CN107195956A - The energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet - Google Patents

The energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet Download PDF

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CN107195956A
CN107195956A CN201710335097.5A CN201710335097A CN107195956A CN 107195956 A CN107195956 A CN 107195956A CN 201710335097 A CN201710335097 A CN 201710335097A CN 107195956 A CN107195956 A CN 107195956A
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conductive substrates
nanometer sheet
metallic
germanate
storage material
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CN201710335097.5A
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CN107195956B (en
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高国新
向阳
何适
吴虎
董碧桃
丁书江
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Xian Jiaotong University
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Xian Jiaotong University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The preparation method of supported bi-metallic germanate nanometer sheet composite energy-storage material in a kind of conductive substrates, the method of hydro-thermal reaction is first passed through in the upright bimetallic germanate nanometer sheet of conductive substrates superficial growth, the composite of the bimetallic germanate nanometer sheet of conductive surface growing upright can be obtained after then being calcined in nitrogen;It is characteristic of the invention that using simple chemical synthesis means, preparing and being superior to supported bi-metallic germanate nanometer sheet composite energy-storage material in the conductive substrates of traditional material with high-specific surface area, good conductivity, capacity and stability.

Description

The energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet
Technical field
The present invention relates to the preparation method of energy storage material, more particularly to conductive substrates supported bi-metallic germanate nanometer sheet Energy storage material preparation method, and in particular to zinc germanate, germanic acid nickel, germanic acid cobalt, germanic acid iron, germanic acid manganese, germanic acid calcium, germanic acid strontium, germanium The preparation of the conductive substrates composite such as the nanometer sheets such as sour barium and nickel foam, foam copper, steel disc, titanium sheet, carbon cloth, carbon paper.
Technical background
Lithium ion battery as a kind of high volume energy density and high-quality energy density energy storage device, with work electricity Pressure is high, the low advantage of self-discharge rate, is obtained in portable electric appts, electric automobile and extensive energy storage extensively Using.Graphite is widely used negative material in current commercial li-ion battery, but its theoretical specific capacity only has 372mA h g-1, can not increasingly meet practical application request.Find the material with height ratio capacity, excellent cycle performance and high rate performance It is the focus studied at present to substitute graphite.In numerous negative materials reported, germanium metal (Ge) is due to high reason By capacity, excellent electronic conductivity and lithium ion diffusion rate, the special attention of researcher is received.But, pure germanium Electrode material can occur alloy-removal alloying with lithium metal in charge and discharge process and react, and Volume Changes are very big (about 370%), Cause the serious efflorescence of electrode material and capacity rapid decrease during charge and discharge cycles.In order to overcome these shortcomings, bimetallic germanium Silicate material is developed as electrode material.On the one hand, the oxide that bimetallic oxide is formed in charge and discharge process can delay The Volume Changes rushed during alloy-removal alloying, on the other hand the price of non-germanium metal is lower than germanium.Although this strategy is led The reduction of a part of capacity has been caused, but has improved the stability and high rate performance of electrode material, electrode material is also reduced Cost.
The storage lithium performance of a certain determination electrode material is improved, generally there are two kinds of strategies.One is it is various to prepare classification Nanostructured, such as nanometer sheet, nanosphere or nano wire, nanostructured can bring big specific surface area so that electrode material with The contact of electrolyte is more abundant, shortens the transmission range of lithium ion and provides more electrochemical reaction avtive spots.Its Two be to be combined material with conductive substrates so that material can be easier to obtain electronics, more fully react, so as to improve material The actual capacity of material.
In summary, can effectively it be carried by the regulation of the Nomenclature Composition and Structure of Complexes to electrode material and with the compound of conductive substrates The lithium ion storage capacity and cycle life of high electrode material.Bimetallic germanate nano material is shown as lithium-ion electric The good potentiality of pond negative material, the bimetallic germanate of the nanosizing such as nano particle, nano wire and nanometer rods is answered at present Condensation material and the material compound with the conductive substrates such as nickel foam are reported.But still lack a kind of effective, universality Method prepares conductive substrates supported bi-metallic germanate nanosheet composite material.
The content of the invention
In order to overcome the defect of prior art, it is an object of the invention to provide a kind of conductive substrates supported bi-metallic germanic acid The energy storage material preparation method of salt nanometer sheet, passes through the bimetallic germanic acid of direct growth composition, structure-controllable in conductive substrates Salt nanometer sheet, improves the lithium ion storge quality of bimetallic germanate, and directly as lithium ion battery electrode material.
In order to achieve the above object, the technical scheme is that:
The energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet, comprises the following steps:
The first step:Weigh the salt of 0.5~4mmol metal ion, 1mmol germanium oxide, the 16 of 0.5~5mmol Alkyl trimethyl ammonium bromide, is added to the in the mixed solvent of 20~100mL deionized waters and 5~50mL ethylene glycol composition, ultrasound It is scattered 5~25 minutes;
Second step:Liquid scattered in step one is transferred in the suitable autoclave of volume, and added in kettle Enter the conductive substrates for the arbitrary shape size that can be accommodated, in reaction 1-24 hours at 120-180 DEG C;
3rd step:Step 2 products therefrom is calcined 0.5~4 hour for 200~450 DEG C in inert atmosphere stove, heating speed Rate is controlled in 1~5 DEG C of min-1;Resulting product is exactly conductive substrates supported bi-metallic germanate nanometer sheet composite construction material Material.
In metal ion salt described in step one contained metal ion include but is not limited to zinc, nickel, cobalt, iron, manganese, Calcium, strontium, barium, the species of the salt of metal ion include but is not limited to sulfate, acetate, chloride.
Conductive substrates described in step 2 include but is not limited to nickel foam, foam copper, steel disc, titanium sheet, carbon cloth, carbon paper.
The conductive substrates supported bi-metallic germanate nanometer sheet sandwich prepared using the present invention has following Feature:
(1) higher specific surface area, so as to provide more active reaction sites, improves electrochemical efficiency;
(2) good conductivity, with electronics more more preferable than pure metal oxides and ion conduction rate;
(3) relative to conventional electrode materials, synthesized energy storage material has higher specific discharge capacity and preferably circulation Stability;
(4) it can directly cut and be used as lithium ion cell electrode piece, eliminate traditional material and stir slurry, the step of coating Suddenly.
The species and property of extreme enrichment bimetallic germanate and conductive substrates composite are expanded it by this method significantly Application, to be multiple with new structure and excellent properties nano structural conductive base load bimetallic germanate nanometer sheet The industrial production of condensation material and extensively using laying the foundation.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of foamed nickel supported zinc germanate nanometer sheet sandwich.
Fig. 2 is the foamed nickel supported zinc germanate nanometer sheet sandwich of cyclic voltammetry test in first, second He Volt-ampere curve in 3rd circulation.
Fig. 3 is foamed nickel supported zinc germanate nanometer sheet sandwich in 200mAg-1First, second under current density, Voltage-capacity curve in ten, the 100th and the 500th circulations.
Fig. 4 is foamed nickel supported zinc germanate nanometer sheet sandwich in 200mAg-1Capacity versus cycle under current density Frequency curve.
Fig. 5 is that high rate performance of the foamed nickel supported zinc germanate nanometer sheet sandwich under different current densities is bent Line.
Fig. 6 is that foamed nickel supported zinc germanate nanometer sheet sandwich is assembled into after battery with pure germanic acid Zinc material Impedance curve
Fig. 7 is the scanning electron microscope (SEM) photograph that foam copper loads germanic acid cobalt nanometer sheet sandwich.
Embodiment
With reference to embodiment, the present invention is described further.
Embodiment one
The present embodiment comprises the following steps:
The first step:Weigh 2mmol anhydrous zinc chloride, 1mmol germanium oxide, 1mmol cetyl trimethyl bromination Ammonium, is added to the in the mixed solvent of 30mL deionized waters and 10mL ethylene glycol composition, ultrasonic disperse 10 minutes;
Second step:Liquid scattered in step one is transferred in the autoclave that volume is 40mL, and in kettle 2 × the 5cm cut rectangular foam nickel is added, in reaction 6 hours at 170 DEG C;
3rd step:Step 2 products therefrom is calcined 2 hours for 450 DEG C in inert atmosphere stove, heating rate is controlled at 1 DEG C min-1;Resulting product is exactly foamed nickel supported zinc germanate nanosheet composite material.
Foamed nickel supported zinc germanate nanometer sheet sandwich performance test such as Fig. 1~Fig. 3 institutes that the present embodiment is obtained Show:Fig. 1 is the scanning electron microscope (SEM) photograph of foamed nickel supported zinc germanate nanometer sheet sandwich;Fig. 2 is what cyclic voltammetry was tested Volt-ampere curve of the foamed nickel supported zinc germanate nanometer sheet sandwich in first, second, and third circulation;Fig. 3 is bubble Foam Ni zinc germanate nanometer sheet sandwich is in 200mA g-1First, second under current density, the tenth, the 100th and Voltage-capacity curve in 500 circulations;Fig. 4 is foamed nickel supported zinc germanate nanometer sheet sandwich in 200mA g-1 Capacity versus cycle frequency curve under current density;Fig. 5 is foamed nickel supported zinc germanate nanometer sheet sandwich in different electricity High rate performance curve under current density;Fig. 6 is foamed nickel supported zinc germanate nanometer sheet sandwich and pure zinc germanate material Material is assembled into the impedance curve after battery.With reference to six figures it can be seen that the foamed nickel supported zinc germanate nanometer that the present embodiment is obtained Piece sandwich has homogeneous pattern, and for high power capacity, excellent cycle performance, high rate performance and high electrical conductivity Lithium ion battery negative material.
Embodiment two
The present embodiment comprises the following steps:
The first step:Weigh 4mmol cobalt nitrate, 1mmol germanium oxide, 3mmol cetyl trimethylammonium bromide, plus Enter the in the mixed solvent to 20mL deionized waters and 20mL ethylene glycol composition, ultrasonic disperse 10 minutes;
Second step:Liquid scattered in step one is transferred in the autoclave that volume is 45mL, and in kettle 2 × the 5cm cut rectangular foam copper is added, in reaction 3 hours at 180 DEG C;
3rd step:Step 2 products therefrom is calcined 3 hours for 200 DEG C in inert atmosphere stove, heating rate is controlled at 2 DEG C min-1;Resulting product is exactly foam copper load germanic acid cobalt nanosheet composite material.
Resulting foam copper loads scanning electron microscopic picture such as Fig. 7 of germanic acid cobalt nanosheet composite material, and for height The lithium ion battery negative material of capacity and excellent cycle performance,.
Embodiment three
The present embodiment comprises the following steps:
The first step:Weigh 0.5mmol calcium acetate, 1mmol germanium oxide, 0.5.5mmol cetyl trimethyl bromine Change ammonium, be added to the in the mixed solvent of 20mL deionized waters and 5mL ethylene glycol composition, ultrasonic disperse 5 minutes;
Second step:Liquid scattered in step one is transferred in the autoclave that volume is 30mL, and in kettle The a diameter of 2cm cut circular carbon cloth or carbon paper is added, in reaction 24 hours at 120 DEG C;
3rd step:Step 2 products therefrom is calcined 4 hours for 200 DEG C in inert atmosphere stove, heating rate is controlled at 3 DEG C min-1;Resulting product is exactly carbon cloth or carbon paper load germanic acid calcium nanosheet composite material.
Resulting carbon cloth or carbon paper load germanic acid calcium nanosheet composite material is with high power capacity and excellent cycle performance Lithium ion battery negative material.
Example IV
The present embodiment comprises the following steps:
The first step:Weigh 4mmol nickel sulfate, 1mmol germanium oxide, 5mmol cetyl trimethylammonium bromide, plus Enter the in the mixed solvent to 100mL deionized waters and 50mL ethylene glycol composition, ultrasonic disperse 25 minutes;
Second step:Liquid scattered in step one is transferred in the autoclave that volume is 180mL, and in kettle 2 × the 5cm cut rectangle steel disc or titanium sheet is added, in reaction 12 hours at 150 DEG C;
3rd step:Step 2 products therefrom is calcined 0.5 hour for 350 DEG C in inert atmosphere stove, heating rate is controlled 5 ℃min-1;Resulting product is exactly steel disc or titanium sheet load germanic acid nickel nano film composite.
Resulting steel disc or titanium sheet load germanic acid nickel nano film composite is with high power capacity and excellent cycle performance Lithium ion battery negative material.

Claims (4)

1. the energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet, it is characterised in that including following step Suddenly:
The first step:Weigh the salt of 0.5~4mmol metal ion, 1mmol germanium oxide, 0.5~5mmol cetyl Trimethylammonium bromide, is added to the in the mixed solvent of 20~100mL deionized waters and 5~50mL ethylene glycol composition, ultrasonic disperse 5 ~25 minutes;
Second step:Liquid scattered in step one is transferred in the suitable autoclave of volume, and adds in kettle energy The conductive substrates of the arbitrary shape size enough accommodated, in reaction 1-24 hours at 120-180 DEG C;
3rd step:Step 2 products therefrom is calcined 0.5~4 hour for 200~450 DEG C in inert atmosphere stove, heating rate control System is in 1~5 DEG C of min-1;Resulting product is exactly conductive substrates supported bi-metallic germanate nanometer sheet sandwich.
2. the energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet according to claim 1, its Be characterised by, in the metal ion salt described in step one contained metal ion include but is not limited to zinc, nickel, cobalt, iron, Manganese, calcium, strontium, barium, the species of the salt of metal ion include but is not limited to sulfate, acetate, chloride.
3. the energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet according to claim 1, its It is characterised by, conductive substrates described in step 2 include but is not limited to nickel foam, foam copper, steel disc, titanium sheet, carbon cloth, carbon paper.
4. the energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet according to claim 1, its It is characterised by, comprises the following steps:
The first step:Weigh 2mmol anhydrous zinc chloride, 1mmol germanium oxide, 1mmol cetyl trimethylammonium bromide, plus Enter the in the mixed solvent to 30mL deionized waters and 10mL ethylene glycol composition, ultrasonic disperse 10 minutes;
Second step:Liquid scattered in step one is transferred in the autoclave that volume is 40mL, and added in kettle 2 × the 5cm cut rectangular foam nickel, in reaction 6 hours at 170 DEG C;
3rd step:Step 2 products therefrom is calcined 2 hours for 450 DEG C in inert atmosphere stove, heating rate is controlled in 1 DEG C of min-1;Resulting product is exactly foamed nickel supported zinc germanate nanosheet composite material.
CN201710335097.5A 2017-05-12 2017-05-12 The energy storage material preparation method of conductive substrates supported bi-metallic germanate nanometer sheet Expired - Fee Related CN107195956B (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN108448108A (en) * 2018-02-25 2018-08-24 商丘师范学院 The preparation method and applications of germanic acid manganese nanometer sheet with high charge-discharge capacity
CN109037652A (en) * 2018-08-16 2018-12-18 福州大学 A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure
CN110085454A (en) * 2019-05-16 2019-08-02 上海理工大学 A kind of electrode material and preparation method thereof, application
CN110875470A (en) * 2018-08-29 2020-03-10 天津大学 Amorphous germanium-based nanowire-graphene nano composite lithium ion battery cathode material and preparation method thereof
CN114122366A (en) * 2021-12-07 2022-03-01 滨州学院 Cobalt germanate composite microsphere material and preparation method thereof

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CN105810903A (en) * 2016-03-14 2016-07-27 商丘师范学院 GaGeO3/graphene nanometer composite material and preparation method thereof
CN106169572A (en) * 2016-09-18 2016-11-30 复旦大学 A kind of N doping cladding germanium composite lithium ion battery negative material and its preparation method and application

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JPS5912503A (en) * 1982-07-13 1984-01-23 日本電信電話株式会社 Method of producing solid electrolyte thin film
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CN109037652A (en) * 2018-08-16 2018-12-18 福州大学 A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure
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CN110875470A (en) * 2018-08-29 2020-03-10 天津大学 Amorphous germanium-based nanowire-graphene nano composite lithium ion battery cathode material and preparation method thereof
CN110875470B (en) * 2018-08-29 2021-04-06 天津大学 Amorphous germanium-based nanowire-graphene nano composite lithium ion battery cathode material and preparation method thereof
CN110085454A (en) * 2019-05-16 2019-08-02 上海理工大学 A kind of electrode material and preparation method thereof, application
CN110085454B (en) * 2019-05-16 2022-01-25 上海理工大学 Electrode material and preparation method and application thereof
CN114122366A (en) * 2021-12-07 2022-03-01 滨州学院 Cobalt germanate composite microsphere material and preparation method thereof
CN114122366B (en) * 2021-12-07 2023-09-22 滨州学院 Cobalt germanate composite microsphere material and preparation method thereof

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