CN105609747B - A kind of combination electrode of electrochemistry storage lithium and preparation method thereof - Google Patents

A kind of combination electrode of electrochemistry storage lithium and preparation method thereof Download PDF

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CN105609747B
CN105609747B CN201610187220.9A CN201610187220A CN105609747B CN 105609747 B CN105609747 B CN 105609747B CN 201610187220 A CN201610187220 A CN 201610187220A CN 105609747 B CN105609747 B CN 105609747B
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graphene
sncos
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combination electrode
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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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Abstract

Combination electrode the invention discloses a kind of electrochemistry storage lithium and preparation method thereof, combination electrode SnCoS4Active material of the graphene composite nano material as electrochemistry storage lithium.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 nano materials of graphene, the SnCoS that will be obtained4The composite nano materials of graphene are tuned into paste with acetylene black, Kynoar, are coated onto rolling on copper foil and obtain the combination electrode of electrochemistry storage lithium.The combination electrode has the advantages of electrochemistry storage lithium specific capacity is high, stable cycle performance and good high-rate charge-discharge capability.

Description

A kind of combination electrode 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 more particularly to use SnCoS4- graphene The electrochemistry storage lithium combination electrode of composite nano materials as electrochemistry storage lithium active material and preparation method thereof, belongs to lithium ion Electrode material and its technical field in electrochemistry storage lithium combination electrode application.
Background technology
High-performance electric chemistry storage lithium electrode material and its electrochemistry store lithium electrode in application for high-performance lithium from The research and development of sub- battery are of great significance.SnS2Nano material has higher electrochemistry storage lithium capacity, and (its theoretical capacity is 645mAh/g), have a good application prospect in high performance lithium ion battery.But due to its relatively low electrical conductivity and The larger variation of volume in charge and discharge process, causes to use SnS2Electrochemistry prepared by nano material stores lithium electrode in charge and discharge process In its store lithium capacity can rapid decay.Recently, some researches show that can improve tinbase by introducing other transition metal element to receive The performance of rice material electrochemical storage lithium electrode.Such as Cu2SnS3, Cu2ZnSnS4Electrochemistry as lithium ion battery negative material is stored up Lithium performance is above simple SnS2Nano material electrode.Cobalt sulfide nano material is also a kind of with compared with high electrochemical storage lithium The lithium ion battery negative material of capacity, but similarly there are capacity in charge and discharge process to decline for single cobalt sulfide nano material Subtract the shortcomings that very fast.
Graphene has high electrical conductivity and charged mobility, great specific surface area, good flexible and chemical stabilization Property.By by metal oxide or sulfide nano-material with the compound prepared composite material of graphene without with the electricity done Chemistry storage lithium capacity, and charge-discharge performance and high power charging-discharging characteristic with enhancing.Such as, SnO2- graphene is compound Nano material, SnS2- graphene composite nano material, cobalt sulfide-graphene composite nano material etc. are shown than simple SnO2、SnS2Or cobalt sulfide has higher electrochemistry storage lithium capacity and superior charge and discharge cycles stability.But these are multiple The space that the electrochemistry storage lithium performance of condensation material also further improves.
The present invention provides a kind of electrochemistry storage lithium combination electrode and preparation method thereof, combination electrode SnCoS4- stone The composite nano materials of black alkene store lithium active material for electrochemistry.With with SnS2- graphene and CoS2- graphene composite Nano material Expect the combination electrode prepared for electrochemistry storage lithium active material, present invention SnCoS4The composite nano materials of-graphene are electricity Electrochemistry storage lithium combination electrode prepared by chemically reactive substance have higher electrochemistry storage lithium capacity, excellent cycle performance and The high power charging-discharging characteristic significantly increased.But up to the present, it is this to use SnCoS4The composite nano materials of-graphene Combination electrode for storing lithium active material for electrochemistry and preparation method thereof yet there are no open report.
The content of the invention
It is an object of the invention to provide a kind of electrochemistry storage lithium combination electrode and preparation method thereof, the electricity of the combination electrode Chemistry storage lithium active material is SnCoS4The composite nano materials of-graphene, the composite nano materials are by SnCoS4Composite Nano Crystalline substance is supported on graphene and is formed, wherein SnCoS4The ratio between amount of substance of composite nanocrystalline and graphene is 1:2, combination electrode Component and its mass percentage content be：SnCoS4The composite nano materials of-graphene are 80%, acetylene black 10%, are gathered inclined Vinyl fluoride 10%.It is as follows that the electrochemistry stores the step of preparation method of lithium combination electrode：
(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 C4- graphene composite nano material；
(2) by the above-mentioned SnCoS being prepared4- graphene composite nano material stores lithium as the electrochemistry of combination electrode Active material, it is fully mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% Conjunction is tuned into uniform paste, and each component mass percent is：SnCoS4- graphene composite nano material 80%, acetylene black 10%, which is equably coated onto on the copper foil as collector by Kynoar 10%, dry, and electricity is obtained after rolling Chemistry storage lithium combination electrode.
Compared with the prior art, present invention SnCoS4The composite nano materials of-graphene store lithium active matter for electrochemistry Electrochemistry storage lithium combination electrode prepared by matter and preparation method thereof has the advantages that following notable and technological progress：Although study table It is bright, with simple SnS2Or fluidisation cobalt nano material compares, and uses SnS2- graphene composite nano material and fluidisation cobalt-graphene Composite nano materials for the electrode that electrochemistry stores the preparation of lithium active material there is higher electrochemistry to store lithium capacity, electrochemistry storage Lithium specific capacity can reach 900-1000mAh/g (quality based on electrochemistry storage lithium active material), and with preferable charge and discharge Electric cycle performance and improved high power charging-discharging characteristic, but its electrochemistry storage lithium performance also has the sky further promoted Between.The present invention the result shows that, use SnCoS4The composite nano materials of-graphene store the compound of lithium chemical substance preparation for electrochemistry Electrode ratio SnS2- graphene composite nano material and SnS2Combination electrode prepared by-graphene composite nano material has higher Electrochemistry storage lithium specific capacity and the high power charging-discharging characteristic that significantly increases.The reason is that due to：SnS2For typical stratiform Structure crystal, and CoS2Crystal is not stratiform, when the crystal of both different structures generates simultaneously in hydrothermal solution, mutually There are mutual interference, cause the SnCoS generated4With SnS2Or CoS2Crystal is different from.This different crystal material is in water Influencing each other for growth in hot 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 compound receive by thinner nanocrystal Meter Jing.This SnCoS4Compound nanocrystalline structure is lived with the composite nano materials that graphene is compounded to form as electrochemistry storage lithium Property chemical substance prepare combination electrode can show further enhance electrochemistry storage lithium performance, be especially showing ratio SnS2- graphene and CoS2- graphene composite nano material combination electrode has higher electrochemistry storage lithium capacity and significantly increases High power charging-discharging characteristic.The SnCoS of the present invention4One step hydrothermal preparing process of-graphene composite nano material and its multiple Composite electrode preparation has the characteristics that simple for process, convenient and is easily enlarged application.
Description of the drawings
Fig. 1：The XRD diagram of different composite nano material prepared by hydro-thermal method of the present invention：(a)SnS2/ graphene, (b) CoS2/ Graphene, (c) SnCoS4/ graphene composite nano material；
Fig. 2：The SEM patterns of composite material prepared by Fig. 2 hydro-thermal methods of the present invention, (a) SnS2/ graphene, (b) CoS2/ graphite Alkene and (c) SnCoS4/ graphene composite nano material；
Fig. 3：The TEM/HRTEM photos of composite material prepared by Fig. 3 hydro-thermal hairs of the present invention, (a, b) SnS2/ graphene, (c, d)CoS2/ graphene and (e, f) SnCoS4/ graphene composite nano material；
Fig. 4：(a)SnS2/ graphene, (b) CoS2/ graphene, (c) SnCoS4SnCoS (d)4/ graphene composite Nano Charge-discharge performance of the electrochemistry storage lithium combination electrode of material preparation under 100mA/g current densities；
Fig. 5：(a)SnS2/ graphene, CoS2/ graphene, SnCoS4And SnCoS4Electrification prepared by/graphene composite material Learn charge/discharge rate property of the storage lithium combination electrode under different current densities.
Specific embodiment
It is further illustrated the present invention below in conjunction with drawings and examples.
(1)SnCoS4It is prepared by the hydro-thermal method of-graphene composite nano 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 SnCoS4- graphene is multiple Close nano material；
(2) by the above-mentioned SnCoS being prepared4- graphene composite nano material stores lithium as the electrochemistry of combination electrode Active material, it is fully mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% Conjunction is tuned into uniform paste, and each component mass percent is：SnCoS4- graphene composite nano material 80%, acetylene black 10%, which is equably coated onto on the copper foil as collector by Kynoar 10%, dry, and electricity is obtained after rolling Chemistry storage lithium combination electrode.
Comparative example：As a comparison, it is prepared for SnCoS with similar hydrothermal method4Nano material, and using it as electrochemistry It stores lithium active material and prepares electrochemistry storage lithium electrode.
(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 stores lithium active material as the electrochemistry of combination electrode, with The N-Methyl pyrrolidone solution of the Kynoar of acetylene black and mass fraction 5% is sufficiently mixed under stiring to be tuned into uniformly Paste, each component mass percent are：SnCoS4Nano material 80%, acetylene black 10%, Kynoar 10% paste this Shape object is equably coated onto on the copper foil as collector, dry, and electrochemistry storage lithium combination electrode is obtained after rolling.
Comparative example：As a comparison, it is prepared for SnS with similar hydrothermal method2/ graphene composite nano material, and use it Electrochemistry storage lithium electrode is prepared as electrochemistry storage lithium active material.
(1)SnS2It is prepared by/graphene composite nano material and its hydro-thermal：By the SnCl of 3.0mmol4·5H2O and 15.0mmol L-cysteines are added in 100mL deionized waters, and are sufficiently stirred and to be formed uniform solution；By 6.0mmol's Graphene oxide ultrasonic disperse obtains uniform suspension into 60mL deionized waters, in the case where being stirred continuously, by graphene oxide Hanging drop be added in the solution of front, be stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to 200mL bands Have in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, seal, reacted in 180 DEG C of insulating box for 24 hours, after naturally cool to room temperature Afterwards, by precipitation and centrifugal separation, and fully washed with deionized water and absolute ethyl alcohol, it is true at 80 DEG C that hydro-thermal black product will be obtained After the dry 12h of sky, what is finally prepared obtains SnS2/ graphene composite nano material；
(2) by the above-mentioned SnS being prepared2/ graphene composite nano material is lived as the electrochemistry storage lithium of combination electrode Property substance, is sufficiently mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% Uniform paste is tuned into, each component mass percent is：SnS2/ graphene composite nano material is 80%, acetylene black 10%, The paste is equably coated onto on the copper foil as collector by Kynoar 10%, dry, and electrochemistry storage is obtained after rolling Lithium combination electrode.
Comparative example：As a comparison, it is prepared for CoS with similar hydrothermal method2/ graphene composite nano material, and use it Electrochemistry storage lithium electrode is prepared as electrochemistry storage lithium active material.
(1)CoS2It is prepared by/graphene composite nano material and its hydro-thermal：By the CoCl of 3.0mmol2·6H2O and 15.0mmol L-cysteines are added in 50mL deionized waters, and are sufficiently stirred and to be formed uniform solution；By 6.0mmol's Graphene oxide ultrasonic disperse obtains uniform suspension into 60mL deionized waters, in the case where being stirred continuously, by graphene oxide Hanging drop be added in the solution of front, be stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to 200mL bands Have in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, seal, reacted in 180 DEG C of insulating box for 24 hours, after naturally cool to room temperature Afterwards, by precipitation and centrifugal separation, and fully washed with deionized water and absolute ethyl alcohol, it is true at 80 DEG C that hydro-thermal black product will be obtained After the dry 12h of sky, what is finally prepared obtains CoS2/ graphene composite nano material；
(2) by the above-mentioned CoS being prepared2/ graphene composite nano material is lived as the electrochemistry storage lithium of combination electrode Property substance, is sufficiently mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% Uniform paste is tuned into, each component mass percent is：CoS2/ graphene composite nano material is 80%, acetylene black 10%, The paste is equably coated onto on the copper foil as collector by Kynoar 10%, dry, and electrochemistry storage is obtained after rolling Lithium combination electrode.
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 XPS4- graphene composite nano material, SnCoS4Nano material, SnS2- Graphene composite nano material and CoS2- graphene composite nano material is characterized.
Electrochemistry stores lithium performance test：With it is above-mentioned be prepared electrochemistry storage lithium combination electrode be working electrode, full of It is assembled into the test battery of lithium ion battery in the glove box of argon gas, metallic lithium foil is to electrode and reference electrode, and polypropylene is thin Film (Celgard-2300) be membrane, 1.0M LiPF6EC/DMC solution (volume ratio 1:1) it is electrolyte.Perseverance electricity at room temperature The electrochemistry storage lithium performance of charge-discharge test test and the more above-mentioned composite nano materials being prepared is flowed, charging and discharging currents exist 100-1000mA/g, charging/discharging voltage section are 3.0~0.005V.
Elemental Composition analysis shows SnCoS4Sn in/graphene composite nano material:Co:The ratio between amount of substance of S is 1: 0.96:3.97, meet SnCoS4；SnS2Sn in/graphene:The ratio between amount of substance of S is 1:1.96, meet SnS2；CoS2/ stone Co in 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 nano material shows stronger diffraction maximum, and meets SnS2Standard powder diffraction card (JCPDS Card No.23-0677), illustrates SnS in composite material2For typical stratiform knot Structure；CoS2/ graphene composite nano 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 ° show more low intensive diffraction maximum, and intensity is significantly less than SnS2/ graphene composite Nano material and CoS2/ graphene Composite Nano material, illustrate to be supported on the SnCoS on graphene4Nano-particle has smaller size, in addition SnCoS4/ stone Black alkene composite nano materials also belong to SnS without display2(001) peak of layer structure.
The SEM morphology characterizations of Fig. 2 show, SnS2/ graphene composite nano material shows the SnS of sheet2It is evenly dispersed in The graphene nanometer sheet surface of fold；CoS2The CoS of the spheroidal of/graphene composite nano material display size about 100nm2 Nano-particle is wrapped or is dispersed in graphene nano on piece；SnCoS4/ graphene composite nano material display size is smaller The SnCoS of (about 35nm)4Nano-particle is wrapped or is dispersed in graphene nanometer sheet.
The TEM/HRTEM characterization results of Fig. 3 are shown, in SnS2In/graphene composite nano material, the SnS of layer structure2 Nanometer sheet is uniformly dispersed in the graphene nanometer sheet surface of fold, and (001), (100), the interlamellar spacing in (101) face are respectively 0.59th, 0.32 and 0.27nm, the SnS with layer structure2Crystal is consistent；In CoS2In/graphene composite nano material, CoS2 Nano-particle is dispersed in graphene nano on piece, (200), (210), the interlamellar spacing in (311) face are respectively 0.27,0.25, 0.17nm, with CoS2Crystal is consistent；In SnCoS4In/graphene composite nano material, SnCoS4Nano-particle has thinner Size, and be evenly dispersed in graphene nanometer sheet；Fig. 3 (f) also further demonstrates that SnCoS4Nano-particle has been shown more The composite nanocrystalline of the small nanocrystalline composition of refinement, size is about 3-6nm.
Fig. 4 shows that charge-discharge performance test shows under 100mA/g current densities at room temperature：With SnS2/ graphene And CoS2Electrochemistry storage lithium combination electrode prepared by/graphene composite Nano material is compared, SnCoS4/ graphene composite nano material The electrochemistry storage lithium combination electrode of preparation shows higher electrochemistry storage lithium reversible specific capacity and excellent stable circulation performance, Its reversible capability of charging and discharging reaches 1490mAh/g, and after 200 times cycle, reversible capacity does not change substantially.In contrast, SnS2/ The reversible lithium storage capacity of graphene composite nano material electrode from initial 1096mAh/g be gradually reduced 200 times cycle 924mAh/g；CoS2The reversible capacity of/graphene composite nano material electrode can be reached for 1205mAh/g；SnCoS4Nanometer material The reversible capacity of material gradually decreases to the 303mAh/g of 200 Xun Huans from initial 1184mAh/g.Therefore, SnCoS4/ graphene The electrochemistry storage lithium reversible specific capacity of combination electrode prepared by composite nano materials is above SnS2/ graphene, CoS2/ graphene And SnCoS4The electrode of preparation, charge-discharge performance are also significantly better than SnS2/ graphene and SnCoS4Prepared by nano material Electrode.
The test of the high rate performance under different charging and discharging currents density of Fig. 5 shows in 200,500 He of current density During 1000mA/g, SnCoS4The electrochemistry of combination electrode prepared by/graphene composite nano material stores lithium reversible capacity 1336,1235 and 1145mAh/g, and stable cycle performance is also shown under different current densities；In contrast, SnS2The respective value of electrode prepared by/graphene composite nano material is 1068,930 and 787mAh/g respectively；CoS2/ graphene The respective value of composite nano materials electrode is 988,892 and 783mAh/g respectively；SnCoS4The respective value of electrode is 770 respectively, 480,265mAh/g.
Therefore, Electrochemical results illustrate, and with SnS2/ graphene and CoS2Prepared by/graphene composite nano material Combination electrode is compared, and uses SnCoS4Electrochemistry storage lithium combination electrode prepared by/graphene composite nano material not only has higher Electrochemistry storage lithium reversible specific capacity and excellent cycle performance, and show the high power charging-discharging characteristic significantly increased.

Claims (2)

1. a kind of electrochemistry stores lithium combination electrode, which is characterized in that the electrochemistry storage lithium active material of combination electrode is SnCoS4- The composite nano materials of graphene, the composite nano materials are by SnCoS4Composite nanocrystalline is supported on graphene and is formed, Middle SnCoS4The ratio between molal quantity of composite nanocrystalline and graphene is 1: 2, the component and its mass percentage content of combination electrode For：SnCoS4The composite nano materials of-graphene are 80%, acetylene black 10%, Kynoar 10%.
A kind of 2. preparation method of electrochemistry storage lithium combination electrode described in claim 1, which is characterized in that the preparation method The step of it 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 C4- graphene composite nano material；
(2) by the above-mentioned SnCoS being prepared4- graphene composite nano material stores lithium active matter as the electrochemistry of combination electrode Matter with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% is sufficiently mixed and is tuned under stiring The paste is equably coated onto on the copper foil as collector by uniform paste, dry, and electrochemistry storage lithium is obtained after roll-in Combination electrode.
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