a molar ratio of 1:2:2:2. a saturated aqueous solution of hydrogen peroxide and potassium dichromate are added to an acetonitrile solvent to obtain a mixed solution;
  • the mixed solution containing a ruthenium-based polymer-graphene composite material was subjected to vacuum filtration, washing, and vacuum drying to obtain a ruthenium-based polymer-graphene composite powder.
  • a method for preparing a quinone compound-graphene composite material provided by the second aspect of the present invention has a simple process and is easy to realize industrial production.
  • an embodiment of the present invention provides a method for preparing a quinone compound-graphene composite material, comprising the following steps:
  • the azide compound monomer is aminated by a nitration reduction method to obtain a mixed liquid containing an aminated quinone compound monomer;
  • the mixed solution containing the amidated quinone compound monomer is filtered, washed, and dried to obtain an aminated hydrazine compound monomer powder;
  • amidated hydrazine compound monomer powder is added to an electrolyte solution of a propylene carbonate organic solvent, and the aminated quinone compound monomer is polymerized by a three-electrode system constant potential polymerization method.
  • aminated hydrazine-based polymer To an aminated hydrazine-based polymer;
  • the mixed dispersion is refluxed at 100 to 120 ° C for 48 to 72 hours under the protection of nitrogen. After the reaction is completed, the product is subjected to suction filtration, washing and drying to obtain a terpene polymer-graphene composite material.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or an isomer of any of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the reaction at 50 to 60 ° C for 5 to 15 hours is carried out under stirring and ultrasonic dispersion.
  • a method for preparing a terpene compound-graphene composite material provided by the third aspect of the present invention has a simple process and is easy to realize industrial production.
  • an embodiment of the present invention provides a flexible lithium secondary battery including a flexible battery case and a flexible positive electrode, a flexible negative electrode, a diaphragm, and an electrolysis in the flexible battery case.
  • a separator disposed between the flexible positive electrode and the flexible negative electrode, the flexible positive electrode comprising a positive active material, the positive active material being a terpenoid-graphene composite, the terpenoid-graphite
  • the olefin composite material includes a quinone compound and a graphene, and the quinone compound is chemically bonded to the surface of the graphene, and the quinone compound is a quinone compound or a quinone polymer.
  • the flexible negative electrode comprises a negative active material, which is graphene, carbon nanotube, silicon thin film or tin thin film.
  • a flexible lithium secondary battery provided by the fourth aspect of the present invention has high flexibility, high rate performance, high energy density and high stability, and is suitable for use in future flexible electronic devices.
  • the bismuth compound-graphene composite material provided by the first aspect of the present invention is composed of a graphene compound with high conductivity and a ruthenium compound, which has high energy density, high flexibility, high conductivity and high.
  • the stability solves the problems of poor electrical conductivity and poor stability of the organic positive electrode material in the prior art, and the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • the preparation method of the quinone compound-graphene composite material provided by the second aspect and the third aspect of the present invention has a simple process and is easy to realize industrial production.
  • a flexible lithium secondary battery provided by the fourth aspect of the present invention has high flexibility, high rate performance, high energy density and high stability, and is suitable for use in future flexible electronic devices.
  • FIG. 1 is a flow chart of preparation of a pair of benzoquinone-graphene composite materials according to an embodiment of the present invention
  • FIG. 2 is a flow chart of preparing a polyaminated ruthenium-graphene composite material according to an embodiment of the present invention
  • FIG. 3 is a flow chart of preparing a polyaminated ruthenium-graphene composite material according to an embodiment of the present invention
  • Inventive Example of the structure of a flexible lithium secondary battery Inventive Example of the structure of a flexible lithium secondary battery. detailed description
  • the embodiments of the present invention are further described below in various embodiments.
  • the embodiment of the invention is not limited Specific examples are set forth below. Changes can be implemented as appropriate within the scope of the invariable primary rights.
  • the first aspect of the present invention provides a bismuth compound-graphene composite material, which has high energy density, high flexibility, high electrical conductivity and high stability, and solves the poor electrical conductivity of the organic positive electrode material in the prior art.
  • the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • an embodiment of the present invention provides a quinone compound-graphene composite material comprising a quinone compound and graphene, the quinone compound being chemically bonded to the surface of the graphene, and the quinone compound is ruthenium. a compound-like monomer or a terpenoid polymer.
  • the quinone compound-graphene composite material provided by the embodiment of the invention has high energy density, high flexibility, high electrical conductivity, and high stability.
  • terpenoids have higher specific capacity and redox potential; dicarbonyls in terpenoids have electrochemical sites, and an oxygen atom on each carbonyl group generates an electron during discharge, and lithium ions are intercalated to form lithium enolate. Salt; lithium ion extraction during charging, carbonyl reduction, reversible intercalation and deintercalation of lithium ions through conversion between carbonyl and enol structures; better structural stability during electrochemical reaction, and therefore better Cycle stability.
  • Graphene has excellent electrical conductivity and flexibility, and can significantly improve the electrical conductivity and flexibility of the composite material, making the composite material suitable for use as a positive electrode material for preparing flexible electrodes, and having high capacity.
  • the graphene surface comprises a carboxyl functional group
  • the terpenoid compound comprises an amino functional group
  • the quinone compound is bonded by an amide bond formed by the amino functional group and the carboxyl functional group.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or an isomer of any of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the terpenoid polymer is any one or more of benzoquinone, naphthoquinone, anthracene and phenanthrenequinone A polymer formed, or an isomer of any one of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone or a plurality of isomers.
  • the mass of the quinone compound is 20 to 80% by mass of the quinone compound-graphene composite.
  • the graphene in the quinone compound-graphene composite material of the present invention is graphene oxide.
  • the bismuth compound-graphene composite material provided by the first aspect of the present invention is composed of a graphene compound with high conductivity and a ruthenium compound, which has high energy density, high flexibility, high conductivity and high stability.
  • the problem that the organic positive electrode material in the prior art has poor electrical conductivity and poor stability is solved, and the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • an embodiment of the present invention provides a method for preparing a quinone compound-graphene composite material, comprising the following steps:
  • the azide compound monomer is aminated by a nitration reduction method to obtain a mixed liquid containing an aminated quinone compound monomer;
  • the mixed solution containing the amidated quinone compound monomer is filtered, washed, and dried to obtain an aminated hydrazine compound monomer powder;
  • the graphene oxide powder is added to a mixed acid of a concentrated ratio of concentrated sulfuric acid and concentrated nitric acid, and reacted at 50 to 60 ° C for 5 to 15 hours, followed by suction filtration, washing and vacuum drying to obtain surface carboxylated graphene. Powder
  • the mixed dispersion is refluxed at 100-120 ° C for 48-72 h under nitrogen protection.
  • the product is subjected to suction filtration, washing and drying to obtain a quinone compound-graphene composite material.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or an isomer of any one of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the specific operation of aminating the quinone compound monomer by the nitration reduction method is: nitrating the quinone compound monomer with a mixed acid of concentrated sulfuric acid and concentrated nitric acid to obtain a nitridium quinone monomer, and then using the sulphide Sodium is reduced.
  • the mixed acid of concentrated sulfuric acid and concentrated nitric acid is preferably
  • the reaction at 50 to 60 ° C for 5 to 15 hours is carried out under stirring and ultrasonic dispersion.
  • the method for preparing the quinone compound-graphene composite further comprises: weighing the quinone compound-graphene composite material, perchloric acid, and the like according to a molar ratio of 1:2:2:2. a saturated aqueous solution of hydrogen peroxide and potassium dichromate are added to an acetonitrile solvent to obtain a mixed solution;
  • the mixed solution containing a ruthenium-based polymer-graphene composite material was subjected to vacuum filtration, washing, and vacuum drying to obtain a ruthenium-based polymer-graphene composite powder.
  • the above is a process in which a monomer of a quinone compound is polymerized, and the polymerization occurs in a quinone-based compound in which a hydrogen group which is bonded to a benzene ring and an amino group which is aligned with an amino group are formed in a head-to-tail manner.
  • a method for preparing a quinone compound-graphene composite material provided by the second aspect of the present invention has a simple process and is easy to realize industrial production.
  • an embodiment of the present invention provides a method for preparing a quinone compound-graphene composite material, comprising the following steps: _
  • the azide compound monomer is aminated by a nitration reduction method to obtain a mixed liquid containing an aminated quinone compound monomer;
  • the mixed solution containing the amidated quinone compound monomer is filtered, washed, and dried to obtain an aminated hydrazine compound monomer powder;
  • aminated quinone compound monomer powder is added to an electrolytic solution of a propylene carbonate organic solvent, and the aminated quinone compound monomer is polymerized by a three-electrode system constant potential polymerization method to obtain an aminated hydrazine.
  • the mixed dispersion is refluxed at 100 to 120 ° C for 48 to 72 hours under the protection of nitrogen. After the reaction is completed, the product is subjected to suction filtration, washing and drying to obtain a terpene polymer-graphene composite material.
  • the quinone compound monomer is any one of benzoquinone, naphthoquinone, anthracene, phenanthrenequinone, or an isomer of any of benzoquinone, naphthoquinone, anthracene, and phenanthrenequinone.
  • the reaction at 50 to 60 ° C for 5 to 15 hours is carried out under stirring and ultrasonic dispersion.
  • the specific operation of aminating the quinone compound monomer by the nitration reduction method is: nitrating the quinone compound monomer with a mixed acid of concentrated sulfuric acid and concentrated nitric acid to obtain a nitridium quinone monomer, and then using the sulphide Sodium is reduced.
  • the mixed acid of concentrated sulfuric acid and concentrated nitric acid is preferably
  • a method for preparing a terpene compound-graphene composite material provided by the third aspect of the present invention has a simple process and is easy to realize industrial production.
  • an embodiment of the present invention provides a flexible lithium secondary battery including a flexible battery case and a flexible positive electrode, a flexible negative electrode, a diaphragm, and an electrolysis in the flexible battery case.
  • a separator disposed between the flexible positive electrode and the flexible negative electrode, the flexible positive electrode comprising a positive active material, the positive active material being a terpenoid-graphene composite, the terpenoid-graphite
  • the olefin composite material includes a quinone compound and a graphene, and the quinone compound is chemically bonded to the surface of the graphene, and the quinone compound is a quinone compound or a quinone polymer.
  • the flexible negative electrode comprises a negative active material, which is graphene, carbon nanotube, silicon thin film or tin thin film.
  • the flexible positive electrode comprises a positive current collector
  • the flexible negative electrode comprises a negative current collector
  • the cathode current collector is a metal foil current collector or a graphene film.
  • the anode current collector is a metal foil current collector or a graphene film.
  • the metal foil current collector includes a copper foil, an aluminum foil, or the like.
  • the flexible positive electrode and the flexible negative electrode include a binder and a conductive agent, and as long as the binder can bond the active material and the conductive agent particles together, a known binder substance such as poly can be used.
  • a binder substance such as poly can be used.
  • Vinylidene fluoride PVDF X polytetrafluoroethylene (PTFE X carboxymethyl cellulose sodium (CMC X styrene butadiene rubber (SBR), etc.
  • the conductive agent is a substance that can improve the surface conductivity of the active material. _
  • a known conductive agent such as conductive graphite, carbon black, carbon fiber, carbon nanotube, graphene, metal fine powder or the like can be used.
  • the selection of the electrolytic solution is not particularly limited, and any conventionally known electrolytic solution may be used.
  • the separator is a polyolefin separator, a polyvinyl alcohol separator, a polyvinyl chloride separator, a polytetrafluoroethylene separator, a polystyrene separator, a polyvinylphenol separator, a polymethyl methacrylate separator, a polyimide separator. Or polyethylene terephthalate separator.
  • the flexible battery casing is made of an aluminum-plastic composite film.
  • the flexible positive electrode is made of a terpenoid-graphene composite material. That is, the quinone compound-graphene composite serves as a flexible positive electrode, and constitutes a flexible lithium secondary battery with a flexible negative electrode, a separator, an electrolyte, and a flexible battery case.
  • a flexible lithium secondary battery provided by the fourth aspect of the present invention has high flexibility, high rate performance, high energy density and high stability, and is suitable for use in future flexible electronic devices.
  • the bismuth compound-graphene composite material provided by the first aspect of the present invention is composed of a graphene compound with high conductivity and a ruthenium compound, which has high energy density, high flexibility, high conductivity and high.
  • the stability solves the problems of poor electrical conductivity and poor stability of the organic positive electrode material in the prior art, and the composite material can be used as a positive electrode material for preparing a flexible electrode.
  • the preparation method of the quinone compound-graphene composite material provided by the second aspect and the third aspect of the present invention has a simple process and is easy to realize industrial production.
  • a flexible lithium secondary battery provided by the fourth aspect of the present invention has high flexibility, high rate performance, high energy density and high stability, and is suitable for use in future flexible electronic devices.
  • a method for preparing a quinone compound-graphene composite material comprising the following steps:
  • Step S11 amination of phenylhydrazine: using a nitration reduction method to treat p-benzoquinone with concentrated sulfuric acid and concentrated nitric acid
  • the mixed acid is nitrated to obtain dinitrobenzene p-benzoquinone, and then sodium sulfide is added for reduction to obtain a mixed solution containing aminated p-benzoquinone, and the mixture is filtered, washed and dried to obtain an aminated p-benzoquinone powder; amination
  • the reaction formula is as shown in (1):
  • Step S12 graphene carboxylation: adding a mixed acid of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 to the graphene oxide powder, reacting at 60 ° C for 12 hours under stirring and ultrasonic dispersion, and filtering through a filter membrane, After washing with distilled water and vacuum drying, a carboxylated graphene powder having a large amount of carboxyl groups attached to the surface is obtained; the chemical structural formula of the carboxylated graphene is as shown in the formula (2):
  • Step S13 amidation and compounding: adding the excess aminated p-benzoquinone powder obtained in the above step S11 and the carboxylated graphene powder obtained in the above step S12 to water, and ultrasonicating for 2 hours to obtain a mixed dispersion, The mixed dispersion was refluxed at 120 ° C for 72 h under the protection of nitrogen N 2 to cause amidation reaction (as shown in formula (3)).
  • FIG. 1 is a flow chart showing the preparation of a benzoquinone-graphene composite material of the present embodiment.
  • a method for preparing a quinone compound-graphene composite material comprising the following steps:
  • Step S21 1,5-hydrazine amination: 1,5-fluorene is nitrated with mixed acid of concentrated sulfuric acid and concentrated nitric acid to obtain 1,5-dinitroguanidine by sodium nitrate reduction method, and then sodium sulfide is added for reduction. A mixed solution containing 1,5-diaminoanthracene is obtained, and the mixed solution is filtered, washed, and dried to obtain a 1,5-diaminoanthracene powder; the amination reaction formula is as shown in the formula (4) Shown as follows: (4);
  • Step S22 graphene carboxylation: adding a mixed acid of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 to the graphene oxide powder, reacting at 50 ° C for 12 h under stirring and ultrasonic dispersion, and filtering through a filter membrane, After washing with distilled water and vacuum drying, a carboxylated graphene powder having a large amount of carboxyl groups attached to the surface is obtained;
  • Step S23 amidation recombination: adding the excess 1,5-diaminophosphonium powder obtained in the above step S21 and the carboxylated graphene powder in the above step S22 to water, and ultrasonicating for 2 hours to obtain a mixed dispersion. And the mixed dispersion is refluxed at 120 ° C for 72 h under the protection of nitrogen N 2 to cause an amidation reaction (as shown in formula (5)).
  • the product is filtered through a filter, washed, and dried under vacuum at 60 ° C to obtain a graphene composite material having a surface-bonded p-amino group, ie, a ruthenium-graphene composite material;
  • S24 amino polymerization: a quantitative amount of ruthenium-graphene, perchloric acid (lmol/L) and hydrogen peroxide (saturated aqueous solution) and potassium dichromate are added to a molar ratio of 1:2:2:2.
  • Fig. 2 is a flow chart showing the preparation of the polyaminated ruthenium-graphene composite material of the present embodiment.
  • a method for preparing a quinone compound-graphene composite material comprising the following steps:
  • Step S31 1,5-hydrazine amination: 1,5-fluorene is nitrated in concentrated sulfuric acid with mixed acid to obtain 1,5-dinitroguanidine by sodium nitrate reduction, and sodium sulfide is added to obtain 1 a mixed solution of 5-diaminoguanidine, the mixture is filtered, washed, and dried to obtain a 1,5-diaminoguanidine powder;
  • Step S32 amino polymerization: adding 1,5-diaminoguanidine powder to an electrolyte solution of a propylene carbonate organic solvent, using a three-electrode system of potentiostatic polymerization, the polymerization mainly occurs in the monomer
  • the hydrogen of the amino group and the amino group attached to the benzene ring which is mainly formed by head-to-tail connection, forms a poly(1,5-diamino) macromolecular chain, ie, poly(1,5-diaminoguanidine); amino polymerization
  • Step S33 graphene carboxylation: adding a mixed acid of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1 to the graphene oxide powder, reacting at 60 ° C for 12 h under stirring and ultrasonic dispersion, and filtering through a filter membrane, After washing with distilled water and vacuum drying, a carboxylated graphene powder having a large amount of carboxyl groups attached to the surface is obtained;
  • Step S34 amidation and recombination: adding the excess poly(1,5-diaminophosphonium) powder obtained in the above step S31 and the carboxylated graphene powder in the above step S33 to water, and ultrasonically mixing for 2 hours to obtain a mixed dispersion. a liquid, the mixed dispersion was refluxed at 120 ° C for 72 h under a nitrogen N 2 protection, and an amidation reaction occurred (as shown in formula (8)).
  • FIG. 3 is a flow chart showing the preparation of the polyaminated ruthenium-graphene composite material of the present embodiment.
  • the flexible lithium secondary battery (400) includes a flexible battery case (404) and a flexible positive electrode (401) located in the flexible battery case (404), a flexible negative electrode (402) (403), and an electrolyte impregnated in the flexible battery case (404), the separator (403) being disposed between the flexible positive electrode (401) and the flexible negative electrode (402).
  • the flexible positive electrode (401) The p-benzoquinone-graphene composite material obtained in the above first embodiment was used as the positive electrode active material, and the flexible negative electrode (402) was made of graphene as the negative electrode active material.
  • the positive electrode active material is mixed with a benzoquinone-graphene composite material and a binder of polyvinylidene fluoride and a conductive carbon nanotube, and a certain amount of an organic solvent, nitromethylpyrrolidone, is added to prepare a positive electrode slurry.
  • the obtained positive electrode slurry is uniformly coated on the aluminum foil current collector, and after baking and tableting, a positive electrode pole piece is obtained;
  • the negative active material graphene is mixed with a binder polyvinylidene fluoride and a conductive carbon nanotube, and a certain amount of an organic solvent, nitromethylpyrrolidone, is added to prepare a negative electrode slurry, and the obtained negative electrode slurry is obtained.
  • the material is evenly coated on the copper foil current collector, and after baking and tableting, the negative electrode pole piece is obtained; the positive electrode piece, the PP/PE/PP polyolefin separator and the negative electrode piece obtained above are sequentially stacked and assembled, and electrolysis is added.
  • a flexible lithium secondary battery having a quinone compound-graphene composite material as a positive electrode active material can be obtained.
  • a flexible lithium secondary battery using the polyaminated ruthenium-graphene composite material obtained in the above Example 2 as a positive electrode active material was assembled into a flexible lithium secondary battery in the same manner as in Example 4.
  • Embodiment 6 A flexible lithium secondary battery using the polyaminated ruthenium-graphene composite material obtained in the above Example 3 as a positive electrode active material was assembled into a flexible lithium secondary battery in the same manner as in Example 4.
  • a flexible lithium secondary battery which was assembled into a flexible lithium secondary battery in the same manner as in Example 4, using p-benzoquinone as a positive electrode active material.
  • a flexible lithium secondary battery which was assembled into a flexible lithium secondary battery in the same manner as in Example 4, using polyaminated ruthenium as a positive electrode active material.
  • effects are provided, for example, to evaluate the performance of the products provided by the embodiments of the present invention.
  • the flexible lithium secondary batteries obtained in Examples 4 to 6 and Comparative Examples _ ⁇ were subjected to a charge and discharge cycle and a rate performance test using a battery performance tester.
  • the cycle test voltage range is 1.5 ⁇ 3.6V, the current is 0.2C, the battery capacity after 50 cycles is recorded and the capacity retention rate is calculated; the test voltage range is 1.5 ⁇ 3.6V, the current is 5.0C, and the discharge capacity is recorded. And calculate the rate discharge ratio.
  • the flexible lithium secondary battery was repeatedly bent 10 times in a lateral direction and a longitudinal direction at a bending angle of not more than 10 degrees, and then subjected to a charge and discharge cycle and a magnification test, and the test conditions were the same as above.
  • the test results are shown in Table 1:
  • the results of Table 1 illustrate that the flexible lithium secondary battery provided by the embodiment of the present invention has good rate performance and cycle performance, and can maintain good rate performance and cycle performance after bending. This is because the flexible lithium secondary battery provided by the embodiment of the present invention uses a bismuth compound-graphene composite material as a positive electrode active material, and the composite material is compounded with a high conductivity conductive graphene and a ruthenium compound, and has high energy density. High flexibility, high electrical conductivity and high stability make it suitable for flexible battery preparation.

Abstract

一种醌类化合物-石墨烯复合材料，包括醌类化合物和石墨烯，所述醌类化合物键合在所述石墨烯表面，所述醌类化合物为醌类化合物单体或醌类聚合物。该醌类化合物-石墨烯复合材料具有高能力密度、高柔性、高导电性和高稳定，可作为制备柔性电极的正极材料。还提供该复合材料的制备方法，以及采用该材料作为正极活性材料的柔性锂二次电池。

Description

一种醌类化合物-石墨烯复合材料及其制备方法和柔性锂二次电池 本申请要求于 2013 年 12 月 31 日提交中国专利局的申请号为 201310752362.1 ,其发明名称为 "一种醌类化合物-石墨烯复合材料及其制备方 法和柔性锂二次电池 "的中国专利申请的优先权，其全部内容通过引用结合在 本申请中。 技术领域
本发明涉及能源材料领域，特别是涉及一种醌类化合物-石墨烯复合材料 及其制备方法和柔性锂二次电池。 背景技术
为了满足人们对电子产品小型化日益增长的需求，柔性的可穿戴的便携电 子产品成为了未来的发展趋势，比如电子纸、 可卷绕的显示屏、 电子标签和柔 性传感器等；柔性储能器件是由柔性电极、 电解液和柔性封装材料等组成，其 中柔性电极的开发是其研制的关键。
化合物或聚合物也可适于制备柔性储能器件的电极材料。有机锂离子电池 通常采用化合物或有机聚合物作为电池的正极材料，有机正极材料多采用有机 导电聚合物及其复合材料（如聚苯胺、 聚噻吩、 聚吡咯、 聚乙块等）、 有机硫 化物或多硫化物（如聚 2,5-二巯基-噻二唑、 多硫化碳块、 多硫代聚苯胺）、 含氧官能团化合物（醌类及其聚合物、 酸酐为代表的羰基化合物等）。
上述有机正极材料具有理论容量高 (400-900mAh/g)、 合成廉价、 可循环利 用、机械柔性、分子高度可设计等优点，但是有机正极材料普遍存在电导性低、 反应体系中电解液要求量大且易溶于有机电解液中 ，材料稳定性性能差，使电 池的循环性能和功率性能都远远低于传统锂离子电池 c 发明内容
有鉴于此，本发明实施例第一方面提供了一种醌类化合物-石墨烯复合材 料，该复合材料具有高能量密度、 高柔性、 高导电性和高稳定性，解决了现有 技术中有机正极材料电导性差、稳定性不佳等问题，该复合材料可作为制备柔 性电极的正极材料。
第一方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料，包括 醌类化合物和石墨烯，所述醌类化合物化学键合在所述石墨烯表面，所述醌类 化合物为醌类化合物单体或醌类聚合物。
本发明实施例提供的醌类化合物-石墨烯复合材料，具有高能量密度、 高 柔性、 高导电性、 以及高稳定性。 其中 ，醌类化合物具有较高的比容量和氧化 还原电位；醌类化合物中的双羰基具有电化学活性点，放电时每个羰基上的氧 原子得一个电子，同时嵌入锂离子生成烯醇锂盐；充电时锂离子脱出 ，羰基还 原，通过羰基和烯醇结构之间的转换实现锂离子可逆地嵌入和脱嵌；在电化学 反应过程中具有较好的结构稳定性，因此具有较好的循环稳定性。石墨烯具有 优良的导电性和柔性，能可显著提高复合材料的导电性能和柔性，使复合材料 适用于作为制备柔性电极的正极材料， 同时具有高容量。
优选地，所述石墨烯表面包含羧基功能基团 ，所述醌类化合物包含氨基功 能基团 ，所述醌类化合物通过所述氨基功能基团和所述羧基功能基团形成的酰 胺键键合在所述石墨烯表面。
优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述醌类聚合物为苯醌、 萘醌、 蒽醌以及菲醌中的任一种或多种 形成的聚合物，或者苯醌、 萘醌、蒽醌以及菲醌中任一种的异构体或多种的异 构体形成的聚合物。
优选地，所述醌类化合物的质量占所述醌类化合物-石墨烯复合材料质量 的 20~80%。
本发明实施例第一方面提供的醌类化合物-石墨烯复合材料，采用高导电 性能的石墨烯与醌类化合物复合，该复合材料具有高能量密度、 高柔性、 高导 电性和高稳定性，解决了现有技术中有机正极材料电导性差、稳定性不佳等问 题，该复合材料可作为制备柔性电极的正极材料。
第二方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料的制备 方法，包括以下步骤：
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液；
将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于 50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类化合物单体粉体和所述表面羧基化石墨烯粉体加入到 水或乙醇中 ，进行超声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类化合物单体 -石墨烯复合材料。 优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。 优选地，所述醌类化合物 -石墨烯复合材料的制备方法进一步包括如下步 按照摩尔比 1:2:2:2称取所述醌类化合物单体 -石墨烯复合材料、 高氯酸、 过氧化氢饱和水溶液和重铬酸钾加入到乙腈溶剂中 ，得到混合溶液；
向所述混合溶液中滴加重铬酸钾的饱和水溶液， 在氩气保护下 ， 于 30~50°C下反应 48~72h ,得到含有醌类聚合物-石墨烯复合材料的混合液； 将所述含有醌类聚合物-石墨烯复合材料的混合液进行减压抽滤、 洗涤， 真空干燥，得到醌类聚合物-石墨烯复合材料粉体。
本发明实施例第二方面提供的一种醌类化合物 -石墨烯复合材料的制备方 法，工艺简单，易于实现产业化生产。
第三方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料的制备 方法，包括以下步骤：
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液；
将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将所述氨基化醌类化合物单体粉体加入到丙烯碳酸酯有机溶剂的电解液 中 ，采用三电极体系的恒电位聚合法，使所述氨基化醌类化合物单体聚合，得 到氨基化醌类聚合物；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于
50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类聚合物和羧基化石墨烯粉体加入到水或乙醇中 ，进行超 声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类聚合物 -石墨烯复合材料。
优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。 本发明实施例第三方面提供的一种醌类化合物 -石墨烯复合材料的制备方 法，工艺简单，易于实现产业化生产。
第四方面，本发明实施例提供了一种柔性锂二次电池，包括柔性电池外壳 和位于所述柔性电池外壳内的柔性正极、 柔性负极、 隔膜，以及灌注于所述柔 性电池外壳内的电解液，所述隔膜设置于所述柔性正极和所述柔性负极之间 ， 所述柔性正极包括正极活性材料，所述正极活性材料为醌类化合物-石墨烯复 合材料，所述醌类化合物-石墨烯复合材料包括醌类化合物和石墨烯，所述醌 类化合物化学键合在所述石墨烯表面，所述醌类化合物为醌类化合物单体或醌 类聚合物。
优选地，所述柔性负极包括负极活性材料，所述负极活性材料为石墨烯、 碳纳米管、 硅薄膜或锡薄膜。 本发明实施例第四方面提供的一种柔性锂二次电池，具有高柔性、 高倍率 性能、 高能量密度和高稳定性，适合用于未来的柔性电子器件。
综上，本发明实施例第一方面提供的醌类化合物-石墨烯复合材料，采用 高导电性能的石墨烯与醌类化合物复合，该复合材料具有高能量密度、高柔性、 高导电性和高稳定性，解决了现有技术中有机正极材料电导性差、稳定性不佳 等问题，该复合材料可作为制备柔性电极的正极材料。本发明实施例第二方面、 第三方面提供的醌类化合物-石墨烯复合材料的制备方法，工艺简单，易于实 现产业化生产。本发明实施例第四方面提供的一种柔性锂二次电池，具有高柔 性、 高倍率性能、 高能量密度和高稳定性，适合用于未来的柔性电子器件。
本发明实施例的优点将会在下面的说明书中部分阐明 ，一部分根据说明书 是显而易见的，或者可以通过本发明实施例的实施而获知。 附图说明
图 1为本发明实施例一对苯醌-石墨烯复合材料的制备流程图 ；
图 2为本发明实施例二聚氨基化蒽醌-石墨烯复合材料的制备流程图 ； 图 3为本发明实施例三聚氨基化蒽醌-石墨烯复合材料的制备流程图 ； 图 4为本发明实施例柔性锂二次电池的结构示意图。 具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出 ，对于本技术领域的 普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改 进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限 定于以下的具体实施例。 在不变主权利的范围内 ，可以适当的进行变更实施。 本发明实施例第一方面提供了一种醌类化合物-石墨烯复合材料，该复合 材料具有高能量密度、 高柔性、 高导电性和高稳定性，解决了现有技术中有机 正极材料电导性差、稳定性不佳等问题，该复合材料可作为制备柔性电极的正 极材料。
第一方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料，包括 醌类化合物和石墨烯，所述醌类化合物化学键合在所述石墨烯表面，所述醌类 化合物为醌类化合物单体或醌类聚合物。
本发明实施例提供的醌类化合物-石墨烯复合材料，具有高能量密度、 高 柔性、 高导电性、 以及高稳定性。 其中 ，醌类化合物具有较高的比容量和氧化 还原电位；醌类化合物中的双羰基具有电化学活性点，放电时每个羰基上的氧 原子得一个电子，同时嵌入锂离子生成烯醇锂盐；充电时锂离子脱出 ，羰基还 原，通过羰基和烯醇结构之间的转换实现锂离子可逆地嵌入和脱嵌；在电化学 反应过程中具有较好的结构稳定性，因此具有较好的循环稳定性。石墨烯具有 优良的导电性和柔性，能可显著提高复合材料的导电性能和柔性，使复合材料 适用于作为制备柔性电极的正极材料， 同时具有高容量。
优选地，所述石墨烯表面包含羧基功能基团 ，所述醌类化合物包含氨基功 能基团 ，所述醌类化合物通过所述氨基功能基团和所述羧基功能基团形成的酰 胺键键合在所述石墨烯表面。
优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述醌类聚合物为苯醌、 萘醌、 蒽醌以及菲醌中的任一种或多种 形成的聚合物，或者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体或多种的异 构体形成的聚合物。
优选地，所述醌类化合物的质量占所述醌类化合物-石墨烯复合材料质量 的 20~80%。
本发明实施例醌类化合物-石墨烯复合材料中的石墨烯为氧化石墨烯。 本发明实施例第一方面提供的醌类化合物-石墨烯复合材料，采用高导电 性能的石墨烯与醌类化合物复合，该复合材料具有高能量密度、 高柔性、 高导 电性和高稳定性，解决了现有技术中有机正极材料电导性差、稳定性不佳等问 题，该复合材料可作为制备柔性电极的正极材料。
第二方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料的制备 方法，包括以下步骤：
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液；
将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于 50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类化合物单体粉体和所述表面羧基化石墨烯粉体加入到 水或乙醇中 ，进行超声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类化合物单体 -石墨烯复合材料。 优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述采用硝化还原法将醌类化合物单体氨基化的具体操作为 ：将 醌类化合物单体用浓硫酸和浓硝酸的混酸硝化得到硝基化醌类化合物单体，再 采用硫化钠进行还原。
本发明实施例中浓硫酸和浓硝酸的混酸，浓硫酸和浓硝酸的体积比优选为
3:1。
优选地，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。 优选地，所述醌类化合物 -石墨烯复合材料的制备方法进一步包括如下步 按照摩尔比 1:2:2:2称取所述醌类化合物单体 -石墨烯复合材料、 高氯酸、 过氧化氢饱和水溶液和重铬酸钾加入到乙腈溶剂中 ，得到混合溶液；
向所述混合溶液中滴加重铬酸钾的饱和水溶液， 在氩气保护下 ， 于 30~50°C下反应 48~72h ,得到含有醌类聚合物-石墨烯复合材料的混合液； 将所述含有醌类聚合物-石墨烯复合材料的混合液进行减压抽滤、 洗涤， 真空干燥，得到醌类聚合物-石墨烯复合材料粉体。
上述为醌类化合物单体发生聚合反应的过程，其聚合反应发生在醌类化合 物单体中与苯环相连的氨基和氨基对位的氢以头尾连接方式形成醌类聚合物。
本发明实施例第二方面提供的一种醌类化合物 -石墨烯复合材料的制备方 法，工艺简单，易于实现产业化生产。
第三方面，本发明实施例提供了一种醌类化合物-石墨烯复合材料的制备 方法，包括以下步骤： _
10
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液；
将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将所述氨基化醌类化合物单体粉体加入到丙烯碳酸酯有机溶剂的电解液 中 ，采用三电极体系的恒电位聚合法，使所述氨基化醌类化合物单体聚合，得 到氨基化醌类聚合物；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于
50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类聚合物和羧基化石墨烯粉体加入到水或乙醇中 ，进行超 声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类聚合物 -石墨烯复合材料。
优选地，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或 者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
优选地，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。 优选地，所述采用硝化还原法将醌类化合物单体氨基化的具体操作为 ：将 醌类化合物单体用浓硫酸和浓硝酸的混酸硝化得到硝基化醌类化合物单体，再 采用硫化钠进行还原。
本发明实施例中浓硫酸和浓硝酸的混酸，浓硫酸和浓硝酸的体积比优选为
3:1。 上述氨基化醌类化合物单体聚合得到氨基化醌类聚合物的过程中 ，聚合反 应发生在醌类化合物单体中与苯环相连的氨基和氨基对位的氢以头尾连接方 式形成醌类聚合物。
本发明实施例第三方面提供的一种醌类化合物 -石墨烯复合材料的制备方 法，工艺简单，易于实现产业化生产。
第四方面，本发明实施例提供了一种柔性锂二次电池，包括柔性电池外壳 和位于所述柔性电池外壳内的柔性正极、 柔性负极、 隔膜，以及灌注于所述柔 性电池外壳内的电解液，所述隔膜设置于所述柔性正极和所述柔性负极之间 ， 所述柔性正极包括正极活性材料，所述正极活性材料为醌类化合物-石墨烯复 合材料，所述醌类化合物-石墨烯复合材料包括醌类化合物和石墨烯，所述醌 类化合物化学键合在所述石墨烯表面，所述醌类化合物为醌类化合物单体或醌 类聚合物。
优选地，所述柔性负极包括负极活性材料，所述负极活性材料为石墨烯、 碳纳米管、 硅薄膜或锡薄膜。
优选地，所述柔性正极包括正极集流体，所述柔性负极包括负极集流体。 优选地，所述正极集流体为金属箔集流体或石墨烯薄膜。
优选地，所述负极集流体为金属箔集流体或石墨烯薄膜。所述金属箔集流 体包括铜箔、 铝箔等。
所述柔性正极和柔性负极包括粘结剂和导电剂，所述粘结剂只要是可以将 活性材料和导电剂颗粒粘结在一起的物质即可，可以使用公知的粘结剂物质， 如聚偏氟乙烯（PVDF X 聚四氟乙烯（PTFE X 羧甲基纤维素钠（CMC X 丁 苯橡胶（ SBR )等。所述导电剂只要是可以改善活性材料表面导电性能的物质 _
12
即可，可以使用公知的导电剂，如导电石墨类、 碳黑类、 碳纤维、 碳纳米管、 石墨烯、 金属微粉等。所述电解液的选择不作特殊限定，现有公知的电解液均 可。
优选地，所述隔膜为聚烯烃隔膜、 聚乙烯醇隔膜、 聚氯乙烯隔膜、 聚四氟 乙烯隔膜、 聚苯乙烯隔膜、 聚乙烯苯酚隔膜、 聚甲基丙烯酸甲酯隔膜、 聚酰亚 胺隔膜或聚对苯二甲酸乙二醇酯隔膜。
优选地，所述柔性电池外壳的材质为铝塑复合膜。
在本发明的其他优选实施方式中 ，所述柔性正极由醌类化合物-石墨烯复 合材料制成。 即所述醌类化合物-石墨烯复合材料充当柔性正极，与柔性负极、 隔膜、 电解液以及柔性电池外壳构成柔性锂二次电池。
本发明实施例第四方面提供的一种柔性锂二次电池，具有高柔性、 高倍率 性能、 高能量密度和高稳定性，适合用于未来的柔性电子器件。
综上，本发明实施例第一方面提供的醌类化合物-石墨烯复合材料，采用 高导电性能的石墨烯与醌类化合物复合，该复合材料具有高能量密度、高柔性、 高导电性和高稳定性，解决了现有技术中有机正极材料电导性差、稳定性不佳 等问题，该复合材料可作为制备柔性电极的正极材料。本发明实施例第二方面、 第三方面提供的醌类化合物-石墨烯复合材料的制备方法，工艺简单，易于实 现产业化生产。本发明实施例第四方面提供的一种柔性锂二次电池，具有高柔 性、 高倍率性能、 高能量密度和高稳定性，适合用于未来的柔性电子器件。
实施例一
一种醌类化合物-石墨烯复合材料的制备方法，包括以下步骤：
步骤 S11 ,对苯醌氨基化：采用硝化还原法将对苯醌用浓硫酸和浓硝酸的 混酸硝化得到二硝基化对苯醌，再加入硫化钠进行还原，得到含有氨基化对苯 醌的混合液，将混合液经过滤、 洗涤、 干燥，得到氨基化对苯醌粉体；氨基化 反应式如式（ 1 所示：
Figure imgf000014_0001
( 1 )；
步骤 S12 ,石墨烯羧基化：在氧化石墨烯粉体中加入浓硫酸和浓硝酸体积 比 3:1的混酸，在搅拌和超声分散的条件下于 60°C反应 12h ,经滤膜抽滤、 蒸 馏水洗涤和真空干燥后得到表面连接有大量羧基的羧基化石墨烯粉体；羧基化 石墨烯的化学结构式如式（ 2 )所示：
(
： 、 '¾：1
( 2 )；
步骤 S13 ,酰胺化复合：将上述步骤 S11中所得的过量的氨基化对苯醌粉 体和上述步骤 S12中所得羧基化石墨烯粉体加入到水中 ，超声 2h ,得到混合 分散液，将所述混合分散液在氮气 N2保护下，于 120°C回流 72h ,发生酰胺化 反应（如式（ 3 )所示），
Figure imgf000014_0002
( 3 ) 反应完毕后，将生成物经滤膜抽滤、 洗涤并于 60°C真空干燥，得到表面 连接对氨基化苯醌基团的石墨烯复合材料，即对苯醌 -石墨烯复合材料。 图 1 所示为本实施例对苯醌 -石墨烯复合材料的制备流程图。
实施例二
一种醌类化合物-石墨烯复合材料的制备方法，包括以下步骤：
步骤 S21 , 1,5-蒽醌氨基化：采用硝化还原法将 1,5-蒽醌用浓硫酸和浓硝酸 的混酸硝化得到 1,5-二硝基化蒽醌，再加入硫化钠进行还原，得到含有 1,5-二 氨基化蒽醌的混合液，将混合液经过滤、 洗涤、 干燥，即可得到 1,5-二氨基化 蒽醌粉体；氨基化反应式如式（ 4 )所示：
Figure imgf000015_0001
( 4 )；
步骤 S22 ,石墨烯羧基化：在氧化石墨烯粉体中加入浓硫酸和浓硝酸体积 比 3:1的混酸，在搅拌和超声分散的条件下于 50°C反应 12h ,经滤膜抽滤、 蒸 馏水洗涤和真空干燥后得到表面连接有大量羧基的羧基化石墨烯粉体；
步骤 S23 ,酰胺化复合：将上述步骤 S21中所得的过量的 1,5-二氨基化蒽 醌粉体和上述步骤 S22中的羧基化石墨烯粉体加入到水中 ，超声 2h ,得到混 合分散液，将所述混合分散液在氮气 N2保护下，于 120°C回流 72h ,发生酰胺 化反应（如式（5 )所示），
Figure imgf000016_0001
( 5 ) ;
反应完毕后，将生成物经滤膜抽滤、 洗涤并于 60°C真空干燥，得到表面 连接对氨基化蒽醌基团的石墨烯复合材料，即氨基化蒽醌-石墨烯复合材料； 步骤 S24，氨基聚合：按照摩尔比 1:2:2:2称取定量的氨基化蒽醌-石墨烯、 高氯酸 (lmol/L)及过氧化氢 (饱和水溶液)和重铬酸钾加入到乙腈溶剂中 ，混合 均勻后缓慢滴加重铬酸钾的饱和水溶液，经搅拌在氩气保护和 35°C条件下反 应 72 h后，减压抽滤、 去离子水洗涤， 80°C真空干燥 24h ,得到固体粉体，即 聚 -石墨烯复合材料。 氨基聚合反应的反应式如（ 6 )所示：
Figure imgf000016_0002
( 6 )。
图 2所示为本实施例聚氨基化蒽醌 -石墨烯复合材料的制备流程图。
实施例三
一种醌类化合物-石墨烯复合材料的制备方法，包括以下步骤：
步骤 S31 , 1,5-蒽醌氨基化：采用硝化还原法将 1,5-蒽醌在浓硫酸中用混酸 硝化得到 1,5-二硝基化蒽醌，加入硫化钠还原，得到含有 1,5-二氨基化蒽醌的 混合液，将混合液经过滤、 洗涤、 干燥，即可得到 1,5-二氨基化蒽醌粉体； 步骤 S32 ,氨基聚合：将 1,5-二氨基化蒽醌粉体加入到以丙烯碳酸酯有机 溶剂的电解液中、采用三电极体系的恒电位聚合法，其聚合反应主要发生在单 体中与苯环相连的氨基和氨基对位的氢，它们以头尾连接方式为主形成聚 1,5- 二氨基蒽醌大分子链，即聚 1,5-二氨基化蒽醌；氨基聚合反应的反应式如式（ 7 ) 所示：
Figure imgf000017_0001
步骤 S33 ,石墨烯羧基化：在氧化石墨烯粉体中加入浓硫酸和浓硝酸体积 比 3:1的混酸，在搅拌和超声分散的条件下于 60°C反应 12h ,经滤膜抽滤、 蒸 馏水洗涤和真空干燥后得到表面连接有大量羧基的羧基化石墨烯粉体；
步骤 S34 ,酰胺化复合：将上述步骤 S31中所得的过量的聚 1,5-二氨基化 蒽醌粉体和上述步骤 S33中的羧基化石墨烯粉体加入到水中 ，超声 2h ,得到 混合分散液，将所述混合分散液在氮气 N2保护下，于 120°C回流 72h ,发生酰 胺化反应（如式（ 8 )所示），
Figure imgf000017_0002
反应完毕后，将生成物经滤膜抽滤、 洗涤并于 60°C真空干燥，得到表面 连接对氨基化蒽醌基团的石墨烯复合材料，即聚氨基化蒽醌-石墨烯复合材料( 图 3所示为本实施例聚氨基化蒽醌 -石墨烯复合材料的制备流程图。
实施例四
—种柔性锂二次电池，结构示意图如图 4所示，该柔性锂二次电池（ 400 ) 包括柔性电池外壳（ 404 )和位于柔性电池外壳（ 404 )内的柔性正极 (401)、 柔性负极（ 402 隔膜（ 403 ) ,以及灌注于柔性电池外壳（ 404 )内的电解液， 所述隔膜（ 403 )设置于柔性正极（ 401 )和柔性负极（ 402 )之间。 其中 ，柔 性正极（ 401 )采用上述实施例一得到的对苯醌-石墨烯复合材料作为正极活性 材料，柔性负极（ 402 )采用石墨烯作为负极活性材料。
正极极片的制备：将正极活性材料对苯醌-石墨烯复合材料与粘结剂聚偏 氟乙烯、 导电剂碳纳米管混合，并加入一定量的有机溶剂氮甲基吡咯烷酮，制 备得到正极浆料，将所得正极浆料均勻涂覆在铝箔集流体上，经烘烤、 压片后 得到正极极片；
负极极片的制备：将负极活性材料石墨烯与粘结剂聚偏氟乙烯、导电剂碳 纳米管混合，并加入一定量的有机溶剂氮甲基吡咯烷酮，制备得到负极浆料， 将所得负极浆料均勻涂覆在铜箔集流体上，经烘烤、 压片后得到负极极片； 将上述所得正极极片、 PP/PE/PP聚烯烃隔膜、 负极极片顺序叠放并组装， 添加电解液后采用柔性电池外壳进行封装，即可得到醌类化合物 -石墨烯复合 材料作为正极活性材料的柔性锂二次电池。
实施例五
一种柔性锂二次电池，采用上述实施例二得到的聚氨基化蒽醌-石墨烯复 合材料作为正极活性材料，按照实施例四相同的方法组装成柔性锂二次电池。
实施例六 一种柔性锂二次电池，采用上述实施例三得到的聚氨基化蒽醌-石墨烯复 合材料作为正极活性材料，按照实施例四相同的方法组装成柔性锂二次电池。
对比例一
一种柔性锂二次电池，采用对苯醌作为正极活性材料，按照实施例四相同 的方法组装成柔性锂二次电池。
对比例二
一种柔性锂二次电池，采用聚氨基化蒽醌作为正极活性材料，按照实施例 四相同的方法组装成柔性锂二次电池。
效果实施例 为有力支持本发明实施例的有益效果，提供效果实施例如 下，用以评测本发明实施例提供的产品的性能。
将实施例四〜六以及对比例 _~二所得柔性锂二次电池，采用电池性能测试 仪进行充放电循环和倍率性能测试。其中循环测试电压范围为 1.5~3.6V ,电流 大小为 0.2C ,记录循环 50次后的电池容量并计算容量保持率；倍率测试电压 范围为 1.5~3.6V , 电流大小为 5.0C ,记录放电容量并计算倍率放电比率。
为了进一步测试电池柔性，将所述的柔性锂二次电池，按一定横向和纵向 ， 按不大于 10度的弯折角度反复弯折 10次，再进行充放电循环和倍率测试，测 试条件同上。 测试结果如表 1所示：
各实施例与对比例中柔性锂二次电池的性能比较 正极材料放电 5.0C倍率放 0.2C循环容量 弯折后 5.0C倍率 弯折后 0.2C循环 容量（ mAh/g ) 电比率（ % ) 保持率（ % ) 放电比率（ % ) 容量保持率（ % ) 实施例四 155.3 79.1% 68.4% 71.4% 实施例五 231.2 84.1% 78.7% 70.3% 65.6% 实施例六 254.6 86.3% 84.2% 71.8% 72.6% 对比例一 124.1 54.2% 60.2% 32.4% 38.4% 对比例二 201.8 45.8% 57.3% 28.7% 40.2%
表 1的结果说明 ：本发明实施例提供的柔性锂二次电池具有良好倍率性能 与循环性能，且弯折后仍能保持良好倍率性能与循环性能。这是由于，本发明 实施例提供的柔性锂二次电池采用了醌类化合物-石墨烯复合材料作为正极活 性材料，该复合材料采用高导电性能的石墨烯与醌类化合物复合，具有高能量 密度、 高柔性、 高导电性和高稳定性，能很好地适用于柔性电池制备。

Claims

权 利 要 求
1、 一种醌类化合物-石墨烯复合材料，其特征在于，包括醌类化合物和石 墨烯，所述醌类化合物化学键合在所述石墨烯表面，所述醌类化合物为醌类化 合物单体或醌类聚合物。
2、 如权利要求 1所述的醌类化合物-石墨烯复合材料，其特征在于，所述 石墨烯表面包含羧基功能基团 ，所述醌类化合物包含氨基功能基团 ，所述醌类 化合物通过所述氨基功能基团和所述羧基功能基团形成的酰胺键键合在所述 石墨稀表面。
3、 如权利要求 1或 2所述的醌类化合物-石墨烯复合材料，其特征在于， 所述醌类化合物单体为苯醌、萘醌、蒽醌、菲醌中的任一种，或者苯醌、萘醌、 蒽醌以及菲醌中任一种的异构体。
4、 如权利要求 1或 2所述的醌类化合物-石墨烯复合材料，其特征在于， 所述醌类聚合物为苯醌、萘醌、蒽醌以及菲醌中的任一种或多种形成的聚合物， 或者苯醌、萘醌、蒽醌以及菲醌中任一种的异构体或多种的异构体形成的聚合 物。
5、 如权利要求 1或 2所述的醌类化合物-石墨烯复合材料，其特征在于， 所述醌类化合物的质量占所述醌类化合物-石墨烯复合材料质量的 20~80%。
6、 一种醌类化合物-石墨烯复合材料的制备方法，其特征在于，包括以下 步骤：
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液； 将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于
50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类化合物单体粉体和所述表面羧基化石墨烯粉体加入到 水或乙醇中 ，进行超声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类化合物单体 -石墨烯复合材料。
7、 如权利要求 6所述的醌类化合物-石墨烯复合材料的制备方法，其特征 在于，所述醌类化合物单体为苯醌、萘醌、蒽醌、菲醌中的任一种，或者苯醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
8、 如权利要求 6或 7所述的醌类化合物-石墨烯复合材料的制备方法， 其特征在于，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。
9、 如权利要求 6或 7所述的醌类化合物-石墨烯复合材料的制备方法，其 特征在于，进一步包括如下步骤：
按照摩尔比 1:2:2:2称取所述醌类化合物单体 -石墨烯复合材料、 高氯酸、 过氧化氢饱和水溶液和重铬酸钾加入到乙腈溶剂中 ，得到混合溶液；
向所述混合溶液中滴加重铬酸钾的饱和水溶液， 在氩气保护下 ， 于 30~50°C下反应 48~72h ,得到含有醌类聚合物-石墨烯复合材料的混合液； 将所述含有醌类聚合物-石墨烯复合材料的混合液进行减压抽滤、 洗涤， 真空干燥，得到醌类聚合物 -石墨烯复合材料。
10、 一种醌类化合物-石墨烯复合材料的制备方法，其特征在于，包括以 下步骤：
采用硝化还原法将醌类化合物单体氨基化，得到含有氨基化醌类化合物单 体的混合液；
将所述含有氨基化醌类化合物单体的混合液进行过滤、 洗涤、 干燥，得到 氨基化醌类化合物单体粉体；
将所述氨基化醌类化合物单体粉体加入到丙烯碳酸酯有机溶剂的电解液 中 ，采用三电极体系的恒电位聚合法，使所述氨基化醌类化合物单体聚合，得 到氨基化醌类聚合物；
将氧化石墨烯粉体加入到预设比例的浓硫酸和浓硝酸的混酸中 ， 于
50~60°C下反应 5~15h后，进行抽滤、 洗涤和真空干燥操作，得到表面羧基化 石墨烯粉体；
将所述氨基化醌类聚合物和羧基化石墨烯粉体加入到水或乙醇中 ，进行超 声分散得到混合分散液；
将所述混合分散液在氮气保护下，于 100~120°C回流反应 48~72h，反应完 毕后，将生成物经抽滤、 洗涤、 干燥，得到醌类聚合物 -石墨烯复合材料。
11、 如权利要求 10所述的醌类化合物-石墨烯复合材料的制备方法，其特 征在于，所述醌类化合物单体为苯醌、 萘醌、 蒽醌、 菲醌中的任一种，或者苯 醌、 萘醌、 蒽醌以及菲醌中任一种的异构体。
12、如权利要求 10或 11所述的醌类化合物-石墨烯复合材料的制备方法， 其特征在于，所述 50~60°C反应 5~15h是在搅拌和超声分散的条件下进行的。
13、 一种柔性锂二次电池，其特征在于，包括柔性电池外壳和位于所述柔 性电池外壳内的柔性正极、 柔性负极、 隔膜，以及灌注于所述柔性电池外壳内 的电解液，所述隔膜设置于所述柔性正极和所述柔性负极之间 ，所述柔性正极 包括正极活性材料，所述正极活性材料为醌类化合物-石墨烯复合材料，所述 醌类化合物-石墨烯复合材料包括醌类化合物和石墨烯，所述醌类化合物化学 键合在所述石墨烯表面，所述醌类化合物为醌类化合物单体或醌类聚合物。
14、 如权利要求 13所述的柔性锂二次电池，其特征在于，所述柔性负极 包括负极活性材料，所述负极活性材料为石墨烯、碳纳米管、硅薄膜或锡薄膜。
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