WO2016045558A1 - Composite positive electrode material and preparation method therefor - Google Patents

Composite positive electrode material and preparation method therefor Download PDF

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WO2016045558A1
WO2016045558A1 PCT/CN2015/090103 CN2015090103W WO2016045558A1 WO 2016045558 A1 WO2016045558 A1 WO 2016045558A1 CN 2015090103 W CN2015090103 W CN 2015090103W WO 2016045558 A1 WO2016045558 A1 WO 2016045558A1
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positive electrode
feof
graphene
electrode composite
fef
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张艳丽
王莉
何向明
赵鹏
金玉红
李建军
尚玉明
高剑
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江苏华东锂电技术研究院有限公司
清华大学
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    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a positive electrode composite material based on iron fluoride oxide and a preparation method thereof.
  • Ferric oxyfluoride can be regarded as a structure formed by replacing FeF 2 with O. Compared with strongly ionic FeF 2 , FeOF contains more chemical bonds Fe-O, which makes FeOF more conductive than FeF 2 (both band gaps are 1.5 eV and 3 eV, respectively). At the same time, Fe in FeOF is +3 valence, and can react three electrons in the electrochemical process.
  • a positive electrode composite material is a graphene-FeOF composite material comprising FeOF particles bonded by chemical bonds and graphene.
  • a positive electrode composite material is a functionalized graphene comprising a carbon atom layer passing through FeOF particles and graphene, and the FeOF particles are chemically bonded to a carbon atom layer of graphene.
  • a method for preparing a positive electrode composite material comprising the steps of: uniformly mixing iron fluoride and graphene oxide in a liquid solvent to form a solid-liquid mixture; and mixing the solid-liquid mixture in a hydrothermal/solvent heat reactor Hydrothermal/solvent thermal reaction at 80 ° C ⁇ 250 ° C.
  • the present invention synthesizes FeOF by ferric fluoride and graphene oxide for the first time.
  • the graphene oxide acts as a reaction raw material to chemically react with iron fluoride, and also serves as a conductive agent in the positive electrode composite material to increase FeOF. Conductivity.
  • FIG. 1 is an SEM image of a positive electrode composite material synthesized in accordance with an embodiment of the present invention.
  • FIG. 2 is an XRD chart of a positive electrode composite material synthesized in accordance with an embodiment of the present invention.
  • Embodiments of the present invention provide a cathode composite material, which is a graphene-FeOF composite material, including FeOF particles and graphene bonded by chemical bonds. FeOF particles are formed in situ on the graphene surface.
  • the particle size of the FeOF particles is preferably from 1 nm to 10 ⁇ m.
  • the graphene may include one or more layers (such as 1 to 10 layers, preferably 1 to 3 layers) of carbon atom layers superposed.
  • the graphene may be graphene oxide, that is, a part of carbon atoms in graphene are bonded to an oxygen atom through a chemical bond.
  • the mass percentage of FeOF in the positive electrode composite may be 2% to 98%, preferably 70% to 95%.
  • a part of the carbon atoms in the graphene are bonded to Fe, O or F in the FeOF particles by a chemical bond, preferably to the O in the FeOF particles.
  • the positive electrode composite can also be regarded as a functionalized graphene.
  • the carbon atom layer of graphene in the conventional functionalized graphene is bonded to a functional group such as an organic group such as S or Cl by a chemical bond.
  • the functionalized graphene functions as a functional group in the FeOF particles.
  • the positive electrode composite can be used in lithium ion batteries or other electrochemical cells.
  • Embodiments of the present invention provide a method for preparing a positive electrode composite material, which includes the following steps:
  • the solid-liquid mixture is subjected to a hydrothermal/solvothermal reaction in a hydrothermal/solvent thermal reactor at 80 ° C to 250 ° C.
  • FeF 3 may or may not contain water of crystallization, preferably containing water of crystallization such as iron fluoride trihydrate (FeF 3 ⁇ 3H 2 O), FeF 3 ⁇ 0.33H 2 O, Fe 1.9 F 4.75 ⁇ 0.95H 2 O, FeF 2.5 ⁇ at least one of 0.5H 2 O, FeF 3 ⁇ H 2 O and amorphous FeF 3 .
  • water of crystallization such as iron fluoride trihydrate (FeF 3 ⁇ 3H 2 O), FeF 3 ⁇ 0.33H 2 O, Fe 1.9 F 4.75 ⁇ 0.95H 2 O, FeF 2.5 ⁇ at least one of 0.5H 2 O, FeF 3 ⁇ H 2 O and amorphous FeF 3 .
  • the graphene oxide reacts with FeF 3 under hydrothermal/solvent conditions to form FeOF in situ on the surface of the carbon atom layer of graphene, thereby bonding with graphene through a chemical bond.
  • the graphene oxide can be completely reduced to graphene.
  • the liquid phase solvent may be water and/or an organic solvent, and the organic solvent preferably contains an oxidizing group (such as -NO 2 , -OH, -COOH, etc.), such as one of ethanol, propanol, acetic acid, and citric acid. Or a variety.
  • an oxidizing group such as -NO 2 , -OH, -COOH, etc.
  • the ratio between water and the organic solvent is not limited. That is, the liquid phase solvent plays a fundamental role in providing a hydrothermal/solvent hot liquid phase reaction environment.
  • FeF 3 can be dissolved to form a solid-liquid mixture with the graphene oxide to make the reaction easier.
  • FeF 3 as small as possible particles can be used as a raw material.
  • the small-sized particles of FeF 3 can also be oxidized under the conditions of hydrothermal/solvent heat at high temperature and high pressure.
  • Graphene reacts to form FeOF.
  • the organic solvent contains an oxidizing group, it can participate as a reactant in the reaction of graphene oxide with FeF 3 to promote FeOF formation.
  • the ratio of water to organic solvent may be from 1:10 to 10:1, preferably from 1:3 to 3:1.
  • the FeF 3 , graphene oxide and liquid phase solvent can be uniformly mixed by mechanical stirring, ball milling or ultrasonic vibration.
  • the hydrothermal/solvent thermal reactor is a sealed autoclave, and the liquid phase solvent in the reaction vessel is vaporized by heating during the reaction to provide a high pressure reaction environment.
  • the soaking time of the hydrothermal/solvent thermal reaction can be from 2 hours to 24 hours. After the reaction, it is naturally cooled to room temperature, and the solid product obtained by filtration in the reaction vessel is opened, that is, the positive electrode composite material, that is, the graphene-FeOF composite material.
  • the morphology of the graphene oxide-FeOF composite is shown in the figure.
  • the nano-scale FeOF particles (40 nm ⁇ 100 nm) are uniformly dispersed on the graphene oxide sheet.
  • the synthesized solid product is characterized by XRD.
  • the diffraction peaks in the spectrum can be assigned to graphene oxide (peak at 11.8°, indicated by arrows) and FeOF (other diffraction peaks in the spectrum). It can be proved that FeF 3 and graphene oxide can be completely converted into graphene oxide-FeOF composite after hydrothermal reaction of mixed solution of ethanol and deionized water.
  • This nanocomposite can be used as an excellent cathode material for lithium ion batteries.
  • the method for synthesizing the raw materials FeF 3 and graphene oxide used in the above reaction is not limited.
  • the preparation method of FeF 3 ⁇ 3H 2 O in the present embodiment includes the following steps;
  • Surfactant such as CTAB is ultrasonically dispersed in deionized water
  • the Fe 3+ solution was dropwise added to the hydrofluoric acid solution under stirring, and stirring was continued until the reaction was completed.
  • the obtained solid product can be further separated by centrifugation and washed with ethanol to neutrality, and dried to obtain FeF 3 ⁇ 3H 2 O.
  • the graphene is prepared by the Hummers method, and the preparation method comprises the following steps:
  • the obtained solid product can be further separated by centrifugation to obtain a graphene oxide suspension.
  • Preparation of graphene oxide Preparation of graphene oxide by Hummers method: the experiment process is: mixing 5 g of graphite, 2.5 g of sodium nitrate, 115 mL of concentrated sulfuric acid in an ice water bath, stirring vigorously for 30 min; adding 30 g of high manganese to it Potassium acid, the graphite was completely oxidized after stirring for 5 h; 200 mL of deionized water was added to the reaction and stirring was continued for 20 min, and 400 mL of deionized water and 20 mL of hydrogen peroxide (30%) were added until the reaction was completed. Centrifuge at 5000 rpm / 30 min, discard the lower precipitate, and store the overhead graphene oxide suspension (4 mg/mL) for later use.
  • the preparation method of the positive electrode composite material provided by the invention utilizes graphene oxide as a reaction raw material to chemically react with FeF 3 and as a conductive agent in the positive electrode composite material to increase the conductivity of FeOF. Since graphene oxide includes one or several layers of carbon atoms, the surface contains an oxygen-containing functional group, and has good dispersibility in an aqueous solution, FeOF can be uniformly formed on the surface of the graphene oxide. Because graphene has good electrical conductivity, large specific surface area and good mechanical properties, it can be used as a carrier for FeOF nanoparticles. After forming a composite with FeOF nanoparticles, graphene can be transferred in the electrochemical process. Electron, increase conductivity, prevent agglomeration, buffer volume change, etc.

Abstract

Provided is a composite positive electrode material. The composite positive electrode material is a graphene-FeOF composite material, and comprises FeOF particles and graphene that are chemically bonded. Also provided is a method for preparing the composite positive electrode material. The method comprises the following steps: uniformly mixing ferric fluoride and graphene oxide in a liquid-phase solvent to form a solid-liquid mixture; and subjecting the solid-liquid mixture to a hydrothermal/solvothermal reaction in a hydrothermal/solvothermal reaction kettle at the temperature of 80ºC to 250ºC.

Description

正极复合材料及其制备方法Positive electrode composite material and preparation method thereof 技术领域Technical field
本发明涉及一种基于氟氧化铁的正极复合材料及其制备方法。The invention relates to a positive electrode composite material based on iron fluoride oxide and a preparation method thereof.
背景技术Background technique
氟氧化铁（FeOF）可以看做用O取代了FeF2而形成的结构。与强离子性FeF2相比，FeOF含有更多化学键Fe-O，这使得FeOF的导电性优于FeF2（两者带隙分别是1.5 eV和3 eV）。同时，FeOF中的Fe为+3价，在电化学过程中可三电子反应，在各个电压区间的反应如下：2V~4.5V：Fe3+OF + Li = LiFe2+OF；0.7V~2V：LiFe2+OF + 2Li = LiF + Li2O + Fe0，理论比容量为885 mAh g-1，可望作为一种大比容量的正极材料。Ferric oxyfluoride (FeOF) can be regarded as a structure formed by replacing FeF 2 with O. Compared with strongly ionic FeF 2 , FeOF contains more chemical bonds Fe-O, which makes FeOF more conductive than FeF 2 (both band gaps are 1.5 eV and 3 eV, respectively). At the same time, Fe in FeOF is +3 valence, and can react three electrons in the electrochemical process. The reaction in each voltage range is as follows: 2V~4.5V: Fe 3+ OF + Li = LiFe 2+ OF; 0.7V~2V LiFe 2+ OF + 2Li = LiF + Li 2 O + Fe 0 , the theoretical specific capacity is 885 mAh g -1 , which is expected to be a positive specific material with a large specific capacity.
现有技术中FeOF的合成方法较为有限。澳洲国立大学的J. G. Thompson和F. J. Brink通过将FeF3和Fe2O3在密闭Pt管中、Ar气氛下、950°C高温发生固相反应首次合成FeOF。美国罗格斯大学的G. G. Amatucci和N. Pereira通过Fe金属与氟硅酸水溶液做前驱体，通过溶液法合成了FeOF。日本九州大学的Shigeto Okada和Ayuko Kitajou以FeF3和Fe2O3为原料，采用压辊淬火法合成出FeO1.1+-1F0.95，这种快速合成方法利于减少生产成本及避免F气氛释放所造成的污染。然而，这三种方法合成出FeOF后，均需要与乙炔黑球磨来增加导电性，而后制备电极片。The synthesis method of FeOF in the prior art is limited. JG Thompson and FJ Brink of the Australian National University first synthesized FeOF by solid-phase reaction of FeF 3 and Fe 2 O 3 in a closed Pt tube under Ar atmosphere at 950 °C. GG Amatucci and N. Pereira of Rutgers University in the United States synthesized FeOF by solution method by using Fe metal and fluorosilicic acid aqueous solution as precursors. Shigeto Okada and Ayuko Kitajou of Kyushu University in Japan used FeF 3 and Fe 2 O 3 as raw materials to synthesize FeO 1.1+-1 F 0.95 by press roll quenching. This rapid synthesis method is beneficial to reduce production cost and avoid F atmosphere release. The pollution caused. However, after synthesizing FeOF by these three methods, it is required to be ball-milled with acetylene to increase conductivity, and then an electrode sheet is prepared.
发明内容Summary of the invention
有鉴于此，确有必要提供一种新的基于氟氧化铁的正极复合材料及其制备方法。In view of this, it is indeed necessary to provide a new iron oxide iron-based positive electrode composite material and a preparation method thereof.
一种正极复合材料，是石墨烯-FeOF复合材料，包括通过化学键结合的FeOF颗粒及石墨烯。A positive electrode composite material is a graphene-FeOF composite material comprising FeOF particles bonded by chemical bonds and graphene.
一种正极复合材料，是功能化石墨烯，包括通过FeOF颗粒及石墨烯的碳原子层，该FeOF颗粒与石墨烯的碳原子层通过化学键结合。A positive electrode composite material is a functionalized graphene comprising a carbon atom layer passing through FeOF particles and graphene, and the FeOF particles are chemically bonded to a carbon atom layer of graphene.
一种正极复合材料的制备方法，其包括以下步骤：将氟化铁及氧化石墨烯在液相溶剂中均匀混合形成一固液混合物；以及将该固液混合物在水热/溶剂热反应釜中80℃~250℃进行水热/溶剂热反应。A method for preparing a positive electrode composite material, comprising the steps of: uniformly mixing iron fluoride and graphene oxide in a liquid solvent to form a solid-liquid mixture; and mixing the solid-liquid mixture in a hydrothermal/solvent heat reactor Hydrothermal/solvent thermal reaction at 80 ° C ~ 250 ° C.
相较于现有技术，本发明首次通过氟化铁与氧化石墨烯合成出FeOF，该氧化石墨烯既作为反应原料与氟化铁进行化学反应，又作为正极复合材料中的导电剂，增加FeOF的导电性。Compared with the prior art, the present invention synthesizes FeOF by ferric fluoride and graphene oxide for the first time. The graphene oxide acts as a reaction raw material to chemically react with iron fluoride, and also serves as a conductive agent in the positive electrode composite material to increase FeOF. Conductivity.
附图说明DRAWINGS
图1为本发明实施例合成的正极复合材料的SEM图。1 is an SEM image of a positive electrode composite material synthesized in accordance with an embodiment of the present invention.
图2为本发明实施例合成的正极复合材料的XRD图。2 is an XRD chart of a positive electrode composite material synthesized in accordance with an embodiment of the present invention.
具体实施方式detailed description
下面将结合附图及具体实施例对本发明提供的正极复合材料及其制备方法作进一步的详细说明。The positive electrode composite material and the preparation method thereof provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
本发明实施例提供一种正极复合材料，是石墨烯-FeOF复合材料，包括通过化学键结合的FeOF颗粒及石墨烯。FeOF颗粒原位生成在石墨烯表面。Embodiments of the present invention provide a cathode composite material, which is a graphene-FeOF composite material, including FeOF particles and graphene bonded by chemical bonds. FeOF particles are formed in situ on the graphene surface.
具体地，FeOF颗粒的粒径尺寸优选为1 nm~10μm。Specifically, the particle size of the FeOF particles is preferably from 1 nm to 10 μm.
可以理解，该石墨烯可以包括一层或多层(如1~10层，优选为1~3层)相叠加的碳原子层。该石墨烯可以为氧化石墨烯，即石墨烯中一部分碳原子与氧原子通过化学键连接。该正极复合材料中FeOF的质量百分含量可以为2%~98%，优选为70%~95%。It can be understood that the graphene may include one or more layers (such as 1 to 10 layers, preferably 1 to 3 layers) of carbon atom layers superposed. The graphene may be graphene oxide, that is, a part of carbon atoms in graphene are bonded to an oxygen atom through a chemical bond. The mass percentage of FeOF in the positive electrode composite may be 2% to 98%, preferably 70% to 95%.
该石墨烯中的一部分碳原子通过化学键与FeOF颗粒中的Fe、O或F连接，优选为与FeOF颗粒中的O连接。A part of the carbon atoms in the graphene are bonded to Fe, O or F in the FeOF particles by a chemical bond, preferably to the O in the FeOF particles.
该正极复合材料也可以看作是一种功能化石墨烯。传统的功能化石墨烯中石墨烯的碳原子层与官能团，如S或Cl等有机基团通过化学键连接。而在本发明中，该功能化石墨烯中充当官能团的是FeOF颗粒。The positive electrode composite can also be regarded as a functionalized graphene. The carbon atom layer of graphene in the conventional functionalized graphene is bonded to a functional group such as an organic group such as S or Cl by a chemical bond. In the present invention, the functionalized graphene functions as a functional group in the FeOF particles.
该正极复合材料可以用于锂离子电池或其他电化学电池中。The positive electrode composite can be used in lithium ion batteries or other electrochemical cells.
本发明实施例提供一种正极复合材料的制备方法，其包括以下步骤：Embodiments of the present invention provide a method for preparing a positive electrode composite material, which includes the following steps:
S1，将氟化铁(FeF3)及氧化石墨烯在液相溶剂中均匀混合形成一固液混合物；以及S1, uniformly mixing iron fluoride (FeF 3 ) and graphene oxide in a liquid solvent to form a solid-liquid mixture;
S2，将该固液混合物在水热/溶剂热反应釜中80℃~250℃进行水热/溶剂热反应。S2, the solid-liquid mixture is subjected to a hydrothermal/solvothermal reaction in a hydrothermal/solvent thermal reactor at 80 ° C to 250 ° C.
FeF3可以含有或不含有结晶水，优选为含有结晶水，如三水合氟化铁(FeF3·3H2O)、FeF3·0.33H2O、Fe1.9F4.75·0.95H2O、FeF2.5·0.5H2O、FeF3·H2O 及无定形FeF3中的至少一种。FeF 3 may or may not contain water of crystallization, preferably containing water of crystallization such as iron fluoride trihydrate (FeF 3 ·3H 2 O), FeF 3 ·0.33H 2 O, Fe 1.9 F 4.75 ·0.95H 2 O, FeF 2.5 · at least one of 0.5H 2 O, FeF 3 ·H 2 O and amorphous FeF 3 .
该氧化石墨烯在水热/溶剂热条件下与FeF3反应，在石墨烯的碳原子层表面原位生成FeOF，从而与石墨烯通过化学键结合。氧化石墨烯中的氧全部参与与FeOF的反应时，可以将氧化石墨烯完全还原为石墨烯。The graphene oxide reacts with FeF 3 under hydrothermal/solvent conditions to form FeOF in situ on the surface of the carbon atom layer of graphene, thereby bonding with graphene through a chemical bond. When all of the oxygen in the graphene oxide participates in the reaction with FeOF, the graphene oxide can be completely reduced to graphene.
该液相溶剂可以为水和/或有机溶剂，该有机溶剂优选含有氧化性基团（如-NO2、-OH、-COOH等），如乙醇、丙醇、乙酸及柠檬酸中的一种或多种。当该液相溶剂为水与有机溶剂的混合溶剂时，水与有机溶剂之间的比例没有限制。也就是说，该液相溶剂起到的基本作用是提供水热/溶剂热的液相反应环境。当该液相溶剂中含有水时，可以使FeF3溶解，从而与氧化石墨烯形成固液混合，使反应更易进行。优选的，可以采用尽量小尺寸颗粒的FeF3作为原料，当该液相溶剂仅为有机溶剂，如乙醇时，小尺寸颗粒的FeF3在水热/溶剂热的高温高压条件下同样可以与氧化石墨烯反应生成FeOF。当该有机溶剂含有氧化性基团时，可以作为反应物参与氧化石墨烯与FeF3的反应，促进FeOF生成。水与有机溶剂的比例可以为1:10~10:1，优选为1:3~3:1。The liquid phase solvent may be water and/or an organic solvent, and the organic solvent preferably contains an oxidizing group (such as -NO 2 , -OH, -COOH, etc.), such as one of ethanol, propanol, acetic acid, and citric acid. Or a variety. When the liquid phase solvent is a mixed solvent of water and an organic solvent, the ratio between water and the organic solvent is not limited. That is, the liquid phase solvent plays a fundamental role in providing a hydrothermal/solvent hot liquid phase reaction environment. When water is contained in the liquid phase solvent, FeF 3 can be dissolved to form a solid-liquid mixture with the graphene oxide to make the reaction easier. Preferably, FeF 3 as small as possible particles can be used as a raw material. When the liquid solvent is only an organic solvent such as ethanol, the small-sized particles of FeF 3 can also be oxidized under the conditions of hydrothermal/solvent heat at high temperature and high pressure. Graphene reacts to form FeOF. When the organic solvent contains an oxidizing group, it can participate as a reactant in the reaction of graphene oxide with FeF 3 to promote FeOF formation. The ratio of water to organic solvent may be from 1:10 to 10:1, preferably from 1:3 to 3:1.
该FeF3、氧化石墨烯及液相溶剂可通过机械搅拌、球磨或超声振荡等方式混合均匀。The FeF 3 , graphene oxide and liquid phase solvent can be uniformly mixed by mechanical stirring, ball milling or ultrasonic vibration.
该水热/溶剂热反应釜为密封的高压釜，反应过程中通过加热使反应釜内部液相溶剂气化，从而提供高压反应环境。该水热/溶剂热反应的保温时间可以为2小时~24小时。反应后自然冷却至室温，打开反应釜过滤得到的固态产物，即为所述正极复合材料，也就是石墨烯-FeOF复合材料。The hydrothermal/solvent thermal reactor is a sealed autoclave, and the liquid phase solvent in the reaction vessel is vaporized by heating during the reaction to provide a high pressure reaction environment. The soaking time of the hydrothermal/solvent thermal reaction can be from 2 hours to 24 hours. After the reaction, it is naturally cooled to room temperature, and the solid product obtained by filtration in the reaction vessel is opened, that is, the positive electrode composite material, that is, the graphene-FeOF composite material.
请参阅图1，产物氧化石墨烯-FeOF复合材料的形貌如图所示，纳米级FeOF颗粒（40 nm×100 nm）均匀分散于氧化石墨烯片层上。请参阅图2，通过XRD表征合成的固态产物，谱图中的衍射峰可分别归属为氧化石墨烯（11.8°处的峰，箭头标注）和FeOF（谱图中的其他衍射峰）。由此可以证明FeF3与氧化石墨烯在乙醇和去离子水的混合溶液水热反应后，可以完全转化为氧化石墨烯-FeOF复合材料。这种纳米复合材料可以作为优良的锂离子电池正极材料。Referring to Figure 1, the morphology of the graphene oxide-FeOF composite is shown in the figure. The nano-scale FeOF particles (40 nm × 100 nm) are uniformly dispersed on the graphene oxide sheet. Referring to Figure 2, the synthesized solid product is characterized by XRD. The diffraction peaks in the spectrum can be assigned to graphene oxide (peak at 11.8°, indicated by arrows) and FeOF (other diffraction peaks in the spectrum). It can be proved that FeF 3 and graphene oxide can be completely converted into graphene oxide-FeOF composite after hydrothermal reaction of mixed solution of ethanol and deionized water. This nanocomposite can be used as an excellent cathode material for lithium ion batteries.
上述反应采用的原料FeF3及氧化石墨烯的合成方法不限，本实施例中FeF3·3H2O的制备方法包括以下步骤；The method for synthesizing the raw materials FeF 3 and graphene oxide used in the above reaction is not limited. The preparation method of FeF 3 ·3H 2 O in the present embodiment includes the following steps;
将表面活性剂（如CTAB）在去离子水中超声分散；Surfactant (such as CTAB) is ultrasonically dispersed in deionized water;
加入氯化铁溶解在该去离子水中，得到Fe3+溶液；以及Adding ferric chloride dissolved in the deionized water to obtain a Fe 3+ solution;
在搅拌条件下将该Fe3+溶液逐滴滴入氢氟酸溶液中，继续搅拌至反应完全。The Fe 3+ solution was dropwise added to the hydrofluoric acid solution under stirring, and stirring was continued until the reaction was completed.
得到的固态产物可进一步通过离心分离，并用乙醇洗涤至中性，烘干后得到FeF3·3H2O。The obtained solid product can be further separated by centrifugation and washed with ethanol to neutrality, and dried to obtain FeF 3 ·3H 2 O.
本实施例中采用Hummers方法制备氧化石墨烯，制备方法包括以下步骤：In this embodiment, the graphene is prepared by the Hummers method, and the preparation method comprises the following steps:
在冰水浴中将石墨、硝酸钠、1浓硫酸混合并搅拌；Mixing and stirring graphite, sodium nitrate, and 1 concentrated sulfuric acid in an ice water bath;
加入高锰酸钾，继续搅拌至石墨被完全氧化；Add potassium permanganate and continue stirring until the graphite is completely oxidized;
向反应物中加入去离子水和双氧水，搅拌至反应完全。Deionized water and hydrogen peroxide were added to the reaction and stirred until the reaction was completed.
得到的固态产物可进一步通过离心分离，得到氧化石墨烯悬浮液。The obtained solid product can be further separated by centrifugation to obtain a graphene oxide suspension.
实施例1Example 1
三水合氟化铁FeF3·3H2O的制备：将0.1g CTAB加入到30mL去离子水中，超声分散；而后向其中加入18 g FeCl3·6H2O得到Fe3+溶液；在强力搅拌下，将Fe3+溶液逐滴滴入HF（38%，50mL）之中，继续搅拌2h至反应完全。离心并用乙醇洗涤至中性，将沉淀在普通烘箱中60°C下干燥10h，得到三水合氟化铁FeF3·3H2O。Preparation of ferric fluoride trihydrate FeF 3 ·3H 2 O: 0.1 g CTAB was added to 30 mL of deionized water and ultrasonically dispersed; then 18 g of FeCl 3 ·6H 2 O was added thereto to obtain Fe 3+ solution; under strong stirring The Fe 3+ solution was added dropwise to HF (38%, 50 mL) and stirring was continued for 2 h until the reaction was completed. The mixture was centrifuged and washed with ethanol until neutral, and the precipitate was dried in a normal oven at 60 ° C for 10 h to obtain iron fluoride trihydrate FeF 3 ·3H 2 O.
氧化石墨烯的制备：采用Hummers方法制备氧化石墨烯，实验过程是：在冰水浴中将5 g石墨、2.5 g硝酸钠、115 mL浓硫酸混合，强力搅拌30 min；向其中加入30 g高锰酸钾，继续搅拌5h后石墨被完全氧化；向反应物中加入200 mL去离子水继续搅拌20 min，加入400mL去离子水和20mL双氧水（30%）至反应完全。离心5000 rpm / 30 min，丢掉下方沉淀，取上方氧化石墨烯悬浮液（4 mg/mL）保存备用。Preparation of graphene oxide: Preparation of graphene oxide by Hummers method: the experiment process is: mixing 5 g of graphite, 2.5 g of sodium nitrate, 115 mL of concentrated sulfuric acid in an ice water bath, stirring vigorously for 30 min; adding 30 g of high manganese to it Potassium acid, the graphite was completely oxidized after stirring for 5 h; 200 mL of deionized water was added to the reaction and stirring was continued for 20 min, and 400 mL of deionized water and 20 mL of hydrogen peroxide (30%) were added until the reaction was completed. Centrifuge at 5000 rpm / 30 min, discard the lower precipitate, and store the overhead graphene oxide suspension (4 mg/mL) for later use.
石墨烯-FeOF复合材料的制备：取所制备的氧化石墨烯悬浮液（4 mg/mL）10 mL，与80 mg所制备的FeF3·3H2O、25mL乙醇混合，超声分散30 min；而后将混合液置于水热釜中，升温至120°C，保温10 h。而后自然冷却至室温。Preparation of graphene-FeOF composite: 10 mL of the prepared graphene oxide suspension (4 mg/mL) was mixed with 80 mg of FeF 3 ·3H 2 O and 25 mL of ethanol, and ultrasonically dispersed for 30 min; The mixture was placed in a hydrothermal kettle, warmed to 120 ° C, and kept for 10 h. It is then naturally cooled to room temperature.
本发明提供的正极复合材料的制备方法利用氧化石墨烯既作为反应原料与FeF3进行化学反应，又作为正极复合材料中的导电剂，增加FeOF的导电性。由于氧化石墨烯包括一层或几层碳原子层，表面含有含氧官能团，在水溶液中有良好的分散性，FeOF可均匀的生成在氧化石墨烯表面。由于石墨烯具有良好的导电性、较大的比表面积和很好的力学性能性能，可以作为FeOF纳米粒子的载体；与FeOF纳米粒子构成复合材料后，在电化学过程中，石墨烯起到传递电子、增加导电性、防止团聚、缓冲体积变化等作用。The preparation method of the positive electrode composite material provided by the invention utilizes graphene oxide as a reaction raw material to chemically react with FeF 3 and as a conductive agent in the positive electrode composite material to increase the conductivity of FeOF. Since graphene oxide includes one or several layers of carbon atoms, the surface contains an oxygen-containing functional group, and has good dispersibility in an aqueous solution, FeOF can be uniformly formed on the surface of the graphene oxide. Because graphene has good electrical conductivity, large specific surface area and good mechanical properties, it can be used as a carrier for FeOF nanoparticles. After forming a composite with FeOF nanoparticles, graphene can be transferred in the electrochemical process. Electron, increase conductivity, prevent agglomeration, buffer volume change, etc.
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。In addition, those skilled in the art can make other changes in the spirit of the present invention. Of course, the changes made in accordance with the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

  1. 一种正极复合材料，其特征在于，是石墨烯-FeOF复合材料，包括通过化学键结合的FeOF颗粒及石墨烯。A positive electrode composite material characterized by being a graphene-FeOF composite material comprising FeOF particles bonded by chemical bonds and graphene.
  2. 如权利要求1所述的正极复合材料，其特征在于，该FeOF颗粒的粒径尺寸为1 nm~10 μm。The positive electrode composite according to claim 1, wherein the FeOF particles have a particle size of from 1 nm to 10 μm.
  3. 如权利要求1所述的正极复合材料，其特征在于，该正极复合材料中FeOF的质量百分含量为2%~98%。The positive electrode composite according to claim 1, wherein the positive electrode composite has a FeOF content of 2% to 98% by mass.
  4. 如权利要求1所述的正极复合材料，其特征在于，该正极复合材料中FeOF的质量百分含量为70%~95%。The positive electrode composite according to claim 1, wherein the positive electrode composite has a mass percentage of FeOF of 70% to 95%.
  5. 如权利要求1所述的正极复合材料，其特征在于，该FeOF颗粒原位生成在该石墨烯表面。The positive electrode composite according to claim 1, wherein the FeOF particles are formed in situ on the graphene surface.
  6. 一种正极复合材料，其特征在于，是功能化石墨烯，包括通过FeOF颗粒及石墨烯的碳原子层，该FeOF颗粒与石墨烯的碳原子层通过化学键结合。A positive electrode composite material characterized by functionalized graphene comprising a carbon atom layer passing through FeOF particles and graphene, the FeOF particles being chemically bonded to a carbon atom layer of graphene.
  7. 一种正极复合材料的制备方法，其包括以下步骤：A method for preparing a positive electrode composite material, comprising the steps of:
    将氟化铁及氧化石墨烯在液相溶剂中均匀混合形成一固液混合物；以及Iron fluoride and graphene oxide are uniformly mixed in a liquid solvent to form a solid-liquid mixture;
    将该固液混合物在水热/溶剂热反应釜中80℃~250℃进行水热/溶剂热反应。The solid-liquid mixture is subjected to a hydrothermal/solvothermal reaction in a hydrothermal/solvent thermal reactor at 80 ° C to 250 ° C.
  8. 如权利要求7所述的正极复合材料的制备方法，其特征在于，该氟化铁为FeF3·3H2O、FeF3·0.33H2O、Fe1.9F4.75·0.95H2O、FeF2.5·0.5H2O、FeF3·H2O 及无定形FeF3中的至少一种。The method for preparing a positive electrode composite according to claim 7, wherein the iron fluoride is FeF 3 ·3H 2 O, FeF 3 ·0.33H 2 O, Fe 1.9 F 4.75 ·0.95H 2 O, FeF 2.5 At least one of 0.5H 2 O, FeF 3 ·H 2 O, and amorphous FeF 3 .
  9. 如权利要求7所述的正极复合材料的制备方法，其特征在于，该液相溶剂为水及乙醇的组合。The method for producing a positive electrode composite according to claim 7, wherein the liquid phase solvent is a combination of water and ethanol.
  10. 如权利要求7所述的正极复合材料的制备方法，其特征在于，该水热/溶剂热反应的保温时间为2小时~24小时。The method for preparing a positive electrode composite according to claim 7, wherein the hydrothermal/solvent thermal reaction has a holding time of from 2 hours to 24 hours.
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