CN110350160A - A kind of combination electrode of electrochemical lithium storage and preparation method thereof - Google Patents

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

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CN110350160A
CN110350160A CN201910519237.3A CN201910519237A CN110350160A CN 110350160 A CN110350160 A CN 110350160A CN 201910519237 A CN201910519237 A CN 201910519237A CN 110350160 A CN110350160 A CN 110350160A
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graphene
combination electrode
lithium storage
composite nano
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李丹
高根芳
宋文龙
陈卫祥
施璐
李靖
田庆山
甄爱钢
罗秋月
陈羽婷
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Tianneng Battery Group Co Ltd
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    • 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
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    • 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
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    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M10/052—Li-accumulators
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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Abstract

The invention discloses combination electrode of a kind of electrochemical lithium storage and preparation method thereof, combination electrode MoS2‑Bi2S3Active material of/the graphene composite nano material as electrochemical lithium storage.Its preparation step is: under the conditions of existing for the graphene oxide, passing through Bi (NO3)3、Na2MoO4With the hydro-thermal reaction of the mixed solution of L-cysteine under hydrothermal conditions, Bi is prepared2S3‑MoS2/ graphene composite nano material, the Bi that will be obtained2S3‑MoS2/ graphene composite nano material and acetylene black, Kynoar are tuned into uniform slurry, are coated onto rolling on copper foil and obtain the combination electrode of electrochemical lithium storage.The combination electrode has the advantages that high electrochemical lithium storage reversible specific capacity, stable cycle performance and high-rate charge-discharge capability are good.

Description

A kind of combination electrode of electrochemical lithium storage and preparation method thereof
Technical field
The present invention relates to a kind of electrochemical lithium storage combination electrodes and preparation method thereof, more particularly to use Bi2S3-MoS2/ graphite Electrochemical lithium storage combination electrode and preparation method thereof of the alkene composite nano materials as electrochemical lithium storage active material, belong to lithium from Sub-electrode material and its technical field applied in electrochemical lithium storage combination electrode.
Background technique
High-performance electric chemistry store up lithium electrode material and its in electrochemical lithium storage electrode application for high-performance lithium from The research and development of sub- battery are of great significance.MoS2(its theoretical capacity is nano material electrochemistry with higher storage lithium capacity 670mAh/g), it is with a wide range of applications in high performance lithium ion battery.But due to its lower conductivity and The biggish variation of volume in charge and discharge process causes it to store the rapid decay of lithium capacity in charge and discharge process.Bismuth sulfide nano Material is also a kind of lithium ion battery negative material with compared with high electrochemical storage lithium capacity, but single bismuth sulfide nano material Material similarly haves the shortcomings that capacity attenuation is very fast in charge and discharge process.Recent research indicate that being vulcanized by two different metals Nano material (such as SnS that object is compounded to form2-MoS2And Ni3S2-MoS2Composite material etc.) as lithium ion battery negative material Electrochemical lithium storage performance is above single nano metal sulfide material.The reason of its chemical property enhances is two kinds of differences The composite nano materials that are formed of metal sulfide the electricity that there is heterogeneous composite construction and more electrochemistry lithiumations-to go lithiumation it is right Reaction.Although the electrochemical lithium storage performance for the composite nano materials that two different metal sulfides are formed makes moderate progress, compared with Low conductivity still affects further enhancing for its electrochemical lithium storage performance.
Graphene has high conductivity and charged mobility, great specific surface area, good flexible and chemical stabilization Property.By the way that sulfide nano-material is compound with graphene, not only there is prepared composite material high electrochemistry storage lithium to hold Amount, and with stable charge-discharge performance and significantly increase high power charging-discharging characteristic.Such as: MoS2Graphene composite wood Material, bismuth sulfide-graphene composite material etc. are shown than individual MoS2Or there is bismuth sulfide higher electrochemistry storage lithium to hold Amount and superior charge and discharge cycles stability.But what the electrochemistry of these composite materials storage lithium performance also further increased Space.
The present invention provides a kind of electrochemical lithium storage combination electrode and preparation method thereof, which is used Bi2S3-MoS2/ graphene composite nano material is the active material of electrochemical lithium storage.With with MoS2/ graphene and Bi2S3/ graphite Alkene composite nano materials are the combination electrode of electrochemical lithium storage active material preparation, present invention Bi2S3-MoS2/ graphene is compound Nano material as combination electrode prepared by electrochemical lithium storage active material have higher electrochemical lithium storage reversible specific capacity, Excellent cycle performance and the high power charging-discharging characteristic further significantly increased.But up to the present, this to use Bi2S3- MoS2/ graphene composite nano material is that the combination electrode and preparation method thereof of electrochemical lithium storage active material yet there are no open report Road.
Summary of the invention
The purpose of the present invention is to provide a kind of electrochemical lithium storage combination electrode and preparation method thereof, the electricity of the combination electrode Chemistry storage lithium active material is Bi2S3-MoS2The composite nano materials of/graphene, the composite nano materials are by MoS2Nanometer sheet And Bi2S3Nanoparticle forms composite construction, and is equably supported on graphene and is formed.The component and its quality of combination electrode Degree are as follows: Bi2S3-MoS2The composite nano materials of/graphene are 80%, acetylene black 10%, Kynoar 10%. The step of preparation method of the electrochemical lithium storage combination electrode, is as follows:
(1) by the Bi (NO of metering3)3·5H2O、Na2MoO4·2H2O and L-cysteine are add to deionized water, and It is sufficiently stirred, obtains uniform mixed solution, Bi (NO in hydro-thermal reaction solution3)3With Na2MoO4The ratio between the amount of substance be 1: 9 ~1: 4, the amount of the substance of L-cysteine is Bi (NO3)3With Na2MoO45 times of the sum of the amount of substance；
(2) in deionized water by graphene oxide ultrasonic disperse, uniform suspension is obtained, under constant stirring by oxygen Graphite alkene hanging drop is added in above-mentioned mixed solution, and continues to stir 2h, is calculated with the amount of the substance of carbon, graphene oxide Substance amount be equal to Bi (NO3)3With Na2MoO42 times of the sum of the amount of substance, obtained reaction mixture is transferred to band Have in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, reacted for 24 hours at 200 DEG C after sealing, then cooled to room temperature, by water The precipitated product that thermal response obtains is centrifugated, and is sufficiently washed with deionized water and dehydrated alcohol, finally the vacuum at 80 DEG C Bi is obtained after dry 12h2S3-MoS2/ graphene composite nano material, the molar ratio of Bi and Mo therein are 1: 9~1: 4.
(3) by the above-mentioned Bi being prepared2S3-MoS2Active matter of/the graphene composite nano material as electrochemical lithium storage Matter is sufficiently mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and Kynoar and is tuned into uniform slurry, should MoS in slurry2-Bi2S3The mass ratio of/graphene composite nano material, acetylene black and Kynoar is 80: 10: 10, will Acquired uniform sizing material is equably coated on the copper foil as collector, and 120 DEG C of vacuum drying 12h obtain electrification after rolling Learn the combination electrode of storage lithium.
Compared with the prior art, present invention Bi2S3-MoS2The composite nano materials of/graphene are electrochemical lithium storage activity The electrochemical lithium storage combination electrode and preparation method thereof of substance preparation has the advantages that following significant and technological progress: although with list One MoS2Or Bi2S3Nano material compares, MoS2/ graphene composite material or Bi2S3/ graphene composite material has higher Electrochemical lithium storage specific capacity, electrochemical lithium storage specific capacity can achieve 900-1000mAh/g, and have improved charge and discharge The high power charging-discharging characteristic of cycle performance and enhancing, but its electrochemical lithium storage performance also has the space further promoted. With MoS2/ graphene and Bi2S3/ graphene composite material is compared, Bi of the invention2S3-MoS2/ graphene composite nano material tool The high power charging-discharging characteristic for having higher electrochemical lithium storage reversible specific capacity and further enhancing.Its chemical property is further The main reason for enhancing, is: the MoS of hydro-thermal preparation2Microscopic appearance is mainly exemplary two dimensional laminar nano piece, and hydro-thermal preparation Bi2S3Mainly the biggish similar shuttle of particle or olivary microscopic appearance are shown, as the Bi (NO in hydro-thermal reaction solution3)3 And Na2MoO4When existing simultaneously, in hydrothermal reaction process, MoS2And Bi2S3Nucleation and growth almost either simultaneously or alternately carrying out, It due to both different sulfide nucleation and grows there are mutual interference and influence, leads to tiny area in hydro-thermal reaction system The variation of reaction condition makes MoS generated2With the less number of plies and more edge, while the Bi generated2S3Partial size Also become smaller, and and MoS2It is combined with each other, Bi2S3-MoS2Composite construction and hydrothermal reduction graphene oxide are further compound Form Bi2S3-MoS2/ graphene composite nano material, due to its Bi2S3, MoS2, formed between graphene three uniform Heterojunction structure and Bi2S3-MoS2Bimetallic sulfide has more electrochemistry lithiumations/go lithiated electrode reaction electricity right.Cause This, and with MoS2/ graphene or Bi2S3/ graphene composite material is compound as electrochemical lithium storage prepared by electroactive substance Electrode is compared, present invention Bi2S3-MoS2The electrochemistry storage that/graphene composite nano material is prepared as electroactive substance The high power charging-discharging characteristic that lithium combination electrode has higher electrochemistry storage lithium reversible specific capacity and further enhances.
Detailed description of the invention
Fig. 1: the XRD diagram of the different composite material of hydro-thermal method preparation of the present invention: (a) MoS2/ graphene, (b) Bi2S3- MoS2/ graphene -1 (Bi: Mo=1: 9), (c) Bi2S3-MoS2/ graphene -2 (Bi: Mo=1: 4), (d) Bi2S3-MoS2/ graphite Alkene -3 (Bi: Mo=1: 1) and (e) Bi2S3/ graphene complex
Fig. 2: the SEM pattern of the composite material of hydro-thermal method preparation of the present invention, (a) MoS2/ graphene, (b) Bi2S3-MoS2/ Graphene -1 (Bi: Mo=1: 9), (c) Bi2S3-MoS2/ graphene -2 (Bi: Mo=1: 4), (d) Bi2S3-MoS2/ graphene -3 (Bi: Mo=1: 1) and (e) Bi2S3/ graphene composite material.
Fig. 3: the TEM/HRTEM photo of the composite material of hydro-thermal hair preparation of the present invention, (a, b) MoS2/ graphene, (c, d) Bi2S3-MoS2/ graphene -1 (Bi: Mo=1: 9), (e, f) Bi2S3-MoS2/ graphene -2 (Bi: Mo=1: 4), (g, h) Bi2S3- MoS2/ graphene -3 (Bi: Mo=1: 1), (i, j) Bi2S3/ graphene composite material
Fig. 4: MoS2/ graphene, Bi2S3-MoS2/ graphene -1 (Bi: Mo=1: 9), Bi2S3-MoS2/ graphene -2 (Bi: Mo=1: 4), and Bi2S3-MoS2/ graphene -3 (Bi: Mo=1: 1) and Bi2S3/ graphene composite material electrode is in 100mA/g electric current Charge-discharge performance under density
Fig. 5: MoS2/ graphene, Bi2S3-MoS2/ graphene -1 (Bi: Mo=1: 9), Bi2S3-MoS2/ graphene -2 (Bi: Mo=1: 4), and Bi2S3-MoS2/ graphene -3 (Bi: Mo=1: 1) and Bi2S3/ graphene composite material electrode is close in different electric currents Charge/discharge rate property under degree
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and examples.
Bi is prepared by a step hydro-thermal reaction approach253-MoS2/ graphene composite nano material, and with the composite wood Material prepares electrochemical lithium storage combination electrode as electroactive substance.
(1)Bi2S3-MoS2The preparation of/graphene composite nano material: by the Bi of x mmol (x=0.15,0.3,0.75) (NO3)3·5H2The Na of O and (1.5-x) mmol2MoO4·2H2O and 7.5mmol L-cysteine is added to 50mL deionization In water, and it is sufficiently stirred and forms uniform mixed solution；By the graphene oxide ultrasonic disperse of freshly prepd 3mmol 20mL's In deionized water, uniform suspension is obtained, under constant stirring, the hanging drop of graphene oxide is added to the mixing of front In solution, it is stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to the water that 100mL has polytetrafluoroethylliner liner In thermal response kettle, sealing is reacted for 24 hours in 200 DEG C of insulating box, after room temperature, by precipitation and centrifugal separation, and It is sufficiently washed with deionized water and dehydrated alcohol, will obtain finally obtaining after hydro-thermal black product is dried in vacuo 12h at 80 DEG C Bi2S3-MoS2/ graphene composite nano material, preparation-obtained 3 composite nano materials are denoted as MoS respectively2-Bi2S3/ stone Black alkene -1, MoS2-Bi2S3/ graphene -2 and MoS2-Bi2S3/ graphene -3, the molar ratio of Bi and Mo therein are respectively 1: 9,1 : 4 and 1: 1；
(2) by the above-mentioned Bi being prepared2S3-MoS2/ graphene composite nano material is stored up as the electrochemistry of combination electrode Lithium active material, it is abundant under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% Mixing is tuned into uniform slurry, each component mass percent are as follows: Bi2S3-MoS2/ graphene composite nano material 80%, acetylene black 10%, which is equably coated on the copper foil as collector by Kynoar 10%, is dried in vacuo at 110-120 DEG C, Electrochemical lithium storage combination electrode is obtained after rolling.
Comparative example 1: as a comparison, MoS is prepared for similar hydrothermal method2/ graphene composite material, and using its as Electrochemical lithium storage active material prepares electrochemical lithium storage electrode.
(1)MoS2Prepared by the hydro-thermal of/graphene composite material: by 1.5mmol Na2MoO4·2H2O and 7.5mmol L- half Cystine is added in 50mL deionized water, and is sufficiently stirred and to be formed uniform mixed solution；By the oxidation of freshly prepd 3mmol Graphene ultrasonic disperse obtains uniform suspension in 20mL deionized water, under constant stirring, by the outstanding of graphene oxide Supernatant liquid is added drop-wise in the mixed solution of front, is stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to 100mL band Have in the hydrothermal reaction kettle of polytetrafluoroethylliner liner, seals, reacted in 200 DEG C of insulating box for 24 hours, after naturally cool to room temperature Afterwards, it by precipitation and centrifugal separation, and is sufficiently washed with deionized water and dehydrated alcohol, it is true at 80 DEG C that hydro-thermal black product will be obtained After the dry 12h of sky, MoS is finally obtained2/ graphene composite material；
(2) by the above-mentioned MoS being prepared2The electrochemical lithium storage active matter of/graphene composite material as combination electrode Matter is sufficiently mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and the Kynoar of mass fraction 5% and is tuned into Uniform slurry, each component mass percent are as follows: MoS2/ graphene nano material 80%, acetylene black 10%, Kynoar 10%, which is equably coated on the copper foil as collector, is dried in vacuo at 110-120 DEG C, obtains electrification after rolling Learn storage lithium combination electrode.
Comparative example 2: as a comparison, Bi2S is prepared for similar hydrothermal method3/ graphene composite nano material, is used in combination It prepares electrochemical lithium storage electrode as electrochemical lithium storage active material.
(1)Bi2S3Prepared by the hydro-thermal of/graphene composite material: by 1.5mmol Bi (NO3)3·5H2O and 7.5mmol L- Cysteine is added in 50mL deionized water, and is sufficiently stirred and to be formed uniform mixed solution；By the graphene oxide of 3mmol Ultrasonic disperse obtains uniform suspension in 20mL deionized water, under constant stirring, by the hanging drop of graphene oxide It is added in the mixed solution of front, is stirred for 2h at room temperature；The mixed reactant finally obtained is transferred to 100mL with poly- four In the hydrothermal reaction kettle of vinyl fluoride liner, sealing is reacted for 24 hours in 200 DEG C of insulating box, will after room temperature Precipitation and centrifugal separation, and sufficiently washed with deionized water and dehydrated alcohol, hydro-thermal black product vacuum at 80 DEG C will be obtained and done After dry 12h, Bi2S is finally obtained3/ graphene composite material；
(2) by the above-mentioned Bi being prepared2S3/ graphene composite nano material is living as the electrochemical lithium storage 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% It is tuned into uniform slurry, each component mass percent are as follows: Bi2S3/ graphene composite nano material is 80%, and acetylene black 10% is gathered The slurry is equably coated on the copper foil as collector by vinylidene 10%, is dried in vacuo at 110-120 DEG C, after rolling Obtain electrochemical lithium storage combination electrode.
The characterization of material microstructure and pattern: it uses X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope/height Resolved transmittance Electronic Speculum (TEM/HRTEM) and XPS obtain MoS to prepared by above example and comparative example2-Bi2S3/ graphene is multiple Close nano material, MoS2/ graphene composite material, Bi2S3/ graphene composite material is characterized.
Electrochemical lithium storage performance test: it is working electrode with the above-mentioned electrochemical lithium storage combination electrode that is prepared, is being full of The test battery of lithium ion battery is assembled into the glove box of argon gas, metallic lithium foil is to electrode and reference electrode, and polypropylene is thin Film (Celgard-2300) is diaphragm, 1.0M LiPF6EC/DMC solution (volume ratio 1: 1) be electrolyte.Perseverance electricity at room temperature The electrochemical lithium storage 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.
The XRD characterization of Fig. 1 is the results show that MoS2/ graphene composite material is in 2 θ=14.4 °, 32.7 °, 33.5 ° and 57.2 ° show 4 diffraction maximums, correspond to 2H-MoS2(002) of (JPCDS no.37-1492), (100), (101), (110) Face.In addition occur 1 new diffraction maximum (* label), interlamellar spacing 0.96nm at 2 θ=9.2 °.Bi2S3/ graphene is multiple The XRD diagram of condensation material meets Bi2S3Standard diffraction card (JPCDS No.17-0320), stronger diffraction maximum illustrates Bi2S3With good crystallinity.Fig. 1 (b, c, d) is shown for MoS2-Bi2S3/ graphene composite nano material, as Bi contains The increase of amount, Bi2S3XRD peak intensity gradually increase, and MoS2XRD peak intensity gradually die down, it is molten that this is mainly due to hydro-thermals Bi in liquid3+Presence and Bi2S3And MoS2Syntrophism results in MoS2Crystallinity reduce, in addition as crystallization is more preferable Bi2S3The increase of content, MoS2Content it is relatively low, make to crystallize low MoS in composite material2The peak XRD almost observe not It arrives.
The SEM morphology characterization of Fig. 2 shows, MoS2/ graphene composite material shows the MoS largely intersected2Nanometer sheet is dispersed in On graphene.Bi2S3/ graphene composite material shows the Bi of olive shape2S3Particle is evenly dispersed on graphene.From Fig. 2 (b, c, d) is as can be seen that with Bi2S3The increase of content, composite material pattern gradually change, especially Bi2S3-MoS2/ The composite material of graphene -2 (Bi: Mo=1: 4) shows many tiny Bi2S3Nanoparticle and curved MoS2Nanometer sheet After forming composite construction, it is uniformly dispersed on the surface of graphene.
The TEM/HRTEM characterization result of Fig. 3 shows, MoS2The display of/graphene composite material intersects curved MoS2Nanometer sheet In dispersion on the surface of graphene.The interlamellar spacing of 0.64nm corresponds to MoS in Fig. 3 (b)2(002) face, the interlamellar spacing of 0.95nm is corresponding The peak * in XRD diagram.Bi2S3/ graphene composite material shows Bi2S3Particle is grown on graphene, and partial size is about 140- 320nm, interlamellar spacing are that 0.39nm and 0.50nm respectively corresponds (220) and (120) face.Bi2S3Regular lattice fringe illustrates its tool The crystallinity having had.Fig. 3 (c-h) shows and MoS2/ graphene is compared, Bi2S3-MoS2/ graphene composite nano material shows, It is dispersed in MoS on graphene2Nanometer sheet has the less number of plies, and more boundaries and disordered structure.Especially MoS2- Bi2S3The composite nano materials sample of/graphene -2 (Bi: Mo=1: 4), MoS2The number of plies of nanometer sheet significantly reduces, and occurs Many short sheet-like morphologies, with more tiny Bi2S3Nanocomposites together after, equably load on the surface of graphene.
Fig. 4 is that different electrochemical lithium storage combination electrodes at room temperature survey under 100mA/g current density by charge-discharge performance Examination as a result, and MoS2/ graphene combination electrode and Bi2S3/ graphene combination electrode is compared, and Bi is used2S3-MoS2/ graphene is multiple The combination electrode for closing nano material preparation shows higher electrochemical lithium storage reversible specific capacity and excellent stable circulation performance, Especially use Bi2S3-MoS2The combination electrode of/graphene -2 (Bi: Mo=1: 4) composite nano materials preparation, electrochemical lithium storage Reversible capacity reaches 1140mAh g-1, its reversible specific capacity stills remain in 1117mAh g after 100 circles recycle-1, compared to 1st decaying enclosed almost without capacity, it is shown that excellent charge-discharge performance.In contrast, MoS2/ graphene compound electric The electrochemical lithium storage reversible specific capacity of pole is 952mAh g-1, its reversible specific capacity is 891mAh g after 100 circles recycle-1； Bi2S3The reversible specific capacity of/graphene combination electrode is 946mAh g-1, but with the increase of circulating ring number, reversible specific volume Amount is decreased obviously, and reversible specific capacity is 732mAh g after 100 circle circulations-1, it is the 77.3% of reversible specific capacity for the first time.Therefore, With MoS2/ graphene combination electrode and Bi2S3/ graphene combination electrode is compared, and Bi is used2S3-MoS2/ graphene composite nano material Electrochemical lithium storage combination electrode as electroactive substance preparation shows higher electrochemical lithium storage reversible specific capacity, and With better charge and discharge cycles stability.
Fig. 5 is multiplying power property test result of the electrochemical lithium storage combination electrode under different charging and discharging currents density, with MoS2/ graphene combination electrode and Bi2S3/ graphene combination electrode is compared, and Bi is used2S3-MoS2/ graphene composite nano material system Standby electrochemical lithium storage combination electrode not only has higher electrochemical lithium storage reversible specific capacity, but also shows further increasing Strong high power charging-discharging characteristic.Fig. 5 is shown, when charging and discharging currents density is 1000mA/g, uses Bi2S3-MoS2/ graphene- The electrochemical lithium storage reversible specific capacity of electrochemical lithium storage combination electrode of 2 (Bi: Mo=1: 4) composite nano materials preparation is 870mAh g-1, and show stable cycle performance.In contrast, when charging and discharging currents density is 1000mA/g, MoS2/ The electrochemical lithium storage reversible specific capacity of graphene combination electrode is 711mAh g-1, Bi2S3The electrochemistry of/graphene combination electrode Storage lithium reversible specific capacity is 593mAh g-1.Therefore, with MoS2/ graphene combination electrode and Bi2S3/ graphene combination electrode phase Than this present invention Bi2S3-MoS2It is compound that/graphene composite nano material as electroactive substance prepares electrochemical lithium storage Electrode shows the high power charging-discharging characteristic further significantly increased.

Claims (2)

1. a kind of electrochemical lithium storage combination electrode, which is characterized in that the electrochemical lithium storage active material of combination electrode is Bi2S3- MoS2The composite nano materials of/graphene, the composite nano materials are by MoS2Nanometer sheet and Bi2S3Nanoparticle forms compound Structure, and be equably supported on graphene and formed.The component and its mass percentage content of combination electrode are as follows: Bi2S3-MoS2/ The composite nano materials of graphene are 80%, acetylene black 10%, Kynoar 10%.
2. a kind of preparation method of electrochemical lithium storage combination electrode described in claim 1, which is characterized in that the preparation method The step of it is as follows:
(1) by the Bi (NO of metering3)3·5H2O、Na2MoO4·2H2O and L-cysteine are add to deionized water, and sufficiently Stirring, obtains uniform mixed solution, Bi (NO in hydro-thermal reaction solution3)3With Na2MoO4The ratio between the amount of substance be 1: 9~1: 4, the amount of the substance of L-cysteine is Bi (NO3)3With Na2MoO45 times of the sum of the amount of substance；
(2) in deionized water by graphene oxide ultrasonic disperse, uniform suspension is obtained, stone will be aoxidized under constant stirring Black alkene hanging drop is added in above-mentioned mixed solution, and continues to stir 2h, is calculated with the amount of the substance of carbon, the object of graphene oxide The amount of matter is equal to Bi (NO3)3With Na2MoO42 times of the sum of the amount of substance, obtained reaction mixture is transferred to poly- In the hydrothermal reaction kettle of tetrafluoroethene liner, reacted for 24 hours at 200 DEG C after sealing, then cooled to room temperature, hydro-thermal is anti- The precipitated product centrifuge separation that should be obtained, and sufficiently washed with deionized water and dehydrated alcohol, finally it is dried in vacuo at 80 DEG C Bi is obtained after 12h2S3-MoS2/ graphene composite nano material, the molar ratio of Bi and Mo therein are 1: 9~1: 4.
(3) by the above-mentioned Bi being prepared2S3-MoS2Active material of/the graphene composite nano material as electrochemical lithium storage, It is sufficiently mixed under stiring with the N-Methyl pyrrolidone solution of acetylene black and Kynoar and is tuned into uniform slurry, the slurry Middle Bi2S3-MoS2The mass ratio of/graphene composite nano material, acetylene black and Kynoar is 80: 10: 10, by gained It is equably coated on the copper foil as collector to uniform sizing material, 120 DEG C of vacuum drying 12h, electrochemistry storage is obtained after rolling The combination electrode of lithium.
CN201910519237.3A 2019-06-14 2019-06-14 A kind of combination electrode of electrochemical lithium storage and preparation method thereof Pending CN110350160A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102142537A (en) * 2011-02-25 2011-08-03 浙江大学 Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof
CN105609747A (en) * 2016-03-29 2016-05-25 浙江兴海能源科技股份有限公司 Composite electrode of electrochemical storage lithium and preparation method thereof
CN109768216A (en) * 2019-01-29 2019-05-17 山西大学 A kind of flexible electrode material and its preparation method and application

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CN102142537A (en) * 2011-02-25 2011-08-03 浙江大学 Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof
CN105609747A (en) * 2016-03-29 2016-05-25 浙江兴海能源科技股份有限公司 Composite electrode of electrochemical storage lithium and preparation method thereof
CN109768216A (en) * 2019-01-29 2019-05-17 山西大学 A kind of flexible electrode material and its preparation method and application

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Application publication date: 20191018