CN110311117A - A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method - Google Patents

A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method Download PDF

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CN110311117A
CN110311117A CN201910610310.8A CN201910610310A CN110311117A CN 110311117 A CN110311117 A CN 110311117A CN 201910610310 A CN201910610310 A CN 201910610310A CN 110311117 A CN110311117 A CN 110311117A
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mos
magnesium
lithium
solution
double salt
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侯小江
常天骄
杨艳玲
石洪昌
潘俊
王祎
冯雷
张荔
锁国权
叶晓慧
朱建锋
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/36—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method load the flower-shaped two-dimension nano materials MoS of one layer of high-activity nano in EG surface in situ with good conductivity by a step hydrothermal method2, by the high conductivity and MoS of EG2High activity and layer structure feature can effectively promote Li in positive electrode+Efficient saturation intercalation/deintercalation, improve the capacity and multiplying power property of double salt batteries.In addition, EG@MoS2Li can be effectively relieved+Intercalation/deintercalation causes material pulverizing problem caused by positive electrode volume expansion/contraction, to improve the cyclical stability of the double salt ion batteries of magnesium-lithium, improves battery life.

Description

A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method
Technical field
The invention belongs to secondary power battery material technical fields, and in particular to a kind of MoS2The double salt ion electricity of@EG magnesium-lithium Pond positive electrode and its construction method.
Background technique
Along with the development and social progress of the mankind, the energy is the necessity of daily life for the development and utilization of the energy, " drive " human lives and social progress.Population sharp increase and heavy industry Rapid Expansion, cause energy demand constantly to rise, And it largely consumes environmental problem caused by fossil energy gradually to show.In addition traditional fossil energy is non-renewable and by mistake Degree exploitation forces the whole world to fall into fossil energy exhaustion and the awkward situation with environmental pollution, develops and uses clean and effective renewable energy The sustainable energy and the current energy resource system of upgrading in source are extremely urgent.The mankind always spare no effort to explore respective new energy Energy replacement is actively promoted in source.Energy upgrading each time can mean that the progress of social productive forces, promote social economy's hair Exhibition.
Energy storage material is essential in today's society, and as portable device sharply increases, energy storage material and device Demand is more more and more urgent.As energy storage device, lithium ion battery achieves immense success in commercial rechargeable battery market.So And lithium ion reserves are limited, cost is high, lithium dendrite growth leads to battery short circuit, or even cause fire, the problems such as capacity is limited It forces people to have to the new ion battery of demand to substitute lithium ion battery, meets the needs of social development.Due to low cost, No dendrite and bielectron redox character, capacity height (magnesium 3833mAhcm-3, Li 2046mAhcm-3) etc. it is significant special Sign, it is the novel ion battery for being expected to large-scale use that rechargeable magnesium ion battery, which shows great advantage,.Therefore, magnesium from Sub- battery is receive more and more attention.
Although Magnesium ion battery correlative study is repeatedly reported, there is preferable Mg2+Ion is embedded in kinetics The high-voltage anode material of matter is very limited, seriously hinders the application of Magnesium ion battery.Due to Mg2+Ionic charge density compared with Greatly, Mg is seriously constrained there are stronger coulomb active force between cell positive material2+Ion moving in positive electrode It moves, leads to the lower electrochemical utilization rate of positive electrode and high rate performance.Therefore, the most of lithium ion batteries developed at present Positive electrode and not applicable and Magnesium ion battery.The double salt battery systems of the lithium magnesium constructed in recent years, can significantly solve magnesium ion The problem of battery encounters.Specific practice is using the positive electrode of embedding lithium, magnesium anode material and to contain Mg2+And Li+Ion is consolidated State electrolyte constructs ion battery systems.Make anode that efficient Li occur+Mg occurs for ion deinsertion reaction, cathode2+Ion Dissolution and deposition reaction, so that low capacity of lithium ion battery, at high cost, Li dendrite and Magnesium ion battery deintercalation power be effectively relieved The problems such as, pushes the application of magnesium-based energy-storage battery.
Currently, embedding lithium anode material ingredient used in lithium ion battery and double salt batteries is single, structure is simple, exists and leads Electrically insufficient, active lower, structural instability lacks the problems such as channel of quick deintercalation ion, seriously constrains lithium ion It is rapidly saturated intercalation/deintercalation, reduces capacity, multiplying power property and the cyclical stability of battery system.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that providing a kind of MoS2@EG The double salt ion cell positive materials of magnesium-lithium and its construction method, it is former on the surface EG with good conductivity by a step hydrothermal method The position load flower-shaped two-dimension nano materials MoS of one layer of high-activity nano2, by the high conductivity and MoS of EG2High activity and stratiform Design feature can effectively promote Li in positive electrode+Efficient saturation intercalation/deintercalation, capacity and the multiplying power for improving double salt batteries be special Property.In addition, MoS2Li can be effectively relieved in@EG+Intercalation/deintercalation causes material dusting caused by positive electrode volume expansion/contraction Problem improves battery life to improve the cyclical stability of the double salt ion batteries of magnesium-lithium.
The invention adopts the following technical scheme:
A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium, positive electrode are EG load MoS in situ2Nano flower-like Composite material, EG account for 5~20wt.%, MoS280~95wt.% of flower-like nanometer material accounting.
Another technical solution of the present invention is that one kind constructs MoS described in claim 12The double salt ion batteries of@EG magnesium-lithium The method of positive electrode, comprising the following steps:
S1, EG is dispersed in acetone soln and is impregnated, be then dried for standby after clear water cleaning；
S2, sodium molybdate, hydroxylamine hydrochloride and thiocarbamide are dissolved in deionized water obtained mixed solution；
In S3, the mixed solution for obtaining surfactant addition step S2, and adjust solution ph；
S4, it EG that step S1 is obtained is added obtains hydrothermal solution in the solution after step S3 adjusts pH value and carries out hydro-thermal Reaction obtains reaction product；
S5, by reaction product obtained by step S4 after cooled to room temperature, then through dehydrated alcohol and deionized water washing, Centrifugation is for several times, last vacuum dried, obtains step hydrothermal synthesis (x) MoS2The double salt ion cell positive materials of@EG magnesium-lithium (x)MoS2@EG。
Specifically, impregnating 30min in step S1, clear water is cleaned 3 times, and vacuum drying temperature is 60~80 DEG C, the time 10 ~14h.
Specifically, in step S2, sodium molybdate, hydroxylamine hydrochloride and the molten ratio between deionized water of thiocarbamide be (0.6~ 1.0g): (0.55~0.95g): (1.0~1.8g): (40~80mL).
Specifically, surfactant is cetyl trimethylammonium bromide, cetyl trimethylammonium bromide in step S3 Ratio with mixed solution is (0.15~0.20g): (40~80mL).
Specifically, adjusting solution ph in step S3 are as follows: adjusting pH value of solution with the HCL of 2mol/L is 4~8.
Specifically, step S4 specifically: the ratio of EG and the solution after adjusting pH value are (0.006~0.024g): (42~ 84mL), hydrothermal solution is transferred in hydrothermal reaction kettle after 1~3h of magnetic agitation, and reaction kettle is placed in baking oven, at 180 DEG C React 12~36h.
Specifically, being centrifuged 3~6 times in step S5.
Specifically, vacuum drying temperature is 60~80 DEG C in step S5, drying time is 10~14h.
Compared with prior art, the present invention at least has the advantages that
The present invention provides a kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium, it is negative using magnesium metal as battery Pole, lithium ion battery electrode material (x) MoS2@EG nanocomposite is used cooperatively Li as anode+And Mg2+Ion coexists Double salt electrolytes.In charge and discharge process, magnesium metal cathode side is happens is that Mg2+The deposition of ion dissolves out reaction, and Positive electrode side is main happens is that Li+Abjection/the insertion reaction of ion in the material.EG prepared by the present invention is negative in situ Carry MoS2Nano composite anode material can make full use of the high conductivity and MoS of EG2High activity and laminar microstructure, efficiently promote Make Li+The quick intercalation/deintercalation of ion improves battery capacity and kinetic characteristics；EG can be effectively delayed as special carbon form Solution is because of Li+Volume expansion/contraction problem that ion insertion abjection has caused positive time mentions to inhibit positive electrode dusting High battery cycle life.
A kind of MoS of the present invention2The construction method of the double salt ion cell positive materials of@EG magnesium-lithium, passes through a step hydrothermal method The flower-shaped two-dimension nano materials MoS of one layer of high-activity nano is loaded in EG surface in situ with good conductivity2, by the highly conductive of EG Property and MoS2High activity and layer structure feature can effectively promote Li in positive electrode+Efficient saturation intercalation/deintercalation, improve The capacity and multiplying power property of double salt batteries.In addition, EG loads MoS2Li can be effectively relieved+Intercalation/deintercalation causes positive electrode volume Material pulverizing problem caused by expansion/contraction improves to improve the cyclical stability of the double salt ion batteries of magnesium-lithium Battery life.
Further, EG is dispersed in acetone soln and is impregnated, then drying is in order to molten by acetone after clear water cleaning The strong dissolution characteristics of liquid remove the tissue such as the greasy dirt on the surface EG, improve surface cleanliness and activity, increase MoS in water-heat process2 Adhesive force, to improve MoS2With the binding force of EG, the circulating temperature of battery is promoted.
Further, sodium molybdate, hydroxylamine hydrochloride and thiocarbamide are dissolved in deionized water and mixed solution is made is to promote Make the full and uniform mixing of reactant, contact sufficient reactant when hydrothermal reaction condition has can fast reaction, formed target Product.
Further, by the obtained mixed solution of surfactant addition step S2, and adjust solution ph be in order to By the guiding function of surfactant, the MoS of form specific morphology2Stratified nano materials --- nano flower-like MoS2Stratiform mistake Metal sulfide is crossed, the specific surface area of material is increased, retains more active edges out, electrode material when improving battery charging and discharging Electro-chemical activity.
Further, hydrothermal solution is obtained in the solution after the EG that step S1 is obtained to be added to step S3 adjusting pH value to go forward side by side Row hydro-thermal reaction obtains reaction product；The purpose of adjustment PH is to adjust and hydrolyze to form MoS2Reaction condition, make it more Conducive to the performance of Action of Surfactant, to obtain the MoS of feature of interest2Nano material.
Further, hydrothermal solution is obtained in the solution after the EG that step S1 is obtained to be added to step S3 adjusting pH value to go forward side by side It is to adhere to form flower-shaped MoS in EG surface in situ by hydrothermal synthesis that row hydro-thermal reaction, which obtains reaction product,2To be formed Composite nano materials.
Further, step S5 washing and centrifugation can remove solvent, recycle target product, that is, MoS2@EG。
Further, the influence of air is eliminated in step S5 vacuum drying treatment removal target product during moisture, Obtain the not contaminated active nano composite material of clean surface.
In conclusion the present invention improves cathode material structure stability, charge-discharge power and capacity are improved, and obtain The charge and discharge cycles stability obtained.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is (x) MoS that the present invention synthesizes2The microscopic appearance figure of the double salt ion cell positive materials of@EG magnesium-lithium, In, (a) is a kind of MoS2@EG transmits shape appearance figure, (b) is another kind MoS2@EG transmits shape appearance figure, (c) is a kind of MoS2@EG is saturating High-Resolution Map is penetrated, (d) is another kind MoS2@EG transmits High-Resolution Map；
Fig. 2 is MoS of the present invention2The Raman spectrum test result figure of@EG sample.
Specific embodiment
The present invention provides a kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium are EG load MoS in situ2Nanometer Flower-shaped composite material；MoS2In@EG nanocomposite, the content x=5~20wt.%, MoS of EG2Flower-like nanometer material accounting 80~95wt.%.A kind of MoS of the present invention2The construction method of the double salt ion cell positive materials of@EG magnesium-lithium, including following step It is rapid:
S1, EG pretreatment
EG is dispersed in acetone soln and is impregnated, the impurity such as greasy dirt on the surface EG are removed, improves EG surface-active and affine Property, clear water is cleaned 3 times, is dried for standby；
S2, solution are prepared
Weigh respectively 0.6~1.0g sodium molybdate, 0.55~0.95g hydroxylamine hydrochloride and 1.0~1.80g thiocarbamide be dissolved in 40~ In 80mL deionized water；
S3, surfactant is added and pH value adjustment:
Then it weighs 0.15~0.20g cetyl trimethylammonium bromide (CTAB) to be added in the solution, uses 2mol/L HCL adjustment pH value of solution be 4~8, obtain solution；
S4, hydrothermal synthesis
0.006~0.024g EG that step S1 is obtained is added in the solution that step S3 is obtained and obtains hydrothermal solution, it will be upper After stating 1~3h of hydrothermal solution magnetic agitation, it is transferred in the hydrothermal reaction kettle of 200mL, and reaction kettle is placed in baking oven, 180 DEG C 12~36h of conditioned response.
S5, collection of products
Reaction product obtained by step S4 is washed after cooled to room temperature, then through dehydrated alcohol with deionized water repeatedly It washs, be centrifuged 3~6 times, finally in 60~80 DEG C of vacuum oven constant temperature dry 10~14h, obtain a step hydrothermal synthesis (x) MoS2Double salt ion cell positive material (x) MoS of@EG magnesium-lithium2@EG。
Construction method of the present invention improves the double salt cell positive material electric conductivity of magnesium lithium and activity, improves cathode material structure not Stablize, it is high, of fine quality without dendrite generation and embedding lithium anode material stable structure, kinetics to give full play to magnesium cathode efficiency for charge-discharge Different feature shows good charge discharge characteristic, prepares high capacity, safety, long-life power battery.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.The present invention being described and shown in usually here in attached drawing is real The component for applying example can be arranged and be designed by a variety of different configurations.Therefore, below to the present invention provided in the accompanying drawings The detailed description of embodiment be not intended to limit the range of claimed invention, but be merely representative of of the invention selected Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
One kind (x) MoS2The double salt ion cell positive materials of@EG magnesium-lithium are EG load MoS in situ2Nano flower-like composite wood Material；(x)MoS2In@EG nanocomposite, EG accounts for x=5~20wt.%, MoS280~95wt.% of flower-like nanometer material accounting.
X=5wt.% in the present embodiment.
The present invention also proposes a kind of MoS2The synthetic method of the double salt ion cell positive materials of@EG magnesium-lithium, including, specifically Process is:
S1, EG pretreatment
EG is dispersed in acetone soln and is impregnated, the impurity such as greasy dirt on the surface EG are removed, improves EG surface-active and affine Property；
S2, solution are prepared
0.6g sodium molybdate, 0.55g hydroxylamine hydrochloride and 1.0g thiocarbamide is weighed respectively to be dissolved in 40mL deionized water；
S3, surfactant are added and pH value is adjusted
Then it weighs 0.15g cetyl trimethylammonium bromide (CTAB) to be added in the solution, with the HCl tune of 2mol/L Whole pH value of solution is 4, obtains solution；
S4, hydrothermal synthesis
The 0.006g EG that step S1 is obtained is added in the solution obtained to step S3 and obtains hydrothermal solution, by above-mentioned water It after hot solution magnetic agitation 1h, is transferred in the hydrothermal reaction kettle of 200mL, and reaction kettle is placed in baking oven, in 180 DEG C of condition React 12h.
S5, collection of products
Reaction product obtained by step S4 is washed after cooled to room temperature, then through dehydrated alcohol with deionized water repeatedly It washs, be centrifuged 3 times, finally in 60 DEG C of vacuum oven constant temperature dry 10h, obtain step hydrothermal synthesis (5wt.%) MoS2@EG magnesium- The double salt ion cell positive materials of lithium.
Embodiment 2
One kind (x) MoS2The double salt ion cell positive materials of@EG magnesium-lithium are EG load MoS in situ2Nano flower-like composite wood Material；(x)MoS2In@EG nanocomposite, EG accounts for x=5~20wt.%, MoS280~95wt.% of flower-like nanometer material accounting.
X=10wt.% in the present embodiment.
The present invention also proposes a kind of MoS2The synthetic method of the double salt ion cell positive materials of@EG magnesium-lithium, including, specifically Process is:
S1, EG pretreatment
EG is dispersed in acetone soln and is impregnated, the impurity such as greasy dirt on the surface EG are removed, improves EG surface-active and affine Property；
S2, solution are prepared
0.8g sodium molybdate, 0.75g hydroxylamine hydrochloride and 1.4g thiocarbamide is weighed respectively to be dissolved in 60mL deionized water；
S3, surfactant are added and pH value is adjusted
Then it weighs 0.17g cetyl trimethylammonium bromide (CTAB) to be added in the solution, with the HCL tune of 2mol/L Whole pH value of solution is 6, obtains solution；
S4, hydrothermal synthesis
The 0.012g EG that step S1 is obtained is added in the solution obtained to step S3 and obtains hydrothermal solution, by above-mentioned water It after hot solution magnetic agitation 2h, is transferred in the hydrothermal reaction kettle of 200mL, and reaction kettle is placed in baking oven, in 180 DEG C of condition Reaction is for 24 hours.
S5, collection of products
Reaction product obtained by step S4 is washed after cooled to room temperature, then through dehydrated alcohol with deionized water repeatedly It washs, be centrifuged for several times, finally in 70 DEG C of vacuum oven constant temperature dry 12h, obtain step hydrothermal synthesis (10wt.%) MoS2@EG The double salt ion cell positive materials of magnesium-lithium.
Embodiment 3
One kind (x) MoS2The double salt ion cell positive materials of@EG magnesium-lithium are EG load MoS in situ2Nano flower-like composite wood Material；(x)MoS2In@EG nanocomposite, EG accounts for x=5~20wt.%, MoS280~95wt.% of flower-like nanometer material accounting.
X=20wt.% in the present embodiment.
The present invention also proposes a kind of MoS2The synthetic method of the double salt ion cell positive materials of@EG magnesium-lithium, detailed process is such as Under:
S1, EG pretreatment
EG is dispersed in acetone soln and is impregnated, the impurity such as greasy dirt on the surface EG are removed, improves EG surface-active and affine Property；
S2, solution are prepared
1.0g sodium molybdate, 0.95g hydroxylamine hydrochloride and 1.8g thiocarbamide is weighed respectively to be dissolved in 80mL deionized water；
S3, surfactant are added and pH value is adjusted
Then it weighs 0.20g cetyl trimethylammonium bromide (CTAB) to be added in the solution, with the HCL tune of 2mol/L Whole pH value of solution is 8, obtains solution；
S4, hydrothermal synthesis
The 0.024g EG that step S1 is obtained is added in the solution obtained to step S3 and obtains hydrothermal solution, by above-mentioned water It after hot solution magnetic agitation 3h, is transferred in the hydrothermal reaction kettle of 200mL, and reaction kettle is placed in baking oven, in 180 DEG C of condition React 36h.
S5, collection of products
Reaction product obtained by step S4 is washed after cooled to room temperature, then through dehydrated alcohol with deionized water repeatedly It washs, be centrifuged for several times, finally in 80 DEG C of vacuum oven constant temperature dry 14h, obtain step hydrothermal synthesis (20wt.%) MoS2@EG The double salt ion cell positive materials of magnesium-lithium.
The MoS of synthesized preparation in different embodiments2@EG nanometer combined electrode material because MoS2 and EG ratio not Together, different performance differences is showed, wherein MoS2Has high electrochemical activity, EG has high conductivity.Different positive electrodes Charge/discharge capacity, kinetic characteristics and cycle characteristics have certain difference.Overall performance comes out, and the more initial capacities of EG are more Height, but cyclical stability is poor.
Referring to Fig. 1, (10wt.%) MoS2The double salt ion cell positive material transmitted electron shape appearance figures of@EG magnesium-lithium, from As can be seen that a step hydro-thermal synthesis process works well in figure, the nanometer MoS that hydro-thermal is formed2It can uniformly load in situ outer The surface EG added.As can be seen, by one step hydro thermal method, EG high-efficient carrier with good conductivity nano flower-like MoS2It is living Property transition metal sulfide, and formed MoS2Synusia spacing is uniform, is anode Li during subsequent double salt battery electrochemicals+'s The space that intercalation/deintercalation is provided convenience.The high conductivity and MoS of EG2High electrochemical activity mutually cooperate with, show good Electrochemical properties, the charge-discharge power characteristic of the double salt ion batteries of magnesium-lithium and capacity performance are well.
Referring to Fig. 2, sample is respectively in 378cm after EG is added-1、427cm-1And 1580cm-1There is characteristic peak, wherein 378cm-1And 427cm-1It is MoS2Characteristic peak, 1580cm-1It is the characteristic peak of carbon, corresponds to added by this test EG。
Wherein, MoS2The characteristic peak of@EG (10wt.%) composite sample is significantly lower than MoS2The characteristic peak of@EG (20wt.%), Also demonstrate that EG has enhancing MoS2The effect of characteristic peak, and increasing with EG content, the characteristic peak of carbon also significantly increase By force.
The present invention is using magnesium metal as battery cathode, lithium ion battery electrode material (x) EG@MoS2Nanocomposite As anode, it is used cooperatively Li+And Mg2+Double salt electrolytes that ion coexists.In charge and discharge process, magnesium metal cathode side Happens is that Mg2+The deposition of ion dissolves out reaction, and positive electrode side is main happens is that Li+Ion in the material de- Out/insertion reaction.
EG prepared by the present invention loads MoS in situ2Nano composite anode material, can make full use of EG high conductivity and MoS2High activity and laminar microstructure, efficiently promote Li+The quick intercalation/deintercalation of ion, improves battery capacity and dynamics is special Property；EG is can be effectively relieved as special carbon form because of Li+The volume expansion that ion insertion abjection has caused positive time/ Contraction problem improves battery cycle life to inhibit positive electrode dusting.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention Protection scope within.

Claims (9)

1. a kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium, which is characterized in that positive electrode is EG load MoS in situ2 Nano flower-like composite material, EG account for 5~20wt.%, MoS280~95wt.% of flower-like nanometer material accounting.
2. one kind constructs MoS described in claim 12The method of the double salt ion cell positive materials of@EG magnesium-lithium, which is characterized in that The following steps are included:
S1, EG is dispersed in acetone soln and is impregnated, be then dried for standby after clear water cleaning；
S2, sodium molybdate, hydroxylamine hydrochloride and thiocarbamide are dissolved in deionized water obtained mixed solution；
In S3, the mixed solution for obtaining surfactant addition step S2, and adjust solution ph；
S4, it EG that step S1 is obtained is added obtains hydrothermal solution in the solution after step S3 adjusts pH value and carries out hydro-thermal reaction Obtain reaction product；
S5, by reaction product obtained by step S4 after cooled to room temperature, then through dehydrated alcohol and deionized water washing, centrifugation For several times, last vacuum dried, obtain step hydrothermal synthesis (x) MoS2The double salt ion cell positive materials (x) of@EG magnesium-lithium MoS2@EG。
3. construction method according to claim 2, which is characterized in that in step S1,30min is impregnated, clear water cleans 3 times, Vacuum drying temperature is 60~80 DEG C, and the time is 10~14h.
4. construction method according to claim 2, which is characterized in that in step S2, sodium molybdate, hydroxylamine hydrochloride and thiocarbamide are molten Ratio between deionized water is (0.6~1.0g): (0.55~0.95g): (1.0~1.8g): (40~80mL).
5. construction method according to claim 2, which is characterized in that in step S3, surfactant is cetyl three The ratio of methyl bromide ammonium, cetyl trimethylammonium bromide and mixed solution is (0.15~0.20g): (40~80mL).
6. construction method according to claim 2, which is characterized in that in step S3, adjust solution ph are as follows: use 2mol/L HCL adjustment pH value of solution be 4~8.
7. construction method according to claim 2, which is characterized in that step S4 specifically: EG and adjust pH value after it is molten The ratio of liquid is (0.006~0.024g): (42~84mL), hydrothermal solution are transferred to hydrothermal reaction kettle after 1~3h of magnetic agitation In, and reaction kettle is placed in baking oven, in 180 DEG C of 12~36h of reaction.
8. construction method according to claim 2, which is characterized in that in step S5, be centrifuged 3~6 times.
9. construction method according to claim 2, which is characterized in that in step S5, vacuum drying temperature is 60~80 DEG C, drying time is 10~14h.
CN201910610310.8A 2019-07-08 2019-07-08 A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method Pending CN110311117A (en)

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CN111403742A (en) * 2020-03-25 2020-07-10 陕西科技大学 Pod-shaped MoS2-SnO2Magnesium-lithium hybrid ion battery anode material and synthesis method and application thereof
CN111403743A (en) * 2020-03-25 2020-07-10 陕西科技大学 MoS2@ CuS @ EG nano hollow flower-shaped magnesium-lithium double-salt battery positive electrode material and preparation method and application thereof
CN112909258A (en) * 2021-02-06 2021-06-04 陕西科技大学 Flexible positive and negative electrode material for high-performance magnesium-lithium double-salt ion battery and preparation method thereof

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Application publication date: 20191008