CN107452951B - XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure - Google Patents
XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure Download PDFInfo
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Abstract
The present invention relates to XS2@YSe2The preparation method of core-shell structure electrode material, wherein X, Y system transition metal element, belong to sodium-ion battery field of material technology, utilize the novel XS of two step solvent structures2@YSe2Electrode material is especially prepared for FeS as typical example2@FeSe2Electrode material has simultaneously carried out detailed measurement.The preparation method is easy to operate, the period is short, at low cost；FeS as the invention preparation of typical example2@FeSe2Electrode material have the characteristics that big specific capacity, the cycle life of overlength, excellent high rate performance, using safe, at low cost and environmental-friendly, the shortcomings that having shown wide application prospect, effectively overcome carbon-coated core-shell structure electrode material.
Description
Technical field
The invention belongs to sodium-ion battery field of material technology, and in particular to XS2@YSe2The system of core-shell particles electrode material
Preparation Method.
Background technique
Lithium ion battery due to it is high with energy density, have extended cycle life, high/low temperature is adaptable and environmentally protective etc. special
It puts and is widely studied and applied.However since content of the lithium resource in the earth's crust is seldom (about 0.0065%), and people
The demand of smart grid, portable electronic product and electric car is constantly increased, this allow for lithium resource occur it is tight
The scarcity of weight and the continuous rise for resulting in lithium ion battery price.For lithium metal, metallic sodium and lithium are in same
Main group is to show similar physicochemical properties.Simultaneously sodium resource reserve it is abundant, it is widely distributed and it is cheap so that
Favor of the sodium-ion battery as the potential replacer of lithium ion battery by researcher.But sodium-ion battery compared to lithium from
For sub- battery there is also fatal disadvantage, its radius is 1.34 times of lithium ion radius, will cause it during deintercalation
The deformation of electrode material lattice structure and the collapsing of material morphology structure, to show unsatisfactory performance.
Therefore seek that there is the electrode material of larger interlamellar spacing to have great importance.
For the carbon material of layer structure, they have been widely used in the lithium ion battery of business, but
It is reversible deintercalation when it is as sodium-ion battery cathode due to the smaller sodium ion difficult to realize of interlamellar spacing, possesses it
Relatively low specific capacity.And Transition-metal dichalcogenide such as CoSe, MoS2, WS2And FeS2Deng similar with graphite due to having
Layer structure and cheap, the features such as being easy to get be considered as a kind of very promising sodium-ion battery material.And
And this kind of material as sodium-ion battery cathode when not only every mole of metal ion can react with multiple electronics, but also
There is conversion and alloy reaction mechanisms, so that they have charming theoretical capacity.But only drawback is that work as sodium ion
Material can be made to generate huge volume expansion when reversible deintercalation in these materials, caused between electrode material and electrolyte
Contact area is lost, while the collapsing of electrode material structure causes the dynamics of sodium ion deintercalation also to will receive apparent influence,
The capacity of electrode material and service life is finally made quickly decaying occur.Recently, researchers are keen to coat using carbon material
Heterojunction structure of the transient metal sulfide to construct nucleocapsid goes to solve the problems, such as above-mentioned.Such as Cho et al. is prepared for
Carbon-coated FeSe2@rGO composite nano-fiber material obtains 412mAh g after enclosing as sodium-ion battery cathode circulation 150-1.But the cycle life of these carbon-coated materials still is below 2000 circles, is unable to satisfy and commercially produces on a large scale.This
Outside, carbon material as electrode material component units due to low theoretical capacity and tap density can hinder composite materials into
The development of one step.Therefore, constructing one will be very by the Core-shell structure material that two kinds of different Transition-metal dichalcogenides form
The advantages of combination each got well, overcomes the shortcomings that current carbon-coated core-shell structure electrode material in turn.
Summary of the invention
In view of this, the object of the present invention is to provide XS2@YSe2The anode material of lithium-ion battery of core-shell structure
Preparation method, the electrode material of preparation are capable of providing excellent sodium storge quality, have broad application prospects.
In order to achieve the above objectives, the invention provides the following technical scheme:
XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure, includes the following steps:
(1) XS is prepared using solvent-thermal method2Micron ball intermediate product is as basic material；
(2) intermediate product obtained in step (1) is added in the precursor solution containing the source X or Y and selenium source, and led to
It crosses solvent-thermal method and obtains XS2@YSe2Core-shell particles electrode material；
Wherein, the X and Y is each independently transition metal, preferably Fe, Co, Ni, Sb or Sn, and X and Y can phases
It is same or different.
Further, described X, Y are Fe, XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure,
Include the following steps:
(1) by a certain amount of source of iron, sulphur source and urea (CH4N2O it) is added in organic mixed solution and stirs, then will
Suspension is transferred in pyroreaction kettle, is put into air dry oven and is carried out pyroreaction, allows reaction kettle natural cooling thereafter, will be anti-
Answer the FeS in kettle2Micron ball is washed with deionized water and dehydrated alcohol, and is dried in a vacuum drying oven；
(2) a certain amount of source of iron and selenium source are dissolved in a certain amount of deionized water first and continue to stir, then dripped
Add a certain amount of hydrazine hydrate i.e. N2H4.H2O in the above solution and continues to stir, then by a certain amount of of step (1) preparation
FeS2Micron ball is added in above-mentioned mixed solution and stirs, and finally suspension is transferred in pyroreaction kettle, and it is dry to be put into air blast
Dry case carries out pyroreaction, allows reaction kettle natural cooling thereafter, by the FeS in reaction kettle2@FeSe2Core-shell particles deionized water
It washs with dehydrated alcohol, then dries in a vacuum drying oven.
Further, source of iron is one of ferrous sulfate, iron ammonium sulfate and frerrous chloride or more in the step (1)
Kind, sulphur source is that ferrous sulfate, thiocarbamide, sublimed sulfur or thioacetamide are one or more.
Further, the molar ratio of the source of iron, sulphur source and the urea that are added in the step (1) is 1:(1~3): (1~7).
Further, organic mixed solution is N, N dimethyl formyl, that is, C in the step (1)3H7NO and ethylene glycol are
(CH2OH)2。
Further, in the step (1) by suspension be transferred in the reaction kettle of 10~100ml 150~200 DEG C of high temperature it is anti-
It answers 8~12 hours.
Further, source of iron is iron ammonium sulfate, one of ferrous sulfate and frerrous chloride or more in the step (2)
Kind, selenium source is selenium powder (Se).
Further, the ratio of the selenium source and hydrazine hydrate that are added in the step (2) is 1g:(2.5~62.5) ml.
Further, source of iron, selenium source and the FeS being added in the step (2)2The molar ratio of microballoon is 1:(2~4): (1~
3)。
Further, in the step (2) by suspension be transferred in the reaction kettle of 10~100ml 150~200 DEG C of high temperature it is anti-
It answers 10~24 hours.
The invention also discloses using XS made from the above method2@YSe2Core-shell particles electrode material is in sodium-ion battery
Application.
The beneficial effects of the present invention are:
The present invention utilizes the novel XS of two step solvent structures2@YSe2(X, Y are transition metal) core-shell particles electrode
Material.Such electrode material has cyclical stability, excellent high rate performance and the big reversible capacity of overlength, can make
Used for the negative electrode material of sodium-ion battery, and preparation process is simple and convenient, the cost of raw material is cheap, required preparation condition compared with
It is low, it is convenient for commercial applications.
Detailed description of the invention
It with X, Y is that Fe is in the present invention to keep the purpose of the present invention, technical scheme and beneficial effects clearer
Example, is prepared for FeS2@FeSe2The anode material of lithium-ion battery of core-shell structure simultaneously provides following attached drawing and is illustrated:
Fig. 1 is 1 gained FeS of embodiment2The scanning electron microscope (SEM) photograph of microballoon, transmission electron microscope picture and energy spectrum diagram；
Fig. 2 is 1 gained FeS of embodiment2The XRD diagram of microballoon；
Fig. 3 is 1 gained FeS of embodiment2@FeSe2The scanning electron microscope (SEM) photograph of core-shell particles electrode material, transmission electron microscope picture and energy
Spectrogram；
Fig. 4 is 1 gained FeS of embodiment2@FeSe2The XRD diagram of core-shell particles electrode material；
Fig. 5 is 1 gained FeS of embodiment2@FeSe2The XPS of core-shell particles electrode material schemes；
Fig. 6 is 1 gained FeS of embodiment2@FeSe2Core-shell particles electrode material sweeps the CV curve of speed in difference.
Fig. 7 is 1 gained FeS of embodiment2@FeSe2The high rate performance figure of core-shell particles electrode material；
Fig. 8 is with FeS2@FeSe2The half-cell of core-shell particles electrode material preparation is in 1Ag-1Circulation under current density is surveyed
Try curve graph；
Fig. 9 is with FeS2@FeSe2The half-cell of core-shell particles electrode material preparation is in 5Ag-1Circulation under current density is surveyed
Try curve graph；
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail, but illustrated embodiment not as
Limitation of the invention.Test method without specific conditions in preferred embodiment, usually according to normal condition, or according to examination
Condition proposed by agent manufacturer carries out.
Embodiment 1
By taking X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core-shell structure
(1) FeS is prepared2Sphere material:
Firstly, by the FeSO of 1mmol4.7H2O is dissolved in mixed containing 15ml N-N dimethylformamide and 20ml ethylene glycol
It closes and is stirred 30 minutes in solution, then, the urea of 5mmol is added in above-mentioned solution and is stirred 30 minutes, it finally will be above-mentioned
Suspension is transferred in the autoclave of 50ml, puts it into 180 DEG C of air dry oven 12 hours of reaction.Finally by gained
Product deionized water and dehydrated alcohol eccentric cleaning；
(2) FeS is prepared2@FeSe2Core-shell particles electrode material:
By the Fe (NH of 1mmol4)2(SO4)2.6H2O and 2mmol Se is dissolved in the deionized water of 30ml, and stirs 30
Minute.Then the hydrazine hydrate of 4ml is added in the above solution and stirs 30 minutes, by FeS made from 1mmol step (1)2Micron
Ball is added in above-mentioned solution and stirs 30 minutes.Finally above-mentioned suspension is transferred in the autoclave of 50ml, by it
It is put into 180 DEG C of air dry oven 24 hours of reaction.Finally by products therefrom deionized water and dehydrated alcohol eccentric cleaning.
Embodiment 2
By taking X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core-shell structure
(1) FeS is prepared2Sphere material:
Firstly, by the Fe (NH of 1mmol4)2(SO4)2.6H2O is dissolved in containing 15ml N-N dimethylformamide and 20ml
It is stirred in the mixed solution of ethylene glycol 30 minutes, then, the urea of 5mmol is added in above-mentioned solution and is stirred 30 minutes,
Finally above-mentioned suspension is transferred in the autoclave of 50ml, puts it into 180 DEG C of air dry oven 12 hours of reaction.
Finally by products therefrom deionized water and dehydrated alcohol eccentric cleaning；
(2) FeS is prepared2@FeSe2Core-shell particles electrode material:
By the FeCl of 1mmol2.4H2O and 4mmol Se is dissolved in the deionized water of 40ml, and is stirred 40 minutes.Then
The hydrazine hydrate of 10ml is added in the above solution and stirs 30 minutes, by FeS made from 1mmol step (1)2Micron ball is added to
In above-mentioned solution and stir 30 minutes.Finally above-mentioned suspension is transferred in the autoclave of 100ml, puts it into air blast
200 DEG C of drying box 10 hours of reaction.Finally by products therefrom deionized water and dehydrated alcohol eccentric cleaning.
Embodiment 3
By taking X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core-shell structure
(1) FeS is prepared2Sphere material:
Firstly, by the FeCl of 1mmol2.4H2The CH of O and 2mmol4N2S is dissolved in containing 15ml N-N dimethylformamide
With stirred in the mixed solution of 20ml ethylene glycol 30 minutes, then, the urea of 5mmol is added in above-mentioned solution and stirs 30
Minute, finally above-mentioned suspension is transferred in the autoclave of 50ml, 180 DEG C of air dry oven is put it into and reacts 12
Hour.Finally by products therefrom deionized water and dehydrated alcohol eccentric cleaning；
(2) FeS is prepared2@FeSe2Core-shell particles electrode material:
By the Fe (NH of 1mmol4)2(SO4)2.6H2O and 3mmol Se is dissolved in the deionized water of 40ml, and stirs 40
Minute.Then the hydrazine hydrate of 8ml is added in the above solution and stirs 30 minutes, by FeS made from 1mmol step (1)2Micron
Ball is added in above-mentioned solution and stirs 30 minutes.Finally above-mentioned suspension is transferred in the autoclave of 100ml, by it
It is put into 150 DEG C of air dry oven 20 hours of reaction.Secondary, dehydrated alcohol finally is washed with deionized in products therefrom to be centrifuged
Cleaning is primary.
Embodiment 4
With the FeS prepared in embodiment 12@FeSe2Electrode material makes sodium-ion battery and gained battery correlated performance is surveyed
Examination
FeS made from Example 12@FeSe2Electrode material and acetylene black, CMC binder 60:30:10 in mass ratio are mixed
It closes, adds suitable deionized water, be ground to paste in the agate mortar, on the copper foil for being 13mm coated in diameter, then
Copper foil is then transferred them to obtain the negative electrode tab of sodium-ion battery full of argon gas in 120 DEG C of vacuum drying 12h
The assembling of button cell is carried out in glove box, button cell model is CR2032, and metallic sodium piece is used as to electrode, and diaphragm is poly- third
Alkene microporous barrier Celgard 2400 or glass fibre, electrolyte are the NaCF of 1mol/L3SO3(solvent is diethylene glycol two to solution
Methyl ether solution).After assembled battery is placed 6h or more, electrochemical property test, voltage are carried out in Land test macro
Range is 0.5~2.9V.
Fig. 1 is FeS2Scanning electron microscope, transmission electron microscope and the energy spectrum diagram of micron ball.By scanning electron microscope (SEM) photograph it can be seen that big scale
Face FeS smooth of uniform morphology2Micron ball is packed together, and each micron of bulb diameter is about in 2um.By FeS2Micron ball
Energy spectrum diagram shows that the material includes Fe and S element, and two kinds of elements are uniformly distributed on micron ball.
Fig. 2 is FeS2The X-ray diffractogram of micron ball, it can be seen that the material has good cubic phase crystalline texture,
And do not detect the presence of other miscellaneous peaks, illustrate synthesized FeS2Micron ball purity with higher.
Fig. 3 is FeS2@FeSe2Scanning electron microscope, transmission electron microscope and the energy spectrum diagram of nucleocapsid micron ball.It can be with by scanning electron microscope (SEM) photograph
Find out that exhibiting high surface is coarse but micron ball of uniform morphology is packed together, and each microsphere diameter remains within the left side 2um
It is right.And it clearly observed the presence of core-shell structure by projecting Electronic Speculum.By FeS2@FeSe2Nucleocapsid micron ball carries out power spectrum
The bright core-shell material of chart includes Fe, S and Se element, and these three elements are uniformly distributed on micron ball.
Fig. 4 is FeS2@FeSe2The X diffraction of nucleocapsid micron ball carries out material phase analysis.As seen from the figure, the core-shell structure by cube
The FeS of phase2With the FeSe of orthorhombic phase2It forms and they has good crystal structure, furthermore do not detect depositing for other miscellaneous peaks
Illustrating synthesized FeS2@FeSe2Nucleocapsid micron ball purity with higher.
Fig. 5 is FeS2@FeSe2The x-ray photoelectron spectroscopy figure of nucleocapsid micron ball.As seen from the figure, the material is mainly by Fe,
Tri- kinds of element compositions of Se and S.
Fig. 6 is FeS2@FeSe2Core-shell particles electrode material sweeps the test of the cyclic voltammetric (CV) under speed in difference.It can by figure
Know, all curve detections to the presence for there are 6 redox peaks, and curve, with fast increase is swept, curve shape holding is good,
Illustrate FeS2@FeSe2The high rate performance that core-shell material has had.
Fig. 7 is FeS2@FeSe2The high rate performance test chart of core-shell particles electrode material.As seen from the figure, the material is in electric current
Density is by 10 to 0.1A g-1Change procedure in, discharge capacity is by 203mAh g-1Increase to 596mAh g-1, illustrate FeS2@
FeSe2Core-shell material has excellent high rate performance.
Fig. 8 is FeS2@FeSe2Core-shell particles electrode material is in 1Ag-1Cyclical stability test, as seen from the figure, electrode follows
Its specific discharge capacity still has 350mAh g after ring 2700 encloses-1, capacity retention rate is 97%, illustrates that the material shows outstanding follow
Ring performance.
Fig. 9 is FeS2@FeSe2Core-shell particles electrode material is in 5Ag-1Cyclical stability test, as seen from the figure, electrode follows
Its specific discharge capacity still has 301.5mAh g after ring 3850 encloses-1, capacity retention rate is 105.5%, illustrates that the material shows outstanding person
Cycle performance out.
It should be noted that in the present invention, the either corresponding dripping quantity of the selection of source of iron, sulphur source and selenium source, reaction temperature
The parameters such as degree, reaction time can be made corresponding adjustment by common knowledge.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (12)
1.XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure, which comprises the steps of:
(1) XS is prepared using solvent-thermal method2Micron ball intermediate product is as basic material；
(2) intermediate product obtained in step (1) is added in the mixed solution containing the source X or Y and selenium source, and passes through solvent
Thermal method obtains XS2@YSe2Core-shell particles electrode material；
Wherein, the X and Y is Fe, Co, Ni, Sb or Sn, and X and Y can be identical or different.
2. preparation method as described in claim 1, which is characterized in that described X, Y are Fe.
3. preparation method as claimed in claim 2, which comprises the steps of:
(1) by a certain amount of source of iron, sulphur source and urea (CH4N2O it) is added in organic mixed solution and stirs, then will suspend
Liquid is transferred in pyroreaction kettle, is put into air dry oven and is carried out pyroreaction, reaction kettle natural cooling is allowed thereafter, by reaction kettle
In FeS2Micron ball is washed with deionized water and dehydrated alcohol, and is dried in a vacuum drying oven；
(2) a certain amount of source of iron and selenium source are dissolved in a certain amount of deionized water first and continue to stir, water is then added dropwise
Close hydrazine, that is, N2H4.H2O, and continue to stir, it is subsequently added into the FeS of step (1) preparation2Micron ball, and stir, finally by suspension
It is transferred in pyroreaction kettle, is put into air dry oven and carries out pyroreaction, allow reaction kettle natural cooling thereafter, it will be in reaction kettle
FeS2@FeSe2Core-shell particles are washed with deionized water and dehydrated alcohol, are then dried in a vacuum drying oven.
4. preparation method according to claim 3, which is characterized in that source of iron is ferrous sulfate, sulfuric acid in the step (1)
One of ferrous ammonium and frerrous chloride are a variety of, and sulphur source is that ferrous sulfate, thiocarbamide, sublimed sulfur and thioacetamide are a kind of or more
Kind.
5. preparation method according to claim 3, which is characterized in that source of iron, sulphur source and the urine being added in the step (1)
The molar ratio of element is 1:(1~3): (1~7).
6. preparation method according to claim 3, which is characterized in that organic mixed solution is N, N bis- in the step (1)
Methylformamide, that is, C3H7NO and ethylene glycol are (CH2OH)2。
7. preparation method according to claim 3, which is characterized in that suspension is transferred to 10 in the step (1)~
It is reacted 8~12 hours for 150~200 DEG C of high temperature in the reaction kettle of 100ml.
8. preparation method according to claim 3, which is characterized in that source of iron is iron ammonium sulfate, sulphur in the step (2)
One of sour ferrous and frerrous chloride is a variety of, and selenium source is selenium powder (Se).
9. preparation method according to claim 3, which is characterized in that the selenium source and hydrazine hydrate being added in the step (2)
Ratio be 1g:(2.5~62.5) ml.
10. preparation method according to claim 3, which is characterized in that the source of iron that is added in the step (2), selenium source and
FeS2The molar ratio of micron ball is 1:(2~4): (1~3).
11. preparation method according to claim 3, which is characterized in that suspension is transferred to 10 in the step (2)~
It is reacted 10~24 hours for 150~200 DEG C of high temperature in the reaction kettle of 100ml.
12. using XS made from any one of claim 1~11 the method2@YSe2Core-shell particles electrode material is in sodium ion electricity
Application in pond.
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| CN113745475B (en) * | 2021-08-23 | 2022-10-14 | 哈尔滨工程大学 | Graphene/iron diselenide composite material for lithium ion battery cathode material and preparation method thereof |
| CN114023931B (en) * | 2021-09-28 | 2023-06-13 | 多助科技(武汉)有限公司 | FeSe 2 Nitrogen-carbon-coated FeS core-shell structure composite material and preparation and application thereof |
| CN115911286B (en) * | 2022-10-27 | 2024-10-01 | 哈尔滨理工大学 | Preparation method and application of iron selenide/molybdenum selenide heterostructure electrode material |
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