CN105609747A - Composite electrode of electrochemical storage lithium and preparation method thereof - Google Patents

Composite electrode of electrochemical storage lithium and preparation method thereof Download PDF

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CN105609747A
CN105609747A CN201610187220.9A CN201610187220A CN105609747A CN 105609747 A CN105609747 A CN 105609747A CN 201610187220 A CN201610187220 A CN 201610187220A CN 105609747 A CN105609747 A CN 105609747A
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graphene
storage lithium
sncos
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徐云
周培成
陈卫祥
叶剑波
陈倩男
吴晓潭
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Zhejiang Xinghai Energy Technology Co.,Ltd.
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ZHEJIANG XINGHAI ENERGY TECHNOLOGY Co Ltd
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Abstract

The invention discloses a composite electrode of electrochemical storage lithium and a preparation method thereof. The composite electrode adopts a SnCoS4-graphene composite nano material as an active substance of the electrochemical storage lithium. The preparation method comprises the following steps: in the presence of oxidized graphene, performing the hydrothermal reaction for a mixed solution of SnCl4, CoCl2 and L-cysteine under a hydrothermal condition to prepare the SnCoS4-graphene composite nano material; mixing the prepared SnCoS4-graphene composite nano material, acetylene black and polyvinylidene fluoride to obtain paste; and coating a copper foil with the paste, and rolling to obtain the composite electrode of the electrochemical storage lithium. The composite electrode has the advantages of high electrochemical storage lithium specific capacity, stable cycling performance and good high-magnification charging-discharging performance.

Description

Combination electrode of a kind of electrochemistry storage lithium and preparation method thereof
Technical field
The present invention relates to a kind of electrochemistry storage lithium combination electrode and preparation method thereof, relate in particular to and use SnCoS4-Graphene composite Nano materialMaterial is as electrochemistry storage lithium combination electrode of electrochemistry storage lithium active material and preparation method thereof, belong to li-ion electrode materials andIn the technical field of electrochemistry storage lithium combination electrode application.
Background technology
The electrode material of high-performance electric chemistry storage lithium and the application in electrochemistry storage lithium electrode thereof are for high performance lithium ion batteryResearch and develop significant. SnS2Nano material has higher electrochemistry storage lithium capacity (its theoretical capacity is 645mAh/g),In high performance lithium ion battery, have a good application prospect. But, in its lower electrical conductivity and charge and discharge processThe variation that volume is larger, causes using SnS2Electrochemistry storage lithium electrode prepared by nano material is its storage lithium capacity meeting in charge and discharge processDecay fast. Recently, there are some researches show by introducing other transition metal and can improve tinbase nano material electrochemistry storage lithiumThe performance of electrode. As Cu2SnS3，Cu2ZnSnS4As the electrochemical lithium storage performance of lithium ion battery negative material all higher than merelySnS2Nano material electrode. Cobalt sulfide nano material be also a kind of have negative compared with the lithium ion battery of high electrochemical storage lithium capacityUtmost point material, but there is too capacity attenuation shortcoming faster in charge and discharge process in single cobalt sulfide nano material.
Graphene has high electrical conductivity and charged mobility, specific area, good flexibility and chemical stability greatly. LogicalCross metal oxide or sulfide nano-material and the compound prepared composite of Graphene without thering is the electrochemistry storage lithium doingCapacity, and there is charge-discharge performance and the high power charging-discharging characteristic of enhancing. As, SnO2-Graphene composite nano materials,SnS2-Graphene composite nano materials, cobalt sulfide-Graphene composite nano materials etc. has all shown than simple SnO2、SnS2Or sulphurChange cobalt and there is higher electrochemistry storage lithium capacity and more excellent charge and discharge cycles stability. But the electrochemistry of these compositesStorage lithium performance also has the space of further improving.
The invention provides a kind of electrochemistry storage lithium combination electrode and preparation method thereof, this combination electrode SnCoS4Answering of-GrapheneClosing nano material is electrochemistry storage lithium active material. With use SnS2-Graphene and CoS2-Graphene composite nano materials is electrochemistryCombination electrode prepared by storage lithium active material, the present invention SnCoS4The composite nano materials of-Graphene is electroactive substanceThe electrochemistry storage lithium combination electrode of preparation has higher electrochemistry storage lithium capacity, excellent cycle performance and the high power significantly strengtheningRate charge-discharge characteristic. But, up to the present, this SnCoS that uses4The composite nano materials of-Graphene is that electrochemistry storage lithium is livedCombination electrode of property material and preparation method thereof yet there are no open report.
Summary of the invention
The object of the present invention is to provide a kind of electrochemistry storage lithium combination electrode and preparation method thereof, the electrochemistry of this combination electrodeStorage lithium active material is SnCoS4The composite nano materials of-Graphene, this composite nano materials is by SnCoS4Composite nanocrystalline is negativeBe loaded on Graphene and form, wherein SnCoS4Composite nanocrystalline is 1:2 with the ratio of the amount of substance of Graphene, the group of combination electrodePoint and mass percentage content be: SnCoS4The composite nano materials of-Graphene is 80%, acetylene black 10%, polyvinylidene fluorideAlkene 10%. The preparation method's of this electrochemistry storage lithium combination electrode step is as follows:
(1) by the SnCl of metering4·5H2O、CoCl2·6H2O and Cys join in deionized water, and fully stir,Obtain uniform mixed solution, SnCl in solution4With CoCl2The ratio of amount of substance be 1:1, the amount of substance of CysFor SnCl4With CoCl25 times of amount of substance sum, be then dispersed in deionized water ultrasonic graphene oxide, obtain allEven suspension is added to graphene oxide hanging drop in above-mentioned mixed solution under constantly stirring, and continues to stir 2h, oxygenThe amount of substance (amount of substance with carbon calculates) of functionalized graphene equals SnCl4With CoCl22 times of amount of substance sum, lastThe reactant mixture obtaining is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, and sealing, at the insulating box of 180 DEG CMiddle reaction 24h, after naturally cooling to room temperature, the precipitated product centrifugation that hydro-thermal is obtained, and by deionized water and anhydrousEthanol fully washs, and finally at 80 DEG C, after vacuum drying 12h, obtains SnCoS4-Graphene composite nano materials;
(2) by the above-mentioned SnCoS preparing4-Graphene composite nano materials is as the electrochemistry storage lithium active matter of combination electrodeMatter, under agitation fully to mix furnishing equal with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%Even pastel, each constituent mass percentage is: SnCoS4-Graphene composite nano materials 80%, acetylene black 10%, partially poly-PVF 10%, is coated onto this pastel on the Copper Foil of collector equably, dry, obtains electrochemistry storage lithium multiple after roll extrusionComposite electrode.
Compared with the prior art, the present invention SnCoS4The composite nano materials of-Graphene is the preparation of electrochemistry storage lithium active materialElectrochemistry storage lithium combination electrode and preparation method thereof there is following significant advantage and technological progress: although research show, with listPure SnS2Or fluidisation cobalt nano material compares, use SnS2-Graphene composite nano materials and fluidisation cobalt-Graphene composite NanoMaterial is that electrode prepared by electrochemistry storage lithium active material has higher electrochemistry storage lithium capacity, and its electrochemistry storage lithium specific capacity canTo reach 900-1000mAh/g (based on the quality of electrochemistry storage lithium active material), and there is good charge-discharge performance and changeKind high power charging-discharging characteristic, but its electrochemistry storage lithium performance also has the space of further lifting. Result of the present invention shows,Use SnCoS4The composite nano materials of-Graphene is combination electrode ratio SnS prepared by electrochemistry storage lithium chemical substance2-Graphene is multipleClose nano material and SnS2Combination electrode prepared by-Graphene composite nano materials has higher electrochemistry storage lithium specific capacity and aobviousThe high power charging-discharging characteristic that work strengthens. Its reason is due to SnS2For typical layer structure crystal, and CoS2Crystal is notStratiform, when the crystal of these two kinds of different structures produces in hydrothermal solution simultaneously, there is mutually mutual interference, cause rawThe SnCoS becoming4With SnS2Or CoS2Crystal is not identical. The mutual shadow of the growth of this different crystal material in hydrothermal solutionPilot causes the obtained SnCoS that loads on Graphene surface4Nano particle has less size, further also finds GrapheneThe SnCoS of upper load4Nano particle forms composite nanocrystalline by thinner nanocrystal. This SnCoS4Compound nanometerThe combination electrode that the composite nano materials that crystal structure and Graphene are compounded to form is prepared as electrochemistry storage lithium active chemistry is passableShow the electrochemistry storage lithium performance further strengthening, especially shown and compared SnS2-Graphene and CoS2-Graphene composite Nano materialMaterial combination electrode has higher electrochemistry storage lithium capacity and the high power charging-discharging characteristic significantly strengthening. SnCoS of the present invention4-It is simple, convenient and be easy to expand that the preparation of one step hydrothermal preparing process of Graphene composite nano materials and combination electrode thereof has techniqueThe feature of application.
Brief description of the drawings
Fig. 1: the XRD figure of different composite nano material prepared by hydro-thermal method of the present invention: (a) SnS2/ Graphene, (b) CoS2/ graphiteAlkene, (c) SnCoS4/ Graphene composite nano materials;
The SEM pattern of composite prepared by Fig. 2: Fig. 2 hydro-thermal method of the present invention, (a) SnS2/ Graphene, (b) CoS2/ graphiteAlkene and (c) SnCoS4/ Graphene composite nano materials;
Fig. 3: Fig. 3 hydro-thermal of the present invention is sent out the TEM/HRTEM photo of the composite of preparation, (a, b) SnS2/ Graphene, (c,d)CoS2/ Graphene and (e, f) SnCoS4/ Graphene composite nano materials;
Fig. 4: (a) SnS2/ Graphene, (b) CoS2/ Graphene, (c) SnCoS4(d) SnCoS4/ Graphene composite nano materialsThe charge-discharge performance of the electrochemistry storage lithium combination electrode of preparation under 100mA/g current density;
Fig. 5: (a) SnS2/ Graphene, CoS2/ Graphene, SnCoS4And SnCoS4Electrochemistry storage lithium prepared by/graphene composite materialThe charge/discharge rate property of combination electrode under different current densities.
Detailed description of the invention
Further illustrate the present invention below in conjunction with drawings and Examples.
(1)SnCoS4The hydro-thermal method preparation of-Graphene composite nano materials: by the SnCl of 1.5mmol4·5H2O、1.5mmolCoCl2·6H2O and 15.0mmolL-cysteine join in 100mL deionized water, and fully stir and form uniformlyMixed solution; Be distributed in 60mL deionized water ultrasonic the graphene oxide of 6.0mmol, obtain uniform suspension,Under constantly stirring, the hanging drop of graphene oxide is added in mixed solution above, under room temperature, stirs again 2h; To finally obtainTo mixed reactant transfer in the hydrothermal reaction kettle of 200mL with polytetrafluoroethylliner liner, sealing, the perseverance of 180 DEG CIn incubator, react 24h, after naturally cooling to room temperature, by precipitation and centrifugal separation, and fully wash with deionized water and absolute ethyl alcoholWash, will obtain hydro-thermal black product at 80 DEG C after vacuum drying 12h, that finally prepares obtains SnCoS4-Graphene is compound to be receivedRice material;
(2) by the above-mentioned SnCoS preparing4-Graphene composite nano materials is as the electrochemistry storage lithium active matter of combination electrodeMatter, under agitation fully to mix furnishing equal with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%Even pastel, each constituent mass percentage is: SnCoS4-Graphene composite nano materials 80%, acetylene black 10%, partially poly-PVF 10%, is coated onto this pastel on the Copper Foil of collector equably, dry, obtains electrochemistry storage lithium multiple after roll extrusionComposite electrode.
Comparative example: as a comparison, prepared SnCoS with similar hydrothermal method4Nano material, and store as electrochemistry using itLithium active material is prepared electrochemistry storage lithium electrode.
(1)SnCoS4Nano material and hydro-thermal preparation thereof: by the SnCl of 1.5mmol4·5H2The CoCl of O, 1.5mmol2·6H2OJoin in 160mL deionized water with 15.0mmolL-cysteine, and fully stir the uniform mixed solution of formation; WillTo this mixed solution transfer in the hydrothermal reaction kettle of 200mL with polytetrafluoroethylliner liner, sealing, the perseverance of 180 DEG CIn incubator, react 24h, after naturally cooling to room temperature, by precipitation and centrifugal separation, and fully wash with deionized water and absolute ethyl alcoholWash, will obtain hydro-thermal black product and after vacuum drying 12h, finally prepare SnCoS at 80 DEG C4Nano material;
(2) by the above-mentioned SnCoS preparing4Nano material is as the electrochemistry storage lithium active material of combination electrode, with acetylene blackAnd the 1-METHYLPYRROLIDONE solution of the Kynoar of mass fraction 5% under agitation fully mixes the uniform pastel of furnishing,Each constituent mass percentage is: SnCoS4Nano material 80%, acetylene black 10%, Kynoar 10%, by this pastelBe coated onto equably on the Copper Foil as collector, dry, after roll extrusion, obtain electrochemistry storage lithium combination electrode.
Comparative example: as a comparison, prepared SnS with similar hydrothermal method2/ Graphene composite nano materials, and with it as electricityChemistry storage lithium active material is prepared electrochemistry storage lithium electrode.
(1)SnS2/ Graphene composite nano materials and hydro-thermal preparation thereof: by the SnCl of 3.0mmol4·5H2O and 15.0mmolL-Cysteine joins in 100mL deionized water, and fully stirs the uniform solution of formation; By the graphite oxide of 6.0mmolAlkene is ultrasonic to be distributed in 60mL deionized water, obtains uniform suspension, under constantly stirring, by the suspension of graphene oxideDrop is added in solution above, stirs 2h under room temperature again; The mixed reactant finally obtaining is transferred to 200mL with poly-In the hydrothermal reaction kettle of tetrafluoroethene inner bag, sealing is reacted 24h in the insulating box of 180 DEG C, after naturally cooling to room temperature,By precipitation and centrifugal separation, and fully wash with deionized water and absolute ethyl alcohol, will obtain hydro-thermal black product vacuum at 80 DEG CAfter dry 12h, that finally prepares obtains SnS2/ Graphene composite nano materials;
(2) by the above-mentioned SnS preparing2/ Graphene composite nano materials is store lithium active material as the electrochemistry of combination electrode,Under agitation fully to mix furnishing uniform with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%Pastel, each constituent mass percentage is: SnS2/ Graphene composite nano materials is 80%, acetylene black 10%, Kynoar10%, this pastel is coated onto equably on the Copper Foil of collector, dry, after roll extrusion, obtain electrochemistry storage lithium combination electrode.
Comparative example: as a comparison, prepared CoS with similar hydrothermal method2/ Graphene composite nano materials, and with it as electricityChemistry storage lithium active material is prepared electrochemistry storage lithium electrode.
(1)CoS2/ Graphene composite nano materials and hydro-thermal preparation thereof: by the CoCl of 3.0mmol2·6H2O and 15.0mmolCys joins in 50mL deionized water, and fully stirs the uniform solution of formation; By the graphite oxide of 6.0mmolAlkene is ultrasonic to be distributed in 60mL deionized water, obtains uniform suspension, under constantly stirring, by the suspension of graphene oxideDrop is added in solution above, stirs 2h under room temperature again; The mixed reactant finally obtaining is transferred to 200mL with poly-In the hydrothermal reaction kettle of tetrafluoroethene inner bag, sealing is reacted 24h in the insulating box of 180 DEG C, after naturally cooling to room temperature,By precipitation and centrifugal separation, and fully wash with deionized water and absolute ethyl alcohol, will obtain hydro-thermal black product vacuum at 80 DEG CAfter dry 12h, that finally prepares obtains CoS2/ Graphene composite nano materials;
(2) by the above-mentioned CoS preparing2/ Graphene composite nano materials is store lithium active material as the electrochemistry of combination electrode,Under agitation fully to mix furnishing uniform with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%Pastel, each constituent mass percentage is: CoS2/ Graphene composite nano materials is 80%, acetylene black 10%, polyvinylidene fluorideAlkene 10%, is coated onto this pastel on the Copper Foil of collector equably, dry, obtains electrochemistry storage lithium compound electric after roll extrusionThe utmost point.
With X-ray diffraction (XRD), ESEM (SEM), transmission electron microscope/high-resolution-ration transmission electric-lens (TEM/HRTEM),Element energy disperse spectroscopy (EDS) and XPS are to the above-mentioned SnCoS for preparing4-Graphene composite nano materials, SnCoS4Nano material,SnS2-Graphene composite nano materials and CoS2-Graphene composite nano materials characterizes.
Electrochemistry storage lithium performance test: prepare electrochemistry to store lithium combination electrode be working electrode with above-mentioned, be full of argon gasIn glove box, be assembled into the test battery of lithium ion battery, metallic lithium foil is to electrode and reference electrode, polypropylene film(Celgard-2300) be barrier film, 1.0MLiPF6EC/DMC solution (volume ratio 1:1) be electrolyte. Perseverance under room temperatureElectric current discharges and recharges the electrochemistry storage lithium performance of experiment test and the more above-mentioned composite nano materials preparing, and charging and discharging currents exists100-1000mA/g, charging/discharging voltage interval is 3.0～0.005V.
Elemental Composition is analysed and is shown, SnCoS4In/Graphene composite nano materials, the ratio of the amount of substance of Sn:Co:S is1:0.96:3.97, meet SnCoS4；SnS2In/Graphene, the ratio of the amount of substance of Sn:S is 1:1.96, meets SnS2；CoS2/ stoneIn Graphene, the ratio of the amount of substance of Co:S is 1:2.03, meets CoS2。
The XRD characterization result of Fig. 1 shows, SnS2/ Graphene composite nano materials has shown stronger diffraction maximum, and meets SnS2Standard powder diffraction card (JCPDSCardNo.23-0677), illustrates SnS in composite2For typical layer structure;CoS2/ Graphene composite nano materials has also shown stronger diffraction maximum, and meets CoS2Standard powder diffraction card (JCPDSno.41-1471)。SnCoS4/ Graphene composite Nano is in 2 θ=9.32 °, and 17.78 °, 28.92 °, 32.56 ° and 51.22 ° have shownLow intensive diffraction maximum, its intensity is significantly less than SnS2/ Graphene composite Nano material and CoS2/ Graphene composite Nano material, sayUnderstand the SnCoS loading on Graphene4Nano particle has less size, in addition SnCoS4/ Graphene composite nano materialsDo not show and belong to SnS yet2(001) peak of layer structure.
The SEM morphology characterization of Fig. 2 shows, SnS2/ Graphene composite nano materials shows the SnS of sheet2Be evenly dispersed in pleatThe graphene nanometer sheet surface of wrinkle; CoS2The CoS of the spheroidal of the about 100nm of/Graphene composite nano materials display size2ReceiveRice corpuscles is wrapped or is dispersed on graphene nanometer sheet; SnCoS4/ Graphene composite nano materials display size less (approximately 35Nm) SnCoS4Nano particle is wrapped or is dispersed in graphene nanometer sheet.
The TEM/HRTEM characterization result of Fig. 3 shows, at SnS2In/Graphene composite nano materials, the SnS of layer structure2Nanometer sheet is dispersed in the graphene nanometer sheet surface of fold uniformly, and the interlamellar spacing of its (001), (100), (101) face respectivelyBe 0.59,0.32 and 0.27nm, with the SnS of layer structure2Crystal is consistent; At CoS2In/Graphene composite nano materials,CoS2Nano particle is dispersed on graphene nanometer sheet, the interlamellar spacing of its (200), (210), (311) face is respectively 0.27,0.25,0.17nm, with CoS2Crystal is consistent; At SnCoS4In/Graphene composite nano materials, SnCoS4Nano particle toolThere is thinner size, and be evenly dispersed in graphene nanometer sheet; Fig. 3 (f) also further shows SnCoS4Nano particle is aobviousShow that its size is about 3-6nm by the more tiny nanocrystalline composite nanocrystalline forming.
Fig. 4 demonstration, under room temperature, under 100mA/g current density, charge-discharge performance test shows: with SnS2/ Graphene andCoS2Electrochemistry storage lithium combination electrode prepared by/Graphene composite Nano material is compared, SnCoS4The preparation of/Graphene composite nano materialsElectrochemistry storage lithium combination electrode shown higher electrochemistry storage lithium reversible specific capacity and excellent stable circulation performance, it charges and dischargeElectricity reversible capacity reaches 1490mAh/g, and after 200 circulations, reversible capacity does not change substantially. By comparison, SnS2/ graphiteThe reversible lithium storage capacity of alkene composite nano materials electrode reduces the 924mAh/g of 200 circulations gradually from initial 1096mAh/g;CoS2The reversible capacity of/Graphene composite nano materials electrode can be reached for 1205mAh/g; SnCoS4Nano material reversibleCapacity is reduced to the 303mAh/g of 200 circulations gradually from initial 1184mAh/g. Therefore, SnCoS4/ Graphene is compound to be receivedThe electrochemistry storage lithium reversible specific capacity of combination electrode prepared by rice material is all higher than SnS2/ Graphene, CoS2/ Graphene and SnCoS4The electrode of preparation, its charge-discharge performance is also significantly better than SnS2/ Graphene and SnCoS4Electrode prepared by nano material.
The high rate performance test under different charging and discharging currents density of Fig. 5 shows, at current density 200,500 and 1000mA/gTime, SnCoS4The electrochemistry storage lithium reversible capacity of combination electrode prepared by/Graphene composite nano materials is respectively 1336,1235And 1145mAh/g, and under different current densities, also show stable cycle performance; In contrast, SnS2/ Graphene is multipleThe respective value of closing electrode prepared by nano material is respectively 1068,930 and 787mAh/g; CoS2/ Graphene composite nano materialsThe respective value of electrode is respectively 988,892 and 783mAh/g; SnCoS4The respective value of electrode is respectively 770,480,265mAh/g.
Therefore, Electrochemical results explanation, and uses SnS2/ Graphene and CoS2Prepared by/Graphene composite nano materials compoundElectrode is compared, and uses SnCoS4Electrochemistry storage lithium combination electrode prepared by/Graphene composite nano materials not only has higher electrochemistryStore lithium reversible specific capacity and excellent cycle performance, and shown the high power charging-discharging characteristic of remarkable enhancing.

Claims (2)

1. an electrochemistry storage lithium combination electrode, is characterized in that, the electrochemistry storage lithium active material of combination electrode is SnCoS4-The composite nano materials of Graphene, this composite nano materials is by SnCoS4Composite nanocrystalline loads on Graphene and forms, whereinSnCoS4Composite nanocrystalline is 1:2 with the ratio of the molal quantity of Graphene, and the component of combination electrode and mass percentage content thereof are:SnCoS4The composite nano materials of-Graphene is 80%, acetylene black 10%, Kynoar 10%.
2. a preparation method for electrochemistry storage lithium combination electrode claimed in claim 1, is characterized in that described preparation sideThe step of method is as follows:
(1) by the SnCl of metering4·5H2O、CoCl2·6H2O and Cys join in deionized water, and fully stir,Obtain uniform mixed solution, SnCl in solution4With CoCl2The ratio of amount of substance be 1:1, the amount of substance of CysFor SnCl4With CoCl25 times of amount of substance sum, be then dispersed in deionized water ultrasonic graphene oxide, obtain allEven suspension is added to graphene oxide hanging drop in above-mentioned mixed solution under constantly stirring, and continues to stir 2h, withThe amount of substance of carbon calculates, and the amount of substance of graphene oxide equals SnCl4With CoCl22 times of amount of substance sum, lastThe reactant mixture obtaining is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, and sealing, at the insulating box of 180 DEG CMiddle reaction 24h, after naturally cooling to room temperature, the precipitated product centrifugation that hydro-thermal is obtained, and by deionized water and anhydrousEthanol fully washs, and finally at 80 DEG C, after vacuum drying 12h, obtains SnCoS4-Graphene composite nano materials;
(2) by the above-mentioned SnCoS preparing4-Graphene composite nano materials is as the electrochemistry storage lithium active matter of combination electrodeMatter, under agitation fully to mix furnishing equal with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass fraction 5%Even pastel, is coated onto this pastel on the Copper Foil of collector equably, dry, obtains electrochemistry storage lithium multiple after roll extrusionComposite electrode.
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