CN109713258A - A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application - Google Patents

A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application Download PDF

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CN109713258A
CN109713258A CN201811487667.3A CN201811487667A CN109713258A CN 109713258 A CN109713258 A CN 109713258A CN 201811487667 A CN201811487667 A CN 201811487667A CN 109713258 A CN109713258 A CN 109713258A
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graphene
molybdenum sulfide
cobalt
carbon composite
doped molybdenum
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张文惠
岳鹿
陈介民
倪杰
徐洁
茅思佳
徐琪
关荣锋
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Yangcheng Institute of Technology
Yancheng Institute of Technology
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Abstract

The invention discloses a kind of cobalt doped molybdenum sulfide-graphene-carbon composites and its preparation method and application, by being proportionally added into cobalt salt, sodium molybdate, graphene oxide water solution and thiocarbamide in the aqueous solution of sugar, it is transferred in hydrothermal reaction kettle hydro-thermal reaction under fixed temperature after ultrasonic mixing is uniform, prepares cobalt doped molybdenum sulfide-graphene-carbon composite via sintering processes after washing, drying.The invention also discloses the composite material and its applications.The present invention according to molybdenum sulfide as sode cell negative electrode material the characteristics of, using the excellent graphene of electric conductivity and carbon as complex media, the electron conduction and storage sodium capacity of composite material are increased substantially using cobalt doped, step preparation has the molybdenum sulfide based combined electrode material of height ratio capacity and long circulation life.The present invention prepares that raw material is cheap, and operating procedure is simple, and the charge-discharge performance of high income, material is excellent, is convenient for industrialized production, easy to spread.

Description

A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application
Technical field
The present invention relates to anode material of lithium-ion battery technical fields, and in particular to a kind of cobalt doped molybdenum sulfide-graphene- Carbon composite and its preparation method and application.
Background technique
With electric power transport and large-scale fast development, a large amount of battery material will be needed, to establish the intelligence of large capacity It can power grid.Lithium resource has that resource is not abundant and is unevenly distributed, as people more and more use so that lithium provides The price in source is risen sharply, this plays restriction effect to its extensive development.The ground shell resource of sodium is very rich, and price Cheap, this is being a kind of advantage to the epoch that renewable resource largely needs.It is right due to the electrochemistry similitude between lithium and sodium It is advanced grind make internal disorder or usurp for develop sodium-ion battery paved road.However, since radius ratio radius is big, so sodium ion is embedded in and deposits Storage mechanism is also to have key scientific challenges.Developing and explore suitable host material can accommodate and promote sodium ion reversible embedding Entering abjection is problem in the urgent need to address.
MoS2Because of its special layer structure, there is variable Atomic coordinate and electronic structure, electronics and lattice vibration There is very strong interaction, the weaker Van der Waals force of interlayer is conducive to light metal ion (such as Li between normal quantum (phonon)+、Na+、Mg2+Deng) insertion and deintercalation, while MoS2Also have good electric double layer charge storage, and Mo atom have from For+divalent to the oxidation state of+6 valences, it is a kind of change that performance is fabulous that these characteristics, which determine its theoretical lithium storage content with higher, Power electrode material is learned, to be widely studied.In view of excellent storage lithium performance, and its interlamellar spacing has 0.62nm than graphite Greatly, it can provide bigger ion channel the architectural characteristic excellent by its free shuttling etc., can also be shown in sodium ion storage Excellent performance.
Further study show that the change comparison surface area and absorption property of appearance structure have larger impact, to influence To MoS2Storage sodium performance and cyclical stability;On the other hand, due to MoS2Size for layer structure, interlamellar spacing directly determines The insertion ability of sodium ion, and the change of appearance structure the insertion of sodium ion and deintercalation channel and interlamellar spacing are generated it is certain It influences, to influence the cyclical stability of sodium-ion battery;In addition, the change of appearance structure, there is the transfer passages of carrier Certain influence, this will significantly affect the forthright again of sodium-ion battery.MoS is able to achieve by doping2Regulation (the Wang of interlamellar spacing H,Tsai C,Kong D,et al.Transition-metal doped edge sites in vertically aligned MoS2,catalysts for enhanced hydrogen evolution[J].Nano reserarch,2015,8(2): 566-575.) it has been indisputable fact.
In order to further increase the performance of base material of cathode material, for MoS2The bulk effect of the negative electrode material of this kind of high capacity The disadvantage low with conductivity greatly, by it and compound, the buffers active material with the good carrier of elasticity, the stable and electrically conductive performance of performance Volume change, the effective way of its cyclical stability will be improved while being to maintain high capacity.Carbon is due to possessing lighter matter Many advantages, such as amount, preferable electric conductivity, lower intercalation potential, volume change is small and cheap during deintercalation etc., is wide It is general to be used in anode material.Graphene is due to having many advantages, such as that two-dimensional structure, conductivity are high, elasticity is good, extensively The general carbon complex object that is used as is studied.
But up to this point, a step applies to transition metal element doped, carbon coating, graphene compound three simultaneously Improve stratiform MoS2This technology of sodium performance is stored up, is also rarely reported both at home and abroad.This is because the doping of transition metal, carbon source and Graphene oxide rich in functional group as raw material addition to MoS2Pattern and structure be affected, be difficult to control its stabilization The generation of crystal phase structure.
Summary of the invention
For the deficiency of existing issue, the first purpose of the invention is to provide a kind of cobalt doped molybdenum sulfide-graphene-carbon The preparation method of composite material.
A second object of the present invention is to provide a kind of cobalt doped molybdenum sulfide-graphene-carbon composites.
Third object of the present invention is to provide a kind of cobalt doped molybdenum sulfide-graphene-carbon composite prepare sodium from The application of sub- battery.
The technical solution used to solve the technical problems of the present invention is that:
A kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method, by sugar aqueous solution in proportion Cobalt salt, sodium molybdate, graphene oxide water solution and thiocarbamide is added, it is transferred in hydrothermal reaction kettle after ultrasonic mixing is uniform Hydro-thermal reaction under fixed temperature prepares cobalt doped molybdenum sulfide-graphene-carbon composite via sintering processes after washing, drying.
Further, the preparation method specifically includes the following steps:
(1) sugar juice of molar concentration is prepared;
(2) graphite oxide powder is taken to be scattered in the sugar juice of step (1), abundant ultrasound 1h;
(3) sodium molybdate is added, then weighs cobalt salt ultrasound 30min, is eventually adding thiocarbamide stirring 1h;
(4) mixed liquor obtained by step (3) is transferred in reaction kettle and reacts 10-48h in 150-220 DEG C of hydro-thermal case;It is cooling, It filters, it is dry, it is sintered in tube furnace, cobalt doped molybdenum sulfide-graphene-carbon composite is prepared.
Further, the sugar juice includes the monosaccharide of glucose and fructose, the disaccharide of sucrose and other solubilities Polysaccharide etc., molar concentration 0.01-0.1mol/L;
Further, the additional amount of the graphite oxide powder is 0.05-0.5 times of sodium molybdate additional amount;The cobalt Salt is one of cobalt acetate and acetylacetone cobalt rich in acetate or acetyl group, and additional amount is sodium molybdate additional amount 0.025-0.25 times;Thiocarbamide additional amount is 2~5 times of sodium molybdate additional amount;
Further, the sintering processes condition are as follows: in Ar, Ar/H2Under gaseous mixture or He atmosphere 400~800 DEG C into Row heat treatment 1-12h;
Further, the doping mole of cobalt is 0.05-5% in the composite material;The content of molybdenum sulfide is 50- 90%;The content of graphene is 5-20%.
Cobalt doped molybdenum sulfide-graphene-carbon composite that above-mentioned preparation method is prepared.
Above-mentioned cobalt doped molybdenum sulfide-application of the graphene-carbon composite in sodium-ion battery.
Beneficial effect
The present invention prepares cobalt doped sulphur according to the feature in sode cell negative electrode material charge and discharge cycles, by one step hydro thermal method Change molybdenum-graphene-carbon composite, using the excellent graphene of electric conductivity and carbon as complex media, using cobalt doped come The electron conduction and storage sodium capacity of composite material are increased substantially, step preparation has height ratio capacity and long circulation life Molybdenum sulfide based combined electrode material.The present invention prepares that raw material is cheap, and operating procedure is simple, high income, the charge-discharge performance of material It is excellent, it is convenient for industrialized production.The present invention improves the long circulating performance and rate capability of active material obvious.In addition, this Solvent used in inventing is water, and one of raw material is sugar etc., environmental-friendly and reproducible, low in cost, has preferable rule Modelling application potential, industrial prospect are good.
Detailed description of the invention
Fig. 1 is the XRD spectrum of sample obtained by embodiment and comparative example;Wherein a, b are the XRD of comparative example;C~f is to implement The XRD spectrum of sample prepared by example 1~4, Co-doped MoS2/ G/C-i, i=1,2,3,4, respectively correspond Examples 1 to 4;
Fig. 2 is the SEM photograph of sample obtained by embodiment and comparative example, and wherein a is comparative example Co-doped (cobalt doped) MoS2The compound SEM photograph of/graphene;B is comparative example Co-doped MoS2The compound SEM photograph of (cobalt doped)/carbon;C, d is The SEM photograph of sample prepared by embodiment 1;(scale in figure is 1 micron)
Electrode prepared by Fig. 3, the negative electrode material prepared for embodiment and comparative example is in 500mAg-1Charging and discharging currents it is close Cycle performance test curve under degree;
Fig. 4, electrode prepared by sample is prepared in 1Ag for Examples 1 to 4-1Charging and discharging currents density under cyclicity Energy test curve, wherein Co-doped MoS2/ G/C-i, i=1,2,3,4, respectively correspond Examples 1 to 4.
Specific embodiment
The present invention is described in further details with reference to embodiments.Production is not specified in agents useful for same or instrument and equipment Manufacturer, it is accordingly to be regarded as the conventional products that can be bought by market.
Embodiment 1:
35mL is measured, the glucose solution of 0.05mol/L takes the graphite oxide powder of 0.05g to be scattered in a certain amount of grape In sugar juice, abundant ultrasound 1h;After 0.2g sodium molybdate stirring 10min is added, 0.015g cobalt acetate ultrasonic agitation 15min is weighed, 0.4g thiocarbamide is added to stir to being completely dissolved.Reaction kettle is fitted into react for 24 hours in 200 DEG C of hydro-thermal casees.It is heavy to be cooled to room temperature centrifugation It forms sediment and collects product (ethyl alcohol is washed 2 times).Dry, 600 DEG C of argon gas are sintered 3h.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing Uniformly, 60 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with sodium piece by electrode in 2025 battery cases Pole, using polyethylene film as diaphragm, with 1M NaClO4It is electrolyte assembling electricity in EC:EMC:DMC (volume ratio 1/1/1)+5%FEC Pond carries out constant current charge-discharge test.
Embodiment 2
35mL is measured, the fructose soln of 0.02mol/L takes the graphite oxide powder of 0.005g to be scattered in a certain amount of glucose In solution, abundant ultrasound 1h;After 0.1g sodium molybdate stirring 10min is added, 0.015g cobalt acetate ultrasonic agitation 15min is weighed, is added Enter 0.5g thiocarbamide to stir to being completely dissolved.It is fitted into reaction kettle and reacts 10h in 220 DEG C of hydro-thermal casees.It is cooled to room temperature centrifugation It collects product (ethyl alcohol is washed 2 times).Dry, 400 DEG C of He gas are sintered 12h.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing Uniformly, 70 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with lithium piece by electrode in 2025 battery cases Pole, using polyethylene film as diaphragm, with 1M LiPF6EC/DEC (v/v=1/1) is that electrolyte assembled battery carries out constant current charge and discharge Electrical testing.
Embodiment 3
35mL is measured, the sucrose solution of 0.05mol/L takes the graphite oxide powder of 0.1g to be scattered in a certain amount of glucose molten In liquid, abundant ultrasound 1h;After 1g sodium molybdate stirring 10min is added, 0.025g cobalt acetate ultrasonic agitation 15min is weighed, 2g is added Thiocarbamide is stirred to being completely dissolved.It is fitted into reaction kettle and reacts 48h in 150 DEG C of hydro-thermal casees.It is cooled to room temperature centrifugation and collects production Object (ethyl alcohol is washed 2 times).It is dry, 800 DEG C of Ar/H2Gaseous mixture is sintered 12h.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing Uniformly, 60 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with sodium piece by electrode in 2025 battery cases Pole, using polyethylene film as diaphragm, with 1M NaClO4It is electrolyte assembling electricity in EC:EMC:DMC (volume ratio 1/1/1)+5%FEC Pond carries out constant current charge-discharge test.
Embodiment 4
35mL is measured, the maltose solution of 0.01mol/L takes the graphite oxide powder of 0.05g to be scattered in a certain amount of grape In sugar juice, abundant ultrasound 1h;After 0.2g sodium molybdate stirring 10min is added, 0.05g cobalt acetate ultrasonic agitation 15min is weighed, is added Enter 0.4g thiocarbamide to stir to being completely dissolved.Reaction kettle is fitted into react for 24 hours in 180 DEG C of hydro-thermal casees.It is cooled to room temperature centrifugation It collects product (ethyl alcohol is washed 2 times).Dry, 500 DEG C of argon gas are sintered 6h.
After sintered material is fully ground and carbon black and carboxymethyl cellulose according to 70: 15: 15 ratio, mixing Uniformly, 60 DEG C of vacuum drying 4h after film, are prepared combination electrode.It is to electricity with sodium piece by electrode in 2025 battery cases Pole, using polyethylene film as diaphragm, with 1M NaClO4It is electrolyte assembling electricity in EC:EMC:DMC (volume ratio 1/1/1)+5%FEC Pond carries out constant current charge-discharge test.
Material characterization and electrochemical property test
It is mutually tested below by object to the appearance structure of composite material and by cycle performance test prepared by the present invention The electrochemistry of composite material can be carried out test and characterization.
1, XRD analysis
Fig. 1 is the XRD spectrum of Examples 1 to 4.It can be seen from the chart, sample prepared by Examples 1 to 4 is corresponding MoS2Structure.In addition a steamed bun peak can be clearly apparent at 25 ° or so.The peak is the characteristic peak of amorphous carbon.Comparative example Co- doped MoS2Sample is then in 25 ° of characteristic peaks without the carbon.It is made that XRD analysis shows that agraphitic carbon structure is present in embodiment In standby sample.
2, morphology analysis
A is embodiment comparative example Co-doped MoS2The compound SEM photograph of/graphene, as can be seen that institute from photo The MoS of preparation2Structure has obvious stratiform structure type;B is embodiment comparative example Co-doped MoS2The compound SEM of/carbon shines Piece can be seen from the chart that grainy surface layer structure type is unobvious;C/d is that the SEM of sample prepared by embodiment 1 shines Piece, as can be seen that material prepared surface is almost without layer structure, completely presentation nutty structure from photo.
3, cycle performance is tested
Fig. 3 is electrode prepared by the negative electrode material of the comparative example preparation of embodiment in 500mAg-1Charging and discharging currents it is close Cycle performance test curve under degree, can be seen from the chart, simple MoS2Cycle performance is very poor, does not have substantially after 100 circulations There is capacity;After carrying out cobalt doped to material, electrode is prepared in 500mAg-1Charging and discharging currents density under reversible capacity obviously mention Height, 100 times circulation after be able to maintain 300mAhg-1Above reversible capacity.
Fig. 4 is that Examples 1 to 4 prepares electrode prepared by sample in 1Ag-1Charging and discharging currents density under cycle performance Test curve.Sample prepared by embodiment is used as sode cell cathode and preferable cycle performance is presented, and prepared electrode exists 1A·g-1Charging and discharging currents density it is lower 100 times circulation after be able to maintain 350mAhg-1Above reversible capacity compares Fig. 3 Comparative example material, reversible capacity greatly improves electrode under high currents.
In conclusion the present invention is prepared in cobalt doped molybdenum sulfide-graphene-carbon composite, graphene is as skeleton material Material, amorphous carbon act on active MoS as covering material2.The combination of two kinds of carbon materials protects MoS from inside and outside dual2 Material, so that active material particle great volume expansion in charge and discharge process is effectively inhibited, to greatly change It has been apt to the cycle performance of material.In addition cobalt doped equally has significant contribution to the conductivity of material and reversible capacity.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with the attached claims be protection Range.

Claims (8)

1. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method, which is characterized in that by the water-soluble of sugar It is proportionally added into cobalt salt, sodium molybdate, graphene oxide water solution and thiocarbamide in liquid, it is transferred to water after ultrasonic mixing is uniform Hydro-thermal reaction under fixed temperature in thermal response kettle prepares cobalt doped molybdenum sulfide-graphene-via sintering processes after washing, drying Carbon composite.
2. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method according to claim 1, feature It is, specifically includes the following steps:
(1) sugar juice of molar concentration is configured;
(2) graphite oxide powder is taken to be scattered in the sugar juice of step (1), 1 h of abundant ultrasound;
(3) sodium molybdate is added in above-mentioned steps, then weighs cobalt salt 30 min of ultrasound, is eventually adding thiocarbamide and stirs 1 h;
(4) mixed liquor obtained by step (3) is transferred in reaction kettle and reacts 10-48 h in 150-220 DEG C of hydro-thermal case;It is cooling, it takes out Filter, dry, cobalt doped molybdenum sulfide-graphene-carbon composite is prepared in tube furnace sintering.
3. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method according to claim 2, feature It is, the sugar juice is the aqueous solution of monosaccharide or disaccharide, and molar concentration is 0.01-0.1 mol/L.
4. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method according to claim 1 or 2, special Sign is that the additional amount of the graphite oxide powder is 0.05-0.5 times of sodium molybdate additional amount;The cobalt salt is rich in second One of the cobalt acetate and acetylacetone cobalt of acidic group or acetyl group, additional amount are 0.025-0.25 times of sodium molybdate additional amount; Thiocarbamide additional amount is 2~5 times of sodium molybdate additional amount.
5. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method according to claim 1 or 2, special Sign is, the sintering processes condition are as follows: in Ar, Ar/H2Heat treatment 1- is carried out for 400~800 DEG C under gaseous mixture or He atmosphere 12 h。
6. a kind of cobalt doped molybdenum sulfide-graphene-carbon composite preparation method according to claim 1 or 2, special Sign is that the doping mole of cobalt is 0.05-5% in the composite material;The content of molybdenum sulfide is 50-90%;Graphene contains Amount is 5-20%.
7. cobalt doped molybdenum sulfide-graphene-carbon composite that preparation method of any of claims 1 or 2 is prepared.
8. cobalt doped molybdenum sulfide-application of the graphene-carbon compound cathode materials in sodium-ion battery as claimed in claim 9.
CN201811487667.3A 2018-12-06 2018-12-06 A kind of cobalt doped molybdenum sulfide-graphene-carbon composite and its preparation method and application Pending CN109713258A (en)

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CN112436113A (en) * 2020-11-13 2021-03-02 内蒙古杉杉科技有限公司 Sodium-ion battery negative electrode material and preparation method and application thereof
CN112850690A (en) * 2021-01-08 2021-05-28 北京化工大学 Preparation method and sodium storage application of graphene-loaded double-transition metal sulfide composite material
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CN113241440A (en) * 2021-05-20 2021-08-10 中国科学院过程工程研究所 Molybdenum disulfide/sulfur-doped graphene composite material and preparation method and application thereof
CN113299893A (en) * 2021-05-22 2021-08-24 信阳师范学院 Molybdenum disulfide @ graphite alkyne composite material, and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110311122A (en) * 2019-07-12 2019-10-08 青岛大学 Carbon coating molybdenum disulfide/graphene nanocomposite material preparation method and application
CN111377481A (en) * 2020-03-20 2020-07-07 苏州科技大学 Application of cobalt-doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production
CN112072081A (en) * 2020-07-14 2020-12-11 广东工业大学 MXene material loaded with cobalt molybdenum sulfide and preparation method thereof
CN112436113A (en) * 2020-11-13 2021-03-02 内蒙古杉杉科技有限公司 Sodium-ion battery negative electrode material and preparation method and application thereof
CN112850690A (en) * 2021-01-08 2021-05-28 北京化工大学 Preparation method and sodium storage application of graphene-loaded double-transition metal sulfide composite material
CN113078302A (en) * 2021-03-09 2021-07-06 华北电力大学 Method for preparing sodium-ion battery composite negative electrode material by using large-interlayer-distance two-dimensional layered graphene-like loaded metal sulfide
CN113241440A (en) * 2021-05-20 2021-08-10 中国科学院过程工程研究所 Molybdenum disulfide/sulfur-doped graphene composite material and preparation method and application thereof
CN113241440B (en) * 2021-05-20 2022-08-05 中国科学院过程工程研究所 Molybdenum disulfide/sulfur-doped graphene composite material and preparation method and application thereof
CN113299893A (en) * 2021-05-22 2021-08-24 信阳师范学院 Molybdenum disulfide @ graphite alkyne composite material, and preparation method and application thereof

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