CN104795543B - A kind of concave convex rod base sulphur composite and preparation method thereof and stored energy application - Google Patents

A kind of concave convex rod base sulphur composite and preparation method thereof and stored energy application Download PDF

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CN104795543B
CN104795543B CN201510169014.0A CN201510169014A CN104795543B CN 104795543 B CN104795543 B CN 104795543B CN 201510169014 A CN201510169014 A CN 201510169014A CN 104795543 B CN104795543 B CN 104795543B
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convex rod
concave convex
graphene
preparation
sulphur
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CN104795543A (en
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解勤兴
刘建强
张玉江
周姝雯
郑安冉
解超
张宇峰
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Tianjin Polytechnic 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 discloses a kind of using concave convex rod as sulphur composite of carrier and preparation method thereof and stored energy application：Surface modification is carried out with graphene by concave convex rod or by concave convex rod, it is compound by solid phase fusion or liquid-phase impregnation process progress with elemental sulfur.Concave convex rod/sulphur the composite prepared with this method is used as lithium sulfur battery anode material, can effectively adsorb the polysulfide generated in charge and discharge process, suppresses shuttle effect, improves the cyclical stability of lithium-sulfur cell.For the present invention using natural concave convex rod and elemental sulfur as raw material, aboundresources, cost is low, simple for process.

Description

A kind of concave convex rod base sulphur composite and preparation method thereof and stored energy application
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, more particularly to a kind of concave convex rod base lithium-sulfur rechargeable battery just Pole material and preparation method thereof.
Background technology
Lithium-sulfur cell theoretical specific capacity is 1672mAh/g, and 2600Wh/kg is up to than energy, has two stable electric discharges Voltage platform, performance is more excellent compared with traditional lithium ion battery, it is considered to be the secondary electricity of current most attraction One of pond body system.But the long-chain polysulphides generated in charge and discharge process are soluble in electrolyte and cause electrode active material Loss, and " more sulphion shuttle effects " occurs cause that capacity attenuation is very fast, coulombic efficiency is relatively low.In order to overcome this defect, Generally sulphur and porous carbon, metal oxide etc. are carried out compound to suppress the dissolving of polysulfide, such as Nazar (Nature Materials, 2009,8：Mesoporous carbon CMK-3 500-506) is prepared for using hard template method, it is then that it is compound with sulphur, obtain Sulfur content is 70% CMK-3/ sulphur composites, and specific capacity and cycle performance have compared with elemental sulfur to be greatly improved. (electronic component and material, 2007,26 (8) such as horse duckweed：42-45) use nano-metal-oxide (V2O5, TiO2) compound with elemental sulfur Metal oxide/sulphur composite is prepared for, significantly improves the cycle performance of sulfur electrode.But porous carbon described above, gold The preparation technologies such as category oxide are cumbersome, it is necessary to which substantial amounts of alkali and/or acid, cost is high simultaneously easily to pollute environment.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention is using nano-fiber materials concave convex rod as matrix, by it It is compound with elemental sulfur and be used as lithium sulfur battery anode material to realize the purpose of energy storage.Concave convex rod has special physical chemistry Matter and processing performance, it is widely used in fields such as oil, chemical industry, building materials, papermaking, medicine, agriculturals, but in new energy field still It is not applied.Due to can effectively adsorb discharge and recharge with high-specific surface area, loose structure and strong adsorptivity, concave convex rod Caused polysulfide in journey, reduces the loss of active material, and suppresses " more sulphion shuttle effects ", so as to improve sulphur electricity The chemical property of pole.
Because concave convex rod is non-conductive, the present invention with conductive graphene piece modification concave convex rod surface, improve electric conductivity and Further suppress the dissolving of polysulfide while mechanical strength, improve the specific capacity and cycle performance of material.
The technical solution adopted in the present invention is：
The graphene of use is one or both of graphene oxide, reduced graphene；
The content of graphene is 0-20wt%.
Concave convex rod is impregnated in graphene solution and dried, be repeated several times to obtain the concave convex rod of certain graphene content/ Graphene composite material.Gained concave convex rod/graphene composite material is entered with elemental sulfur by solid phase fusion or liquid-phase impregnation process Row is compound, obtains concave convex rod/graphene/sulfur composite positive electrode material.
The invention provides a kind of using concave convex rod, graphene and sulphur as the lithium-sulphur cell positive electrode energy storage material of raw material and preparation Method, raw material sources enrich, and technique is simple, no toxic intermediates generation；Material can be significantly inhibited in charge and discharge process The dissolving of polysulfide, improve the cyclical stability of electrode.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of concave convex rod.
Fig. 2 is the scanning electron microscope (SEM) photograph of concave convex rod/graphene composite material.
Fig. 3 is the scanning electron microscope (SEM) photograph of concave convex rod/sulphur composite.
Fig. 4 is the scanning electron microscope (SEM) photograph of concave convex rod/graphene/sulphur composite.
Fig. 5 is the X-ray diffraction spectrogram of sulphur, concave convex rod, concave convex rod/sulphur and concave convex rod/graphene/sulphur composite.
Fig. 6 is the charging and discharging curve of concave convex rod/sulphur composite.
Fig. 7 is the charging and discharging curve of concave convex rod/graphene/sulphur composite.
Fig. 8 is the cycle performance figure of sulphur, concave convex rod/sulphur and concave convex rod/graphene/sulphur.
Embodiment
Embodiment 1：The preparation of concave convex rod/graphene composite material (graphene content is 2%)
0.2 gram of concave convex rod (see Fig. 1) is added into the dilute ammonia solution that appropriate pH is about 10, then 0.1% graphene Ultrasonic immersing 10-20 minutes and drying in solution.Aforesaid operations are repeated, until obtaining concave convex rod/stone that graphene content is 2% Black alkene composite (see Fig. 2).In fig. 2 without the graphene film for finding to dissociate.
Embodiment 2：The preparation of concave convex rod/sulphur composite (graphene content is 0%)
Concave convex rod (graphene content is 0%) is well mixed with elemental sulfur according to 7: 3 mass ratio, in closed system 155 degree are heated 12 hours.Concave convex rod/sulphur composite that sulfur content is 30% is obtained after cooling (see Fig. 3).From x-ray powder It can be seen that sulphur is wholly absent with its compound rear characteristic diffraction peak of concave convex rod in diffraction spectrogram (Fig. 5), illustrate that sulphur is completely adsorbed Exist in the pore structure of concave convex rod and as an amorphous form.
Embodiment 3：The preparation of concave convex rod/graphene/sulphur composite (graphene content is 2%)
Concave convex rod/graphene composite material is well mixed with elemental sulfur according to 7: 3 mass ratio, in closed system 155 degree are heated 12 hours.Concave convex rod/graphene/sulphur composite that sulfur content is 30% is obtained after cooling (see Fig. 4).Penetrated from X It can be seen that sulphur is wholly absent with its compound rear characteristic diffraction peak of concave convex rod/graphene in line powder diffractogram (Fig. 5), explanation Sulphur is adsorbed in the pore structure of concave convex rod/graphene composite material and existed as an amorphous form completely.
Embodiment 4：The electrochemical property test of material
Using the electrochemical properties of button cell system test material at room temperature, wherein electrolyte is 0.1M LiNO3+ 1.0M LITHSI/DME+DOL (volume ratio 1: 1), charge-discharge test is carried out using blue electric CT2001A types battery test system, Voltage range is 1.7-2.6V.As a result it is as follows：
(1) as seen from Figure 6, the charging and discharging curve of concave convex rod/sulphur and concave convex rod/graphene/sulphur composite is presented two Individual discharge voltage plateau, wherein the platform at~2.35V, which correspond to elemental sulfur, is reduced into high price long-chain lithium polysulphides (Li2Sn, 4≤ N≤8) reaction ,~2.05V correspond to long-chain lithium polysulphides and is further reduced generation more lithium sulfide (Li at a low price2Sn, n≤2). Drastically increase in latter stage of charging (~2.50V) voltage and show that the shuttle effect of polysulfide has obtained effective suppression, it was confirmed that be recessed Convex rod base sulphur composite has excellent energy-storage property.
(2) as seen from Figure 7, the 0.2C first discharge specific capacities of concave convex rod/sulphur and concave convex rod/graphene/sulphur composite Respectively 904.6 and 949.6mAh/g, specific capacity remains 321.6 and 532.4mAh/g, cycle performance respectively after 50 circulations And specific capacity is superior to elemental sulfur.The electrochemical energy storage performance after graphene modified concave convex rod is significantly improved simultaneously.

Claims (8)

1. a kind of preparation method of concave convex rod base sulphur composite, it is concretely comprised the following steps：Concave convex rod is soaked in graphene solution Stain, then it is dried to obtain concave convex rod/grapheme material；Concave convex rod/grapheme material and sulphur are soaked by solid phase fusion or liquid phase The progress of stain method is compound, obtains concave convex rod/graphene/sulfur composite positive electrode material, wherein graphene content is 0-20wt%.
A kind of 2. preparation method of concave convex rod base sulphur composite according to claim 1, it is characterised in that the graphene For one or two in graphene oxide and reduced graphene.
A kind of 3. preparation method of concave convex rod base sulphur composite according to any one of claim 1~2, it is characterised in that Graphene carries out surface modification with the compound of nitrogen atom.
4. a kind of preparation method of concave convex rod base sulphur composite according to claim 1, it is characterised in that concave convex rod is with containing The compound of nitrogen-atoms carries out surface modification.
A kind of 5. preparation method of the base of concave convex rod according to claim 1 sulphur composite, it is characterised in that the concave convex rod/ Grapheme material is the carrier of active sulfur, and adsorbs the polysulfide generated in charge and discharge process.
A kind of 6. preparation method of the base of concave convex rod according to claim 1 sulphur composite, it is characterised in that the concave convex rod/ Grapheme material is compound with other lithium sulfur battery anode materials and improves energy-storage property.
7. a kind of concave convex rod base sulphur composite, the material is prepared by the method any one of right 1~4.
8. the concave convex rod base sulphur composite described in claim 7 is used as lithium-sulphur cell positive electrode energy storage material.
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CN105727885A (en) * 2016-04-14 2016-07-06 宁波市砥中材料应用有限公司 Preparation method for graphene environmental pollution cleaning agent
CN108923039A (en) * 2018-07-09 2018-11-30 天津工业大学 A kind of preparation method of concave convex rod based nano silicon material
CN109360970B (en) * 2018-11-20 2022-04-08 肇庆市华师大光电产业研究院 Positive electrode material of lithium-sulfur primary battery and preparation method of positive electrode material
CN109921091B (en) * 2019-03-18 2021-05-18 珠海冠宇电池股份有限公司 Composite material for lithium ion battery, preparation method of composite material and lithium ion battery containing composite material
CN110783555A (en) * 2019-09-16 2020-02-11 安徽若水化工有限公司 Nano silicon material with low cost and high yield and preparation method thereof
CN111276683B (en) * 2020-02-14 2022-03-18 中南大学 Silicon dioxide sulfur positive electrode rich in aluminum hydroxyl and preparation method thereof
CN111261837B (en) * 2020-03-27 2022-02-15 中南大学 Cathode material of pentafluoromagnesium aluminum/nitrogen carbon-doped lithium sulfur battery and preparation method thereof

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