CN106450218A - Method for in-situ synthesis of carbon-nitrogen coated zinc-manganese oxide - Google Patents

Method for in-situ synthesis of carbon-nitrogen coated zinc-manganese oxide Download PDF

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Publication number
CN106450218A
CN106450218A CN201610978885.1A CN201610978885A CN106450218A CN 106450218 A CN106450218 A CN 106450218A CN 201610978885 A CN201610978885 A CN 201610978885A CN 106450218 A CN106450218 A CN 106450218A
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China
Prior art keywords
manganese
carbon
nitrogen
zinc
mixture
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Pending
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CN201610978885.1A
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Chinese (zh)
Inventor
何丹农
吴晓燕
张春明
段磊
王严
魏国栋
金彩虹
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Priority to CN201610978885.1A priority Critical patent/CN106450218A/en
Publication of CN106450218A publication Critical patent/CN106450218A/en
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a method for in-situ synthesis of a carbon-nitrogen coated zinc-manganese oxide. ZIF-8 and manganese salt are added into a ball milling tank, a homogeneous medium is added for dispersion, and ball balling is conducted for 2-5 h, wherein the molar ratio of Zn to Mn is 1:2; the mixture is dried for 4-6 h at 100-120 DEG C under the vacuum condition, then the mixture is heated for 3-5 h at 250-300 DEG C under the inert atmosphere condition, then the mixture is forged for 4-6 h at 600-800 DEG C, and ZnMn2O4@C-N is obtained. Metal-organic framework (MOF)2-methylimidazole zinc salt (ZIF-8) serve as a zinc source, a carbon source and a nitrogen source, ZnMn2O4@C-N is prepared through ball milling and a high-temperature solid phase method, carbon coating can improve conductivity of a material, and particle growth can be prevented in the forging process. Meanwhile, nitrogen doping can further improve the conductivity of the material in carbon, electrochemical properties of the material are improved, and the specific discharge capacity is 390 mAh/g after 50 times of circulation. The preparation method is relatively simple and easy to operate.

Description

A kind of method that fabricated in situ carbon-to-nitrogen coats zinc-manganese oxygen
Technical field
The present invention relates to a kind of preparation method of lithium cell negative pole material, more particularly to a kind of fabricated in situ carbon-to-nitrogen cladding The method of zinc-manganese oxygen.
Background technology
With the progress of technology, lithium ion battery will be widely used in the neck such as electric automobile, Aero-Space and biological medicine Domain, therefore, research and development power lithium ion battery and associated materials are significant.For power lithium-ion electric For pond, its key is to improve power density and energy density, and power density and energy density improve is electrode material at all Material, the particularly improvement of negative material.
Material with carbon element is the material being studied and being applied to lithium ion battery commercialization earliest by people, is still that everybody closes so far One of emphasis of note and research, but there are some defects in carbon negative pole material：During Battery formation, react formation SEI with electrolyte Film, leads to consuming and relatively low coulombic efficiency first of electrolyte；During over-charging of battery, may be in carbon electrodes precipitating metal Lithium, forms Li dendrite and causes short circuit, leads to temperature to raise, battery explosion；In addition, diffusion coefficient in material with carbon element for the lithium ion is relatively Little, lead to battery not enable high current charge-discharge, thus limiting the range of application of lithium ion battery.
ZnMn2O4It is a kind of composite oxides of spinel structure, be a kind of wide variety of magnetic material, also may be used at present As lithium ion battery negative material, higher Li is had by conversion and alloying reaction+Storage volume.This material is recognized For being a kind of promising ion cathode material lithium of tool.
Content of the invention
For overcoming the deficiencies in the prior art, the present invention provides a kind of fabricated in situ ZnMn2O4The method of@C-N.
A kind of fabricated in situ carbon-to-nitrogen coats the method for zinc-manganese oxygen it is characterised in that described carbon-to-nitrogen cladding zinc-manganese oxygen is ZnMn2O4@C-N, the concretely comprising the following steps of the method：
（1）Mol ratio is Zn/Mn=1:2 ZIF-8 and manganese salt add in ball grinder, add uniform dielectric dispersion, ball milling 2-5 h；
（2）250 by said mixture 100 ~ 120 DEG C of drying 4 ~ 6 h under vacuum, then under inert atmosphere conditions, ~ 300 DEG C are first heated 3 ~ 5 h, then 600 ~ 800 DEG C of calcining 4 ~ 6 h, obtain ZnMn2O4@C-N.
Described manganese salt is one of manganese acetate, manganese nitrate, manganese citrate and manganese oxalate or a combination thereof.
Described uniform dielectric is one of ethanol, acetone or a combination thereof.
Described noble gases are nitrogen, one kind of argon or a combination thereof.
The invention provides a kind of method that fabricated in situ carbon-to-nitrogen coats zinc-manganese oxygen, the present invention is with metallic organic framework （MOF）2-methylimidazole zinc salt（ZIF-8）For zinc source, carbon source and nitrogen source, prepare ZnMn using ball milling assisted with high-temperature solid phase method2O4@ C-N, carbon coating can not only improve the electric conductivity of material, and can stop granular grows in calcination process；Meanwhile, nitrogen is mixed The miscellaneous electric conductivity that can further improve material in carbon, and then improve the chemical property of material, discharge after 50 circulations specific volume Measure as 390 mAh/g.This preparation technology is relatively easy, easy to operate.
Brief description
Fig. 1 is embodiment 1ZnMn2O4The cycle life figure of@C-N.
Specific embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these Examples of implementation.
Embodiment one：
By mole than for Zn/Mn=1:2 ZIF-8 and manganese acetate add in ball grinder, add ethanol to disperse, and ball milling 2 h will Said mixture 100 DEG C of drying 6 h under vacuum, then under inert atmosphere conditions, 250 DEG C are first heated 5 h, then 600 DEG C of calcining 6 h, obtain ZnMn2O4@C-N.Fig. 1 is ZnMn2O4Cycle life under 200 mA/g electric current densities for the@C-N Figure, first discharge specific capacity is 1520 mAh/g, and after 10 circulations, specific discharge capacity is relatively stable, is 412mAh/g, To after 50 circulations, specific discharge capacity is 390 mAh/g.
Embodiment two：
By mole than for Zn/Mn=1:2 ZIF-8 and manganese nitrate add in ball grinder, add acetone to disperse, and ball milling 2 h will Said mixture 120 DEG C of drying 4 h under vacuum, then under inert atmosphere conditions, 300 DEG C are first heated 3 h, then 700 DEG C calcining 5 h, obtain ZnMn2O4@C-N.
Embodiment three：
By mole than for Zn/Mn=1:2 ZIF-8 and manganese citrate add in ball grinder, add ethanol to disperse, ball milling 2 h, By said mixture 100 DEG C of drying 6 h under vacuum, then under inert atmosphere conditions, 250 DEG C are first heated 5 h, then 750 DEG C of calcining 4 h, obtain ZnMn2O4@C-N.

Claims (4)

1. a kind of fabricated in situ carbon-to-nitrogen coats the method for zinc-manganese oxygen it is characterised in that described carbon-to-nitrogen cladding zinc-manganese oxygen is ZnMn2O4@C-N, the concretely comprising the following steps of the method：
（1）Mol ratio is Zn/Mn=1:2 ZIF-8 and manganese salt add in ball grinder, add uniform dielectric dispersion, ball milling 2-5 h；
（2）250 by said mixture 100 ~ 120 DEG C of drying 4 ~ 6 h under vacuum, then under inert atmosphere conditions, ~ 300 DEG C are first heated 3 ~ 5 h, then 600 ~ 800 DEG C of calcining 4 ~ 6 h, obtain ZnMn2O4@C-N.
2. a kind of fabricated in situ carbon-to-nitrogen coats the method for zinc-manganese oxygen it is characterised in that described manganese according to claim 1 Salt is one of manganese acetate, manganese nitrate, manganese citrate and manganese oxalate or a combination thereof.
3. a kind of fabricated in situ carbon-to-nitrogen coats the method for zinc-manganese oxygen it is characterised in that described is equal according to claim 1 Even medium is one of ethanol, acetone or a combination thereof.
4. a kind of fabricated in situ carbon-to-nitrogen coats the method for zinc-manganese oxygen it is characterised in that described is lazy according to claim 1 Property gas be nitrogen, one kind of argon or a combination thereof.
CN201610978885.1A 2016-11-08 2016-11-08 Method for in-situ synthesis of carbon-nitrogen coated zinc-manganese oxide Pending CN106450218A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107681141A (en) * 2017-09-26 2018-02-09 福建师范大学 A kind of anode material of lithium-ion battery of carbon coating boric acid nanosized nickel rods
CN109560273A (en) * 2018-11-21 2019-04-02 重庆文理学院 A kind of zinc manganate/milk carbon composite and preparation method thereof
CN110190272A (en) * 2019-07-09 2019-08-30 齐鲁工业大学 A kind of preparation method of the nanocomposite for water system Zinc ion battery anode
CN111509239A (en) * 2020-04-21 2020-08-07 蔚蓝(广东)新能源科技有限公司 Air electrode for zinc-air battery and preparation method thereof
CN112387250A (en) * 2020-10-21 2021-02-23 广西大学 Imprinted-similar MOF adsorbent and preparation method and application thereof
CN112408496A (en) * 2020-11-09 2021-02-26 邵阳学院 Nitrogen and sulfur co-doped carbon @ FeS nanotube and preparation method and application thereof
CN113871581A (en) * 2021-08-16 2021-12-31 广东轻工职业技术学院 Zinc manganate graphene positive electrode material for regulating and controlling electron density, chemical self-charging aqueous zinc ion battery, and preparation method and application of positive electrode material

Citations (2)

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CN102030372A (en) * 2009-09-30 2011-04-27 清华大学深圳研究生院 Preparation method of nano spinel zinc manganate
CN104538615A (en) * 2014-12-17 2015-04-22 吉林大学 Anode material of lithium ion secondary battery and preparation method thereof

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CN102030372A (en) * 2009-09-30 2011-04-27 清华大学深圳研究生院 Preparation method of nano spinel zinc manganate
CN104538615A (en) * 2014-12-17 2015-04-22 吉林大学 Anode material of lithium ion secondary battery and preparation method thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107681141A (en) * 2017-09-26 2018-02-09 福建师范大学 A kind of anode material of lithium-ion battery of carbon coating boric acid nanosized nickel rods
CN107681141B (en) * 2017-09-26 2020-11-27 福建师范大学 Carbon-coated nickel borate nanorod negative electrode material of sodium ion battery
CN109560273A (en) * 2018-11-21 2019-04-02 重庆文理学院 A kind of zinc manganate/milk carbon composite and preparation method thereof
CN110190272A (en) * 2019-07-09 2019-08-30 齐鲁工业大学 A kind of preparation method of the nanocomposite for water system Zinc ion battery anode
CN111509239A (en) * 2020-04-21 2020-08-07 蔚蓝(广东)新能源科技有限公司 Air electrode for zinc-air battery and preparation method thereof
CN111509239B (en) * 2020-04-21 2021-07-06 蔚蓝(广东)新能源科技有限公司 Air electrode for zinc-air battery and preparation method thereof
CN112387250A (en) * 2020-10-21 2021-02-23 广西大学 Imprinted-similar MOF adsorbent and preparation method and application thereof
CN112387250B (en) * 2020-10-21 2022-05-20 广西大学 Imprinted-similar MOF adsorbent and preparation method and application thereof
CN112408496A (en) * 2020-11-09 2021-02-26 邵阳学院 Nitrogen and sulfur co-doped carbon @ FeS nanotube and preparation method and application thereof
CN113871581A (en) * 2021-08-16 2021-12-31 广东轻工职业技术学院 Zinc manganate graphene positive electrode material for regulating and controlling electron density, chemical self-charging aqueous zinc ion battery, and preparation method and application of positive electrode material
CN113871581B (en) * 2021-08-16 2023-03-03 广东轻工职业技术学院 Zinc manganate graphene positive electrode material for regulating and controlling electron density, chemical self-charging aqueous zinc ion battery, and preparation method and application of positive electrode material

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Application publication date: 20170222