CN106450227A - Method for preparing lithium batteries by hierarchy In2O3/C composite materials - Google Patents

Method for preparing lithium batteries by hierarchy In2O3/C composite materials Download PDF

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Publication number
CN106450227A
CN106450227A CN201611043191.5A CN201611043191A CN106450227A CN 106450227 A CN106450227 A CN 106450227A CN 201611043191 A CN201611043191 A CN 201611043191A CN 106450227 A CN106450227 A CN 106450227A
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China
Prior art keywords
hierarchy
composite
in2o3
lithium battery
utilizes
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CN201611043191.5A
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CN106450227B (en
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洪振生
曾悦峰
康美玲
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Fujian Normal University
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Fujian Normal 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a method for preparing lithium batteries by hierarchy In2O3/C composite materials. The method includes the steps: synthesizing indium-base MOF (metal-organic framework) materials, taking the indium-base metal-organic framework materials as a precursor, and directly calcining the precursor to prepare the hierarchy In2O3/C composite materials; taking the hierarchy In2O3/C composite materials as negative electrodes, and assembling lithium ion batteries. The hierarchy In2O3/C composite materials are simple and convenient to operate, low in cost, high in purity and excellent in performance and can be largely synthesized.

Description

A kind of method preparing lithium battery using hierarchy In2O3/C composite
Technical field
The present invention relates to lithium battery design field, particularly one kind utilize hierarchy In2O3/ C composite prepares lithium electricity The method in pond.
Background technology
Small volume that lithium ion battery has because of it, lightweight, running voltage is high, energy density is high, have extended cycle life, from Discharge rate is little, memory-less effect, advantages of environment protection and be widely applied.Currently it is mainly used in mobile electron to set The fields such as standby, national defense industry, electric automobile.
Porous metal-organic framework compound（MOF）Have that aperture is adjustable, bigger serface, framing structure multiformity, table The advantages of face can be modified, be widely used in absorption and separations, heterogeneous catalysiss, the carrier of metal nanoparticle and template and micro- instead Answer the aspects such as device.While preparing novel structure MOF, MOF is as template and then derivative synthesis lithium ion battery negative material It is the research direction of a rich challenge.Indio material has excellent electron conduction, but with regard to its composite nano materials Preparation and its storage lithium performance report less.
Content of the invention
In view of this, the purpose of the present invention is to propose to a kind of utilize hierarchy In2O3/ C composite prepares lithium battery Method, easy and simple to handle, low cost, purity are high, excellent performance, can synthesize in a large number.
The present invention adopts below scheme to realize：One kind utilizes hierarchy In2O3/ C composite prepares the side of lithium battery Method, specifically includes following steps：
Step S1：By synthesizing indio metal-organic framework material, i.e. MOF, prepare classification as presoma dinectly bruning Structure I n2O3/ C composite；
Step S2：The hierarchy In that step S1 is obtained2O3/ C composite, as negative pole, assembles lithium ion battery.
Further, described step S1 specifically includes following steps：
Step S11：Preparation In-MOF predecessor：In (NO by 50-100 mg3)3•xH2The phthalic acid of O and 25-40 mg is put In the N.N. dimethylformamide of 5-10 ml；
Step S12：Until completely dissolved by solution under 80-100 degree isothermal reaction 30 minutes, product is through washing with alcohol It is dried after 3 times；
Step S13：Drying is put in the tube furnace of argon gas atmosphere after finishing and obtains hierarchy through 400-500 DEG C of roasting 2 h In2O3/C composite.
Further, described step S2 specifically includes following steps：
Step S21：It is uniformly coated on copper sheet do negative pole according to after following mass ratio mixed grinding：
Hierarchy In2O3/ C composite：Politef：Acetylene black=75-85：5-10：10-15；
Step S22：Using lithium metal as positive pole；
Step S23：Using 1 M LiPF6EC+DEC+DMC solution as electrolyte.
Further, in described electrolyte, the ratio of each composition is：EC/DEC/DMC=1/1/1 v/v/v.
Further, step S2 is carried out in the glove box full of argon.
Compared with prior art, the present invention has following beneficial effect：The present invention provide method is easy and simple to handle, low cost, Purity is high, excellent performance, can synthesize in a large number.
Brief description
Fig. 1 is indio metal organic frame presoma in the embodiment of the present invention（MOF）XRD spectrum.
Fig. 2 is hierarchy In in the embodiment of the present invention2O3The X-ray powder diffraction analysis chart of/C composite.
Fig. 3 is scanning electron microscope analysis figure in the embodiment of the present invention.
Fig. 4 is In in the embodiment of the present invention2O3The scanning electron microscope analysis figure of/C composite.
Fig. 5 is hierarchy In in the embodiment of the present invention2O3High rate performance under the different electric current densities for/C composite Figure.
Fig. 6 is hierarchy In in the embodiment of the present invention2O3The cycle performance figure of/C composite.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention will be further described.
Present embodiments provide one kind and utilize hierarchy In2O3The method that/C composite prepares lithium battery, specifically includes Following steps：
Step S1：By synthesizing indio metal-organic framework material, i.e. MOF, prepare classification as presoma dinectly bruning Structure I n2O3/ C composite；
Step S2：The hierarchy In that step S1 is obtained2O3/ C composite, as negative pole, assembles lithium ion battery.
In the present embodiment, described step S1 specifically includes following steps：
Step S11：Preparation In-MOF predecessor：In (NO by 50-100 mg3)3•xH2The phthalic acid of O and 25-40 mg is put In the N.N. dimethylformamide of 5-10 ml；
Step S12：Until completely dissolved by solution under 80-100 degree isothermal reaction 30 minutes, product is through washing with alcohol It is dried after 3 times；
Step S13：Drying is put in the tube furnace of argon gas atmosphere after finishing and obtains hierarchy through 400-500 DEG C of roasting 2 h In2O3/C composite.
In the present embodiment, described step S2 specifically includes following steps：
Step S21：It is uniformly coated on copper sheet do negative pole according to after following mass ratio mixed grinding：
Hierarchy In2O3/ C composite：Politef：Acetylene black=75-85：5-10：10-15；
Step S22：Using lithium metal as positive pole；
Step S23：Using 1 M LiPF6EC+DEC+DMC solution as electrolyte.
In the present embodiment, in described electrolyte, the ratio of each composition is：EC/DEC/DMC=1/1/1 v/v/v.
In the present embodiment, step S2 is carried out in the glove box full of argon.
Preferably, as shown in figure 1, in the present embodiment, indio metal organic frame presoma as seen from Figure 1 （MOF）There is good degree of crystallinity and layer structure.Hierarchy In from Fig. 22O3The X-ray powder diffraction of/C composite Analysis chart can be seen that In2O3The peak position of/C and standard spectrum（PDF#06-0416）Fit like a glove, illustrate that prepared sample is oxygen Change indium.Can be seen that obtained In-MOF persursor material is bar-shaped and rod is about in 2-5 from Fig. 3 scanning electron microscope analysis in figure Um, a diameter of 200-400 nm.And in Fig. 4, can be seen that In2O3/ C composite is then size receiving in 50-100 nm Rice grain, and these granules are by less nanoparticle（About 10 nanometers of particle diameter）Built-up it was demonstrated that this compound receive Rice material has hierarchy.Fig. 5 is hierarchy In2O3High rate performance figure under the different electric current densities for/C composite, Under 0.1A/g, 0.2A/g, 0.5 A/g, 1 A/g and 2 A/g electric current densities, corresponding reversible specific capacity is respectively 620 mAh/ G, 545 mAh/g, 454 mAh/g, 393 mAh/g and 340 mAh/g, illustrate that this material has very excellent high rate performance. As shown in fig. 6, this figure is hierarchy In2O3Cyclic curve figure under/C composite 0.1A/g electric current density, In2O3/ C is multiple The initial charge specific capacity of condensation material is 716.5 mAh/g, and after circulation 90 circle, its reversible specific capacity still can be stablized 713.4 MAh/g, shows good cyclical stability.Due to hierarchy In2O3/ C composite can provide more storage lithiums empty Gap, improves the electric conductivity of integral material, and can effectively alleviate the change in volume that lithium ion deintercalation is brought, can also hinder Only In2O3The reunion of/C particle, thus this composite has preferable application prospect in terms of lithium ion battery electrode material.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modify, all should belong to the covering scope of the present invention.

Claims (5)

1. one kind utilizes hierarchy In2O3/ C composite prepare lithium battery method it is characterised in that：Comprise the following steps：
Step S1：By synthesizing indio metal-organic framework material, i.e. MOF, prepare classification as presoma dinectly bruning Structure I n2O3/ C composite；
Step S2：The hierarchy In that step S1 is obtained2O3/ C composite, as negative pole, assembles lithium ion battery.
2. one kind according to claim 1 utilizes hierarchy In2O3The method that/C composite prepares lithium battery, it is special Levy and be：Described step S1 specifically includes following steps：
Step S11：Preparation In-MOF predecessor：In (NO by 50-100 mg3)3•xH2The phthalic acid of O and 25-40 mg is put In the N.N. dimethylformamide of 5-10 ml；
Step S12：Until completely dissolved by solution under 80-100 degree isothermal reaction 30 minutes, product is through washing with alcohol It is dried after 3 times；
Step S13：Drying is put in the tube furnace of argon gas atmosphere after finishing and obtains hierarchy through 400-500 DEG C of roasting 2 h In2O3/C composite.
3. one kind according to claim 1 utilizes hierarchy In2O3The method that/C composite prepares lithium battery, it is special Levy and be：Described step S2 specifically includes following steps：
Step S21：It is uniformly coated on copper sheet do negative pole according to after following mass ratio mixed grinding：
Hierarchy In2O3/ C composite：Politef：Acetylene black=75-85：5-10：10-15；
Step S22：Using lithium metal as positive pole；
Step S23：Using 1 M LiPF6EC+DEC+DMC solution as electrolyte.
4. one kind according to claim 3 utilizes hierarchy In2O3The method that/C composite prepares lithium battery, it is special Levy and be：In described electrolyte, the ratio of each composition is：EC/DEC/DMC=1/1/1 v/v/v.
5. one kind according to claim 3 utilizes hierarchy In2O3The method that/C composite prepares lithium battery, it is special Levy and be：Step S2 is carried out in the glove box full of argon.
CN201611043191.5A 2016-11-24 2016-11-24 Method for preparing lithium battery by using In2O3/C composite material with hierarchical structure Expired - Fee Related CN106450227B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108039476A (en) * 2017-12-19 2018-05-15 中南大学 A kind of nano indium oxide/carbon composite and preparation method thereof
CN108793228A (en) * 2018-06-26 2018-11-13 江苏师范大学 A kind of synthetic method of carbon-coated indium oxide hollow bar
CN108878158A (en) * 2017-05-16 2018-11-23 中国科学院福建物质结构研究所 A kind of preparation method and purposes of C-base composte material
CN110364702A (en) * 2019-06-11 2019-10-22 杭州电子科技大学 Chinese chestnut shape is classified application of the manganese selenide/carbon composite as lithium ion battery negative material
CN117691096A (en) * 2024-02-04 2024-03-12 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof

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CN106025178A (en) * 2016-06-01 2016-10-12 华南师范大学 Method for preparing metal oxide employing MOF as template and application of metal oxide in negative electrode material of lithium battery
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108878158A (en) * 2017-05-16 2018-11-23 中国科学院福建物质结构研究所 A kind of preparation method and purposes of C-base composte material
CN108878158B (en) * 2017-05-16 2020-02-21 中国科学院福建物质结构研究所 Preparation method and application of carbon-based composite material
CN108039476A (en) * 2017-12-19 2018-05-15 中南大学 A kind of nano indium oxide/carbon composite and preparation method thereof
CN108039476B (en) * 2017-12-19 2020-05-12 中南大学 Nano indium oxide/carbon composite material and preparation method thereof
CN108793228A (en) * 2018-06-26 2018-11-13 江苏师范大学 A kind of synthetic method of carbon-coated indium oxide hollow bar
CN110364702A (en) * 2019-06-11 2019-10-22 杭州电子科技大学 Chinese chestnut shape is classified application of the manganese selenide/carbon composite as lithium ion battery negative material
CN117691096A (en) * 2024-02-04 2024-03-12 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof
CN117691096B (en) * 2024-02-04 2024-04-09 内蒙古工业大学 Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof

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