CN103730661B - A kind of lithium ion battery anode material CuSrGO and preparation method thereof - Google Patents

A kind of lithium ion battery anode material CuSrGO and preparation method thereof Download PDF

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CN103730661B
CN103730661B CN201410040536.6A CN201410040536A CN103730661B CN 103730661 B CN103730661 B CN 103730661B CN 201410040536 A CN201410040536 A CN 201410040536A CN 103730661 B CN103730661 B CN 103730661B
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anode material
cusrgo
preparation
lithium ion
ion battery
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CN103730661A (en
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任玉荣
杨程
丁建宁
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Changzhou University
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Changzhou 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
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • 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 belongs to opto-electronic device preparation field, particularly to a kind of, there is good lithium ion battery anode material of cycle performance and preparation method thereof.Preparation method is, adopts glutathion as sulfur source, in aqueous solvent, first allows Cu2+Stick to GO surface, then pass through hydro-thermal method and make Cu2+React with-the SH in glutathion, form CuS nano-particle, be distributed in GO；Again through second time hydro-thermal method, GO is reduced into rGO, material is thus formed CuS nanoparticles/reduced graphene composite CuSrGO.Use as lithium ion battery anode material, there is significantly high discharge capacity first, reversible capacity and coulombic efficiency.

Description

A kind of lithium ion battery anode material CuSrGO and preparation method thereof
Technical field
The invention belongs to opto-electronic device preparation field, particularly to a kind of, there is good lithium ion battery anode material of cycle performance and preparation method thereof.
Background technology
Secondary cycle lithium ion battery is considered as the desirable energy storage device of mobile electronic device.Electrode material passes through Li+Embed the ability with release that stores deviating to realize energy and determine the performance of lithium ion battery.The research of current lithium ion battery majority all focuses on and finds the electrode material with better cycle performance and discharge capacity.Adulterate Li by the degree of depth and improves Li+Can produce to surmount commercial graphite electrode (372mA h/g or 818mA h/cm with electronics transmission inside electrode3, graphite density is 2.2g/cm3) new high capacity negative pole.
CuS has good electronic conductivity (10-3And higher theoretical capacity (560mAh/g), and when circulation, there is stable discharge curve S/m).Generally, metal sulfide is used as the cathode material of lithium ion battery anode material or lithium battery, both has potential using value.But it is true that be not only sulfide, also have other 3d transistion metal compounds to be used as electrode material and all there is potential using value, because they have different voltage windows.But sulfide is in that the rapid decrease of capacity as the difficult problem that electrode is maximum, because defining the Li dissolving in electrolyte in the process of its discharge and recharge2S。
Graphene (graphene) is material conventional in electrode material preparation field.But pure grapheme material is owing to circulating first, and coulombic efficiency is low and charge and discharge platform is higher, it is impossible to directly as lithium ion battery electrode material.
Summary of the invention
The technical problem to be solved is: overcoming this volumetric expansion contraction change in charge and discharge process of sulfide obvious, internal stress is big, these difficult problems of reversible capacity fast decay,
For solving this technical problem, the technical solution used in the present invention is:
The invention provides a kind of lithium ion battery anode material, form for CuS nanoparticles composite reduction Graphene, CuS nanoparticles/reduced graphene composite CuSrGO, wherein, CuS nanoparticles granule is evenly distributed in Graphene upper and lower surface, and particle diameter is 20nm～50nm.
The preparation method that present invention also offers a kind of above-mentioned anode material, adopts glutathion as sulfur source, in aqueous solvent, first allows Cu2+Stick to GO surface, then pass through hydro-thermal method and make Cu2+React with-the SH in glutathion, form CuS nano-particle, be distributed in GO；Again through second time hydro-thermal method, GO is reduced into rGO, material is thus formed CuS nanoparticles/reduced graphene composite CuSrGO.
The present invention adopts unconventional sulfur source, i.e. glutathion, and it is the tripeptide compound being combined into by glutamic acid, cysteine and glycine, and it is provided that-SH key, energy and Cu2+In conjunction with forming CuS.
The concrete preparation process of the present invention is:
(1) being dispersed in 40 ml deionized water by the graphene oxide GO of 40 milligrams, stirring, ultrasonic disperse uniformly, add the CuSO of 2 mMs4·5H2O, stir, complete ion exchange, add the reduced glutathion of 6 mMs, stir, mixed liquor is loaded reactor, after sealing, puts into air dry oven, heat after 200 DEG C, react 10 hours, naturally cool to room temperature, reactant is filtered, clean, dry, obtain CuS nanoparticles/graphene oxide composite material CuSGO；
(2) CuSGO obtained in step (1) is dispersed in 40 ml deionized water, stirs, add 10 milligrams of NaBH4, stir, again hydro-thermal reaction, heat after 120 DEG C reaction 4 hours, naturally cool to room temperature, reactant is filtered, clean, dry, obtain CuS nanoparticles/reduced graphene composite CuSrGO.
In above-mentioned preparation process, graphene oxide (GO) can be prepared by modified Hummer ＇ s method,
By the complex prepared by above-mentioned steps, there is double; two sandwich structure: graphene sheet layer is clipped in the middle CuS layer, and its CuS inherently sandwich structure, CuS4-CuS3-CuS4Layer is joined together by the S-S limit on summit.
The purposes of the lithium ion battery anode material CuSrGO of the present invention is, by above-mentioned CuS nanoparticles/reduced graphene composite CuSrGO powder, CNT, PVDF, mix by the mass ratio of 70%:20%:10%, the electrode slice that film becomes thickness to be 110 microns, in this, as the working electrode of lithium ion battery.
The beneficial effects of the present invention is: the addition of (1) Graphene can reduce material volumetric expansion asystole in charge and discharge process so that internal stress reduces, the cyclical stability of reinforcing material；(2) there is significantly high discharge capacity first, reversible capacity and coulombic efficiency.Lithium ion battery anode material prepared by the present invention when 0.2C first discharge capacity reach 851mAh/g, reversible capacity reaches 648.1mAh/g first, after circulating at 100 times, reversible capacity reaches 710.7mAh/g, is 4.5 times of pure CuS material (159.7mAh/g).Coulombic efficiency is 99.1%.CuSrGO has good cycle performance.(3) present invention adopts this kind of sulfur source of reduced glutathion, pollution-free, and preparation technology is simple.The new structure of composite prepared by the present invention have not been reported.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained CuS nanoparticles/reduced graphene composite CuSrGO；
Fig. 2 is the transmission electron microscope photo of embodiment 1 gained CuS nanoparticles/reduced graphene composite CuSrGO；
Fig. 3 is embodiment 1 gained CuSrGO first charge-discharge curve when 0.2C；
Fig. 4 is embodiment 1 gained CuSrGO the 100th charging and discharging curve when 0.2C；
Fig. 5 is embodiment 1 gained CuSrGO and the pure CuS comparison curves circulating 100 times when 0.2C；
Fig. 6 is the embodiment 1 gained CuSrGO coulombic efficiency curve circulating 100 times when 0.2C.
Detailed description of the invention
Embodiment 1
A, graphite oxide (GO) are prepared by modified Hummer ＇ s method.
B, 40 milligrams of GO are dispersed in 40 ml deionized water, stir 3 hours, ultrasonic 20 minutes, are and then slowly added to 2 mMs of (0.5 gram) CuSO4·5H2O, stirs 2 hours；It is slow added into 6 mMs of (1.844 grams) reduced glutathion (GSH, C10H17N3O6S), it is stirred for 30 minutes, loads 50 milliliters of stainless steel cauldrons, after sealing, put into air dry oven, heat to 200 DEG C of maintenances 10 hours, naturally cool to room temperature.
C, filtration, with each self-cleaning of deionized water and dehydrated alcohol three times, dry 10 hours at 80 DEG C, obtain CuSGO.
D, again it is dispersed in 40 ml deionized water, stirs 30 minutes, add 10 milligrams of NaBH4, stir 10 minutes, hydro-thermal reaction again, heat to 120 DEG C of maintenances 4 hours, naturally cool to room temperature.
E, filtration, with each self-cleaning of deionized water and dehydrated alcohol three times, dry 10 hours at 80 DEG C, obtain CuSrGO.
Weigh the CuSrGO sample that 420 milligrams of methods adopted in the present embodiment prepare, with 120 milligrams of CNTs, both fully stir evenly, (PVDF is 60 milligrams to be added dropwise to the Kynoar dispersion liquid for preparing, with N-Methyl pyrrolidone for solvent), it is fully ground uniformly pulpous state viscous solution, then on Copper Foil, it is coated into, with scraper, the thin film that thickness is 110 microns, on lamination fastener of motor, electrode slice it is fastened as after solvent volatilizees, electrode slice is put at 100 DEG C vacuum drying 12 hours, working electrode (anode material) in this, as lithium ion battery, charge-discharge performance test is carried out after glove box is assembled into 2032 button cells, LANDCT2001A is adopted to test, testing result is as shown in the drawing.
In above-mentioned lithium ion battery, lithium sheet is as to electrode, the LiPF of 1M6Electrolyte, solvent composition EC:DMC:DEC=1:1:1(volume ratio), barrier film adopts Celgard2400.
In the present embodiment preparation lithium ion battery anode material when 0.2C first discharge capacity reach 851mAh/g, reversible capacity reaches 648.1mAh/g first, 100 times circulate after reversible capacity reach 710.7mAh/g, coulombic efficiency is 99.1%.Specific experiment result is as shown in the drawing.
Comparative example 1:
In this example into, sulfur source is made " 6 mMs of Na2S2O3", all the other preparation processes, parameter are all identical with embodiment 1；The anode material prepared in the present embodiment is assembled into the operation of lithium ion battery, and detection method is also in the same manner as in Example 1.
In the present embodiment preparation lithium ion battery anode material when 0.2C first discharge capacity be 661mAh/g, reversible capacity is 527.9mAh/g first, 100 times circulate after reversible capacity reach 365.7mAh/g.
Comparative example 2:
Sulfur source, in this example, is made into " 6 mMs of Na2S ", and all the other preparation processes, parameter are all identical with embodiment 1；The anode material prepared in the present embodiment is assembled into the operation of lithium ion battery, and detection method is also in the same manner as in Example 1.
In the present embodiment preparation lithium ion battery anode material when 0.2C first discharge capacity be 675mAh/g, reversible capacity is 564.8mAh/g first, 100 times circulate after reversible capacity reach 403.2mAh/g.

Claims (1)

1. the preparation method of a lithium ion battery anode material, it is characterised in that: described anode material is made up of CuS nanoparticles composite reduction Graphene, and in described anode material, the diameter of CuS nanoparticles granule is 20nm；
Described preparation method is, adopts glutathion as sulfur source, in aqueous solvent, first allows Cu2+Stick to GO surface, then pass through hydro-thermal method and make Cu2+React with-the SH in glutathion, form CuS nano-particle, be distributed in GO；Again through second time hydro-thermal method, GO is reduced into rGO, material is thus formed CuS nanoparticles/reduced graphene composite-CuSrGO；
Concretely comprise the following steps,
(1) being dispersed in 40 ml deionized water by the graphene oxide GO of 40 milligrams, stirring, ultrasonic disperse uniformly, add the CuSO of 2 mMs4·5H2O, stir, add the reduced glutathion of 6 mMs, stir, mixed liquor is loaded reactor, after sealing, put into air dry oven, heat after 200 DEG C reaction 10 hours, naturally cool to room temperature, reactant is filtered, clean, dry, obtain CuS nanoparticles/graphene oxide composite material-CuSGO；
(2) CuSGO obtained in step (1) is dispersed in 40 ml deionized water, stirs, add 10 milligrams of NaBH4, stir, again hydro-thermal reaction, heat after 120 DEG C reaction 4 hours, naturally cool to room temperature, reactant is filtered, clean, dry, obtain CuS nanoparticles/reduced graphene composite-CuSrGO.
CN201410040536.6A 2014-01-28 2014-01-28 A kind of lithium ion battery anode material CuSrGO and preparation method thereof Active CN103730661B (en)

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CN105244499A (en) * 2015-08-31 2016-01-13 无锡市嘉邦电力管道厂 Coated and modified anode material of lithium ion battery and preparation method of coated and modified anode material
CN106972161B (en) * 2017-04-05 2019-10-29 深圳市佩成科技有限责任公司 A kind of preparation method of nitrogen-doped graphene/copper sulfide/hollow sulphur composite material
CN107365981B (en) * 2017-08-11 2019-10-25 陕西科技大学 A kind of Al doping CuS/ graphene complex film and preparation method thereof
CN109256282A (en) * 2018-08-03 2019-01-22 无锡泰科纳米新材料有限公司 A kind of preparation method of conductivity type graphene film slurry
CN110534354B (en) * 2019-08-12 2021-10-12 江苏大学 Preparation method and application of composite film electrode with carbon nano tubes inserted in CuS nano particles

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CN101710619A (en) * 2009-12-14 2010-05-19 重庆大学 Electrode plate for lithium ion battery and manufacturing method thereof
CN102760877A (en) * 2012-07-23 2012-10-31 浙江大学 Transition metal sulfide/graphene composite material, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN101710619A (en) * 2009-12-14 2010-05-19 重庆大学 Electrode plate for lithium ion battery and manufacturing method thereof
CN102760877A (en) * 2012-07-23 2012-10-31 浙江大学 Transition metal sulfide/graphene composite material, and preparation method and application thereof

Non-Patent Citations (1)

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