CN104022269B - A kind of native graphite and MnO composite high-performance electrode material and preparation method thereof - Google Patents

A kind of native graphite and MnO composite high-performance electrode material and preparation method thereof Download PDF

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CN104022269B
CN104022269B CN201410254737.6A CN201410254737A CN104022269B CN 104022269 B CN104022269 B CN 104022269B CN 201410254737 A CN201410254737 A CN 201410254737A CN 104022269 B CN104022269 B CN 104022269B
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native graphite
mno
graphite
electrode material
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CN104022269A (en
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王�锋
丁瑜
肖迎波
耿鹏
张行
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Hubei Zhongyi Technology Co ltd
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Hubei Engineering University
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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  • Composite Materials (AREA)
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Abstract

The present invention relates to a kind of native graphite and MnO composite high-performance electrode material and preparation method thereof.The method utilizes KMnO4Solution reacts with native graphite, generates MnO2With the mixture of native graphite, the MnO of generation2It is partially into native graphite and forms intercalation configuration, be partially depositing in native graphite surface, then calcine under indifferent gas atmosphere, utilize the reducing property of native graphite by MnO2It is reduced into MnO, forms the composite of native graphite and MnO.In this preparation method, native graphite, not only as material of main part but also as reducing agent, simplifies technique, and obtains the composite of excellent performance.Interlayer MnO phase supports native graphite interbed and does not caves in, and expands the interlamellar spacing of native graphite, beneficially the quick deintercalation of lithium ion, and does not affect the structure of native graphite, is conducive to promoting the cycle performance of native graphite combination electrode material；The MnO service hoisting capacity of native graphite surface deposition.Capacity height, the native graphite combination electrode material of good cycle is obtained in conjunction with the two.

Description

A kind of native graphite with MnO Composite high-performance electrode material and preparation method thereof
Technical field
The present invention relates to the preparing technical field of lithium ion battery electrode material, be specifically related to the preparation method of a kind of native graphite and MnO composite high-performance electrode material.
Background technology
Lithium rechargeable battery has the features such as voltage height, volume and capacity ratio and specific discharge capacity height, environmental protection, sustainable development to the energy is significant, it is a kind of novel high-energy density secondary battery, is widely used in terms of hybrid vehicle and intelligent grid.But it is along with the fast development of electric automobile He other electronic equipments, the most urgent to high performance lithium ion battery demand.Due to safety and the problem of cyclical stability, one longer developing period of the development experience of negative material in lithium ion battery.Currently, the lithium ion battery negative material of commercialization is based on native graphite sill and Delanium sill.Molecular layer spacing yet with native graphite is nearer, interlayer combines with weak Van der Waals force, when lithium ion deintercalation, native graphite Rotating fields is gradually peeled off and is formed new surface, and produce new SEI film, consume lithium ion in a large number, add irreversible capacity, also promoting natural stone layer of ink efflorescence to accelerate, battery life is greatly shortened.
Mode if, with intercalation, interlayer and outer layer at native graphite build the intercalation phase made new advances, interlayer supports native graphite interbed mutually and does not caves in, form supporting structure, expand the interlamellar spacing of native graphite, be conducive to the quick deintercalation of lithium ion, and do not affect the structure of native graphite, will be advantageous to promote the cycle performance of native graphite combination electrode material；Native graphite outer layer phase service hoisting capacity.Capacity height, the native graphite combination electrode material of good cycle will can be obtained in conjunction with the two.
Requirement for intercalation phase is effectively to react to insert interlayer and depositing at outer layer with native graphite, and material itself also has higher cyclical stability and specific capacity.In numerous cathode oxidation thing materials, the voltage delay of MnO lithium capacity less, embedding is high, current potential is low, polarization is less, is the most potential lithium ion battery negative material.But its electrical conductivity is low, the shortcoming that preparation technology requires height (calcining needs hydrogen-argon-mixed body, dangerous high), it is also desirable to further improve synthetic method.Therefore, use certain synthesis mode, native graphite is combined with MnO, widely collect the length of the two, high performance graphite-based composite negative pole material can be obtained.
Summary of the invention
The defects such as the tap density that it is an object of the invention to generally exist in the graphite cathode material overcoming existing method to prepare is low, structural stability is poor, providing a kind of new lithium ion battery negative material and preparation method thereof, gained negative material has the plurality of advantages such as tap density is high, efficiency for charge-discharge is high, discharge and recharge reaction good reversibility, Stability Analysis of Structures, cycle performance is excellent, product cost is high, preparation process condition is simple.
It is an object of the invention to be achieved by the following technical programs.
A kind of native graphite and MnO composite negative pole material, prepared by following method.Described preparation method, comprises the following steps:
(1) natural flake graphite is carried out spheroidising to mean diameter D50= 17μm；
(2) the process natural flake graphite in step (1) is added KMnO4In the aqueous solution of (analytical pure), stir into uniform dispersion liquid.
Described natural flake graphite and KMnO4Mass percent (70% ~ 95%): (5% ~ 30%)；
Described KMnO4The concentration of aqueous solution is 5g/L.
(3) dispersion liquid in step (2) is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.
(4) 50 DEG C of step (3) products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 500 ~ 700 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.
(5) composite step (4) obtained, ball-milling treatment 4 hours in ball mill, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Compared with prior art, the advantage of the inventive method with have the beneficial effects that:
The present invention is the preparation method of a kind of high activity lithium ion battery negative material, utilizes KMnO4Solution reacts with native graphite, and native graphite, as reducing agent, generates MnO2With the mixture of native graphite, calcine the most under nitrogen atmosphere, utilize the reducing property of native graphite by MnO2It is reduced into MnO, forms the composite of native graphite and MnO.This synthesis makes full use of KMnO4The strong oxidizing property of solution is reacted with native graphite, the MnO of generation2Enter native graphite and form intercalation, increase intercalation spacing, be partially depositing in native graphite surface, service hoisting material capacity.Under the high temperature conditions, profit reduction with carbon MnO under inert atmosphere2Become MnO.Native graphite i.e. as material of main part again as reducing agent, simplify technique, and obtain the composite of excellent performance.Interlayer MnO phase supports native graphite interbed and does not caves in, form supporting structure, expand the quick deintercalation of the interlamellar spacing of native graphite, beneficially lithium ion, and do not affect the structure of native graphite, will be advantageous to promote the cycle performance of native graphite combination electrode material；Native graphite outer layer phase MnO service hoisting capacity.Capacity height, the native graphite combination electrode material of good cycle can be obtained in conjunction with the two.Negative material of the present invention has the plurality of advantages such as tap density is high, efficiency for charge-discharge is high, discharge and recharge reaction good reversibility, Stability Analysis of Structures, cycle performance is excellent, product cost is high, preparation process condition is simple.
Accompanying drawing explanation
Fig. 1 is the charge-discharge performance comparison diagram under the conditions of 0.2C of the combination electrode material obtained by native graphite, embodiment 2 and 4 ~ 6.
Fig. 2 is the cyclic voltammogram of the combination electrode material obtained by embodiment 2.
Fig. 3 is the combination electrode material X-ray diffraction picture obtained by embodiment 2, embodiment 4 ~ 6.
Fig. 4 is the combination electrode material scanning electron microscopic picture obtained by embodiment 2.
Fig. 5 is the combination electrode material scanning electron microscopic picture obtained by embodiment 4.
Fig. 6 is the combination electrode material scanning electron microscopic picture obtained by embodiment 5.
Fig. 7 is the combination electrode material scanning electron microscopic picture obtained by embodiment 6.
Detailed description of the invention
The inventive method will be described in further detail by applicant in conjunction with specific embodiments below, it is therefore intended that makes those skilled in the art it can be clearly understood that the present invention.Following example should not be understood to claims of the present invention is claimed the restriction of scope in any degree.Professional and technical personnel in the field prepare similar composite also in claims of the present invention is claimed the restriction of scope by the amendment of this thinking.
Source chemicals in following example is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and water used is deionized water.
Embodiment 1
A kind of native graphite and the preparation method of MnO composite negative pole material:
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 85wt%:15wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 500 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Embodiment 2
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 85wt%:15wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 600 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Embodiment 3
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 85wt%:15wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 700 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Embodiment 4
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 80wt%:20wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 600 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Embodiment 5
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 90wt%:10wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 600 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Embodiment 6
Natural flake graphite is carried out spheroidising to mean diameter D50=17 μm, add KMnO by natural flake graphite4Aqueous solution in (5g/L), stir into uniform dispersion liquid, natural flake graphite and KMnO4Mass percent 95wt%:5wt%.Dispersion liquid is joined in stainless steel cauldron airtight, be heated to 160 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless.50 DEG C of products therefrom vacuum is dried 5 hours (vacuum-0.1MPa), the most under an argon atmosphere 600 DEG C of heat treatments 10 hours, obtains native graphite and MnO composite.Composite ball-milling treatment 4 hours in ball mill that will obtain, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Composite itself, due to the addition of MnO, significantly improves than the tap density of simple graphite, and the tap density in embodiment is all higher than 2.2g/cm3, and increase with the increase of MnO content.Preparation temperature in embodiment is far below the temperature (the most up to 2800 DEG C) preparing natural graphite cathode combination electrode material in current industrial, has not only saved the energy and also simplify technique, and product cost is higher.
Respectively the sample that embodiment 1 ~ 6 prepares is made half-cell and carry out chemical property mensuration, half-cell assembly method is as follows: composite, special close high KS6 electrically conductive graphite, PVDF are mixed for 80%:15%:5% in mass ratio, mix well with N-Methyl pyrrolidone, stir into thick, it is coated on Copper Foil, it is dried 12 hours under vacuum (-0.1MPa) 60 C, after cooling, is cut into the circular film of diameter about 1cm.Half-cell uses CR2016 type button cell to assemble in glove box, and barrier film is Celgard 2400 polypropylene diaphragm, and electrolyte is 1M LiPF6Ethylene carbonate (EC) and diethyl carbonate (DEC) mixed electrolytic solution (in mixed electrolytic solution, the volume ratio of EC, DEC is 1:1), negative pole is commercialization circle lithium sheet, and electrochemical property test is carried out on blue electricity CT2001A type battery test system (Wuhan Land Electronic Co., Ltd.'s production).
Test result such as Fig. 1 ~ Fig. 7.Fig. 1 result shows, the chemical property of composite is apparently higher than native graphite, but for embodiment 2 and 4 ~ 6, and reaction mass natural flake graphite and KMnO4Mass percent different, cause the MnO in composite the most different from the ratio of native graphite, chemical property obvious difference, certain crystalline flake graphite and KMnO4Mass percent be that the composite property prepared during 85wt%:15wt% is optimum, but regardless of the content of MnO in composite, charging and discharging curve is the most steady, cycle performance is excellent, show that the stability of combination electrode material is high, be primarily due to interlayer MnO phase and support native graphite interbed and do not cave in, form supporting structure, be conducive to the quick deintercalation of lithium ion, and do not affect the structure of native graphite.Work as KMnO4Measuring more is to be strutted by native graphite lamella, but can deposit more MnO, and the bulk effect in charge and discharge process of MnO can cause composite property to decline, less KMnO4Native graphite generation redox reaction that can not be good and excessive, also that enters native graphite intercalation to the Mn oxide of generation, and the scanning electron microscopic picture of Fig. 4 ~ 7 confirms this point.The cyclic voltammogram aggregate performance of Fig. 2 goes out the characteristic cycle curve of graphite.In the X-ray diffraction picture of Fig. 3, (002) peak, face type of graphite is sharp-pointed, shows that the crystal property of material is good.

Claims (4)

1. native graphite and a preparation method for MnO composite high-performance electrode material, comprises the following steps:
(1) natural flake graphite is carried out spheroidising to mean diameter D50= 17μm；
(2) the process natural flake graphite in step (1) is added KMnO4Aqueous solution in, stir into uniform dispersion liquid；Described natural flake graphite and KMnO4Mass percent be (70% ~ 95%): (5% ~ 30%)；
(3) dispersion liquid in step (2) is joined in stainless steel cauldron airtight, be heated to 160 ~ 180 DEG C, be incubated 10 hours, after being cooled to room temperature, sucking filtration, it is washed with deionized water to colourless；
(4) 50 DEG C of step (3) products therefrom vacuum is dried 5 hours, 500 ~ 700 DEG C of heat treatments 10 hours the most under an argon atmosphere, obtains native graphite and MnO composite；
(5) composite step (4) obtained, ball-milling treatment 4 hours in ball mill, the frequency of ball mill is 45Hz, after crossing 200 mesh sieves, i.e. obtains native graphite and MnO composite high-performance electrode material.
Preparation method the most according to claim 1, is characterized in that: KMnO4The concentration of aqueous solution is 5g/L.
Preparation method the most according to claim 1, is characterized in that: the vacuum of step (4) described vacuum is-0.1MPa.
4. the native graphite prepared by the preparation method described in claim 1 or 2 or 3 and MnO composite high-performance electrode material.
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CN104409220B (en) * 2014-11-28 2017-05-17 西北师范大学 Preparation method of manganese dioxide nanowire material and application of manganese dioxide nanowire material as electrode material of supercapacitor
CN104600261B (en) * 2014-12-31 2017-02-22 江苏锋驰绿色电源有限公司 Graphite/Mn3O4 composite material and preparation method and application thereof
CN106159289A (en) * 2016-07-05 2016-11-23 张启辉 Composite of Mn oxide Surface coating graphite and preparation method thereof
CN106299290B (en) * 2016-09-12 2020-01-14 华南理工大学 Amorphous manganese oxide/graphite composite nanomaterial, preparation method thereof and application thereof in lithium ion battery
CN109817948A (en) * 2019-03-04 2019-05-28 河南师范大学 A kind of preparation method of lithium ion battery carbon coating MnO/ crystalline flake graphite combination electrode material
CN112374552B (en) * 2020-11-12 2023-08-01 昆明云大新能源有限公司 Composite modified graphite negative electrode material and preparation method thereof

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CN102810673B (en) * 2012-08-16 2014-06-18 山东大学 Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries

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