CN105609746A - Composite electrode capable of simultaneously electrochemically storing sodium and storing lithium and preparation method of composite electrode - Google Patents
Composite electrode capable of simultaneously electrochemically storing sodium and storing lithium and preparation method of composite electrode Download PDFInfo
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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
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- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention discloses a composite electrode capable of simultaneously electrochemically storing sodium and storing lithium and a preparation method of the composite electrode. The composite electrode takes an SnCoS4 composite nano crystal-graphene composite material as an active substance capable of simultaneously electrochemically storing the sodium and storing the lithium. The preparation method comprises the following steps: under the condition that graphene oxide exists, carrying out a hydrothermal reaction on a mixed solution of SnCl4, CoCl2 and L-cysteine under a hydrothermal condition to prepare the SnCoS4 composite nano crystal-graphene composite material; and blending the obtained SnCoS4 composite nano crystal-graphene composite material with acetylene black, carboxymethylcellulose and polyvinylidene fluoride into paste; coating the paste on a copper foil; and drying and rolling to obtain the composite electrode capable of simultaneously electrochemically storing sodium and storing lithium. The composite electrode capable of simultaneously electrochemically storing sodium and storing lithium has the advantages of high reversible specific capacity, stable circulation property and good high-rate charging/discharging properties.
Description
Technical field
The present invention relates to a kind of simultaneous electrochemical storage sodium and storage lithium combination electrode and preparation method thereof, relate in particular to and use SnCoS4Compound receivingWhat meter Jing-graphene composite material was prepared as electroactive substance can simultaneous electrochemical storage sodium and storage lithium combination electrode andPreparation method, belongs to the applied technical field in electrochemical copolymerization electrode and sodium ion lithium ion composite battery thereof.
Background technology
Lithium ion battery has the advantages such as high specific capacity and long cycle life at mobile communication, Moped Scooter, electronic with itThe field such as automobile and energy storage is widely used, and still, the extensive application of lithium ion battery causes the relative shortage of lithium resourceRise steadily with the raw-material price of lithium resource, as the price of the lithium carbonate 2 times of left and right of having gone up in the previous year. Provide with lithiumSource is compared, and sodium has affluent resources and cheap advantage more, recently about sodium-ion battery and electrochemistry storage sodium material thereofCause the very big interest of people with the research and development of electrode. But, compared with lithium ion battery, the specific capacity of sodium-ion battery and multiplying powerCharacteristic is lower. Can simultaneous electrochemical the sodium ion of storage sodium and storage lithium and lithium ion composite battery can take into account above-mentioned lithium ion battery andThe advantage of sodium-ion battery aspect performance and resource and the problem of existence. Traditional lithium ion battery uses graphite material as negative pole,But because making its electrochemistry, the less interlamellar spacing of graphite cathode material (0.33-0.34nm) stores the poor performance of sodium, its electrochemistry storageThe specific capacity of sodium is almost close to 0. Therefore, graphite material can not be used for preparing answering of simultaneous electrochemical storage sodium and electrochemistry storage lithiumComposite electrode, so research and development have electrochemical active material and the combination electrode thereof of energy simultaneous electrochemical storage sodium and electrochemistry storage lithiumTo sodium ion and the significant and technology using value of lithium ion composite battery.
The SnS of layer structure2Nano material not only has higher electrochemistry storage lithium capacity, has higher electrochemistry storage sodium simultaneouslyCapacity has a good application prospect in lithium ion battery or sodium-ion battery. But, due to its lower electrical conductivity and fillingIn discharge process, the larger variation of volume, causes using SnS2Electrochemistry storage lithium electrode prepared by nano material or electrochemistry storage sodium electrodeThe quick decay of its electrochemistry storage lithium capacity or electrochemistry storage sodium capacity in charge and discharge process. Also tool of cobalt sulfide nano material in additionThere is higher electrochemistry storage lithium capacity, there is good electrochemistry storage sodium performance, simultaneously in lithium ion battery or sodium-ion batteryHave a good application prospect. But electrochemistry storage lithium electrode or electrochemistry prepared by cobalt sulfide nano material are store filling of sodium electrodePut stable circulation poor, the capacity attenuation of its electrochemistry storage lithium or electrochemistry storage sodium is very fast.
Graphene has high electrical conductivity and charged mobility, specific area, good flexibility and chemical stability greatly. LogicalCross by nano metal sulfide material and the compound prepared composite of Graphene not only kept high electrochemistry storage lithium capacity orElectrochemistry is store sodium capacity, and has charge-discharge performance and the high power charging-discharging characteristic of enhancing. As SnS2-Graphene composite woodMaterial, cobalt sulfide-graphene composite material etc. have all shown than simple SnS2Or cobalt sulfide have higher electrochemistry storage lithium capacity orElectrochemistry storage sodium capacity, and there is stable charge-discharge performance. But combination electrode prepared by these compositesElectrochemistry storage lithium performance or electrochemistry storage sodium performance also have space, especially these composites electrification at the same time of further improvingThe application of learning in the combination electrode of storing sodium and storage lithium also needs further research.
The invention provides a kind of can storage sodium and store combination electrode of lithium and preparation method thereof by simultaneous electrochemical, this combination electrode is usedSnCoS4The composite of composite nanocrystalline-Graphene is the active material of simultaneous electrochemical storage sodium and storage lithium. With use SnS2-graphiteAlkene and CoS2-graphene composite material is that the combination electrode that simultaneous electrochemical storage sodium is prepared with the active material of storage lithium is compared, the present inventionUse SnCoS4The composite of composite nanocrystalline-Graphene is energy simultaneous electrochemical storage sodium and storage lithium prepared by electroactive substanceCombination electrode there is the specific capacity of higher simultaneous electrochemical storage sodium and storage lithium and the high power charging-discharging characteristic significantly strengthening, andThere is excellent charge-discharge performance. But, up to the present, this SnCoS that uses4Composite nanocrystalline-Graphene compoundMaterial is yet there are no openly with combination electrode of storing lithium and preparation method thereof by simultaneous electrochemical storage sodium of simultaneous electrochemical active materialReport.
Summary of the invention
The object of the present invention is to provide a kind of can storage sodium and store combination electrode of lithium and preparation method thereof by simultaneous electrochemical, this is multipleThe simultaneous electrochemical storage sodium of composite electrode and storage lithium active material are SnCoS4The composite of composite nanocrystalline-Graphene, this is compoundMaterial is by SnCoS4Composite nanocrystalline loads on Graphene and forms, wherein SnCoS4The material of composite nanocrystalline and GrapheneThe ratio of amount be 1:2, the component of combination electrode and mass percentage content thereof are: SnCoS4Composite nanocrystalline-Graphene compoundMaterial is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%. This simultaneous electrochemical storage sodium and storage lithiumPreparation method's step 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 SnCoS4Composite nanocrystalline-graphene composite material;
(2) by the above-mentioned SnCoS preparing4Composite nanocrystalline-graphene composite material is as the electrochemistry storage sodium of combination electrodeActive material, exists with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Stir the lower uniform pastel of furnishing that fully mixes, each constituent mass percentage is: SnCoS4Composite nanocrystalline-Graphene composite woodMaterial 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this pastel equably as collectionOn the Copper Foil of fluid, dry, after roll extrusion, obtain electrochemistry storage sodium combination electrode.
Compared with the prior art, the present invention SnCoS4The composite of composite nanocrystalline-Graphene is electroactive substance systemStandby can have following significant advantage and technological progress with combination electrode of storing lithium and preparation method thereof by simultaneous electrochemical storage sodium: to the greatest extentPipe research shows, with simple SnS2Or fluidisation cobalt nano material compares, use SnS2-graphene composite material and fluidisation cobalt-stoneChina ink alkene composite is that electrochemistry storage sodium electrode or electrochemistry storage lithium electrode prepared by electroactive substance has higher electrochemistryStorage sodium specific capacity or electrochemistry storage lithium specific capacity, its electrochemistry storage lithium specific capacity can reach 800-1000mAh/g, electrochemistry storageSodium specific capacity can reach 600-700mAh/g (based on the quality of electroactive substance), and has more stable charge and discharge cyclesThe high power charging-discharging characteristic of performance and improvement, but the performance of its electrochemistry storage sodium or electrochemistry storage sodium also has further liftingSpace. But, up to the present, use SnS2-graphene composite material or cobalt sulfide-graphene composite material are that electrochemistry is livedProperty material to prepare the report of combination electrode of simultaneous electrochemical storage sodium and storage lithium also little. Result of the present invention shows, uses SnCoS4The composite of composite nanocrystalline-Graphene is energy simultaneous electrochemical storage sodium and storage lithium combination electrode prepared by electrochemistry chemical substanceRatio SnS2-graphene composite material or SnS2Simultaneous electrochemical storage sodium prepared by-graphene composite material and storage lithium compound electric haveThere are the specific capacity of higher simultaneous electrochemical storage sodium and storage lithium and the high power charging-discharging characteristic significantly strengthening, and there is excellent fillingDischarge cycles stability. Its reason is due to SnS2For typical layer structure crystal, and CoS2Crystal is not stratiform,When the crystal of these two kinds of different structures produces in hydrothermal solution simultaneously, there is mutually mutual interference, cause generateSnCoS4With SnS2Or CoS2Crystal is not identical. The influencing each other of growth of this different crystal material in hydrothermal solution ledCause the obtained SnCoS that loads on Graphene surface4Nano particle has less size, further also finds on Graphene negativeThe SnCoS carrying4Nano particle forms composite nanocrystalline by thinner nanocrystal. This SnCoS4Compound nanocrystalline knotWhat the composite that structure and Graphene are compounded to form was prepared as electroactive substance can simultaneous electrochemical storage sodium and storage lithium compound electricExtremely can show the chemical property of further enhancing, especially show and compared SnS2-Graphene and CoS2-graphene composite materialCombination electrode has the specific capacity of higher simultaneous electrochemical storage sodium and storage lithium and the high power charging-discharging characteristic significantly strengthening, and toolThere is excellent charge and discharge cycles stability.
Brief description of the drawings
Fig. 1: (a) SnS prepared by the present invention2/ graphene composite material, (b) CoS2/ graphene composite material, (c) SnCoS4MultipleClose the XRD figure of nanocrystalline-graphene composite material;
Fig. 2: (a) SnS prepared by the present invention2/ graphene composite material, (b) CoS2/ graphene composite material and (c) SnCoS4The SEM pattern photo of composite nanocrystalline-graphene composite material;
Fig. 3: (a, b) SnS prepared by the present invention2/ graphene composite material, (c, d) CoS2/ graphene composite material and (e, f)SnCoS4The TEM/HRTEM photo of composite nanocrystalline-graphene composite material.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment.
(1)SnCoS4The hydro-thermal method preparation of composite nanocrystalline-graphene composite material: by the SnCl of 1.5mmol4·5H2O、The CoCl of 1.5mmol2·6H2O and 15.0mmolL-cysteine join in 100mL deionized water, and fully stir shapeBecome uniform mixed solution; Be distributed in 60mL deionized water ultrasonic the graphene oxide of 6.0mmol, hanged uniformlySupernatant liquid, under constantly stirring, is added to the hanging drop of graphene oxide in mixed solution above, stirs 2h under room temperature again;The mixed reactant finally obtaining is transferred in the hydrothermal reaction kettle of 200mL with polytetrafluoroethylliner liner, sealing,In the insulating box of 180 DEG C, react 24h, after naturally cooling to room temperature, by precipitation and centrifugal separation, and by deionized water and anhydrousEthanol fully washs, and will obtain hydro-thermal black product at 80 DEG C after vacuum drying 12h, and that finally prepares obtains SnCoS4Composite nanocrystalline-composite nanocrystalline graphene composite material;
(2) by the above-mentioned SnCoS preparing4Composite nanocrystalline-graphene composite material is as simultaneous electrochemical storage sodium and storage lithiumThe electroactive substance of combination electrode, with the N-first of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Base pyrrolidone solution is under agitation fully mixed the uniform pastel of furnishing, and each constituent mass percentage is: SnCoS4Compound receivingMeter Jing-graphene composite material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, by this pastelBe coated onto equably on the Copper Foil as collector, dry, after roll extrusion, obtaining can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
Comparative example: as a comparison, prepared SnCoS with similar hydrothermal method4Nano material, and live using it as electrochemistryProperty material, preparation can simultaneous electrochemical the combination electrode of storage sodium and storage lithium.
(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 lived as the electrochemistry of simultaneous electrochemical storage sodium and storage lithium combination electrodeProperty material, is stirring with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Mix the uniform pastel of lower abundant mixing furnishing, each constituent mass percentage is: SnCoS4Nano material 80%, acetylene black 10%,Carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this pastel on the Copper Foil of collector equably, dry, rollsAfter pressure, obtaining can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
Comparative example: as a comparison, prepared SnS with similar hydrothermal method2/ graphene composite material, and with it as electrochemistryActive material, preparation can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
(1)SnS2/ graphene composite material and hydro-thermal preparation thereof: by the SnCl of 3.0mmol4·5H2O and 15.0mmolL-halfCystine joins in 100mL deionized water, and fully stirs the uniform solution of formation; By the graphene oxide of 6.0mmolUltrasonic being distributed in 60mL deionized water, obtains uniform suspension, under constantly stirring, by the suspension of graphene oxideBe added drop-wise in solution above, under room temperature, stir again 2h; The mixed reactant finally obtaining is transferred to 200mL with poly-fourIn the hydrothermal reaction kettle of PVF 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 material;
(2) by the above-mentioned SnS preparing2/ graphene composite material is as the electrification of simultaneous electrochemical storage sodium and storage lithium combination electrodeLearn active material, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Under agitation fully mix the uniform pastel of furnishing, each constituent mass percentage is: SnS2/ graphene composite material is 80%,Acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto the copper as collector equably using this pastelOn paper tinsel, dry, after roll extrusion, obtaining can simultaneous electrochemical storage sodium and storage lithium combination electrode.
Comparative example: as a comparison, prepared CoS with similar hydrothermal method2/ graphene composite material, and with it as electrochemistryActive material, preparation can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
(1)CoS2/ graphene composite material and hydro-thermal preparation thereof: by the CoCl of 3.0mmol2·6H2O and 15.0mmolL-Cysteine joins in 50mL deionized water, and fully stirs the uniform solution of formation; By the graphene oxide of 6.0mmolUltrasonic being distributed in 60mL deionized water, obtains uniform suspension, under constantly stirring, by the suspension of graphene oxideBe added drop-wise in solution above, under room temperature, stir again 2h; The mixed reactant finally obtaining is transferred to 200mL with poly-fourIn the hydrothermal reaction kettle of PVF 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 material;
(2) by the above-mentioned CoS preparing2/ graphene composite material is as the electrification of simultaneous electrochemical storage sodium and storage lithium combination electrodeLearn active material, with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Under agitation fully mix the uniform pastel of furnishing, each constituent mass percentage is: CoS2/ graphene composite material is 80%,Acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto the copper as collector equably using this pastelOn paper tinsel, dry, after roll extrusion, obtaining can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
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 preparing4Composite nanocrystalline-graphene composite material, SnCoS4NanometerMaterial, SnS2-graphene composite material and CoS2-graphene composite material characterizes.
The test of simultaneous electrochemical storage sodium and storage lithium performance: with above-mentioned storing sodium and store the compound of lithium by simultaneous electrochemical of preparingElectrode is working electrode, is assembled into the test battery of simultaneous electrochemical storage sodium and storage lithium, sodium metal in the glove box that is full of argon gasSheet is to electrode and reference electrode, and glass fibre membrane is barrier film, 0.5mol/LNaPF6+0.5mol/LLiPF6EC/DMCMixed solution (volume ratio 1:1) is the composite electrolyte of sodium ion and lithium ion test battery. Constant current charge-discharge under room temperature is realThe simultaneous electrochemical storage sodium of test examination and the more above-mentioned combination electrode preparing and the performance of storage lithium, charging and discharging currents is 100MA/g or 1000mA/g, charging/discharging voltage interval is 3.0～0.005V.
Elemental Composition is analysed and is shown, SnCoS4In composite nanocrystalline-graphene composite material, 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 material has shown stronger diffraction maximum, and meets SnS2MarkAccurate powder diffraction card (JCPDSCardNo.23-0677), illustrates SnS in composite2For typical layer structure; CoS2/Graphene composite material 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 shown lowerThe diffraction maximum of intensity, its intensity is significantly less than SnS2/ Graphene composite Nano material and CoS2/ Graphene composite Nano material, explanationLoad on the SnCoS on Graphene4Composite nanocrystalline particle has less size, in addition SnCoS4Composite nanocrystalline-graphiteAlkene composite does not yet show and belongs to SnS2(001) peak of layer structure.
The SEM morphology characterization of Fig. 2 shows, SnS2/ graphene composite material shows the SnS of sheet2Be evenly dispersed in foldGraphene nanometer sheet surface; CoS2The CoS of the spheroidal of the about 100nm of/graphene composite material display size2Nano particle quiltWrap up or be dispersed on graphene nanometer sheet; SnCoS4(the about 35nm) that composite nanocrystalline-graphene composite material display size is lessSnCoS4Composite nanocrystalline particle is wrapped or is dispersed in graphene nanometer sheet.
The TEM/HRTEM characterization result of Fig. 3 shows, at SnS2In/graphene composite material, the SnS of layer structure2NanometerSheet is dispersed in the graphene nanometer sheet surface of fold uniformly, the interlamellar spacing of its (001), (100), (101) face is respectively 0.59,0.32 and 0.27nm, with the SnS of layer structure2Crystal is consistent; At CoS2In/graphene composite material, CoS2Nano particleBe 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 composite nanocrystalline-graphene composite material, SnCoS4Composite nanocrystalline particle toolThere is thinner size, and be evenly dispersed in graphene nanometer sheet; Fig. 3 (f) also further shows SnCoS4Composite nanocrystallineParticle has shown that its size is about 3-6nm by the more tiny nanocrystalline composite nanocrystalline forming.
Electrochemical results shows:
Under room temperature under 100mA/g charging and discharging currents density, SnCoS4Prepared by composite nanocrystalline-graphene composite material compoundElectrode, the reversible specific capacity of its simultaneous electrochemical storage sodium and storage lithium initially reaches 1251mAh/g, and after 100 circulations, it is reversibleSpecific capacity is 1218mAh/g, has shown high specific capacity and excellent stable circulation performance; By comparison, SnS2/ Graphene is multipleThe simultaneous electrochemical storage sodium of composite electrode and storage lithium reversible specific capacity initially reach 920mAh/g, after 100 circulations, are 830mAh/g;CoS2The simultaneous electrochemical storage sodium of/graphene composite material electrode and storage lithium reversible capacity initially reach 955mAh/g, follow for 100 timesAfter ring, be 827mAh/g; ; SnCoS4The simultaneous electrochemical storage sodium of nano material electrode and the reversible specific capacity of storage lithium initially reach1030mAh/g is 332mAh/g after 100 circulations. Test result explanation: SnCoS4Composite nanocrystalline-Graphene composite woodThe simultaneous electrochemical storage sodium of the combination electrode of material preparation and storage lithium reversible specific capacity are all apparently higher than SnS2/ Graphene, CoS2/ graphiteAlkene and SnCoS4The simultaneous electrochemical storage sodium of the combination electrode of preparation and the specific capacity of storage lithium, and it is steady to have excellent charge and discharge cyclesQualitative energy.
In the time of charging and discharging currents density 1000mA/g, the simultaneous electrochemical storage sodium of above-mentioned electrode and discharging and recharging doubly of storage lithium are testedRate characteristic, result is: SnCoS4Simultaneous electrochemical storage sodium and the storage of combination electrode prepared by composite nanocrystalline-graphene composite materialThe multiplying power property of lithium is 1020mAh/g; SnS2/ graphene composite material is prepared the simultaneous electrochemical storage sodium of combination electrode and storage lithiumMultiplying power property is 755mAh/g; CoS2/ graphene composite material is prepared the multiplying power of simultaneous electrochemical storage sodium and the storage lithium of combination electrodeCharacteristic is 650mAh/g; SnCoS4The simultaneous electrochemical storage sodium of preparing electrode is 380mAh/g with the multiplying power property of storage lithium. KnotFruit explanation: with SnS2/ Graphene, CoS2/ Graphene and SnCoS4The combination electrode of preparation is compared, SnCoS4Composite nanocrystalline-Combination electrode prepared by graphene composite material has shown the charge-discharge magnification spy of simultaneous electrochemical storage sodium and the storage lithium of remarkable enhancingProperty.
Therefore, Electrochemical results explanation: with use SnS2/ Graphene or CoS2Combination electrode prepared by/graphene composite materialCompare, use SnCoS4Simultaneous electrochemical storage sodium prepared by composite nanocrystalline-graphene composite material and the combination electrode of storage lithium are not onlyThere is the reversible specific capacity of higher simultaneous electrochemical storage sodium and storage lithium and the high power charging-discharging characteristic significantly strengthening, and have excellentDifferent cycle performance.
Claims (2)
1. a combination electrode for simultaneous electrochemical storage sodium and storage lithium, is characterized in that, combination electrode has simultaneous electrochemical storageThe function of sodium and storage lithium, its electro-chemical activity active material is SnCoS4The composite of composite nanocrystalline-Graphene, this is compoundMaterial is by SnCoS4Composite nanocrystalline loads on Graphene and forms, wherein SnCoS4The material of composite nanocrystalline and GrapheneThe ratio of amount be 1:2, the component of combination electrode and mass percentage content thereof are: SnCoS4Composite nanocrystalline-Graphene compoundMaterial is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
2. profit requires the simultaneous electrochemical storage sodium described in 1 and a preparation method who stores the combination electrode of lithium, it is characterized in that,Described preparation method's 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, 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 SnCoS4Composite nanocrystalline-graphene composite material;
(2) by the above-mentioned SnCoS preparing4Composite nanocrystalline-graphene composite material is as the electrochemistry storage sodium of combination electrodeActive material, exists with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Stir the lower uniform pastel of furnishing that fully mixes, this pastel is coated onto equably on the Copper Foil of collector, dry, andAfter roll extrusion, obtaining can simultaneous electrochemical storage sodium and the combination electrode of storing lithium.
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Cited By (4)
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| CN110165171A (en) * | 2019-05-16 | 2019-08-23 | 广东工业大学 | A kind of primary reconstruction nano flower-like cobalt disulfide/rGO composite material and preparation method and application |
| CN110416507A (en) * | 2019-07-12 | 2019-11-05 | 广东工业大学 | A kind of three-dimensional flower-shaped cobalt disulfide of primary reconstruction/MXene composite material and preparation method and application |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN113078302A (en) * | 2021-03-09 | 2021-07-06 | 华北电力大学 | Method for preparing sodium-ion battery composite negative electrode material by using large-interlayer-distance two-dimensional layered graphene-like loaded metal sulfide |
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| CN101144176A (en) * | 2007-07-17 | 2008-03-19 | 北京航空航天大学 | Method for reducing metal and alloy hydroxide gel by hydrogen separated from electrochemistry cathode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110165171A (en) * | 2019-05-16 | 2019-08-23 | 广东工业大学 | A kind of primary reconstruction nano flower-like cobalt disulfide/rGO composite material and preparation method and application |
| CN110165171B (en) * | 2019-05-16 | 2022-05-13 | 广东工业大学 | In-situ self-assembly nano flower-shaped cobalt disulfide/rGO composite material and preparation method and application thereof |
| CN110416507A (en) * | 2019-07-12 | 2019-11-05 | 广东工业大学 | A kind of three-dimensional flower-shaped cobalt disulfide of primary reconstruction/MXene composite material and preparation method and application |
| CN110416507B (en) * | 2019-07-12 | 2022-06-03 | 广东工业大学 | In-situ self-assembly three-dimensional flower-like cobalt disulfide/MXene composite material and preparation method and application thereof |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN112279306B (en) * | 2020-10-21 | 2021-07-06 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN113078302A (en) * | 2021-03-09 | 2021-07-06 | 华北电力大学 | Method for preparing sodium-ion battery composite negative electrode material by using large-interlayer-distance two-dimensional layered graphene-like loaded metal sulfide |
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