CN105514374B - A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof - Google Patents

A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof Download PDF

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CN105514374B
CN105514374B CN201510919439.9A CN201510919439A CN105514374B CN 105514374 B CN105514374 B CN 105514374B CN 201510919439 A CN201510919439 A CN 201510919439A CN 105514374 B CN105514374 B CN 105514374B
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CN105514374A (en
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唐浩林
魏希
王锐
蔡世昌
曾燕
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
    • 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
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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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    • H01M4/36—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
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Abstract

The invention discloses a kind of graphitized carbons to coat manganese OXYFLUORIDE MATERIALS, it is prepared after mixing carbonization with perfluor sulfoacid resin solution using manganese source, specific steps are as follows: be mixed and stirred for manganese source solution and perfluorinated sulfonic resin uniformly, then pH value of solution is adjusted, after being stirred to react, it is successively dried, roasts carbonization, obtain the graphitized carbon cladding manganese OXYFLUORIDE MATERIALS.Carbon in resulting materials of the present invention is in graphitization state, greatly improves the ion and electron transfer rate of material, can act on high circulation stability lithium ion battery negative material, and the preparation process being related to is simple, and generated time is short, is suitble to promote and apply.

Description

A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof
Technical field
The invention belongs to new energy materials fields, and in particular to a kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and its system Preparation Method.
Background technique
Lithium ion battery (LiBs) is widely used in mobile phone, notes due to the advantages such as voltage is high, capacity is big, has extended cycle life The portable communication apparatus such as this computer.However lithium ion battery negative material commercial at present is based on graphite material, graphite Theoretical capacity only has 372mAh/g, is unable to satisfy high-capacity lithium ion cell needs of new generation.It is novel compared to graphite material Carbon material (such as carbon nanotube, mesoporous carbon) and transition group metallic oxide (such as manganese oxide, iron oxide, nickel oxide, copper oxide) With higher specific capacity.However metal oxide in charge and discharge process inevitably along with the great variety of volume, Cause the dusting of electrode material, so as to cause the rapid decay of capacity.
In numerous transition metal oxides, the voltage delay of MnO is relatively small (< 0.8V), the higher (5.43g/ of density cm3), and there is specific capacity high (theoretical value 755.6mAh/g) and low (1.032V (the vs Li/Li of electromotive force+)) the features such as, it is A kind of very potential lithium ion battery negative material.However, as other transition metal oxides, low conductivity and Big volume change has seriously affected capacity, multiplying power and the cycle performance of the material in charge and discharge process, constrain its lithium from The fast development and application of sub- field of batteries.
Researchers once using control particle size, prepared micro nano structure, pore structure, sheet MnO negative electrode material, surface The chemical property of the methods of carbon coating improvement Mn oxide.For example, the MnO film of Li Hong research group preparation, MnO/C are compound Material and MnO/C multi-pore micron ball improve the battery performance of MnO material to a certain extent, wherein MnO/C composite wood Material shows the reversible capacity of 400mAh/g under the electric current of 400mA/g.The MnO/C Coaxial Nanotubes of the preparations such as Ding exist Under the current density of 75.5mA/g releasable 600mAh/g reversible specific capacity (fourth friend, Xu Youlong, grandson's filial piety fly nanometers of MnO lithiums from The preparation of sub- cell negative electrode material and performance [J] .Acta Phys.Chim.Sin, 2013,29:1.).Nano-sheet MnO cathode The core-shell structure MnO/C nanometer rods of the preparations such as material and Sun also improve the chemical property of MnO to a certain extent.However, The technical process of these modified measures is all complex, and manufacturing cost is higher, it is often more important that the chemical property of MnO Promoted it is limited, still farther out apart from industrialization practical application.
Summary of the invention
The object of the present invention is to provide a kind of graphitized carbon cladding manganese oxygen fluoride materials and preparation method thereof, using graphite Change carbon material to coat metal oxyfluoride, in conjunction with the advantage of oxide capacity height and graphitized carbon material good conductivity, The problems such as avoiding the defect in homogenous material structure, preventing electrode material volume change excessive improves its cyclical stability；And it relates to And preparation process it is simple, generated time is short, be suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS, which comprises the following steps:
1) manganese source is soluble in water, stir evenly to obtain manganese source solution for standby；It is standby to prepare uniform alkaline solution of sodium hydroxide With；
2) manganese source solution is mixed with perfluor sulfoacid resin solution, stirs evenly to obtain mixed liquor I；
3) pH value that mixed liquor I is adjusted with alkaline solution of sodium hydroxide, is stirred to react 4~8h, obtains mixed liquor I I, then Mixed liquor I I is dried；
4) desciccate obtained by step 3) is subjected to roasting charing, obtains the graphitized carbon cladding manganese oxyfluoride material Material.
In above scheme, the alkaline solution of sodium hydroxide be sodium hydrate aqueous solution, sodium hydroxide aqueous isopropanol or Sodium hydroxide ethanol solution.
In above scheme, the manganese source is manganese nitrate, manganese sulfate or manganese acetate.
In above scheme, the additive amount of the manganese source and perfluor sulfoacid resin solution is with the Mn of offer and C element respectively Standard, wherein Mn element and the mass ratio of C element are 8:1~1:16.
In above scheme, the step 3) pH value is 6~8.
In above scheme, 3) the described drying temperature is 50~80 DEG C, and drying time is 8~12h.
In above scheme, the roasting carbonization temperature is 600~900 DEG C, and heating rate is 0.5~10 DEG C/min, heat preservation Time is 1~6h.
In above scheme, the atmosphere that the roasting carbonization uses is argon gas or nitrogen.
Manganese OXYFLUORIDE MATERIALS is coated according to the graphitized carbon of above scheme preparation, it is aoxidized by graphitized carbon cladding manganese fluorine Object nano particle forms, and can be used as lithium cell cathode material.
The precursor preparation graphitized carbon cladding manganese oxygen fluoride material that the present invention is directly obtained using liquid phase synthesizing method, and Using the method for electrostatic self-assembled, sulfonate radical is made to wrap up manganese ion, and be carbonized, realizes that graphitized carbon is received in manganese oxygen fluoride The cladding process on rice grain surface has constructed the material being uniformly dispersed and with excellent electrochemical performance, can be used as a kind of electrification Learn the lithium cell cathode material haveing excellent performance.
Compared with prior art, the beneficial effects of the present invention are:
1) in graphitized carbon cladding manganese OXYFLUORIDE MATERIALS of the present invention, the carbon of cladding manganese oxygen fluoride material is in graphite Change state greatly improves the ion and electron transfer rate of material；And manganese oxygen fluoride is in Nanoparticulate, size tunable.
2) graphitized carbon of the present invention cladding manganese oxygen fluoride material is used as lithium ion battery negative material, circulation Excellent in stability, and also have broad application prospects as electrode material for super capacitor.
3) preparation method of the present invention is simple, and the period is short, and experiment condition is simple, is suitble to promote and apply.
Detailed description of the invention
The transmission electron microscope TEM figure that Fig. 1 is gained mixed liquor I I in the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope TEM figure of roasting carbonization products therefrom in the embodiment of the present invention 1.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not It is limited only to the following examples.
Following embodiment unless specific instructions, the commercially available chemical reagent of the reagent of use or industrial products.
Embodiment 1
A kind of graphitized carbon cladding manganese oxygen fluoride material, preparation method includes the following steps:
1) the sodium hydroxide aqueous isopropanol for preparing saturation stirs evenly stand-by；60ml perfluor sulfoacid resin solution is taken to set In three-necked flask, magnetic agitation is uniform；It is 1:16's according to Mn the and C mass ratio that manganese source and perfluor sulfoacid resin solution provide Ratio weighs manganese acetate, is added in 10ml deionized water, magnetic agitation uniform dissolution obtains uniform acetic acid manganese solution；
2) acetic acid manganese solution is slowly added dropwise into perfluor sulfoacid resin solution, 1h is mixed, obtains mixed liquor I；
3) prepared sodium hydroxide aqueous isopropanol is slowly added dropwise into mixed solution I, adjusting its pH is 7, and magnetic force stirs It mixes reaction 8h and obtains mixed liquor I I, mixed liquor I I is placed in 50 DEG C of air dry ovens dry 12h.
4) dried product exhibited is put into aluminium oxide porcelain boat, is placed in tube furnace, first at room temperature with 100mL/min High-purity Ar gas flow purging 2h, air-flow is then decreased to 60mL/min, 800 DEG C is warming up to the rate of 5 DEG C/min and is roasted Carbonization is burnt, 90min is kept the temperature, cools to room temperature with the furnace, obtains black powder, the as graphitized carbon coats manganese oxyfluoride material Material.
The transmission electron microscope TEM figure of mixed liquor I I obtained by the present embodiment is shown in Fig. 1；Roast the transmission electron microscope TEM figure of products therefrom See Fig. 2.By Fig. 1,2 it is found that gained manganese oxyfluoride even particle distribution, surface coated carbon be in graphitization state.It will The graphitized carbon cladding manganese OXYFLUORIDE MATERIALS of preparation is applied to prepare negative electrode of lithium ion battery, in 50mAg-1Current density Discharge capacity is 347mAhg after lower 60 circle of circulation-1, in 200mAg-1Current density under circulation 200 circle after discharge capacity be 312mAh g-1, there is excellent cyclical stability.
Embodiment 2
A kind of graphitized carbon cladding manganese oxygen fluoride material, preparation method includes the following steps:
1) the sodium hydroxide aqueous isopropanol for preparing saturation stirs evenly stand-by；60ml perfluor sulfoacid resin solution is taken to set In three-necked flask, magnetic agitation is uniform；It is 8:1's according to Mn the and C mass ratio that manganese source and perfluor sulfoacid resin solution provide Ratio weighs manganese acetate, is added in 10ml deionized water, magnetic agitation uniform dissolution obtains uniform acetic acid manganese solution；
2) acetic acid manganese solution is slowly added dropwise into perfluor sulfoacid resin solution, 1h is mixed, obtains mixed liquor I；
3) prepared sodium hydroxide aqueous isopropanol is slowly added dropwise into mixed solution I, adjusting its pH is 6, and magnetic force stirs Reaction 4h is mixed, mixed liquor I I is obtained, mixed liquor I I is placed in 50 DEG C of air dry ovens dry 12h.
4) dried product exhibited is put into aluminium oxide porcelain boat, is placed in tube furnace, first at room temperature with 100mL/min High-purity Ar gas flow purging 2h, air-flow is then decreased to 60mL/min, 600 DEG C is warming up to the rate of 1 DEG C/min and is roasted Carbonization is burnt, 60min is kept the temperature, cools to room temperature with the furnace, obtains black powder, is i.e. graphitized carbon coats manganese OXYFLUORIDE MATERIALS.
It is applied to graphitized carbon manufactured in the present embodiment cladding manganese OXYFLUORIDE MATERIALS to prepare negative electrode of lithium ion battery, In 50mAg-1Current density under circulation 60 circle after discharge capacity be 645mAhg-1, in 200mAg-1Current density under recycle Discharge capacity is 721mAh g after 200 circles-1, there is excellent cyclical stability.
Embodiment 3
A kind of graphitized carbon cladding manganese oxygen fluoride material, preparation method includes the following steps:
1) the sodium hydroxide aqueous isopropanol for preparing saturation stirs evenly stand-by；60ml perfluor sulfoacid resin solution is taken to set In three-necked flask, magnetic agitation is uniform；It is 8:1's according to Mn the and C mass ratio that manganese source and perfluor sulfoacid resin solution provide Ratio weighs manganese sulfate, is added in 10ml deionized water, magnetic agitation uniform dissolution obtains uniform manganese sulfate solution；
2) manganese sulfate solution is slowly added dropwise into perfluor sulfoacid resin solution, 1h is mixed, obtains mixed liquor I；
3) prepared sodium hydroxide aqueous isopropanol is slowly added dropwise into mixed solution I, adjusting its pH is 8, and magnetic force stirs Reaction 8h is mixed, mixed liquor I I is obtained, mixed liquor I I is placed in 80 DEG C of air dry ovens dry 8h.
4) dried product exhibited is put into aluminium oxide porcelain boat, is placed in tube furnace, first at room temperature with 100mL/min High-purity Ar gas flow purging 2h, air-flow is then decreased to 60mL/min, 800 DEG C is warming up to the rate of 5 DEG C/min and is roasted Carbonization is burnt, 90min is kept the temperature, cools to room temperature with the furnace, obtains black powder, is i.e. graphitized carbon coats manganese OXYFLUORIDE MATERIALS.
It is applied to graphitized carbon manufactured in the present embodiment cladding manganese OXYFLUORIDE MATERIALS to prepare negative electrode of lithium ion battery, In 50mAg-1Current density under circulation 60 circle after discharge capacity be 535mAhg-1, in 200mAg-1Current density under recycle Discharge capacity is 425mAh g after 200 circles-1, there is excellent cyclical stability.
Embodiment 4
A kind of graphitized carbon cladding manganese oxygen fluoride material, preparation method includes the following steps:
1) the sodium hydroxide aqueous isopropanol for preparing saturation stirs evenly stand-by；60ml perfluor sulfoacid resin solution is taken to set In three-necked flask, magnetic agitation is uniform；It is 4:1's according to Mn the and C mass ratio that manganese source and perfluor sulfoacid resin solution provide Ratio weighs manganese sulfate, is added in 10ml deionized water, magnetic agitation uniform dissolution obtains uniform manganese sulfate solution；
2) manganese sulfate solution is slowly added dropwise into perfluor sulfoacid resin solution, 1h is mixed, obtains mixed liquor I；
3) prepared sodium hydroxide aqueous isopropanol is slowly added dropwise into mixed solution I, adjusting its pH is 7, and magnetic force stirs Reaction 8h is mixed, mixed liquor I I is obtained, mixed liquor I I is placed in 60 DEG C of air dry ovens dry 10h；
4) dried product exhibited is put into aluminium oxide porcelain boat, is placed in tube furnace, first at room temperature with 100mL/min High-purity Ar gas flow purging 2h, air-flow is then decreased to 60mL/min, 900 DEG C is warming up to the rate of 10 DEG C/min and is roasted Carbonization is burnt, 6h is kept the temperature, cools to room temperature with the furnace, obtains black powder, is i.e. graphitized carbon coats manganese OXYFLUORIDE MATERIALS.
It is applied to graphitized carbon manufactured in the present embodiment cladding manganese OXYFLUORIDE MATERIALS to prepare negative electrode of lithium ion battery, In 50mAg-1Current density under circulation 60 circle after discharge capacity be 417mAhg-1, in 200mAg-1Current density under recycle Discharge capacity is 521mAh g after 200 circles-1, there is excellent cyclical stability.
Each raw material proportioning cited by the present invention can realize the bound value of the present invention and each raw material, interval value It can realize the present invention, the bound value and interval value of technological parameter of the invention can realize the present invention, different herein One enumerates embodiment.

Claims (8)

1. a kind of preparation method of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS, which comprises the following steps:
1) manganese source is soluble in water, stir evenly to obtain manganese source solution for standby；It is spare to prepare uniform alkaline solution of sodium hydroxide；
2) manganese source solution is mixed with perfluor sulfoacid resin solution, stirs evenly to obtain mixed liquor I；
3) pH value that mixed liquor I is adjusted with alkaline solution of sodium hydroxide, is stirred to react 4 ~ 8h, obtains mixed liquor I I, then will mixing Liquid II is dried；
4) desciccate obtained by step 3) is subjected to roasting charing, obtains the graphitized carbon cladding manganese OXYFLUORIDE MATERIALS；
The manganese source is manganese nitrate, manganese sulfate or manganese acetate.
2. preparation method according to claim 1, which is characterized in that the alkaline solution of sodium hydroxide is sodium hydroxide water Solution, sodium hydroxide aqueous isopropanol or sodium hydroxide ethanol solution.
3. preparation method according to claim 1, which is characterized in that the addition of the manganese source and perfluor sulfoacid resin solution Amount is subject to the Mn and C element of offer respectively, and wherein Mn element and the mass ratio of C element are 8:1 ~ 1:16.
4. preparation method according to claim 1, which is characterized in that pH value described in step 3) is 6 ~ 8.
5. preparation method according to claim 1, which is characterized in that drying temperature described in step 3) is 50 ~ 80 DEG C, dry Time is 8 ~ 12h.
6. preparation method according to claim 1, which is characterized in that the roasting carbonization temperature is 600 ~ 900 DEG C, heating Rate is 0.5 ~ 10 DEG C/min, and soaking time is 1 ~ 6h.
7. preparation method according to claim 1, which is characterized in that the atmosphere that the roasting carbonization uses is argon gas Or nitrogen.
8. the graphitized carbon of any one of the claim 1 ~ 7 preparation method preparation coats manganese OXYFLUORIDE MATERIALS, feature exists In it is formed by graphitized carbon cladding manganese oxyfluoride nano particle.
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CN110828784B (en) * 2018-08-13 2021-04-20 比亚迪股份有限公司 Lithium battery positive electrode material and preparation method and application thereof
CN109647303B (en) * 2018-12-11 2021-05-07 浙江工业大学 Preparation method and application of perfluorosulfonic acid resin/copper-manganese compound microfibrillated microchannel reactor
CN112436128A (en) * 2020-12-01 2021-03-02 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of manganese-cobalt-oxygen composite two-dimensional carbon material for lithium ion battery cathode
CN113224302B (en) * 2021-05-08 2022-08-05 陕西科技大学 Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof

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