CN104934590A - Preparation method of zinc manganate and graphene composite material - Google Patents

Preparation method of zinc manganate and graphene composite material Download PDF

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Publication number
CN104934590A
CN104934590A CN201510228523.6A CN201510228523A CN104934590A CN 104934590 A CN104934590 A CN 104934590A CN 201510228523 A CN201510228523 A CN 201510228523A CN 104934590 A CN104934590 A CN 104934590A
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composite material
preparation
graphene composite
graphite oxide
coo
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温广武
王东
周薇薇
张永
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WEIHAI YUNSHAN TECHNOLOGY Co Ltd
Harbin Institute of Technology
Harbin Institute of Technology Weihai
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WEIHAI YUNSHAN TECHNOLOGY Co Ltd
Harbin Institute of Technology Weihai
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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
    • H01M4/48—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
    • 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
    • H01M4/62—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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 relates to a preparation method of a zinc manganate and graphene composite material. The preparation method comprises the following steps: firstly preparing a graphite oxide water solution and a metal salt water solution, wherein the mole ratio of Zn(CH3COO)2.2H2O to Mn(CH3COO)2.2H2O in the metal salt water solution is 1: 2, and the molar concentration of the Zn(CH3COO)2.2H2O is 0.05-0.2 M; mixing the metal salt water solution and the graphite oxide water solution in a volume ratio of 1(5-7) under a stirring condition, transferring the mixture into a reaction kettle after uniformly mixed, wherein the temperature of the reaction kettle is 160-190 DEG C, and the reaction time is 6-12 h; and after the reaction kettle is cooled to room temperature, filtering, precipitating and washing the product with deionized water, and performing freeze drying on a sediment product to obtain an in situ synthesized ZnMn2O4/graphene composite material. The preparation method is reasonable in technology, simple and convenient in operation, high in efficiency and low in preparation cost. The prepared zinc manganate and graphene composite material can serve as an anode material for a lithium ion battery, and has the characteristics of high specific area, high specific capacity and long cycle life.

Description

A kind of preparation method of zinc manganate/graphene composite material
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, specifically a kind of method of one-step synthesis used as negative electrode of Li-ion battery zinc manganate/graphene composite material.
Background technology
Along with high development and the progress of human society, the traditional fossil energy that the earth is depended on for existence is day by day deficient, and caused a series of problem of environmental pollution, therefore the exploitation of new forms of energy is very urgent simultaneously.Along with the fast development of information and electronic industry, portable electric appts, mobile communication, digital processor etc. are widely applied, and the demand of fast development to chemical power source particularly high-energy secondary battery of the development of space technology and the demand of defence equipment and electric automobile increases rapidly in addition.The secondary cell of current use mainly contains lithium ion battery, lead-acid battery, nickel-cadmium cell etc., wherein due to lithium ion battery have that open circuit voltage is high, energy density is large, long service life, the advantage such as pollution-free are widely used.
So-called lithium ion battery, refers to the secondary cell that the compound that can carry out reversible removal lithium embedded with two is respectively formed as electrode material.Current commercial lithium ion battery mainly adopts graphite as its negative material, and the shortcoming of this material is theoretical specific capacity low (only having 372mAh/g), cannot meet the demand of portable set and electric automobile fast development.The alloy such as silicon, tin has the advantage of height ratio capacity as lithium ion battery negative material, but the volumetric expansion produced in cyclic process makes its capacity attenuation very fast, limits this kind of material and further applies.The research of nearest transition metal oxide negative material becomes focus, and this kind of material energy densities is high, charging/discharging voltage platform stable, and theoretical embedding lithium capacity is generally 2 ~ 3 times of graphite.Zinc manganate (ZnMn 2o 4) compared to other transition metal oxides, there is aboundresources, advantages of nontoxic raw materials free of contamination advantage while that production cost being low, and its theoretical specific capacity is 3 times of current commercial Li-ion battery graphite cathode material specific capacity up to 1008mAh/g(), be expected to the lithium ion battery negative material that alternative graphite becomes a new generation, but the conductivity of this kind of material and cycle performance need to improve further.Graphene is as a kind of novel two-dimensional material, and under normal temperature, electron mobility is more than 15000cm 2/ VS, if therefore Graphene and zinc manganate compound are obtained zinc manganate/graphene composite material, greatly can improve the conductivity of zinc manganate, the design feature of Graphene flexibility contributes to the change in volume that buffering zinc manganate produces in charge and discharge process simultaneously, thus improves cycle life and the application prospect of material greatly.Less as the research of lithium ion battery negative material for zinc manganate in current world wide, synthesis technique is mostly comparatively complicated and immature, the research of zinc manganate/graphene composite material is very few especially, will be therefore a focus for the research of zinc manganate/graphene lithium ion battery negative material in future.
In the preparation method of existing zinc manganate/graphene composite material, comparatively ripe a kind of document " Chemically Integrated Two-dimensional Hybrid Zinc Manganate/ Graphene Nanosheets with Enhanced Lithium Storage Capability " come from ACS Nano.This preparation method is two-step method, first adopts bath oiling to obtain precursor material, follow-uply rises to high temperature with extremely slow heating rate and calcines, and finally obtains zinc manganate/graphene composite material.Mainly synthesis technique is loaded down with trivial details for above-mentioned preparation method's Problems existing, and complicated operation increases the cost of synthesis zinc manganate/graphene composite material simultaneously.In addition, the organic reaction solvent (ethylene glycol, diethylene glycol (DEG)) that existing preparation method adopts has certain toxicity, limits it as the application prospect of synthesizing zinc manganate/graphene composite material method on a large scale.
Summary of the invention
Technical problem to be solved by this invention overcomes above-mentioned the deficiencies in the prior art, provides a kind of rational technology, easy and simple to handle, efficient, the preparation method of zinc manganate/graphene composite material that cost is low.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of preparation method of zinc manganate/graphene composite material, is characterized in that: it comprises the following steps:
(1) solution preparation: compound concentration is the graphite oxide aqueous solution of 1 ~ 2g/L; Preparing metal saline solution, wherein Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the mol ratio of O is 1:2, Zn (CH 3cOO) 22H 2o molar concentration is 0.05 ~ 0.2M;
(2) solution mixing: under agitation according to aqueous metal salt: above-mentioned metal salt solution is slowly added the graphite oxide aqueous solution by the ratio of graphite oxide aqueous solution volume ratio 1:5 ~ 7, proceeds in reactor after mixing;
(3) hydrothermal growth: adopt hydro thermal method, it is 160 ~ 190 ° of C that temperature of reaction kettle controls, and the reaction time is 6 ~ 12h;
(4) collection of products: reaction terminates, after question response still is cooled to room temperature, precipitated product also with after washed with de-ionized water precipitation, is carried out freeze drying, obtains the ZnMn of fabricated in situ by filtering-depositing 2o 4/ graphene composite material.
The ZnMn that the present invention prepares 2o 4/ graphene composite material, XRD analysis shows that its purity is high, not containing other impurity product; ZnMn 2o 4the N of/graphene composite material 2adsorption and desorption isotherms shows that it is mesoporous material, and average pore diameter is that to record specific area be 100 ~ 140m to 10 ~ 15nm, BET multipoint method 2/ g.ZnMn 2o 4sEM and the TEM photo of/graphene composite material shows that it is loose porous three-dimensional grapheme structure, and bending graphene nanometer sheet interconnects.ZnMn 2o 4nanocrystallinely be evenly distributed on graphene nanometer sheet, tightly together with Graphene In-situ reaction, ZnMn 2o 4the size of nano particle is less than 20nm.The nanocrystalline design feature of this graphene film growth in situ contributes to improving ZnMn 2o 4conductivity, simultaneously the design feature of Graphene flexibility contributes to cushioning ZnMn 2o 4the change in volume produced in charge and discharge process, thus the cycle performance improving negative material greatly.
The present invention adopts one step hydro thermal method to prepare ZnMn first 2o 4/ graphene composite material, greatly simplify ZnMn 2o 4the synthesis technique of/graphene composite material, shortens process cycle, reduces production cost.When it is as lithium ion battery negative material, improve the conductivity of zinc manganate, greatly improve the cycle performance of zinc manganate, there is the series of advantages such as specific area, height ratio capacity and long circulation life, be applicable in various portable electric appts and electric automobile.Against existing technologies, present invention process is reasonable, and easy and simple to handle, efficient, preparation cost is low, is a kind of preparation method of desirable zinc manganate/graphene composite material.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
A preparation method for zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: compound concentration is the graphite oxide aqueous solution of 1 ~ 2g/L; Preparing metal saline solution, wherein Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the mol ratio of O is 1:2, Zn (CH 3cOO) 22H 2o molar concentration is 0.05 ~ 0.2M.
(2) solution mixing: under agitation according to aqueous metal salt: above-mentioned metal salt solution is slowly added the graphite oxide aqueous solution by the ratio of graphite oxide aqueous solution volume ratio 1:5 ~ 7, proceeds in reactor after mixing.The graphite oxide aqueous solution and aqueous metal salt concentration are lower than in technique scheme during least concentration, and productive rate is lower, higher than in technique scheme during maximum concentration, cause reaction uneven.
(3) hydrothermal growth: adopt hydro thermal method, it is 160 ~ 190 ° of C that temperature of reaction kettle controls, and the reaction time is 6 ~ 12h.When reaction temperature is lower than 160 ° of C, form ZnMn 2o 4znMn in/graphene composite material 2o 4degree of crystallinity is not high, simultaneous oxidation graphite reduction degree reduce, when reaction temperature is higher than 190 ° of C, form ZnMn 2o 4znMn in/graphene composite material 2o 4particle size is comparatively large, is unfavorable for the raising of performance, adds production cost simultaneously; When reaction time is lower than 6h, form ZnMn 2o 4znMn in/graphene composite material 2o 4degree of crystallinity is not high, when the reaction time is greater than 12h, form ZnMn 2o 4znMn in/graphene composite material 2o 4particle size is comparatively large, is unfavorable for the raising of performance equally.
(4) collection of products: reaction terminates, after question response still is cooled to room temperature, precipitated product also with after washed with de-ionized water precipitation, is carried out freeze drying, obtains the ZnMn of fabricated in situ by filtering-depositing 2o 4/ graphene composite material.
The ZnMn that the present invention prepares 2o 4/ graphene composite material, XRD analysis shows that its purity is high, not containing other impurity product; ZnMn 2o 4the N of/graphene composite material 2adsorption and desorption isotherms shows that it is mesoporous material, and average pore diameter is that to record specific area be 100 ~ 140m to 10 ~ 15nm, BET multipoint method 2/ g.ZnMn 2o 4sEM and the TEM photo of/graphene composite material shows that it is loose porous three-dimensional grapheme structure, and bending graphene nanometer sheet interconnects.ZnMn 2o 4nanocrystallinely be evenly distributed on graphene nanometer sheet, tightly together with Graphene In-situ reaction, ZnMn 2o 4the size of nano particle is less than 20nm.The nanocrystalline design feature of this graphene film growth in situ contributes to improving ZnMn 2o 4conductivity, simultaneously the design feature of Graphene flexibility contributes to cushioning ZnMn 2o 4the change in volume produced in charge and discharge process, thus the cycle performance improving negative material greatly.
The ZnMn that the present invention prepares 2o 4/ graphene composite material can as lithium ion battery negative material.Electrochemical property test shows its ZnMn after 200 charge and discharge cycles 2o 4/ graphene lithium ion battery negative material reversible specific capacity is still greater than 850mAh/g; ZnMn 2o 4/ graphene lithium ion battery negative material high rate performance is excellent, and when current density is 4A/g, its specific capacity is still higher than 400mAh/g; Ac resistance analysis shows and ZnMn 2o 4compare, ZnMn 2o 4the impedance of/graphene lithium ion battery negative material obviously reduces, and conductivity improves.
The present invention adopts one step hydro thermal method to prepare ZnMn first 2o 4/ graphene composite material, greatly simplify ZnMn 2o 4the synthesis technique of/graphene composite material, shortens process cycle, reduces production cost.When it is as lithium ion battery negative material, improve the conductivity of zinc manganate, greatly improve the cycle performance of zinc manganate, there is the series of advantages such as specific area, height ratio capacity and long circulation life, be applicable in various portable electric appts and electric automobile.Present invention process is reasonable, and easy and simple to handle, efficient, preparation cost is low, is a kind of preparation method of desirable zinc manganate/graphene composite material.
Embodiment 1: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 2g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.1M, Mn (CH 3cOO) 22H 2the concentration of O is 0.2M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 12L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: above-mentioned mixed solution is proceeded in reactor, adopt hydro thermal method, temperature of reaction kettle is set to 180 ° of C, and the reaction time is 12h;
(4) collection of products: reaction terminates, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, obtain the zinc manganate/graphene composite material 38.3 grams of fabricated in situ, its productive rate is 80%, and this productive rate refers to that the actual mass of products therefrom and whole raw material participate in reacting the ratio of the Theoretical Mass calculated, as follows.
Embodiment 2: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 1g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.05M, Mn (CH 3cOO) 22H 2the concentration of O is 0.1M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 12L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: above-mentioned mixed solution is proceeded in reactor, adopt hydro thermal method, temperature of reaction kettle is set to 180 ° of C, and the reaction time is 12h;
(4) collection of products: reaction terminate, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, and obtain the zinc manganate/graphene composite material 21.8 grams of fabricated in situ, its productive rate is 70%.
Embodiment 3: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 2g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.2M, Mn (CH 3cOO) 22H 2the concentration of O is 0.4M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 10L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: above-mentioned mixed solution is proceeded in reactor, adopt hydro thermal method, temperature of reaction kettle is set to 180 ° of C, and the reaction time is 12h;
(4) collection of products: reaction terminate, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, and obtain the zinc manganate/graphene composite material 80.7 grams of fabricated in situ, its productive rate is 75%.
Embodiment 4: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 2g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.1M, Mn (CH 3cOO) 22H 2the concentration of O is 0.2M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 14L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: above-mentioned mixed solution is proceeded in reactor, adopt hydro thermal method, temperature of reaction kettle is set to 160 ° of C, and the reaction time is 12h;
(4) collection of products: reaction terminate, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, and obtain the zinc manganate/graphene composite material 49.7 grams of fabricated in situ, its productive rate is 77%.
Embodiment 5: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 1.5g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.1M, Mn (CH 3cOO) 22H 2the concentration of O is 0.2M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 12L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: above-mentioned mixed solution is proceeded in reactor, adopt hydro thermal method, temperature of reaction kettle is set to 190 ° of C, and the reaction time is 6h;
(4) collection of products: reaction terminate, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, and obtain the zinc manganate/graphene composite material 44 grams of fabricated in situ, its productive rate is 75%.
Embodiment 6: a kind of preparation method of zinc manganate/graphene composite material, it comprises the following steps:
(1) solution preparation: select the graphite oxide that Hummers method is synthesized, compound concentration is the graphite oxide aqueous solution of 1g/L; Preparation Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the aqueous metal salt of O, wherein Zn (CH 3cOO) 22H 2the concentration of O is 0.1M, Mn (CH 3cOO) 22H 2the concentration of O is 0.2M;
(2) solution mixing: under agitation above-mentioned 2L metal salt solution is slowly added in the 12L graphite oxide aqueous solution, solution is mixed;
(3) hydrothermal growth: adopt hydro thermal method, temperature of reaction kettle is set to 180 ° of C, and the reaction time is 9h;
(4) collection of products: reaction terminate, after question response still is cooled to room temperature, filtering-depositing and with washed with de-ionized water precipitation after, precipitated product is carried out freeze drying, and obtain the zinc manganate/graphene composite material 40.2 grams of fabricated in situ, its productive rate is 73%.

Claims (4)

1. a preparation method for zinc manganate/graphene composite material, is characterized in that: it comprises the following steps:
(1) solution preparation: compound concentration is the graphite oxide aqueous solution of 1 ~ 2g/L; Preparing metal saline solution, wherein Zn (CH 3cOO) 22H 2o and Mn (CH 3cOO) 22H 2the mol ratio of O is 1:2, Zn (CH 3cOO) 22H 2o molar concentration is 0.05 ~ 0.2M;
(2) solution mixing: under agitation according to aqueous metal salt: above-mentioned metal salt solution is slowly added the graphite oxide aqueous solution by the ratio of graphite oxide aqueous solution volume ratio 1:5 ~ 7, proceeds in reactor after mixing;
(3) hydrothermal growth: adopt hydro thermal method, temperature of reaction kettle is set to 160 ~ 190 ° of C, and the reaction time is 6 ~ 12h;
(4) collection of products: reaction terminates, after question response still is cooled to room temperature, precipitated product also with after washed with de-ionized water precipitation, is carried out freeze drying, obtains the ZnMn of fabricated in situ by filtering-depositing 2o 4/ graphene composite material.
2. the preparation method of zinc manganate/graphene composite material according to claim 1, is characterized in that: in described step (1) prepare graphite oxide solution concentration be 2g/L, Zn (CH in institute's preparing metal salting liquid 3cOO) 22H 2the concentration of O is 0.1M, Mn (CH 3cOO) 22H 2the concentration of O is 0.2M.
3. the preparation method of zinc manganate/graphene composite material according to claim 1, is characterized in that: aqueous metal salt in described step (2): graphite oxide aqueous solution volume ratio is 1:6.
4. the preparation method of zinc manganate/graphene composite material according to claim 1, is characterized in that: in described step (3), temperature of reaction kettle is 180 ° of C, and the reaction time is 12h.
CN201510228523.6A 2015-05-07 2015-05-07 Preparation method of zinc manganate and graphene composite material Pending CN104934590A (en)

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CN108110250A (en) * 2017-12-29 2018-06-01 南京理工大学 Zinc manganate/lithium iron oxide ion battery cathode material and preparation method thereof
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
CN110474017A (en) * 2019-08-29 2019-11-19 瑞海泊有限公司 The preparation method and applications of mangaic acid zinc electrode
CN110734095A (en) * 2019-10-15 2020-01-31 常州大学 CuMn2O4Preparation method of-graphene supercapacitor composite electrode material
CN114180634A (en) * 2020-09-15 2022-03-15 海安南京大学高新技术研究院 ZnMnO with cage structure4Preparation process of nano sensing material

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108110250A (en) * 2017-12-29 2018-06-01 南京理工大学 Zinc manganate/lithium iron oxide ion battery cathode material and preparation method thereof
CN108110250B (en) * 2017-12-29 2020-04-21 南京理工大学 Zinc manganate/lithium iron oxide negative electrode material of ion battery and preparation method thereof
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
CN110474017A (en) * 2019-08-29 2019-11-19 瑞海泊有限公司 The preparation method and applications of mangaic acid zinc electrode
CN110734095A (en) * 2019-10-15 2020-01-31 常州大学 CuMn2O4Preparation method of-graphene supercapacitor composite electrode material
CN114180634A (en) * 2020-09-15 2022-03-15 海安南京大学高新技术研究院 ZnMnO with cage structure4Preparation process of nano sensing material
CN114180634B (en) * 2020-09-15 2023-06-13 海安南京大学高新技术研究院 ZnMnO with cage-shaped structure 4 Preparation process of nano sensing material

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Application publication date: 20150923