WO2017186079A1 - 一种超容量锂离子电池正极材料及其制备方法和应用 - Google Patents

一种超容量锂离子电池正极材料及其制备方法和应用 Download PDF

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WO2017186079A1
WO2017186079A1 PCT/CN2017/081647 CN2017081647W WO2017186079A1 WO 2017186079 A1 WO2017186079 A1 WO 2017186079A1 CN 2017081647 W CN2017081647 W CN 2017081647W WO 2017186079 A1 WO2017186079 A1 WO 2017186079A1
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lithium ion
lithium
ion battery
positive electrode
transition metal
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French (fr)
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潘锋
段彦栋
张丙凯
郑家新
胡江涛
刘同超
郭华
林原
李文
宋孝河
卓增庆
刘屹东
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • 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
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    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of cathode materials for lithium ion batteries, and in particular to an ultra-capacity lithium ion battery cathode material and a preparation method and application thereof.
  • Lithium-ion batteries have received much attention since their successful development, especially in equipment such as electric vehicles, emergency power reserves, energy storage facilities for wind and solar power generation, and automotive auxiliary power supplies.
  • the performance of lithium-ion batteries depends largely on their cathode materials. Lithium-ion battery cathode materials are an important factor affecting battery capacity and the main technical bottleneck for the development of high-capacity lithium-ion batteries.
  • the cathode materials of the existing lithium ion batteries are mainly LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiMn x Fe y PO 4 , LiNi 1-xy Mn x Co y O 2 (0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1) and LiNi 0.5 Mn 1.5 O 4 several.
  • the nanomaterial of the cathode material and the nanometer cathode material can improve the rapid charge and discharge capacity of the battery.
  • the nano-sized positive electrode material has a large specific surface area, in general, the surface interface cannot store lithium, which in turn causes the nano-sized positive electrode material to have a lower capacity than the ordinary positive electrode material, and has the disadvantages of low tap density and the like. .
  • the nano-sized positive electrode material has a large specific surface area and a relatively large side reaction on the surface.
  • LiMn 1/3 Ni 1/3 Co 1/3 O 2 +2HF+Li+e - ⁇ Li 1-x Mn 1/3 Ni 1/3 O 2 +LiF+H 2 O forming polycarbonate, high Molecular hydrocarbons, NiO, MnCO 3 , Li 2 CO 3 , Li x PF y , Li x PF y O z , NiF 2 , CoF 2 , MnF 2 , etc.
  • These insulating products increase the surface impedance of the material and affect lithium ions. The spread.
  • LiFePO 4 materials commonly used in electric vehicles have poor intrinsic conductivity, usually nano-sized, and carbon-coated on the surface of nano-positive materials.
  • the advantage of carbon coating is that the conductivity of the positive electrode material can be improved and the electrons can be accelerated. Transmission, promoting Li + diffusion, especially at high charge and discharge rates, can greatly reduce the possibility of its own structure being destroyed under a large lithium ion flux.
  • the existing carbon coating treatment method and composite cathode material have not fundamentally solved the problem of lattice interface damage.
  • the purpose of the present application is to provide a new ultra-capacity lithium ion battery cathode material and a preparation method and application thereof.
  • An aspect of the present application discloses a positive electrode material for a super-capacity lithium ion battery, which is composed of a lithium ion positive electrode material containing a transition metal and carbon coated on a surface of a lithium ion positive electrode material, and transition metal and carbon on the surface of the lithium ion positive electrode material are passed.
  • the XC bond is coordinated to form a transition metal-XC chemical bond such that carbon is stably coated on the surface of the positive electrode material; and wherein C is SP3 hybridization and/or SP2 hybridization, and X is at least one of N, O and S Kind.
  • the ultra-capacity lithium ion battery cathode material of the present application is capable of interfacial lithium storage, that is, lithium ions can be stored on the surface of the ultra-capacity lithium ion cathode material containing the coating layer of the present application.
  • the key difference between the super-capacitor lithium ion battery cathode material of the present application and the conventional carbon-coated lithium ion cathode material is that the transition metal on the surface of the lithium ion cathode material and the carbon in the present application are coordinated by XC. Forming a transition metal-XC chemical bond, this structure can repair the lattice interface; a general battery positive electrode material or a conventionally coated lithium ion positive electrode material, such as lithium iron phosphate, the surface of which is a surface end of Li atom. There are five oxygen atoms around the surface of Fe, which causes the FeO 6 octahedron to be destroyed.
  • the Fe atom on the surface of the lithium iron phosphate is passivated by the XC structure, thereby restoring the structure of the FeO 6 octahedron.
  • the role of lattice interface repair, the surface after repair is the surface end of C atom.
  • the positive capacity material of the ultra-capacity lithium ion battery of the present application repairs the lattice boundary of the positive electrode material by using the transition metal-XC chemical bond, not only overcomes the defects caused by the lattice boundary damage, but also increases the lithium storage.
  • the position can increase the position of lithium storage on the surface of the channel through which lithium ions enter and exit, and increase the position of lithium storage on the X side of the transition metal-XC chemical bond, further increasing the gram capacity of the positive electrode material. It can be understood that the key of the present application lies in the repair of the lattice boundary by the transition metal-XC chemical bond.
  • the transition metal may be a transition metal in the conventional conventional transition metal oxide lithium ion cathode material, or may be Other unconventional transition metals are not specifically limited herein; similarly, the transition metal-containing lithium ion cathode material may be various conventional or unconventional lithium ion cathode materials, which are not specifically limited herein. However, in a preferred implementation of the present application, several conventional transition metals, as well as transition metal-containing lithium ion cathode materials, have been specified.
  • any group capable of forming a coordination with a transition metal on the surface of a lithium ion positive electrode material to achieve lattice interface repair can be used in the present application; however, it has been confirmed by experiments that the OC bond is coordinated.
  • the effect of NC bond coordination and SC bond coordination is better; of course, both OC bond coordination, NC bond coordination, and SC bond coordination can be used regardless of production cost or some special requirements. Or three, there is no specific limit here.
  • the transition metal is at least one of Fe, Co, Ni, V, Ti, Mo, Cu, and Mn.
  • the transition metal-containing lithium ion cathode material is a phosphoric acid transition metal lithium cathode material, a silicic acid transition metal lithium cathode material, a boric acid transition metal lithium cathode material, a fluorinated sulfuric acid transition metal lithium cathode material, and a transition metal oxide lithium cathode material.
  • the transition metal is at least at least Fe, Mn, Co, and Ni.
  • the elements are balanced according to the chemical equation, and are not described here; similarly, Li 1+y (M a Z b Y c ) 1-y O 2 and LiMn 2- A' M' a' Z' b' O 4 , regardless of the value of each, will eventually satisfy the chemical equation balance, which is not described here.
  • lithium transition metal phosphate cathode material can also be expressed by the general formula LiM" a" X" b" Y" c" Z d PO 4
  • the lithium transition metal lithium cathode material can also be of the general formula Li 2 M.
  • boric acid transition metal lithium cathode material can also use the formula LiM” a" X" b" Y” c" Z d BO 3 expression, fluorinated sulfuric acid transition
  • the transition metal-containing lithium ion positive electrode material of the present application is a core-shell structure, wherein the inner core is a positive active material, the outer shell is lithium iron phosphate, the surface of the lithium iron phosphate outer shell is coated with carbon, and the carbon passes through the Fe-XC.
  • the coordination structure is stably coated on the surface of the lithium iron phosphate shell, wherein X is at least one of N, O and S; preferably, the thickness of the lithium iron phosphate shell is 1-100 nm.
  • the positive electrode active material may be a general conventional positive electrode active material, and since the lithium iron phosphate outer shell can form a coordination bond between Fe and carbon in lithium iron phosphate to achieve the interface repair effect of the present application,
  • the positive electrode active material as the core may not be specifically limited.
  • the other side of the present application discloses the application of the ultra-capacity lithium ion battery cathode material of the present application in a lithium ion battery, comprising preparing a positive electrode material of a super-capacity lithium ion battery as a positive electrode material of 5 nm to 100 ⁇ m;
  • the C on the surface of the positive electrode material of the ultra-capacity lithium ion battery is connected to each other or at least in contact with each other to form a network structure of a thermally stable conductive or lithium ion-conducting ion.
  • the positive electrode material of the ultra-capacity lithium ion battery capable of interfacial lithium storage of the present application is on the micro-nano level. If it is directly used as a positive electrode material of a battery, due to its polarity, it is easy to have uneven dispersion and easy agglomeration, which affects its Function, so when used as a battery positive material, usually It is made into a positive electrode particle material of 5 nm-100 ⁇ m; and when preparing a positive electrode particle material, the positive electrode material of the ultra-capacity lithium ion battery is a thermally stable secondary network structure formed by C-joining of its surface coating. This structure facilitates the conduction of electrons and lithium ions, thereby achieving ultra-capacity.
  • the positive electrode particle material of 5 nm to 100 ⁇ m in the present application is prepared by spray drying in an implementation manner of the present application, usually by preparing a primary particle of 5-150 nm and then once again.
  • the particles are prepared by spray drying to form secondary particles of 1-100 ⁇ m; generally, secondary particles are used to prepare the positive electrode, and of course, the primary electrode can be directly prepared by using primary particles.
  • the other side of the present application discloses a super-capacity lithium ion battery containing the positive capacity material of the ultra-capacity lithium ion battery of the present application, which can realize lithium storage at the interface, thereby increasing the gram capacity.
  • the method for preparing a super-capacity lithium ion battery comprises: dissolving at least one of the ultra-capacity lithium ion battery positive electrode material capable of interfacial lithium storage of the present application into a suspension, and then performing spray drying at a temperature of 25-220 ° C.
  • a positive secondary particle material of 200 nm to 100 ⁇ m is used for preparing a super-capacity lithium ion battery.
  • the positive electrode material of the ultra-capacity lithium ion battery of the present application may have many types according to the specific coordination bond, the transition metal or the coated lithium ion positive electrode material, and in preparing the ultra-capacity lithium ion battery.
  • One type of super-capacity lithium ion battery cathode material may be used alone or in combination, so that "at least one of the ultra-capacity lithium ion battery cathode materials capable of interfacial lithium storage of the present application is formulated into a suspension" .
  • the positive secondary particle material of 200 nm to 100 ⁇ m is usually prepared by first preparing a primary particle of 5-150 nm, and then making the primary particle into a secondary particulate material.
  • an all-solid lithium battery using the positive capacity material of the ultra-capacity lithium ion battery of the present application is disclosed, and the negative electrode of the all-solid lithium battery is lithium metal or lithium alloy.
  • the super-capacity lithium ion battery cathode material of the present application is suitable for various lithium batteries, and can of course also be used for preparing an all-solid lithium battery.
  • the all-solid lithium battery reference may be made to existing production and processes, and is not specifically limited herein.
  • the positive electrode sheet of the all-solid lithium battery of the present application is made of the positive capacity material of the ultra-capacity lithium ion battery of the present application and the conductive material and the solid electrolyte
  • the conductive material is conductive nano particles, conductive polymer, conductive nanotubes and conductive nanosheets.
  • At least one of the solid electrolytes is an indicator of an inorganic solid electrolyte, an organic solid electrolyte, and an organic/inorganic composite solid electrolyte
  • the anode of the all-solid lithium battery of the present application is a carbon-based material, a super-capacity oxide-based material, Sulfide based material, lithium metal or lithium alloy.
  • the conductive nanoparticles, the conductive nanotubes and the conductive nanosheets of the present application can all adopt existing materials, and the inorganic solid electrolyte, the organic solid electrolyte and the organic/inorganic composite solid electrolyte can also adopt the existing solid electrolyte;
  • the key to the application is to adopt the capable interface of the present application.
  • a lithium-ion ultra-capacity lithium ion battery cathode material and a conductive material and a solid electrolyte are used to form an electrode sheet, as for specific conductive nanoparticles, conductive nanotubes, conductive nanosheets, inorganic solid electrolytes, organic solid electrolytes, and organic/inorganic composite solid electrolytes. Materials that are conventionally used in production and testing can be used.
  • the separator of the all-solid lithium battery may also be an inorganic ceramic film, an organic separator or an inorganic ceramic and an organic composite separator.
  • a further aspect of the present application discloses a method for preparing a positive capacity lithium ion battery cathode material of the present application, comprising preparing an oxygen-containing, sulfur- or nitrogen-containing carbon source into a carbon source solution, and then using the transition metal-containing nanolithium
  • the ionic positive electrode material and the carbon source solution are mixed, placed in a ball mill, ball-milled until the solvent is completely volatilized, and the dried product after volatilization of the solvent is heated to 500-800 ° C under an inert atmosphere, and the temperature is kept for 2-12 hours, and the product is naturally cooled.
  • OC key or SC key or NC key for ultra-capacity lithium ion battery cathode material.
  • the key of the present application is that the transition metal-containing nano-lithium ion cathode material and the carbon source solution are mixed in a ball mill and ball-milled to dry, which can facilitate the formation of transition metal-XC chemical bonds. Thereby achieving the effect of repairing the lattice boundary.
  • the environment of the ball milling it may be in a room temperature environment, or may be in a certain temperature or a vacuum environment, and the ball milling temperature is usually appropriately heated on the basis of room temperature, for example, heating to less than 100 degrees, and is not specifically limited herein. .
  • a transition metal-OC chemical bond is formed under an oxygen-containing carbon source condition
  • a transition metal-SC chemical bond is formed under a sulfur-containing carbon source condition
  • a transition metal-NC chemical bond is formed under a nitrogen-containing carbon source condition
  • the ball milling is carried out under vacuum conditions in which oxygen is insulated under sulfur or nitrogen containing conditions.
  • the oxygen-containing carbon source is at least one of citric acid, glucose and sucrose; the sulfur-containing carbon source is thiol and/or thiophene; the nitrogen-containing carbon source is amino acid and/or melamine; and the concentration of the carbon source solution It is 0.1-2 mol/L.
  • the solvent of the carbon source solution is at least one of water, isopropyl alcohol, ethanol, acetone, and ethylene glycol.
  • the inert atmosphere is nitrogen or argon.
  • the supercapacitor lithium ion battery cathode material of the present application is capable of lithium storage at the interface, and the transition metal-XC chemical bond is used to connect the transition metal-containing lithium ion cathode material and carbon, and the transition metal-XC chemical bond is used to repair the lattice boundary of the cathode material.
  • the interface between the lithium ion positive electrode material and the carbon layer is optimized to form an interface for storing Li
  • the increased lithium storage position includes a position for adding lithium to the surface of the channel through which lithium ions enter and exit, and at the same time in the transition metal -
  • the X-side of the XC chemical bond increases the position of lithium storage, thereby increasing the gram capacity of the positive electrode material, which lays a foundation for the preparation of a super-capacity lithium ion battery.
  • FIG. 1 is a graph showing charge and discharge curves of a conventional carbon-coated lithium ion battery cathode material 83 nm-N and a CO bond-coordinated carbon-coated supercapacitor lithium ion battery cathode material 83 nm-E prepared in the examples of the present application.
  • the charge-discharge curve of the cathode material of the conventional carbon-coated lithium ion battery has a capacity of 168.2 mAh/g, and the solid line is a charge-discharge curve of the positive electrode material of the ultra-capacity lithium ion battery, and the capacity is 194.7 mAh/g;
  • FIG. 2 is a 1000-cycle cycle diagram of a conventional carbon-coated lithium ion battery cathode material 83 nm-N prepared in an embodiment of the present application, and the figures show a battery prepared from a conventional carbon-coated lithium ion battery cathode material having an average particle diameter of 83 nm. , the capacity retention rate after 1000 cycles at 10C 135.12 mAh/g is 99.7%;
  • FIG. 3 is a cycle chart of 1000 times of 83 nm-E of a positive electrode material for a super-capacity lithium ion battery prepared in an embodiment of the present application, and the figure shows a battery prepared by using a positive electrode material of an ultra-capacity lithium ion battery having an average particle diameter of 83 nm at 10 C 157.60.
  • the capacity retention rate after 1000 cycles at mAh/g is 99.5%;
  • FIG. 4 is an X-ray photoelectron spectroscopy diagram of a conventional carbon-coated lithium ion battery cathode material 83 nm-N and a super-capacity lithium ion battery cathode material 83 nm-E prepared in an embodiment of the present application, wherein the upper half is a super capacity.
  • FIG. 5 is a soft X-ray test result of a conventional carbon-coated lithium ion battery cathode material prepared by an embodiment of the present invention at 83 nm-N under different SOC, and a graph is a K-side soft X-ray absorption spectrum of Fe element under different SOC, b diagram A, B, C, D, and E are different SOC markers respectively for the different SOC marker points corresponding to the a diagram;
  • FIG. 6 is a soft X-ray test result of 83 nm-E cathode materials of a super-capacitor lithium ion battery prepared in an embodiment of the present application, and a graph is a K-edge soft X-ray absorption spectrum of Fe under different SOCs, and b is a corresponding figure.
  • A, B, C, D, E, F, and G are different SOC marks respectively;
  • FIG. 7 is a schematic view showing the structure of the LiFePO 4 lattice before and after repair in the embodiment of the present application, wherein a is a schematic diagram of the structure before repair, and b is a schematic diagram of the structure after repair, wherein O represents oxygen, C represents carbon, and Li represents lithium. ion;
  • FIG. 8 is an X-ray photoelectron spectroscopy chart of a CN bond generated by a 42 nm LiFePO 4 material of a positive electrode material of a super-capacity carbon-coated lithium ion battery prepared in an embodiment of the present application;
  • FIG. 9 is a graph showing charge and discharge curves of a conventional carbon-coated lithium ion battery cathode material LiFePO 4 and a CN bond-coordinated carbon-coated supercapacitor lithium ion battery cathode material prepared in an embodiment of the present application, wherein the dotted line is a conventional carbon package.
  • the charge-discharge curve of the cathode material of the lithium-ion battery is 176.7 mAh/g
  • the solid line is the charge-discharge curve of the cathode material of the ultra-capacity lithium ion battery, and the capacity is 186.1 mAh/g;
  • FIG. 10 is an X-ray photoelectron spectroscopy chart of a CS bond generated by a 42 nm LiFePO 4 material of a positive electrode material of a super-capacity carbon-coated lithium ion battery prepared in an embodiment of the present application;
  • FIG. 11 is a graph showing charge and discharge curves of a conventional carbon-coated lithium ion battery cathode material LiFePO 4 and a CS bond-coordinated carbon-coated supercapacitor lithium ion battery cathode material prepared in an embodiment of the present application, wherein the dotted line is a conventional carbon package.
  • the charge and discharge curve of the cathode material of the lithium ion battery is 167.5 mAh/g
  • the solid line is the charge and discharge curve of the cathode material of the ultracapacity lithium ion battery, and the capacity is 187.3 mAh/g;
  • FIG. 12 is a graph showing charge and discharge curves of a carbon material-coordinated carbon-coated supercapacitance carbon-coated lithium ion battery cathode material LiFePO 4 /LiMn 0.6 Fe 0.4 O 4 prepared in an embodiment of the present application;
  • 13 is a graph showing charge and discharge curves of an all-solid LiFePO 4 lithium ion battery prepared in an embodiment of the present application, wherein 1C, 5C, 10C, and 20C respectively represent charge and discharge curves at 1C, 5C, 10C, and 20C magnifications;
  • FIG. 14 is a schematic structural view showing the state of storing lithium ions before and after surface lattice repair of a lithium ion positive electrode material in the embodiment of the present application, wherein a is a schematic structural view before repair, and b is a schematic structural view after repair.
  • the inventors of the present application found that the carbon-coated LiFePO 4 lithium ion positive electrode material prepared by the inventors has been studied by the inventors. The capacity will be improved to different extents.
  • the lithium ion battery prepared by these carbon-coated lithium ion cathode materials can have a battery capacity of 200 mAhg -1 or more, exceeding the theoretical capacity of LiFePO 4 of 200 mAhg -1 .
  • the inventors of the present application conducted intensive studies on carbon-coated lithium ion cathode materials, and found that when a lithium ion cathode material containing a transition metal is carbon coated, the surface of the lithium ion cathode material is The transition metal and carbon are coordinated by the OC bond to form a transition metal-OC chemical bond.
  • This structure can repair the lattice interface of the damaged cathode material. It is confirmed by the calculation of the first principle of quantum chemistry that there is a Fe on the surface of the lithium iron phosphate. The five oxygen atoms are broken FeO 5 octahedrons, so that the surface on the channel through which lithium ions enter and exit cannot store lithium.
  • the calculated lithium storage voltage is -0.13V, so lithium cannot be stored.
  • the Fe atom on the surface of the lithium iron phosphate is passivated by the OC structure, thereby restoring the structure of the FeO 6 octahedron, so that the increased lithium storage position on the surface is included in the channel of lithium ion in and out.
  • the surface becomes a position where lithium can be stored, and the voltage of lithium storage is about 3.2V, which is slightly lower than the voltage of the bulk phase, about 0.1-0.2V lower, and increases at the O edge of the transition Fe-OC chemical bond.
  • Lithium storage position the voltage is about 2.6V, thus increasing the effective g of lithium storage capacity of the positive electrode material.
  • the present application further studies the formation and preparation methods of transition metal-OC chemical bonds, thereby proposing the supercapacitor lithium ion battery cathode material of the present application and a preparation method thereof.
  • a conventional carbon-coated cathode material and a transition metal-O-C chemical bond to repair the lattice interface of the carbon-coated supercapacitor lithium ion battery cathode material were prepared.
  • Conventional carbon-coated positive electrode material 1 g of lithium iron phosphate having an average particle diameter of 83 nm, 0.2 g of glucose, and 5 mL of dispersant ethanol are mixed, and the obtained product is heated to 650 ° C under an argon atmosphere after conventional heating and drying. After constant temperature for 4 h, LiFePO 4 /C composite material was obtained after natural cooling.
  • the supercapacitor lithium ion battery cathode material 1 g of lithium iron phosphate having an average particle diameter of 83 nm, 0.2 g of glucose and 10 mL of dispersant ethanol are mixed and placed in a ball mill to be ball-milled into a nano slurry, and the rotation speed of the ball mill is 350 rpm. Grinding to dry, about 10h ball milling, that is, the dispersant ethanol is completely volatilized, and then placed in an argon atmosphere, heated to 650 ° C, constant temperature 4h, and naturally cooled to obtain the positive capacity material of the ultra-capacity lithium ion battery of this example.
  • the conventional carbon-coated cathode material prepared in this example and the cathode material of the ultra-capacity lithium ion battery were assembled into a battery, and the batteries of the conventional carbon coating and the ultra-capacity carbon-coated cathode material were respectively charged and discharged to FIG. 5 and FIG.
  • the lithium ion battery positive electrode material prepared in this example is prepared into a suspension, and then spray-dried at 100 ° C to prepare a composite positive electrode particle having an average particle diameter of 12 ⁇ m for preparing a lithium ion battery.
  • the positive electrode sheet is prepared by preparing a composite positive electrode particle having an average particle diameter of 12 ⁇ m, acetylene black and PVDF, and then coating it on an Al foil, and the negative electrode is a lithium plate.
  • the assembly of the lithium ion battery is referred to a conventional assembly method, and Repeated.
  • the conventional carbon-coated positive electrode material is directly prepared by slurrying with acetylene black and PVDF and then coated on an Al foil, and the negative electrode is also made of a lithium plate, and assembled into a battery by the same method. .
  • the results of synchrotron radiation soft X-ray absorption spectra of the two cells at different SOCs were then tested.
  • Figures 5 and 6 The test results are shown in Figures 5 and 6.
  • Figure 5 shows the soft X-ray test results of batteries assembled with conventional carbon-coated cathode materials at different SOCs.
  • Figure a shows the K-edge soft X-ray absorption spectrum of Fe under different SOCs. The figure shows the different SOC mark points corresponding to the a picture.
  • Figure 6 shows the soft X-ray test results of the battery assembled with the positive electrode material of the ultra-capacity lithium ion battery under different SOCs. The picture shows the soft X-ray of the K side under different SOCs of Fe element.
  • a is a schematic diagram of the lattice interface structure when no transition metal-OC chemical bond is formed
  • b is a carbon coating
  • Fig. 1 is a graph of charge and discharge. It can be seen from the figure that a battery using a conventional carbon-coated positive electrode material has a capacity of 168.2 mAh g -1 ; a battery prepared from a positive electrode material of a super-capacity lithium ion battery has a capacity of 194.7 mAh g - 1 .
  • Fig. 2 and Fig. 3 are cycle diagrams of 1000 cycles, Fig.
  • Fig. 2 is a cycle diagram of 1000 cycles of a battery using a conventional carbon-coated positive electrode material
  • Fig. 3 is a cycle of 1000 cycles of a battery prepared using a positive electrode material of a super-capacity lithium ion battery.
  • the graph as can be seen from the figure, the battery prepared by the conventional carbon-coated positive electrode material and the ultra-capacity lithium ion battery positive electrode material have very good cycle performance, and the battery capacity retention rate after 1000 cycles is still as high as 99%. the above.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example 1 g of melamine having an average particle diameter of 42 nm LiFePO 4 and 0.3 g of a nitrogen-containing carbon source was dispersed in 10 mL of ethanol, ball-milled to dryness under nitrogen, and then placed in an inert atmosphere. Next, the temperature was raised to 750 ° C, and the temperature was kept for 6 hours, and the positive electrode material of the ultra-capacity lithium ion battery of this example was obtained.
  • the interface between LiFePO 4 and the carbon layer was tested by X-ray photoelectron spectroscopy.
  • the test results are shown in Fig. 8.
  • the X-ray photoelectron spectroscopy indicated the formation of a CN bond; it was confirmed that LiFePO 4 and the carbon layer were in this example. A new interface is formed, the repaired lattice interface.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and are not described here.
  • the test results are shown in Fig. 9.
  • the battery assembled with the positive electrode material of the ultra-capacity lithium ion battery of this example has a battery capacity of 186.1 mAhg -1 .
  • a super-capacity lithium ion battery positive electrode material the average particle diameter of 42 nanometers 1g LiFePO 4 carbon source and a sulfur-containing thiophene 0.2g 8mL of ethanol was dispersed in a ball mill to dryness under nitrogen, and then placed an inert atmosphere Next, the temperature was raised to 850 ° C, and the temperature was kept for 12 hours, and the positive electrode material of the ultra-capacity lithium ion battery of this example was obtained.
  • the interface between LiFePO 4 and the carbon layer was tested by X-ray photoelectron spectroscopy.
  • the test results are shown in Fig. 10.
  • the X-ray photoelectron spectroscopy indicated the formation of a CS bond; it was confirmed that LiFePO 4 and the carbon layer were in this example. A new interface is formed, the repaired lattice interface.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and are not described here.
  • the test results are shown in Fig. 11.
  • the battery assembled with the positive electrode material of the ultra-capacity lithium ion battery of this example has a battery capacity of 187.3 mAhg -1 .
  • the nano-lithium iron phosphate of the first embodiment is replaced by nano-LiMn 2 O 4 , and the nano-LiMn 2 O 4 and sucrose are dispersed into ethanol, and the ball is ground to dry, and then placed. Under an inert atmosphere, the temperature was raised to 650 ° C and the temperature was maintained for 10 h to obtain a positive electrode material for the ultra-capacity lithium ion battery of this example.
  • the interface between LiMn 2 O 4 and the carbon layer was tested by X-ray photoelectron spectroscopy.
  • X-ray photoelectron spectroscopy indicated the formation of CO bonds. It was confirmed that a new bond was formed between LiMn 2 O 4 and the carbon layer in this example.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and are not described here.
  • the test results show that the battery assembled with the positive capacity material of the ultra-capacity lithium ion battery of this example has a battery capacity of 199.2 mAhg -1 , and the battery capacity retention rate after 1000 cycles is still as high as 99% or more.
  • the nano-lithium iron phosphate of the first embodiment is replaced by nano-LiNi 0.5 Mn 1.5 O 4 , and the nano-LiNi 0.5 Mn 1.5 O 4 and sucrose are dispersed into ethanol, and the same is performed by ball milling to dryness. Then, it was placed under an inert atmosphere, heated to 500 ° C, and kept at a constant temperature for 2 hours to obtain a positive electrode material of the ultra-capacity lithium ion battery of this example.
  • X-ray photoelectron spectroscopy was used to test the interface between LiNi 0.5 Mn 1.5 O 4 and the carbon layer. X-ray photoelectron spectroscopy indicated the formation of CO bond; it was confirmed that LiNi 0.5 Mn 1.5 O 4 and carbon layer in this example A new interface is formed, the repaired lattice interface.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and are not described here.
  • the test results show that the battery assembled with the positive capacity material of the ultra-capacity lithium ion battery of this example has a battery capacity of 207.5 mAhg -1 , and the battery capacity retention rate after 1000 cycles is still as high as 99% or more.
  • the nano-LiFePO 4 /LiMn 0.6 Fe 0.4 O 4 adopting the core-shell structure replaces the lithium iron phosphate of the first embodiment, and the LiFePO 4 is a shell layer, and the prepared LiFePO 4 /LiMn 0.6
  • the lithium iron phosphate shell layer of Fe 0.4 O 4 was 5 nm thick.
  • the LiFePO 4 /LiMn 0.6 Fe 0.4 O 4 core-shell structure nano material is prepared by a conventional coating method, and is not specifically limited herein.
  • the ferrous sulfate solution was added to the three-necked flask with continuous stirring and argon gas protection. After 10 minutes, the phosphoric acid solution was added dropwise, stirred for 10 minutes, and then the lithium hydroxide solution was added dropwise, and the temperature was raised after 10 minutes.
  • the temperature was raised to the range of 90-120 ° C, and the second portion of the ferrous sulfate solution was added dropwise to the solution, and the temperature was continuously raised to 180 ° C for 4 hours, then cooled and centrifuged, followed by drying in a vacuum oven at 80 ° C.
  • the nano-LiFePO 4 /LiMn 0.6 Fe 0.4 O 4 and sucrose were dispersed in ethanol, and then ball-milled to dryness, and then placed under an inert atmosphere, and the temperature was raised to 800 ° C, and the temperature was kept for 5 hours to obtain the ultra-capacity lithium ion battery of the present example.
  • Cathode material The nano-LiFePO 4 /LiMn 0.6 Fe 0.4 O 4 and sucrose were dispersed in ethanol, and then ball-milled to dryness, and then placed under an inert atmosphere, and the temperature was raised to 800 ° C, and the temperature was kept for 5 hours to obtain the ultra-capacity lithium ion battery of the present example. Cathode material.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and will not be described here.
  • the test results are shown in Fig. 12.
  • the results show that the battery assembled with the positive capacity material of the ultra-capacity lithium ion battery of this example has a battery capacity of 156.3 mAhg -1 , and the battery capacity retention rate after 1000 cycles is still as high as 99% or more. .
  • LiCo 1/3 Mn 1/3 Ni 1/3 O 2 is used instead of the lithium iron phosphate of the first embodiment, and the nano LiCo 1/3 Mn 1/3 Ni 1/ 3 O 2 and sucrose were dispersed in ethanol, and then ball-milled to dryness, and then placed under an inert atmosphere, and heated to 800 ° C, and kept at a constant temperature for 5 hours to obtain a positive electrode material of the ultra-capacity lithium ion battery of this example.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example was assembled into a battery, and the battery was tested by the Maccor M4200 battery test system.
  • the assembly and test method of the battery were the same as those in the first embodiment, and are not described here.
  • the test results show that the battery assembled with the positive capacity material of the ultra-capacity lithium ion battery of this example has a battery capacity of 200.3 mAhg -1 , and the battery capacity retention rate after 1000 cycles is still as high as 99% or more.
  • the positive electrode material of the ultra-capacity lithium ion battery of this example 1 g of LiFePO 4 having an average particle diameter of 42 nm and 0.2 g of glucose are dispersed in 5 mL of ethanol, ball-milled to dryness under nitrogen, and then placed under an inert atmosphere to raise the temperature.
  • the cathode material of the ultra-capacity lithium ion battery of this example was obtained by heating to 650 ° C for 6 h.
  • the interface between LiFePO 4 and the carbon layer was tested by X-ray photoelectron spectroscopy.
  • the X-ray photoelectron spectroscopy indicated the formation of a CN bond. It was confirmed that a new interface was formed between LiFePO 4 and the carbon layer in this example. The repaired lattice interface.
  • the positive capacity lithium-ion battery cathode material of this example was assembled into an all-solid lithium battery, and the battery was tested by the Maccor M4200 battery test system.
  • the battery assembly and test methods are as follows:
  • positive electrode sheet 1 g of the positive capacity material of the ultra-capacity lithium ion battery prepared in this example, 0.2 g of acetylene black conductive nanoparticles with an average particle diameter of 40 nm, and 0.1 g of the organic solid electrolyte were thoroughly mixed, and then pressed into a tight contact diameter.
  • High-temperature assembly with high-performance all-solid-state lithium battery The positive electrode material is cut according to the battery type and battery type.
  • the positive electrode piece of this example has a diameter of 2 cm.
  • the polymer film was cut according to the size of the positive electrode sheet, and the diameter of the polymer film was slightly larger than the diameter of the positive electrode sheet by 0.1 to 0.2 cm.
  • the lithium sheet selected in this example was used as a negative electrode sheet.
  • the positive electrode sheet, the polymer electrolyte membrane, and the negative electrode sheet were press-bonded in the order of gradient, and packaged with a battery can.
  • lithium ion cathode materials containing Fe, Mn, Co, Ni, etc., such as LiFePO 4 , LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiCo 1/3 Mn 1/3 Ni 1/3 were tested.
  • the transition metal in O 2 is capable of forming a transition metal-XC chemical bond with C such that the carbon is stably coated on the surface of the positive electrode material.
  • X is N, O or S.
  • transition metal ions are exposed at the terminal due to the destruction of the transition metal-O structure, as shown in a of FIG. 7 .
  • a structure of a transition metal-XC chemical bond is generated at the terminal of the transition metal ion, as shown in FIG. 7b, which causes an excess of Li on the surface. storage location.
  • a typical structure is LiMPO 4 , where M is the transition metal Fe, Mn or Co.
  • the average voltage at each position of LiFePO 4 , LiCoPO 4 , LiMnPO 4 , LiFe 0.5 Mn 0.5 PO 4 without C is calculated, and the carbon-coated LiFePO 4 and LiCoPO 4 forming the transition metal MXC chemical bond are respectively calculated.
  • the test positions are four positions S1, S2, S3, and S4 shown in Fig. 14, respectively. The results are shown in Table 1.
  • LiMPO 4 -N is ordinary LiMPO 4 , that is, LiFePO 4 , LiCoPO 4 , LiMnPO 4 , LiFe 0.5 Mn 0.5 PO 4 without C coating;
  • LiMPO 4 -E is ultra-capacity LiMPO 4 That is, the C-coated ultra-capacity lithium ion battery cathode material of this example.
  • the ultra-capacity study is implemented by density functional theory calculations, using VASP (full name Vienna Ab-initio Simulation Package) software to optimize the geometry and electronic structure of each system.
  • VASP full name Vienna Ab-initio Simulation Package
  • the PBE functional of generalized gradient approximation (abbreviated GGA) is used to describe the electron exchange correlation potential.
  • GGA generalized gradient approximation
  • PAW plane wave
  • PAW plane wave
  • the Brillouin zone is Monkhorst-Pack.
  • the convergence criterion of the self-consistent field loop is 10 -5 eV, and the geometry is fully optimized until the value of the residual force on the atom is less than 0.01 eV/A.
  • the calculation of the lithium (Li) average voltage of the unit cell structure is calculated by the following formula (1) using the Nernst relationship:
  • V(x) - ⁇ G/(xF) (1)
  • F is a Faraday constant
  • x is the number of embedded Li
  • ⁇ G is the amount of change in Gibbs free energy
  • M represents a different transition metal
  • ⁇ Li represents the chemical potential of Li
  • E (LiMPO 4 ) and E (MPO 4 ) are the energies of the crystal structures of LiMPO 4 and MPO 4 , respectively.
  • MXC lithium storage interface coating
  • the carbon-coated surface of the present invention has a new lithium storage position on the surface of LiMPO 4 and increases the capacity of LiMPO 4 ; at the position S4, the position on the surface of LiMPO 4 cannot be stored, and lithium is coated after carbon coating.
  • voltage is 2.6-2.8, after the same described in the present application ultra-capacity carbon coating, on the surface of LiMPO 4 adds new lithium storage position, increases capacity of LiMPO 4.
  • the voltage of this part of Li is relatively fixed, and the voltage is between 2.6 and 2.8V, which is also a usable part, as shown in Fig. 14(b). Show. Therefore, as long as the lithium ion positive electrode material capable of forming a transition metal-XC chemical bond can achieve the over-capacity effect of the present application; in addition to the lithium ion positive electrode material of the transition metal containing Fe, Mn, Co, Ni, etc. of Examples 1-7; A conventional lithium ion positive electrode material containing a transition metal of V, Ti, Mo or Cu can also form a transition metal-XC chemical bond, so that the positive electrode material can store more Li.

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Abstract

一种超容量锂离子电池正极材料及其制备方法和应用。超容量锂离子电池正极材料，由含过渡金属的锂离子正极材料和包覆于锂离子正极材料表面的碳组成，锂离子正极材料表面的过渡金属与碳通过X-C键配位，形成过渡金属-X-C化学键，使碳稳定包覆于正极材料表面；其中C为SP3杂化和/或SP2杂化，X为N、O和S中的至少一种。超容量锂离子电池正极材料，通过过渡金属-X-C化学键连接锂离子正极材料和碳，利用过渡金属-X-C化学键对正极材料的表面的晶格边界进行修复，使锂离子正极材料和碳层之间的界面得以优化，形成可储存Li的界面，从而增加正极材料克容量，为制备超容量锂离子电池奠定了基础。

Description

一种超容量锂离子电池正极材料及其制备方法和应用 技术领域
本申请涉及锂离子电池正极材料领域，特别是涉及一种超容量的锂离子电池正极材料及其制备方法和应用。
背景技术
迅速发展起来的二次电池工业，构成了新能源领域的重要部分。锂离子电池自从开发成功以来便备受关注，特别是在诸如电动汽车、应急电力储备、风电与太阳能发电的储能设施以及车用辅助电源等设备中开始应用。锂离子电池的性能很大程度上取决于其正极材料，锂离子电池正极材料是影响电池容量的重要因素，也是高容量锂离子电池发展的主要技术瓶颈。现有的锂离子电池的正极材料主要有LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiFePO4、LiMnxFeyPO4，LiNi1-x-yMnxCoyO2(0＜x＜1，0＜y＜1)和LiNi0.5Mn1.5O4几种。
目前锂离子电池正极材料的一个重要发展和研究方向就是，正极材料的纳米化，纳米化正极材料可以提高电池的快速充放电能力。虽然，纳米化的正极材料比表面积大，但是，在一般的情况下其表面界面不能储锂，反而导致纳米化的正极材料具有比普通正极材料更低的容量，并且具有振实密度低等缺点。
此外，纳米化正极材料的比表面积大，其表面的副反应也比较多。例如LiMn1/3Ni1/3Co1/3O2+2HF+Li+e-→Li1-xMn1/3Ni1/3O2+LiF+H2O，生成聚碳酸酯、高分子碳氢化合物、NiO、MnCO3、Li2CO3、LixPFy、LixPFyOz、NiF2、CoF2、MnF2等，这些绝缘产物会增加材料的表面阻抗，影响锂离子的扩散。并且，由于晶格界面破坏，比表面积越大，晶格破坏面就越多，影响正极材料的电化学性能。目前在电动汽车里常用的LiFePO4材料的本征的导电性性差，通常采用纳米化，在纳米正极材料表面进行碳包覆，碳包覆的好处是，可以提高正极材料的导电性，加快电子传输，促进Li+扩散，特别是在高充放电倍率下能够大大降低其自身结构在较大锂离子通量下被破坏的可能性。但是，现有的碳包覆处理方法和复合正极材料，还是没有从根本上解决晶格界面破坏的问题。
发明内容
本申请的目的是提供一种新的超容量的锂离子电池正极材料及其制备方法和应用。
本申请采用了以下技术方案：
本申请的一方面公开了一种超容量锂离子电池正极材料，由含有过渡金属的锂离子正极材料和包覆于锂离子正极材料表面的碳组成，锂离子正极材料表面的过渡金属与碳通过X-C键配位，形成过渡金属-X-C化学键，使得碳稳定的包覆于正极材料的表面；并且，其中C为SP3杂化和/或SP2杂化，X为N、O和S中的至少一种。本申请的超容量锂离子电池正极材料能够界面储锂，即锂离子可以储在含有本申请的包覆层的超容量锂离子正极材料表面上。
需要说明的是，本申请的超容量锂离子电池正极材料与传统的碳包覆锂离子正极材料相比，其关键区别在于，本申请中锂离子正极材料表面的过渡金属与碳通过X-C配位形成过渡金属-X-C化学键，这种结构可以修复晶格界面；一般的电池正极材料或者传统包覆的锂离子正极材料，例如磷酸铁锂，其磷酸铁锂表面是以Li原子为终端的表面，表面上的Fe周围有五个氧原子，导致FeO6八面体被破坏，当形成过渡金属-X-C化学键时，磷酸铁锂表面Fe原子被X-C结构钝化，从而恢复FeO6八面体的结构，达到晶格界面修复的作用，修复之后的表面是以C原子为终端的表面。
更为重要的是，本申请的超容量锂离子电池正极材料，利用过渡金属-X-C化学键对正极材料的晶格边界进行修复，不仅克服了晶格边界破损造成的缺陷，而且增加了储锂的位置，可以在锂离子进出的通道的表面增加一个储锂的位置，同时在过渡金属-X-C化学键的X边上增加储锂的位置，进一步增加了正极材料的克容量。可以理解，本申请的关键在于过渡金属-X-C化学键对晶格边界的修复，至于过渡金属的具体类型，可以是现有的常规的过渡金属氧化物锂离子正极材料中的过渡金属，也可以是其它的不常规的过渡金属，在此不做具体限定；同样的，含有过渡金属的锂离子正极材料也可以是各种常规或不常规的锂离子正极材料，在此不做具体限定。只是，在本申请的优选实现方式中，对几种常规的过渡金属，以及含过渡金属的锂离子正极材料进行了指定。
还需要说明的是，理论上凡是能够与锂离子正极材料表面的过渡金属形成配位，达到晶格界面修复作用的基团都可以用于本申请；但是，经试验证实，其中O-C键配位、N-C键配位和S-C键配位的效果较好；当然，在不考虑生产成本或者一些特殊需求中，也可以同时采用O-C键配位、N-C键配位和S-C键配位中的两者或三者，在此不做具体限定。
优选的，过渡金属为Fe、Co、Ni、V、Ti、Mo、Cu和Mn中的至少一种。
优选的，含有过渡金属的锂离子正极材料为磷酸过渡金属锂正极材料、硅酸过渡金属锂正极材料、硼酸过渡金属锂正极材料、氟化硫酸过渡金属锂正极材料、过渡金属氧化物锂正极材料中的至少一种；其中，磷酸过渡金属锂正极 材料、硅酸过渡金属锂正极材料、硼酸过渡金属锂正极材料、氟化硫酸过渡金属锂正极材料、过渡金属氧化物锂正极材料中，过渡金属为Fe、Mn、Co、Ni、V、Ti、Mo、Cu中的至少一种；过渡金属氧化物锂正极材料为Li1+y(MaZbYc)1-yO2和/或LiMn2-a’M’a’Z’b’O4，Li1+y(MaZbYc)1-yO2中，M、Z、Y不重复的选自Ni、Mn、Co、V、Ti、Mo、Cu中的一种，0≤a≤1、0≤b≤1、0≤c≤1，并且a+b+c＝1，0≤y≤1；LiMn2-a’M’a’Z’b’O4中，M’和Z’不重复的选自Cr、Co、Ni、Cu、Fe、Mo、Ti和V中的一种，0≤a’≤2、0≤b’≤2。
需要说明的是，磷酸过渡金属锂正极材料、硅酸过渡金属锂正极材料、硼酸过渡金属锂正极材料、氟化硫酸过渡金属锂正极材料中，过渡金属为Fe、Mn、Co、Ni中的至少一种，在过渡金属为多种时，各元素按照化学方程式配平即可，在此不累述；同样的，Li1+y(MaZbYc)1-yO2和LiMn2-a’M’a’Z’b’O4中无论各取值如何，最终也必然满足化学方程式配平，在此不累述。
还需要说明的是，磷酸过渡金属锂正极材料也可以采用通式LiM”a”X”b”Y”c”ZdPO4表达，硅酸过渡金属锂正极材料也可以采用通式Li2M”a”X”b”Y”c”ZdSiO4表达、硼酸过渡金属锂正极材料也可以采用通式LiM”a”X”b”Y”c”ZdBO3表达、氟化硫酸过渡金属锂正极材料也可以采用通式LiM”a”X”b”Y”c”ZdSO4F表达；其中，M”、X”、Y”、Z不重复的选自Fe、Mn、Co、Ni，0≤a”≤1、0≤b”≤1、0≤c”≤1、0≤d≤1，并且a”+b”+c”+d＝1。
优选的，本申请的含有过渡金属的锂离子正极材料为核-壳结构，其中，内核为正极活性材料，外壳为磷酸铁锂，磷酸铁锂外壳的表面包覆碳，碳通过Fe-X-C的配位结构稳定的包覆于磷酸铁锂外壳表面，其中X为N、O和S中的至少一种；优选的，磷酸铁锂外壳的厚度为1-100纳米。
需要说明的是，其中正极活性材料可以是一般的常规的正极活性材料，因为具有磷酸铁锂外壳，可以通过磷酸铁锂中的Fe与碳形成配位键从而达到本申请的界面修复效果，因此，作为内核的正极活性材料可以不做具体限定。
本申请的另一面公开了本申请的超容量锂离子电池正极材料在锂离子电池中的应用，包括将超容量锂离子电池正极材料制备成5nm-100μm的正极颗粒材料；该正极颗粒材料中，超容量锂离子电池正极材料表面的C彼此连接在一起或者至少有一点接触的连接在一起，形成热稳定的导电子或导锂离子的网络结构。
需要说明的是，本申请的能够界面储锂的超容量锂离子电池正极材料是微纳米级别的，如果直接作为电池正极材料使用，由于其极性，容易存在分散不均匀，易团聚，影响其功能发挥，因此，在作为电池正极材料使用时，通常都 是将其制成5nm-100μm的正极颗粒材料；而在制备成正极颗粒材料时，超容量锂离子电池正极材料之间是通过其表面包覆的C连接形成的热稳定的二次网络结构，该结构能够方便电子和锂离子的传导，从而实现超容量。
还需要说明的是，本申请中5nm-100μm的正极颗粒材料，在本申请的一种实现方式中是采用喷雾干燥的方式制备的，通常是先制备5-150nm的一次颗粒，然后再将一次颗粒由喷雾干燥法制备成1-100μm的二次颗粒；一般是采用二次颗粒制备正极，当然，也可以直接采用一次颗粒制备正极。
本申请的另一面公开了一种超容量锂离子电池，该超容量锂离子电池中含有本申请的超容量锂离子电池正极材料，可以实现界面储锂，从而增加克容量。
优选的，超容量锂离子电池的制备方法包括，将至少一种本申请的能够界面储锂的超容量锂离子电池正极材料配成悬浮液，然后在25-220℃温度下进行喷雾干燥，制成200nm-100μm的正极二次颗粒材料，用于制备超容量锂离子电池。
需要说明的是，本申请的超容量锂离子电池正极材料，根据其具体的配位键、过渡金属或所包覆的锂离子正极材料不同，可以有很多种类，在制备超容量锂离子电池时，可以单独采用其中一种超容量锂离子电池正极材料，也可以采用多种配合使用，所以是“将至少一种本申请的能够界面储锂的超容量锂离子电池正极材料配成悬浮液”。
还需要说明的是，制成200nm-100μm的正极二次颗粒材料，通常是先制备5-150nm的一次颗粒，然后再将一次颗粒制成二次颗粒材料。
本申请的再一面公开了一种采用本申请的超容量锂离子电池正极材料的全固态锂电池，全固态锂电池的负极为锂金属或锂合金。
可以理解，本申请的超容量锂离子电池正极材料适用于各种锂电池，当然也可以用于制备全固态锂电池。至于全固态锂电池的其它组分和构件都可以参考现有生产和工艺，在此不做具体限定。
优选的，本申请的全固态锂电池的正极片由本申请的超容量锂离子电池正极材料和导电材料、固态电解质制成，导电材料为导电纳米颗粒、导电高分子、导电纳米管和导电纳米片中的至少一种，固态电解质为无机固态电解质、有机固态电解质和有机/无机复合固态电解质中的指示一种，本申请的全固态锂电池的负极为碳基材料、超容量氧化物基材料、硫化物基材料、锂金属或锂合金。
需要说明的是，本申请的导电纳米颗粒、导电纳米管和导电纳米片都可以采用现有的材料，无机固态电解质、有机固态电解质和有机/无机复合固态电解质同样可以采用现有的固态电解质；本申请的关键在于采用本申请的能够界面 储锂的超容量锂离子电池正极材料与导电材料和固态电解质制成电极片，至于具体的导电纳米颗粒、导电纳米管、导电纳米片、无机固态电解质、有机固态电解质和有机/无机复合固态电解质都可以采用生产和试验中常规使用的材料。
另外，全固态锂电池的隔膜也可以是无机陶瓷膜、有机隔膜或是无机陶瓷和有机复合的隔膜。
本申请的再一面公开了一种本申请的超容量锂离子电池正极材料的制备方法，包括将含氧、含硫或含氮的碳源制备成碳源溶液，然后将含有过渡金属的纳米锂离子正极材料和碳源溶液混合，置于球磨机中，球磨直至溶剂完全挥发，将溶剂挥发后的干燥产物在惰性气氛下，升温至500-800℃，恒温2-12h，自然冷却，即获得含O-C键或S-C键或N-C键的超容量锂离子电池正极材料。
需要说明的是，本申请的关键在于，含过渡金属的纳米锂离子正极材料和碳源溶液混合在球磨机中球磨，球磨使其干燥，这种方式，能够有利于过渡金属-X-C化学键的形成，从而达到修复晶格边界的效果。至于球磨的环境，可以是在室温环境，也可以是在一定的温度或抽真空环境，该球磨温度，通常是以室温为基础进行适当加热，例如加热到小于100度，在此不做具体限定。其中，含氧的碳源条件下即形成过渡金属-O-C化学键，含硫的碳源条件下即形成过渡金属-S-C化学键，含氮的碳源条件下即形成过渡金属-N-C化学键；本申请的优选方案中，在含硫或含氮的条件下时，球磨是在隔绝氧气的真空条件下进行的。
优选的，含氧的碳源为柠檬酸、葡萄糖和蔗糖中的至少一种；含硫的碳源为硫醇和/或噻吩；含氮的碳源为氨基酸和/或三聚氰胺；碳源溶液的浓度为0.1-2mol/L。优选的，碳源溶液的溶剂为水、异丙醇、乙醇、丙酮、乙二醇中的至少一种。
优选的，惰性气氛为氮气或氩气。
本申请的有益效果在于：
本申请的超容量锂离子电池正极材料，能够界面储锂，通过过渡金属-X-C化学键连接含过渡金属的锂离子正极材料和碳，利用过渡金属-X-C化学键对正极材料的晶格边界进行修复，使锂离子正极材料和碳层之间的界面得以优化，形成一个可以储存Li的界面，增加的储锂的位置包括在锂离子进出的通道的表面增加一个储锂的位置，同时在过渡金属-X-C化学键的X边上增加储锂的位置，从而增加了正极材料的克容量，为制备超容量锂离子电池奠定了基础。
附图说明
图1是本申请实施例制备的常规碳包覆锂离子电池正极材料83nm-N和C-O键配位碳包覆的超容量锂离子电池正极材料83nm-E进行的充放电曲线图，图中虚线为常规碳包覆锂离子电池正极材料的充放电曲线，容量为168.2mAh/g，实线为超容量锂离子电池正极材料的充放电曲线，容量为194.7mAh/g；
图2是本申请实施例制备的常规碳包覆锂离子电池正极材料83nm-N的1000次的循环曲线图，图中数字表示平均粒径83nm的常规碳包覆锂离子电池正极材料制备的电池，在10C 135.12mAh/g下1000循环后容量保持率为99.7％；
图3是本申请实施例制备的超容量锂离子电池正极材料83nm-E的1000次的循环曲线图，图中数字表示平均粒径83nm的超容量锂离子电池正极材料制备的电池，在10C 157.60mAh/g下1000循环后容量保持率为99.5％；
图4是本申请实施例制备的常规碳包覆锂离子电池正极材料83nm-N和超容量锂离子电池正极材料83nm-E的X-射线光电子能谱图，图中，上半部分为超容量锂离子电池正极材料83nm-E的X-射线光电子能谱图，下半部分为常规碳包覆锂离子电池正极材料83nm-N的X-射线光电子能谱图；
图5是本申请实施例制备的常规碳包覆锂离子电池正极材料83nm-N不同SOC下的软X-ray测试结果，a图为Fe元素不同SOC下K边软X射线吸收谱，b图为对应于a图的不同SOC标记点，图中A、B、C、D、E分别为不同的SOC标记；
图6是本申请实施例制备的超容量锂离子电池正极材料83nm-E不同SOC下的软X-ray测试结果，a图为Fe元素不同SOC下K边软X射线吸收谱，b图为对应于a图的不同SOC标记点，图中A、B、C、D、E、F、G分别为不同的SOC标记；
图7是本申请实施例中LiFePO4晶格修复前和修复后的结构示意图，a为修复前的结构示意图，b为修复后的结构示意图，图中O表示氧、C表示碳、Li表示锂离子；
图8是本申请实施例制备的超容量碳包覆锂离子电池正极材料42nmLiFePO4材料生成C-N键的X-射线光电子能谱图；
图9是本申请实施例制备的常规碳包覆锂离子电池正极材料LiFePO4和C-N键配位碳包覆的超容量锂离子电池正极材料进行的充放电曲线图，图中虚线为常规碳包覆锂离子电池正极材料的充放电曲线，容量为176.7mAh/g，实线为超容量锂离子电池正极材料的充放电曲线，容量为186.1mAh/g；
图10是本申请实施例制备的超容量碳包覆锂离子电池正极材料42nmLiFePO4材料生成C-S键的X-射线光电子能谱图；
图11是本申请实施例制备的常规碳包覆锂离子电池正极材料LiFePO4和C-S键配位碳包覆的超容量锂离子电池正极材料进行的充放电曲线图，图中虚线为常规碳包覆锂离子电池正极材料的充放电曲线，容量为167.5mAh/g，实线为超容量锂离子电池正极材料的充放电曲线，容量为187.3mAh/g；
图12是本申请实施例制备的C-O键配位碳包覆的超容量碳包覆锂离子电池正极材料LiFePO4/LiMn0.6Fe0.4O4的充放电曲线图；
图13是本申请实施例制备的全固态LiFePO4锂离子电池的充放电曲线图，其中1C、5C、10C、20C分别表示1C、5C、10C、20C倍率下的充放电曲线；
图14是本申请实施例中锂离子正极材料的表面晶格修复前和修复后存放锂离子情况的结构示意图，a为修复前的结构示意图，b为修复后的结构示意图。
具体实施方式
现有技术中也有碳包覆锂离子正极材料的相关研究，本申请的发明人在对碳包覆锂离子正极材料进行研究时发现，发明人所制备的碳包覆LiFePO4锂离子正极材料其容量会有不同程度的提高，由这些碳包覆锂离子正极材料制备的锂离子电池，其电池容量可达到200mAhg-1以上，超过了LiFePO4的理论容量200mAhg-1。针对这样的新发现，本申请的发明人对碳包覆锂离子正极材料进行了深入研究，结果发现，在含有过渡金属的锂离子正极材料进行碳包覆的时候，其中锂离子正极材料表面的过渡金属与碳通过O-C键配位，形成过渡金属-O-C化学键，这种结构能够修复正极材料破损的晶格界面，通过量子化学第一性原理的计算证实，磷酸铁锂表面上的Fe周围有五个氧原子，是破缺的FeO5八面体，使得锂离子进出的通道上的表面不能储锂，计算得到的储锂电压是-0.13V，因此不能储锂，当形成可储锂的超容量界面时，即过渡Fe-O-C化学键时，磷酸铁锂表面Fe原子被O-C结构钝化，从而恢复FeO6八面体的结构，使得表面增加的储锂的位置，包括在锂离子进出的通道上的表面变为可储锂的位置，其储锂的电压在3.2V左右，比体相的电压略低，约低0.1-0.2V，同时在过渡Fe-O-C化学键的O边上又增加储锂的位置，电压在2.6V左右，从而增强了正极材料的有效储锂的克容量。基于这样的发现，本申请进一步对过渡金属-O-C化学键的形成和制备方法进行了研究，从而提出了本申请的超容量锂离子电池正极材料及其制备方法。
在此基础上，本申请进一步的对过渡金属-O-C化学键进行深入研究，结果发现，除O-C键配位以外，N-C键配位和S-C键配位也能达到相当的效果。从 而提出了通过过渡金属-X-C化学键，形成碳包覆锂离子正极材料的超容量锂离子电池正极材料，其中，X为N、O或S。
下面通过具体实施例对本申请作进一步详细说明。以下实施例仅对本申请进行进一步说明，不应理解为对本申请的限制。
实施例一
本例分别制备了常规碳包覆的正极材料，以及过渡金属-O-C化学键修复晶格界面的碳包覆超容量锂离子电池正极材料。
常规的碳包覆正极材料：将1g平均粒径为83纳米的磷酸铁锂、0.2g葡萄糖及5mL分散剂乙醇混合，常规的加热干燥后将所得产物在氩气气氛下，升温至650℃，恒温4h，自然冷却后得到LiFePO4/C复合材料。
超容量锂离子电池正极材料：将1g平均粒径为83纳米的磷酸铁锂、0.2g葡萄糖及10mL分散剂乙醇混合后置于球磨机中球磨成纳米浆料，球磨的转速为350转/min，研磨至干燥，约球磨10h，即分散剂乙醇完全挥发，然后将其置于氩气气氛下，升温至650℃，恒温4h，自然冷却后得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiFePO4与碳层之间的界面进行测试。结果如图4所示，可见，本例的超容量锂离子电池正极材料中存在有更多的C-O键，证实LiFePO4与碳层之间形成了一个新的界面，而常规碳包覆正极材料则没有产生新的界面。
分别将本例制备的常规碳包覆正极材料和超容量锂离子电池正极材料组装成电池，分别将常规碳包覆和超容量碳包覆正极材料的电池充放电至图5和图6中b图中标记的SOC，将电池在手套箱中拆开，将正极片用二甲基碳酸脂清洗后转移至软X-ray测试装置中测试同步辐射软X-ray吸收谱。组装超容量锂离子电池时，将本例制备的锂离子电池正极材料配成悬浮液，然后在100℃下进行喷雾干燥，制成平均粒径为12μm的复合正极颗粒，用于制备锂离子电池；正极片由平均粒径为12μm的复合正极颗粒、乙炔黑及PVDF制备成浆料后涂在Al箔上制成，负极为锂片，锂离子电池的组装参考常规的组装方式，在此不累述。以常规碳包覆正极材料组装电池时，直接将常规碳包覆正极材料与乙炔黑和PVDF制备成浆料后涂在Al箔上制成，负极同样采用锂片，采用相同的方法组装成电池。然后测试两个电池在不同SOC下的同步辐射软X-ray吸收谱结果。
测试结果如5和6所示，图5为常规碳包覆正极材料组装的电池在不同SOC 下的软X-ray测试结果，a图为Fe元素不同SOC下K边软X射线吸收谱，b图为对应于a图的不同SOC标记点，图6为超容量锂离子电池正极材料组装的电池在不同SOC下的软X-ray测试结果，a图为Fe元素不同SOC下K边软X射线吸收谱，b图为对应于a图的不同SOC标记点；图6可见，Fe在其中始终表现为+2价，证明形成了Fe-O共价键，而图5的结果显示，Fe在LiFePO4脱锂后表现为+3价，证明没有形成Fe-O共价键。
对本例的超容量锂离子电池正极材料进行结构模拟，如图7所示，图7中a图为没有形成过渡金属-O-C化学键时的晶格界面结构示意图，b图为碳包覆后，超容量锂离子电池正极材料中形成过渡金属-O-C化学键的晶格界面结构示意图；可见，在没有过渡金属-O-C化学键的情况下，FeO6八面体是不完整的，呈现出破损的晶格界面，如图7中a图所示；当形成过渡金属-O-C化学键时，磷酸铁锂表面Fe原子被O-C结构钝化，从而恢复FeO6八面体的结构，如图7中b图所示，从根本上解决晶格界面破坏的问题。
采用Maccor M4200电池测试系统测试电池，在2.85V-3.8V的电压范围内测试本例的锂离子电池的容量以及1000次循环性能。测试结果分别如图1、图2和图3所示。图1为充放电曲线图，由图可见，采用常规碳包覆正极材料的电池，其容量为168.2mAh g-1；由超容量锂离子电池正极材料制备的电池，其容量为194.7mAh g-1。图2和图3为1000次的循环曲线图，图2是采用常规碳包覆正极材料的电池1000次的循环曲线图，图3是采用超容量锂离子电池正极材料制备的电池1000次的循环曲线图，由图可见，采用常规碳包覆正极材料的电池和超容量锂离子电池正极材料制备的电池，两者的循环性能都非常好，1000次循环后的电池容量保持率仍然高达99％以上。
实施例二
本例的超容量锂离子电池正极材料，将1g平均粒径为42纳米LiFePO4和0.3g含氮碳源三聚氰胺分散到10mL乙醇中，在氮气条件下球磨至干燥，然后将其置于惰性气氛下，升温至750℃，恒温6h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiFePO4与碳层之间的界面进行测试，测试结果如图8所示，X射线光电子能谱表明有C-N键的形成；证实本例中LiFePO4与碳层之间形成了一个新的界面，即修复后的晶格界面。
同样的，将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相 同，在此不累述。测试结果如图9所示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了186.1mAhg-1。
实施例三
本例的超容量锂离子电池正极材料，将1g平均粒径为42纳米LiFePO4和0.2g含硫碳源噻吩分散到8mL乙醇中，在氮气条件下球磨至干燥，然后将其置于惰性气氛下，升温至850℃，恒温12h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiFePO4与碳层之间的界面进行测试，测试结果如图10所示，X射线光电子能谱表明有C-S键的形成；证实本例中LiFePO4与碳层之间形成了一个新的界面，即修复后的晶格界面。
同样的，将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相同，在此不累述。测试结果如图11所示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了187.3mAhg-1。
实施例四
本例的超容量锂离子电池正极材料，采用纳米LiMn2O4替换实施例一的纳米磷酸铁锂，将纳米LiMn2O4和蔗糖分散到乙醇中，同样采用球磨至干燥，然后将其置于惰性气氛下，升温至650℃，恒温10h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiMn2O4与碳层之间的界面进行测试，X射线光电子能谱表明有C-O键的形成；证实本例中LiMn2O4与碳层之间形成了一个新的界面，即修复后的晶格界面。
将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相同，在此不累述。测试结果显示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了199.2mAhg-1，1000次循环后的电池容量保持率仍然高达99％以上。
实施例五
本例的超容量锂离子电池正极材料，采用纳米LiNi0.5Mn1.5O4替换实施例一的纳米磷酸铁锂，将纳米LiNi0.5Mn1.5O4和蔗糖分散到乙醇中，同样采用球磨至 干燥，然后将其置于惰性气氛下，升温至500℃，恒温2h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiNi0.5Mn1.5O4与碳层之间的界面进行测试，X射线光电子能谱表明有C-O键的形成；证实本例中LiNi0.5Mn1.5O4与碳层之间形成了一个新的界面，即修复后的晶格界面。
将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相同，在此不累述。测试结果显示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了207.5mAhg-1，1000次循环后的电池容量保持率仍然高达99％以上。
实施例六
本例的超容量锂离子电池正极材料，采核壳结构的纳米LiFePO4/LiMn0.6Fe0.4O4替换实施例一的纳米磷酸铁锂，LiFePO4为壳层，所制备的LiFePO4/LiMn0.6Fe0.4O4的磷酸铁锂壳层为5nm厚。LiFePO4/LiMn0.6Fe0.4O4核壳结构纳米材料采用常规的包覆方法制备，在此不做具体限定。
LiFePO4/LiMn0.6Fe0.4O4的制备方法：
①将硫酸亚铁，磷酸和氢氧化锂溶解到乙二醇中，三者的比例设定为1:1.275:2.7。同时再量取上述硫酸亚铁的十分之一溶解到乙二醇中。
②将硫酸亚铁溶液加入到三口烧瓶中伴随持续的搅拌和氩气保护，10min后滴加磷酸溶液，搅拌10min然后滴加氢氧化锂溶液，10min后开始升温。
③升温到90-120℃区间内，将第二份硫酸亚铁溶液滴加到溶液中，持续升温到180℃回流4h,然后冷却离心洗涤，接着在80℃的真空干燥箱进行干燥。
④取一定量的3中的产物，称一定量的葡萄糖和抗坏血酸与该产物进行混合，然后在650℃煅烧6h，最终的产物就为包有碳层的磷酸铁锂包覆磷酸铁锰锂材料。
将纳米LiFePO4/LiMn0.6Fe0.4O4和蔗糖分散到乙醇中，同样采用球磨至干燥，然后将其置于惰性气氛下，升温至800℃，恒温5h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiFePO4/LiMn0.6Fe0.4O4与碳层之间的界面进行测试，X射线光电子能谱表明有C-O键的形成；证实本例中LiFePO4/LiMn0.6Fe0.4O4与碳层之间形成了一个新的界面，即修复后的晶格界面。
将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电 池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相同，在此不累述。测试结果如图12所示，结果显示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了156.3mAhg-1，1000次循环后的电池容量保持率仍然高达99％以上。
实施例七
本例的超容量锂离子电池正极材料，采用的LiCo1/3Mn1/3Ni1/3O2替换实施例一的纳米磷酸铁锂，将纳米LiCo1/3Mn1/3Ni1/3O2和蔗糖分散到乙醇中，同样采用球磨至干燥，然后将其置于惰性气氛下，升温至800℃，恒温5h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiCo1/3Mn1/3Ni1/3O2与碳层之间的界面进行测试，X射线光电子能谱表明有C-O键的形成；证实本例中LiCo1/3Mn1/3Ni1/3O2与碳层之间形成了一个新的界面，即修复后的晶格界面。
将本例的超容量锂离子电池正极材料组装成电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法与实施例一相同，在此不累述。测试结果显示，采用本例的超容量锂离子电池正极材料组装的电池，其电池容量达到了200.3mAhg-1，1000次循环后的电池容量保持率仍然高达99％以上。
实施例八
本例的超容量锂离子电池正极材料，将1g平均粒径为42纳米的LiFePO4和0.2g葡萄糖分散到5mL乙醇中，在氮气条件下球磨至干燥，然后将其置于惰性气氛下，升温至650℃，恒温6h，得到本例的超容量锂离子电池正极材料。
采用X射线光电子能谱对LiFePO4与碳层之间的界面进行测试，X射线光电子能谱表明有C-N键的形成；证实本例中LiFePO4与碳层之间形成了一个新的界面，即修复后的晶格界面。
将本例的超容量锂离子电池正极材料组装成全固态锂电池，并采用Maccor M4200电池测试系统对电池进行测试，电池的组装以及测试方法如下：
固态电解质聚合物电解质膜的制备：a.取Mw＝4*106的聚氧乙烯0.26克与乙腈6克置于试样瓶中，60℃下搅拌直至聚氧乙烯全部溶解。b.取0.046克粒径30nm的三氧化二铝置于步骤a处理的试样瓶内，搅拌直至三氧化二铝被均匀分散。c.取0.0161克LiTFSI置于步骤b处理的试样瓶内，搅拌，搅拌速度为30转每分钟，搅拌24小时。d.将步骤c处理后的混合物料，均匀滴在干净的玻璃片上，置于80℃的加热器上蒸走溶剂乙腈，得到聚合物薄膜。
正极片的制备：将1克本例制备的超容量锂离子电池正极材料、0.2克平均粒径40nm的乙炔黑导电纳米颗粒和0.1克有机固态电解质充分混匀，然后压成紧密接触的直径为0.5-2cm的电极片，即本例的正极片。高温用高性能全固态锂电池组装：按照电池型号及电池类型对正极材料进行裁剪，本例的正极片直径为2厘米。依照正极片大小，对聚合物薄膜进行裁剪，聚合物薄膜的直径略大于正极片直径0.1～0.2厘米。本实例中选用的锂片作为负极片。按照正极片、聚合物电解质膜、负极片的梯度顺序进行压合，并用电池外壳进行封装。
测试本例制备的全固态锂电池在100℃，不同倍率下的充放电曲线，测试结果如图13所示。结果显示，100℃的工作温度下1C、5C、10C、20C不同倍率，容量分别为170.1、165.6、129.0、11.3mAh/g；说明本例制备的全固态锂电池具有较好的工作稳定性。
实施例九
本例着重对锂离子正极材料中含有的过渡金属进行了研究。实施例1-7分别试验了含Fe、Mn、Co、Ni等锂离子正极材料，如LiFePO4、LiMn2O4、LiNi0.5Mn1.5O4、LiCo1/3Mn1/3Ni1/3O2中的过渡金属能够与C形成过渡金属-X-C化学键，使得碳稳定的包覆于正极材料的表面。其中，X为N、O或S。
经计算证实，含有过渡金属的锂离子正极材料中，在正极材料的表面，由于过渡金属-O结构的破坏，会在终端暴露出过渡金属离子，如图7中的a图所示。在通过本申请的碳包覆或者修饰后，会在过渡金属离子终端产生一个过渡金属-X-C化学键的结构，如图7中的b图所示，这种结构会造成在表面上产生多余的Li存储位置。典型的结构是LiMPO4，其中M为过渡金属Fe、Mn或Co。
本例，分别计算了未包覆C的LiFePO4、LiCoPO4、LiMnPO4、LiFe0.5Mn0.5PO4各位置处的平均电压；以及形成过渡金属M-X-C化学键的碳包覆的LiFePO4、LiCoPO4、LiMnPO4、LiFe0.5Mn0.5PO4各位置处的平均电压。测试位置分别为图14所示的S1、S2、S3、S4四个位置。结果如表1所示，表1中LiMPO4-N为普通LiMPO4，即没有包覆C的LiFePO4、LiCoPO4、LiMnPO4、LiFe0.5Mn0.5PO4；LiMPO4-E为超容量LiMPO4，即本例的包覆C的超容量锂离子电池正极材料。
本例采用的计算方法如下：
超容量的研究通过密度泛函理论计算来实现，采用VASP(全称Vienna Ab-initio Simulation Package)软件去优化各个系统的几何结构和电子结构。计算采用广义梯度近似(缩写GGA)的PBE泛函来描述电子交换关联势，电子波函数用投影缀加平面波(缩写PAW)，平面波截止能量为400eV，布里渊区采用 Monkhorst-Pack方法。自洽场循环的收敛标准为10-5eV，几何结构进行全优化，直到原子上的残余力的值小于0.01eV/A时收敛完成。
晶胞结构的锂(Li)平均电压的计算利用能斯特关系，由以下公式(1)进行计算：
V(x)＝-ΔG/(xF)     (1)
公式(1)中，F是法拉第常数，x为嵌入Li的个数，ΔG是吉布斯自由能的变化量。
吉布斯自由能的变化量ΔG通过以下公式(2)计算：
ΔG＝E(LiMPO4)–μLi-E(MPO4)     (2)
公式(2)中，M代表不同的过渡金属，μLi表示Li的化学势，E(LiMPO4)和E(MPO4)分别是LiMPO4和MPO4晶体结构的能量。
表1 正极材料表面不同位置上锂的电压
  S1 S2 S3 S4
LiFePO4-N 3.46 2.79 -0.13 -0.11
LiFePO4-E 3.46 3.02 3.01 2.68
LiMnPO4-N 4.00 3.36 -0.17 -0.23
LiMnPO4-E 4.00 3.59 3.50 2.69
LiCoPO4-N 4.59 4.06 -0.23 -0.37
LiCoPO4-E 4.60 4.38 3.40 2.71
LiFe0.5Mn0.5PO4-N 3.68 3.33 -0.15 -0.19
LiFe0.5Mn0.5PO4-E 3.68 3.41 3.02 2.68
LiFe0.5Co0.5PO4-N 3.99 4.00 -0.10 -0.22
LiFe0.5Co0.5PO4-E 4.01 4.04 3.09 2.74
表1的结果显示了LiMPO4(M＝Fe、Co、Mn)及其混合结构(LiFeMnPO4、LiFeCoPO4)，在没有超容量可储锂界面包覆(M-X-C)时，不同储锂位置的电压。首先，在S1位置，即LiMPO4结构内部的位置，无论LiMPO4有没有超容量包覆碳结构，锂的电压不发生变化，说明超容量碳包覆对LiMPO4内部存储锂的性质没有任何影响；同样，在S2位置，即LiMPO4表面上有一半的锂，在超容量碳包覆LiMPO4之后，锂的电压的有微弱增加的趋势，说明碳包覆之后表面锂的电压受到了轻微的影响；在S3位置即LiMPO4表面上满锂状态，未包覆碳时，锂的电压很小且是负值，而在超容量碳包覆之后，锂的电压大大增加，接 近体相电压，说明本申请的界面修复的碳包覆后LiMPO4表面上增加新的储锂位置，提高了LiMPO4的容量；在S4位置，LiMPO4表面上原来不能储锂的位置，在碳包覆之后锂的电压在2.6-2.8，同样说明在采用本申请的超容量碳包覆之后，LiMPO4表面上增加了新的储锂位置，提高了LiMPO4的容量。综上，在LiMPO4表面上只能存放一半的Li，这部分Li的电压与体相接近，能够被利用；而当表面放满Li时，新增加的这一半Li没有电压或电压很小，所以这部分Li不能被利用，如图14的(a)图所示。然而，超容量LiMPO4-E复合了碳氧结构之后，在表面形成了C-O-过渡金属的界面结构，这种结构使得表面能放满Li，且Li的电压接近体相电压，从而使表面多出了50％的Li。同时，在C-O-过渡金属的结构中间也能存放一部分Li，这部分Li的电压相对比较固定，电压在2.6-2.8V之间，也属于可以利用的部分，如图14的(b)图所示。因此，只要能够形成过渡金属-X-C化学键的锂离子正极材料都可以达到本申请的超容量的效果；除实施例1-7的含Fe、Mn、Co、Ni等过渡金属的锂离子正极材料以外，常规的含过渡金属V、Ti、Mo或Cu的锂离子正极材料，同样可以形成过渡金属-X-C化学键，从而使正极材料能够存放更多的Li。
以上内容是结合具体的实施方式对本申请所作的进一步详细说明，不能认定本申请的具体实施只局限于这些说明。对于本申请所属技术领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本申请的保护范围。

Claims (10)

  1. 一种超容量锂离子电池正极材料，由含有过渡金属的锂离子正极材料和包覆于所述锂离子正极材料表面的碳组成，其特征在于：所述锂离子正极材料表面的过渡金属与所述碳通过X-C键配位，形成过渡金属-X-C化学键，使得所述碳稳定的包覆于所述正极材料的表面；并且，其中C为SP3杂化和/或SP2杂化，X为N、O和S中的至少一种。
  2. 根据权利要求1所述的超容量锂离子电池正极材料，其特征在于：所述过渡金属为Fe、Co、Ni、V、Ti、Mo、Cu和Mn中的至少一种。
  3. 根据权利要求1或2所述的超容量锂离子电池正极材料，其特征在于：所述含有过渡金属的锂离子正极材料为磷酸过渡金属锂正极材料、硅酸过渡金属锂正极材料、硼酸过渡金属锂正极材料、氟化硫酸过渡金属锂正极材料、过渡金属氧化物锂正极材料中的至少一种；
    其中，磷酸过渡金属锂正极材料、硅酸过渡金属锂正极材料、硼酸过渡金属锂正极材料、氟化硫酸过渡金属锂正极材料、过渡金属氧化物锂正极材料中，所述过渡金属为Fe、Mn、Co、Ni、V、Ti、Mo、Cu中的至少一种；
    所述过渡金属氧化物锂正极材料为Li1+y(MaZbYc)1-yO2和/或LiMn2-a’M’a’Z’b’O4；
    所述Li1+y(MaZbYc)1-yO2中，M、Z、Y不重复的选自Ni、Mn、Co、V、Ti、Mo、Cu中的一种，0≤a≤1、0≤b≤1、0≤c≤1，并且a+b+c＝1，0≤y≤1；
    所述LiMn2-a’M’a’Z’b’O4中，M’和Z’不重复的选自Cr、Co、Ni、Cu、Fe、Mo、Ti和V中的一种，0≤a’≤2、0≤b’≤2。
  4. 根据权利要求1或2所述的超容量锂离子电池正极材料，其特征在于：所述含有过渡金属的锂离子正极材料为核-壳结构，其中，内核为正极活性材料，外壳为磷酸铁锂，磷酸铁锂外壳的表面包覆碳，所述碳通过Fe-X-C的配位结构稳定的包覆于磷酸铁锂外壳表面，其中X为N、O和S中的至少一种；优选的，磷酸铁锂外壳的厚度为1-100纳米。
  5. 根据权利要求1-4任一项所述的超容量锂离子电池正极材料在锂离子电池中的应用，包括将所述超容量锂离子电池正极材料制备成5nm-100μm的正极颗粒材料，所述正极颗粒材料中超容量锂离子电池正极材料表面的C彼此连接或至少有一点接触在一起形成热稳定的导电子和导锂离子的网络结构。
  6. 一种超容量锂离子电池，其特征在于：所述超容量锂离子电池中含有权利要求1-4任一项所述的超容量锂离子电池正极材料。
  7. 根据权利要求6所述的超容量锂离子电池的制备方法，其特征在于：包括 将至少一种的权利要求1-4任一项所述的超容量锂离子电池正极材料配成悬浮液，然后在25-220℃温度下进行喷雾干燥，制成200nm-100μm的正极二次颗粒材料，用于制备所述超容量锂离子电池。
  8. 一种采用权利要求1-4任一项所述的超容量锂离子电池正极材料的全固态锂电池。
  9. 根据权利要求8所述的全固态锂电池，其特征在于：所述全固态锂电池的正极片由权利要求1-4任一项所述的超容量锂离子电池正极材料和导电材料、固态电解质制成，所述导电材料为导电纳米颗粒、导电高分子、导电纳米管和导电纳米片中的至少一种，所述固态电解质为无机固态电解质、有机固态电解质和有机/无机复合固态电解质中的指示一种，所述全固态锂电池的负极为碳基材料、超容量氧化物基材料、硫化物基材料、锂金属或锂合金。
  10. 根据权利要求1-4任一项所述的超容量锂离子电池正极材料的制备方法，其特征在于：包括将含氧、含硫或含氮的碳源制备成碳源溶液，然后将含过渡金属的纳米锂离子正极材料和碳源溶液混合，置于球磨机中，球磨直至溶剂完全挥发，将干燥产物在惰性气氛下，升温至500-1000℃，恒温2-12h，自然冷却，即获得含O-C键或S-C键或N-C键的超容量锂离子电池正极材料；含氧的碳源为柠檬酸、葡萄糖和蔗糖中的至少一种；含硫的碳源为硫醇和/或噻吩；含氮的碳源为氨基酸和/或三聚氰胺；所述碳源溶液的浓度为0.1-2mol/L；所述碳源溶液的溶剂为水、异丙醇、乙醇、丙酮、乙二醇中的至少一种。
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