CN105609746B - A kind of combination electrode of simultaneous electrochemical storage sodium and storage lithium and preparation method thereof - Google Patents

A kind of combination electrode of simultaneous electrochemical storage sodium and storage lithium and preparation method thereof Download PDF

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CN105609746B
CN105609746B CN201610187217.7A CN201610187217A CN105609746B CN 105609746 B CN105609746 B CN 105609746B CN 201610187217 A CN201610187217 A CN 201610187217A CN 105609746 B CN105609746 B CN 105609746B
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graphene
sodium
lithium
sncos
combination electrode
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CN105609746A (en
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陈卫祥
叶剑波
陈倩男
李辉
陈涛
徐新
苏利伟
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Zhejiang University ZJU
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
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Abstract

The invention discloses a kind of simultaneous electrochemical storage sodium and the combination electrode for storing lithium and preparation method thereof, combination electrode SnCoS4Composite nanocrystalline graphene composite material is as simultaneous electrochemical storage sodium and the active material of storage sodium.Its preparation process is：Under the conditions of existing for graphene oxide, pass through SnCl4、CoCl2With the hydro-thermal reaction of the mixed solutions of L cysteines under hydrothermal conditions, SnCoS is prepared4The composite material of composite nanocrystalline graphene, the SnCoS that will be obtained4The composite material of composite nanocrystalline graphene is tuned into paste with acetylene black, carboxymethyl cellulose and Kynoar, is coated onto on copper foil, dries and rolls to obtain simultaneous electrochemical storage sodium and store the combination electrode of lithium.The simultaneous electrochemical, which stores sodium and storage lithium combination electrode, has the advantages of reversible specific capacity is high, stable cycle performance and good high-rate charge-discharge capability.

Description

A kind of combination electrode of simultaneous electrochemical storage sodium and storage lithium and preparation method thereof
Technical field
The present invention relates to a kind of simultaneous electrochemical storage sodium and storage lithium combination electrode and preparation method thereof more particularly to use SnCoS4Composite nanocrystalline-graphene composite material is as energy simultaneous electrochemical storage sodium prepared by electroactive substance and storage lithium Combination electrode and preparation method thereof, belong to the application technology in electrochemical copolymerization electrode and its sodium ion lithium ion composite battery Field.
Background technology
Lithium ion battery has many advantages, such as high specific capacity and long cycle life in mobile communication, electric boosted with it The fields such as vehicle, electric vehicle and energy storage are widely used, and still, the extensive application of lithium ion battery causes lithium resource The price of relative shortage and lithium resource raw material rises steadily, as the price of lithium carbonate has gone up 2 times of left sides in the previous year It is right.Compared with lithium resource, sodium has more affluent resources and cheap advantage, recently on sodium-ion battery and its electrification The research and development for learning storage sodium material and electrode cause people's great interest.However, compared with lithium ion battery, the ratio of sodium-ion battery Capacity and multiplying power property are relatively low.The sodium ion and lithium ion composite battery of energy simultaneous electrochemical storage sodium and storage lithium can be taken into account above-mentioned Lithium ion battery and sodium-ion battery in terms of performance and resource the advantages of and there are the problem of.Traditional lithium ion battery stone Ink material is as cathode, but since the smaller interlamellar spacing of graphite cathode material (0.33-0.34nm) makes its electrochemistry storage sodium Poor performance, the specific capacity of electrochemistry storage sodium is nearly close to 0.Therefore, graphite material cannot be used for preparing simultaneous electrochemical The combination electrode of sodium and electrochemistry storage lithium is store, so electrification of the research and development with energy simultaneous electrochemical storage sodium and electrochemistry storage lithium It learns active material and its combination electrode is of great significance to sodium ion and lithium ion composite battery and technology application value.
The SnS of layer structure2Nano material not only has higher electrochemistry storage lithium capacity, while has higher electrification Storage sodium capacity is learned, is had a good application prospect in lithium ion battery or sodium-ion battery.But due to its relatively low conductance The larger variation of volume in rate and charge and discharge process, causes to use SnS2Electrochemistry storage lithium electrode or electrochemistry prepared by nano material Store sodium electrode rapid decay of its electrochemistry storage lithium capacity or electrochemistry storage sodium capacity in charge and discharge process.In addition cobalt sulfide is received Rice material also has higher electrochemistry storage lithium capacity, while has preferable electrochemistry storage sodium performance, in lithium ion battery or It has a good application prospect in sodium-ion battery.But electrochemistry prepared by cobalt sulfide nano material stores lithium electrode or electrification Learn storage sodium electrode charge-discharge cycle stablize it is poor, electrochemistry storage lithium or electrochemistry storage sodium capacity attenuation it is very fast.
Graphene has high electrical conductivity and charged mobility, great specific surface area, good flexible and chemical stabilization Property.It is store by the way that the compound prepared composite material of nano metal sulfide material and graphene is not only maintained high electrochemistry Lithium capacity or electrochemistry storage sodium capacity, and charge-discharge performance and high power charging-discharging characteristic with enhancing.Such as SnS2- stone Black alkene composite material, cobalt sulfide-graphene composite material etc. are shown than simple SnS2Or cobalt sulfide has higher electrification Learn storage lithium capacity or electrochemistry storage sodium capacity, and with compared with stabilization charge-discharge performance.But these composite material systems The electrochemistry storage lithium performance or electrochemistry of standby combination electrode store the space that sodium performance also further improves, and especially these are multiple Electrochemistry storage sodium and the application store in the combination electrode of lithium also need to further study condensation material at the same time.
The present invention provides a kind of energy simultaneous electrochemical storage sodium and the combination electrode for storing lithium and preparation method thereof, the compound electrics Pole SnCoS4The composite material of composite nanocrystalline-graphene stores sodium for simultaneous electrochemical and stores the active material of lithium.With with SnS2- graphene and CoS2The combination electrode that-graphene composite material is prepared for the active material that simultaneous electrochemical stores sodium and stores lithium It compares, present invention SnCoS4The composite material of composite nanocrystalline-graphene is electric simultaneously for energy prepared by electroactive substance Chemistry storage sodium and the combination electrode for storing lithium have higher simultaneous electrochemical storage sodium and store the specific capacity of lithium and the height significantly increased Rate charge-discharge characteristic, and with excellent charge-discharge performance.But up to the present, it is this to use SnCoS4It is compound to receive The composite material of meter Jing-graphene for simultaneous electrochemical active material energy simultaneous electrochemical store sodium and store lithium combination electrode and Its preparation method yet there are no open report.
The content of the invention
Combination electrode of sodium and storage lithium and preparation method thereof is store it is an object of the invention to provide a kind of energy simultaneous electrochemical, Electrochemistry storage sodium and storage lithium active material are SnCoS while the combination electrode4The composite material of composite nanocrystalline-graphene, The composite material is by SnCoS4Composite nanocrystalline is supported on graphene and is formed, wherein SnCoS4Composite nanocrystalline and graphene The ratio between the amount of substance be 1:2, the component and its mass percentage content of combination electrode are：SnCoS4Composite nanocrystalline-graphite The composite material of alkene is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.The simultaneous electrochemical stores sodium The step of with the preparation method for storing lithium, is as follows：
(1) by the SnCl of metering4·5H2O、CoCl2·6H2O and L-cysteine are added in deionized water, and fully Stirring, obtains uniform mixed solution, SnCl in solution4With CoCl2The ratio between the amount of substance be 1:1, the substance of L-cysteine Amount be SnCl4With CoCl25 times of the sum of the amount of substance, then by graphene oxide ultrasonic disperse in deionized water, obtain To uniform suspension, be stirred continuously it is lower graphene oxide suspension is added drop-wise in above-mentioned mixed solution, and continue to stir 2h, the amount (being calculated with the amount of the substance of carbon) of the substance of graphene oxide are equal to SnCl4With CoCl2The sum of the amount of substance 2 Times, finally obtained reaction mixture is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, is sealed, at 180 DEG C Insulating box in react for 24 hours, after room temperature, the precipitated product that hydro-thermal is obtained centrifuges, and uses deionization Water and absolute ethyl alcohol fully wash, and SnCoS is obtained after being finally dried in vacuo 12h at 80 DEG C4Composite nanocrystalline-graphene is compound Material；
(2) by the above-mentioned SnCoS being prepared4Electrification of the composite nanocrystalline-graphene composite material as combination electrode Learn storage sodium active material, the N-Methyl pyrrolidone with the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% Solution is sufficiently mixed under stiring is tuned into uniform paste, and each component mass percent is：SnCoS4Composite nanocrystalline-graphite The paste is equably coated onto by alkene composite material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5% As on the copper foil of collector, drying obtains electrochemistry storage sodium combination electrode after rolling.
Compared with the prior art, present invention SnCoS4The composite material of composite nanocrystalline-graphene is electro-chemical activity Energy simultaneous electrochemical storage sodium and the combination electrode of storage lithium prepared by substance and preparation method thereof have the advantages that following notable and skill Art progress：Although research shows and simple SnS2Or fluidisation cobalt nano material compares, and uses SnS2- graphene composite material and Fluidisation cobalt-graphene composite material stores sodium electrode for electrochemistry prepared by electroactive substance or electrochemistry is store lithium electrode and had Higher electrochemistry storage sodium specific capacity or electrochemistry storage lithium specific capacity, electrochemistry storage lithium specific capacity can reach 800- 1000mAh/g, electrochemistry storage sodium specific capacity can reach 600-700mAh/g (quality based on electroactive substance), and have There are relatively stable charge-discharge performance and improved high power charging-discharging characteristic, but its electrochemistry storage sodium or electrochemistry store sodium Performance also there is the space that is further promoted.However, up to the present, use SnS2- graphene composite material or cobalt sulfide-stone The report that black alkene composite material prepares the combination electrode that simultaneous electrochemical stores sodium and storage lithium for electroactive substance is also seldom.This Inventive result shows to use SnCoS4The composite material of composite nanocrystalline-graphene for electrochemistry chemical substance prepare energy simultaneously Electrochemistry stores sodium and storage lithium combination electrode ratio SnS2- graphene composite material or SnS2While prepared by-graphene composite material Electrochemistry, which stores sodium and stores lithium combination electrode, to be had higher simultaneous electrochemical storage sodium and stores the specific capacity of lithium and the height significantly increased Rate charge-discharge characteristic, and with excellent charge and discharge cycles stability.The reason is that due to：SnS2For typical stratiform knot Structure crystal, and CoS2Crystal is not stratiform, when the crystal of both different structures generates simultaneously in hydrothermal solution, is deposited mutually In mutual interference, cause the SnCoS generated4With SnS2Or CoS2Crystal is different from.This different crystal material is in hydro-thermal Influencing each other for growth in solution causes the obtained SnCoS for being supported on graphene surface4Nano-particle has smaller Size, it has further been found that the SnCoS loaded on graphene4Nano-particle forms composite Nano by thinner nanocrystal It is brilliant.This SnCoS4Compound nanocrystalline structure is prepared with the composite material that graphene is compounded to form as electroactive substance Energy simultaneous electrochemical storage sodium and storage lithium combination electrode can show the chemical property further enhanced, be especially showing ratio SnS2- graphene and CoS2- graphene composite material combination electrode has higher simultaneous electrochemical storage sodium and stores the specific capacity of lithium With the high power charging-discharging characteristic significantly increased, and with excellent charge and discharge cycles stability.
Description of the drawings
Fig. 1：(a) SnS prepared by the present invention2/ graphene composite material, (b) CoS2/ graphene composite material, (c) SnCoS4The XRD diagram of composite 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 photos 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 photos of composite nanocrystalline-graphene composite material.
Specific embodiment
It further illustrates the present invention with reference to embodiments.
(1)SnCoS4It is prepared by the hydro-thermal method of composite nanocrystalline-graphene composite material：By the SnCl of 1.5mmol4·5H2O、 The CoCl of 1.5mmol2·6H2O and 15.0mmol L-cysteines are added in 100mL deionized waters, and are sufficiently stirred and to be formed Uniform mixed solution；By the graphene oxide ultrasonic disperse of 6.0mmol into 60mL deionized waters, uniformly suspended Liquid in the case where being stirred continuously, the hanging drop of graphene oxide is added in the mixed solution of front, is stirred for 2h at room temperature；It will The mixed reactant finally obtained is transferred in hydrothermal reaction kettles of the 200mL with polytetrafluoroethylliner liner, sealing, at 180 DEG C Insulating box in react for 24 hours, after room temperature, filled by precipitation and centrifugal separation, and with deionized water and absolute ethyl alcohol Point washing will be obtained after hydro-thermal black product is dried in vacuo 12h at 80 DEG C, and what is finally prepared obtains SnCoS4Composite Nano Crystalline substance-composite nanocrystalline graphene composite material；
(2) by the above-mentioned SnCoS being prepared4Composite nanocrystalline-graphene composite material stores sodium as simultaneous electrochemical With the electroactive substance of storage lithium combination electrode, the Kynoar with acetylene black, carboxymethyl cellulose and mass fraction 5% N-Methyl pyrrolidone solution be sufficiently mixed be tuned into uniform paste under stiring, each component mass percent is： SnCoS4Composite nanocrystalline-graphene composite material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, The paste is equably coated onto on the copper foil as collector, dry, being obtained after rolling can simultaneous electrochemical storage sodium and storage lithium Combination electrode.
Comparative example：As a comparison, it is prepared for SnCoS with similar hydrothermal method4Nano material, and using it as electrochemistry Active material, preparing can simultaneous electrochemical storage sodium and the combination electrode for storing lithium.
(1)SnCoS4It is prepared by nano material and its hydro-thermal：By the SnCl of 1.5mmol4·5H2O, the CoCl of 1.5mmol2· 6H2O and 15.0mmol L-cysteines are added in 160mL deionized waters, and are sufficiently stirred and to be formed uniform mixed solution； The obtained mixed solution is transferred in hydrothermal reaction kettles of the 200mL with polytetrafluoroethylliner liner, sealing, at 180 DEG C It is reacted in insulating box for 24 hours, after room temperature, by precipitation and centrifugal separation, and it is abundant with deionized water and absolute ethyl alcohol Washing will obtain that after hydro-thermal black product is dried in vacuo 12h at 80 DEG C, SnCoS is finally prepared4Nano material；
(2) by the above-mentioned SnCoS being prepared4Nano material is as simultaneous electrochemical storage sodium and the electricity of storage lithium combination electrode Chemically reactive substance, it is molten with the N-Methyl pyrrolidone of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% Liquid is sufficiently mixed under stiring is tuned into uniform paste, and each component mass percent is：SnCoS4Nano material 80%, acetylene Black 10%, which is equably coated onto on the copper foil as collector by carboxymethyl cellulose 5%, Kynoar 5%, Dry, being obtained after rolling can simultaneous electrochemical storage sodium and the combination electrode for storing lithium.
Comparative example：As a comparison, it is prepared for SnS with similar hydrothermal method2/ graphene composite material, and by the use of its as Electroactive substance, preparing can simultaneous electrochemical storage sodium and the combination electrode for storing lithium.
(1)SnS2It is prepared by/graphene composite material and its hydro-thermal：By the SnCl of 3.0mmol4·5H2O and 15.0mmol L- Cysteine is added in 100mL deionized waters, and is sufficiently stirred and to be formed uniform solution；By the graphene oxide of 6.0mmol Ultrasonic disperse obtains uniform suspension into 60mL deionized waters, in the case where being stirred continuously, by the hanging drop of graphene oxide It is added in the solution of front, is stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to 200mL with polytetrafluoroethyl-ne In the hydrothermal reaction kettle of alkene liner, sealing is reacted for 24 hours in 180 DEG C of insulating box, after room temperature, will precipitated It centrifuges, and is fully washed with deionized water and absolute ethyl alcohol, hydro-thermal black product will be obtained and be dried in vacuo 12h at 80 DEG C Afterwards, what is finally prepared obtains SnS2/ graphene composite material；
(2) by the above-mentioned SnS being prepared2/ graphene composite material is as simultaneous electrochemical storage sodium and storage lithium compound electric The electroactive substance of pole, the N- methylpyrroles with the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% Alkanone solution is sufficiently mixed under stiring is tuned into uniform paste, and each component mass percent is：SnS2/ graphene composite wood Expect for 80%, acetylene black 10%, carboxymethyl cellulose 5%, which is equably coated onto as collection by Kynoar 5% Dry on the copper foil of fluid, being obtained after rolling can simultaneous electrochemical storage sodium and storage lithium combination electrode.
Comparative example：As a comparison, it is prepared for CoS with similar hydrothermal method2/ graphene composite material, and by the use of its as Electroactive substance, preparing can simultaneous electrochemical storage sodium and the combination electrode for storing lithium.
(1)CoS2It is prepared by/graphene composite material and its hydro-thermal：By the CoCl of 3.0mmol2·6H2O and 15.0mmol L- Cysteine is added in 50mL deionized waters, and is sufficiently stirred and to be formed uniform solution；The graphene oxide of 6.0mmol is surpassed Sound is distributed in 60mL deionized waters, obtains uniform suspension, and in the case where being stirred continuously, the suspension of graphene oxide is added dropwise Into the solution of front, 2h is stirred at room temperature；The mixed reactant finally obtained is transferred to 200mL with polytetrafluoroethylene (PTFE) In the hydrothermal reaction kettle of liner, sealing, reacted in 180 DEG C of insulating box for 24 hours, after room temperature, will precipitate from The heart separates, and is fully washed with deionized water and absolute ethyl alcohol, will obtain hydro-thermal black product and is dried in vacuo 12h at 80 DEG C Afterwards, what is finally prepared obtains CoS2/ graphene composite material；
(2) by the above-mentioned CoS being prepared2/ graphene composite material is as simultaneous electrochemical storage sodium and storage lithium compound electric The electroactive substance of pole, the N- methylpyrroles with the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% Alkanone solution is sufficiently mixed under stiring is tuned into uniform paste, and each component mass percent is：CoS2/ graphene composite wood Expect for 80%, acetylene black 10%, carboxymethyl cellulose 5%, which is equably coated onto as collection by Kynoar 5% Dry on the copper foil of fluid, being obtained after rolling can simultaneous electrochemical storage sodium and the combination electrode for storing lithium.
With X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope/high-resolution-ration transmission electric-lens (TEM/HRTEM), member SnCoS is prepared to above-mentioned in plain energy disperse spectroscopy (EDS) and XPS4Composite nanocrystalline-graphene composite material, SnCoS4Nanometer material Material, SnS2- graphene composite material and CoS2- graphene composite material is characterized.
Simultaneous electrochemical stores sodium and stores the test of lithium performance：With the above-mentioned energy simultaneous electrochemical storage sodium being prepared and storage lithium Combination electrode for working electrode, simultaneous electrochemical storage sodium is assembled into the glove box full of argon gas and stores the test electricity of lithium Pond, metallic sodium piece are to electrode and reference electrode, and glass fibre membrane is membrane, 0.5mol/L NaPF6+0.5mol/L Li PF6 EC/DMC mixed solutions (volume ratio 1:1) composite electrolyte of battery is tested for sodium ion and lithium ion.Perseverance electricity at room temperature Stream charge-discharge test test and it is more above-mentioned be prepared combination electrode while electrochemistry storage sodium and store lithium performance, charge and discharge For electric current in 100mA/g or 1000mA/g, charging/discharging voltage section is 3.0~0.005V.
Elemental Composition analysis shows SnCoS4Sn in composite nanocrystalline-graphene composite material:Co:The amount of the substance of S it Than for 1:0.96:3.97, meet SnCoS4；SnS2Sn in/graphene:The ratio between amount of substance of S is 1:1.96, meet SnS2； CoS2Co in/stone graphene:The ratio between amount of substance of S is 1:2.03, meet CoS2。
The XRD characterization of Fig. 1 is the results show that SnS2/ graphene composite material shows stronger diffraction maximum, and meets SnS2 Standard powder diffraction card (JCPDS Card No.23-0677), illustrates SnS in composite material2For typical layer structure； CoS2/ graphene composite material also shows stronger diffraction maximum, and meets CoS2Standard powder diffraction card (JCPDS no.41-1471)。SnCoS4/ graphene composite Nano is in 2 θ=9.32 °, 17.78 °, 28.92 °, 32.56 ° and 51.22 ° displays More low intensive diffraction maximum, intensity are significantly less than SnS2/ graphene composite Nano material and CoS2/ graphene composite Nano material , illustrate to be supported on the SnCoS on graphene4Composite nanocrystalline particle has smaller size, in addition SnCoS4Composite Nano Crystalline substance-graphene composite material also belongs to SnS without display2(001) peak of layer structure.
The SEM morphology characterizations of Fig. 2 show, SnS2/ graphene composite material shows the SnS of sheet2It is evenly dispersed in fold Graphene nanometer sheet surface；CoS2The CoS of the spheroidal of/graphene composite material display size about 100nm2Nano-particle It is wrapped or is dispersed in graphene nano on piece；SnCoS4Composite nanocrystalline-graphene composite material display size is smaller (about SnCoS 35nm)4Composite nanocrystalline particle is wrapped or is dispersed in graphene nanometer sheet.
The TEM/HRTEM characterization results of Fig. 3 are shown, in SnS2In/graphene composite material, the SnS of layer structure2Nanometer Piece is uniformly dispersed in the graphene nanometer sheet surface of fold, (001), (100), the interlamellar spacing in (101) face are respectively 0.59, 0.32 and 0.27nm, the SnS with layer structure2Crystal is consistent；In CoS2In/graphene composite material, CoS2Nano-particle point Be dispersed in graphene nano on piece, (200), (210), the interlamellar spacing in (311) face are respectively 0.27,0.25,0.17nm, with CoS2 Crystal is consistent；In SnCoS4In composite nanocrystalline-graphene composite material, SnCoS4Composite nanocrystalline particle has thinner Size, and be evenly dispersed in graphene nanometer sheet；Fig. 3 (f) also further demonstrates that SnCoS4Composite nanocrystalline particle is shown By the more tiny nanocrystalline composite nanocrystalline formed, size is about 3-6nm.
Electrochemical results are shown：
At room temperature under 100mA/g charging and discharging currents density, SnCoS4Prepared by composite nanocrystalline-graphene composite material The reversible specific capacity of combination electrode, simultaneous electrochemical storage sodium and storage lithium initially reaches 1251mAh/g, can after 100 times cycle Inverse specific capacity is 1218mAh/g, it is shown that high specific capacity and excellent stable circulation performance；In contrast, SnS2/ graphene Electrochemistry storage sodium and storage lithium reversible specific capacity initially reach 920mAh/g while combination electrode, are 830mAh/ after 100 Xun Huans g；CoS2Electrochemistry storage sodium and storage lithium reversible capacity initially reach 955mAh/g while/graphene composite material electrode, 100 times It is 827mAh/g after cycling；；SnCoS4The reversible specific capacity of electrochemistry storage sodium and storage lithium initially reaches while nano material electrode It is 332mAh/g after 100 cycles to 1030mAh/g.Test result explanation：SnCoS4Composite nanocrystalline-graphene composite wood Expect that electrochemistry storage sodium and storage lithium reversible specific capacity are obviously higher than SnS while the combination electrode prepared2/ graphene, CoS2/ stone Black alkene and SnCoS4The specific capacity of electrochemistry storage sodium and storage lithium while the combination electrode of preparation, and followed with excellent charge and discharge Ring stability.
In charging and discharging currents density 1000mA/g, the charge and discharge of electrochemistry storage sodium and storage lithium while testing above-mentioned electrode Electric multiplying power property, result are：SnCoS4Electrochemistry is store while combination electrode prepared by composite nanocrystalline-graphene composite material The multiplying power property of sodium and storage lithium is 1020mAh/g；SnS2Electrochemistry stores sodium while/graphene composite material prepares combination electrode Multiplying power property with storage lithium is 755mAh/g；CoS2While/graphene composite material prepares combination electrode electrochemistry storage sodium and The multiplying power property for storing lithium is 650mAh/g；SnCoS4The multiplying power property of electrochemistry storage sodium and storage lithium is while preparing electrode 380mAh/g.As a result illustrate：With SnS2/ graphene, CoS2/ graphene and SnCoS4The combination electrode of preparation is compared, SnCoS4It is multiple Combination electrode prepared by nanocrystalline-graphene composite material is closed to show electrochemistry storage sodium while significantly increase and store filling for lithium Discharge-rate characteristic.
Therefore, Electrochemical results explanation：With with SnS2/ graphene or CoS2/ graphene composite material is prepared compound Electrode is compared, and uses SnCoS4The compound electric of electrochemistry storage sodium and storage lithium while prepared by composite nanocrystalline-graphene composite material Pole not only has higher simultaneous electrochemical storage sodium and stores the reversible specific capacity of lithium and the high power charging-discharging characteristic significantly increased, And with excellent cycle performance.

Claims (2)

1. a kind of simultaneous electrochemical storage sodium and the combination electrode for storing lithium, which is characterized in that combination electrode is store with simultaneous electrochemical The function of sodium and storage lithium, electroactive substance SnCoS4The composite material of composite nanocrystalline-graphene, the composite material It is by SnCoS4Composite nanocrystalline is supported on graphene and is formed, wherein SnCoS4The amount of the substance of composite nanocrystalline and graphene The ratio between for 1: 2, the component and its mass percentage content of combination electrode are：SnCoS4The composite wood of composite nanocrystalline-graphene Expect for 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
2. a kind of preparation method of simultaneous electrochemical storage sodium described in claim 1 and the combination electrode for storing lithium, which is characterized in that The step of preparation method, is as follows：
(1) by the SnCl of metering4·5H2O、CoCl2·6H2O and L-cysteine are added in deionized water, and are sufficiently stirred, Obtain uniform mixed solution, SnCl in solution4With CoCl2The ratio between the amount of substance be 1: 1, the amount of the substance of L-cysteine For SnCl4With CoCl25 times of the sum of the amount of substance, then by graphene oxide ultrasonic disperse in deionized water, obtain Even suspension, be stirred continuously it is lower graphene oxide suspension is added drop-wise in above-mentioned mixed solution, and continue stir 2h, with The amount of the substance of carbon calculates, and the amount of the substance of graphene oxide is equal to SnCl4With CoCl22 times of the sum of the amount of substance, finally Obtained reaction mixture is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, is sealed, in 180 DEG C of insulating box For 24 hours, after room temperature, the precipitated product that hydro-thermal is obtained centrifuges for middle reaction, and with deionized water and anhydrous Ethyl alcohol fully washs, and SnCoS is obtained after being finally dried in vacuo 12h at 80 DEG C4Composite nanocrystalline-graphene composite material；
(2) by the above-mentioned SnCoS being prepared4Composite nanocrystalline-graphene composite material stores sodium as the electrochemistry of combination electrode With storage lithium active material, the N-Methyl pyrrolidone with the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5% Solution is sufficiently mixed under stiring is tuned into uniform paste, which is equably coated onto on the copper foil as collector, Drying, and energy simultaneous electrochemical storage sodium is obtained after roll-in and stores the combination electrode of lithium.
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