CN107452951A - 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, belong to sodium-ion battery field of material technology, the new XS using two step solvent structures2@YSe2Electrode material, as typical example, especially it is prepared for FeS2@FeSe2Electrode material has simultaneously carried out detailed measure.The preparation method is easy to operate, the cycle is short, cost is low；The FeS prepared as the invention of typical example2@FeSe2Electrode material has the characteristics that big specific capacity, the cycle life of overlength, excellent high rate performance, safe to use, cost is low and environment-friendly, has shown wide application prospect, the shortcomings that effectively overcoming the core shell structure electrode material of carbon coating.
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 technology
Lithium ion battery due to energy density it is high, have extended cycle life, high/low temperature strong adaptability and the spy such as green
Put and widely studied and applied.It is seldom yet with content of the lithium resource in the earth's crust（About 0.0065%）, and people
Constantly increase for the demand of intelligent grid, portable type electronic product and electric automobile, this, which allows for lithium resource, occurs seriously
Scarcity and result in the continuous rise of lithium ion battery price.For lithium metal, metallic sodium and lithium are in same master
Race is so as to showing similar physicochemical properties.Sodium resource reserve is abundant, widely distributed and cheap so that sodium simultaneously
Ion battery is favored as the potential replacer of lithium ion battery by researcher.But sodium-ion battery is compared to lithium ion
Battery there is also it is fatal the shortcomings that, its radius is 1.34 times of lithium ion radius, it is caused electricity during deintercalation
The deformation of pole material lattice structure and caving in for material morphology structure, so as to show unsatisfactory performance.Cause
This seeks 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 to possess it due to the reversible deintercalation of the smaller sodium ion difficult to realize of interlamellar spacing when it is as sodium-ion battery negative pole
Relatively low specific capacity.And Transition-metal dichalcogenide such as CoSe, MoS2, WS2And FeS2Deng due to similar with graphite
Layer structure and cheap, the features such as being readily available be considered as a kind of very promising sodium-ion battery material.And
And this kind of material as sodium-ion battery negative pole when not only every mole of metal ion can be reacted with multiple electronics, and
There is conversion and alloy reaction mechanism so that they have charming theoretical capacity.But only drawback is that work as sodium ion
Material can be caused to produce huge volumetric expansion during reversible deintercalation in these materials, caused between electrode material and electrolyte
Contact area is lost, while caving in for electrode material structure causes the dynamics of sodium ion deintercalation also can be significantly affected,
There is quickly decay in the final capacity for causing electrode material and life-span.Recently, researchers are keen to coat using carbon material
Transient metal sulfide goes solve above-mentioned problem so as to build the heterojunction structure of nucleocapsid.Such as Cho et al. is prepared for
The FeSe of carbon coating2@rGO composite nano-fiber materials obtain 412 mAh g after being enclosed as sodium-ion battery negative pole circulation 150-1.But the cycle life of the material of these carbon coatings still is below 2000 circles, can not meet to commercially produce on a large scale.This
Outside, carbon material can hinder entering for composite materials due to low theoretical capacity and tap density as the component units of electrode material
One step develops.Therefore, building a Core-shell structure material being made up of two kinds of different Transition-metal dichalcogenides can be very
The advantages of good combination each of which and then the shortcomings that overcome the core shell structure electrode material of current carbon coating.
The content of the invention
In view of this, 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 can provide excellent sodium storge quality, have broad application prospects.
To reach above-mentioned purpose, the present invention provides following technical scheme：
XS2@YSe2The preparation method of the anode material of lithium-ion battery of core shell structure, comprises the following steps：
（1）XS is prepared using solvent-thermal method2Micron ball intermediate product is as stock；
（2）By step（1）The intermediate product of middle gained is added in the precursor solution containing X or Y sources and selenium source, and by molten
The hot method of agent obtains XS2@YSe2Core-shell particles electrode material；
Wherein, described X and Y is each independently transition metal, preferably Fe, Co, Ni, Sb or Sn, and X and Y can be with identical
It is or different.
Further, described X, Y are Fe, its XS2@YSe2The preparation side of the anode material of lithium-ion battery of core shell structure
Method, comprise 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 suspends
Liquid is transferred in pyroreaction kettle, is put into air dry oven and is carried out pyroreaction, its relief reactor natural cooling, by reactor
In FeS2Micron ball is washed with deionized water and absolute ethyl alcohol, and is dried in vacuum drying chamber；
（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, is then added dropwise one
Quantitative hydrazine hydrate (N2H4.H2O) in above-mentioned solution and continue to stir, a certain amount of FeS for then preparing step (1)2It is micro-
Rice ball is added in above-mentioned mixed solution and stirred, and finally suspension is transferred in pyroreaction kettle, air dry oven is put into and enters
Row pyroreaction, its relief reactor natural cooling, by the FeS in reactor2@FeSe2Core-shell particles deionized water and anhydrous
Ethanol washs, and is then dried in vacuum drying chamber.
Further, the step（1）Middle source of iron is ferrous sulfate (FeSO4.7H2O), iron ammonium sulfate (Fe (NH4)2
(SO4)2.6H2) and frerrous chloride (FeCl O2.4H2O2) in one or more, sulphur source is ferrous sulfate (FeSO4.7H2O), sulphur
Urea (CH4N2S), sublimed sulfur or thioacetamide (CH3CSNH2) one or more.
Further, the step（1）The mol ratio of the source of iron of middle addition, sulphur source and urea is 1：（1~3）:（1~7）.
Further, the step（1）In organic mixed solution be N, N-dimethylformamide (C3H7) and ethylene glycol NO
((CH2OH)2)。
Further, the step（1）It is middle that suspension is transferred in 10 ~ 100 ml reactor into 150 ~ 200 DEG C of high temperature is anti-
Answer 8 ~ 12 hours.
Further, the step（2）Middle source of iron is iron ammonium sulfate (Fe (NH4)2(SO4)2.6H2O), ferrous sulfate
(FeSO4.7H2) and frerrous chloride (FeCl O2.4H2O2) in one or more, selenium source is selenium powder (Se).
Further, the step（2）The selenium source of middle addition and the ratio of hydrazine hydrate are 1g:(2.5~62.5) ml.
Further, the step（2）Source of iron, selenium source and the FeS of middle addition2The mol ratio of microballoon is 1:（2~4）：（1~3）.
Further, the step（2）It is middle that suspension is transferred to 150 ~ 200 DEG C of reactions of high temperature in 10 ~ 100ml reactor
10 ~ 24 hours.
The invention also discloses using XS made from the above method2@YSe2Core-shell particles electrode material is in sodium-ion battery
In application.
The beneficial effects of the present invention are：
The present invention utilizes the new XS of two step solvent structures2@YSe2（X, Y is transition metal）Core-shell particles electrode material
Material.Such electrode material has the cyclical stability, excellent high rate performance and big reversible capacity of overlength, can conduct
The negative material of sodium-ion battery uses, and preparation process is simple and convenient, the cost of raw material is cheap, and required preparation condition is relatively low,
It is easy to commercial applications.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, in the present invention using X, Y be Fe as
Example, is prepared for FeS2@FeSe2The anode material of lithium-ion battery of core shell structure simultaneously provides drawings described below and illustrated.
Fig. 1 is the gained FeS of embodiment 12The scanning electron microscope (SEM) photograph of microballoon, transmission electron microscope picture and energy spectrum diagram.
Fig. 2 is the gained FeS of embodiment 12The XRD of microballoon.
Fig. 3 is the gained FeS of embodiment 12@FeSe2The scanning electron microscope (SEM) photograph of core-shell particles electrode material, transmission electron microscope picture and energy
Spectrogram.
Fig. 4 is the gained FeS of embodiment 12@FeSe2The XRD of core-shell particles electrode material.
Fig. 5 is the gained FeS of embodiment 12@FeSe2The XPS figures of core-shell particles electrode material.
Fig. 6 is the gained FeS of embodiment 12@FeSe2Core-shell particles electrode material sweeps the CV curves of speed in difference.
Fig. 7 is the gained FeS of embodiment 12@FeSe2The high rate performance figure of core-shell particles electrode material.
Fig. 8 is with FeS2@FeSe2Half-cell prepared by core-shell particles electrode material is in 1 A g-1Circulation under current density
Test curve figure.
Fig. 9 is with FeS2@FeSe2Half-cell prepared by core-shell particles electrode material is in 5 A g-1Circulation under current density
Test curve figure.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail, but illustrated embodiment not as
Limitation of the invention.The experimental method of unreceipted actual conditions in preferred embodiment, generally according to normal condition, or according to examination
Condition proposed by agent manufacturer is carried out.
Embodiment 1
So that X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core shell structure
（1）Prepare FeS2Sphere material：
First, by 1 mmol FeSO4.7H2O is dissolved in mixed containing 15 ml N-N dimethylformamides and 20 ml ethylene glycol
Close and stirred 30 minutes in solution, then, 5 mmol urea is added in above-mentioned solution and stirred 30 minutes, finally will be above-mentioned
Suspension is transferred in 50ml autoclave, puts it into 180 DEG C of 12 hours of reaction of air dry oven.Finally by institute
Obtain product deionized water and absolute ethyl alcohol eccentric cleaning；
（2）Prepare FeS2@FeSe2Core-shell particles electrode material:
By 1 mmol Fe (NH4)2(SO4)2.6H2O and 2 mmol Se are dissolved in 30 ml deionized water, and stir 30
Minute.Then 4 ml hydrazine hydrate is added in above-mentioned solution and is stirred 30 minutes, by 1 mmol steps（1）Obtained FeS2It is micro-
Rice ball is added in above-mentioned solution and stirred 30 minutes.Finally above-mentioned suspension is transferred in 50 ml autoclave, will
It is put into 180 DEG C of 24 hours of reaction of air dry oven.Finally by products therefrom deionized water and absolute ethyl alcohol eccentric cleaning.
Embodiment 2
So that X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core shell structure
（1）Prepare FeS2Sphere material：
First, by 1 mmol Fe (NH4)2(SO4)2.6H2O is dissolved in containing 15 ml N-N dimethylformamides and 20 ml second
Stir 30 minutes in the mixed solution of glycol, then, 5 mmol urea is added in above-mentioned solution and stirs 30 minutes, most
Above-mentioned suspension is transferred in 50 ml autoclave afterwards, puts it into 180 DEG C of 12 hours of reaction of air dry oven.
Finally by products therefrom deionized water and absolute ethyl alcohol eccentric cleaning；
（2）Prepare FeS2@FeSe2Core-shell particles electrode material:
By 1 mmol FeCl2.4H2O2It is dissolved in 40 ml deionized water, and stirs 40 minutes with 4 mmol Se.Connect
The hydrazine hydrate that 10 ml are added in above-mentioned solution and stir 30 minutes, by 1 mmol steps（1）Obtained FeS2Micron ball adds
Enter into above-mentioned solution and stir 30 minutes.Finally above-mentioned suspension is transferred in 100 ml autoclave, put
Enter 200 DEG C of 10 hours of reaction of air dry oven.Finally by products therefrom deionized water and absolute ethyl alcohol eccentric cleaning.
Embodiment 3
So that X, Y are Fe as an example, FeS2@FeSe2The preparation method of the anode material of lithium-ion battery of core shell structure
（1）Prepare FeS2Sphere material：
First, by 1 mmol FeCl2.4H2O2 With 2 mmol CH4N2S is dissolved in containing 15 ml N-N dimethylformamides
With stirred in the mixed solution of 20 ml ethylene glycol 30 minutes, then, 5 mmol urea is added in above-mentioned solution and stirred
30 minutes, finally above-mentioned suspension is transferred in 50 ml autoclave, puts it into 180 DEG C of reactions of air dry oven
12 hours.Finally by products therefrom deionized water and absolute ethyl alcohol eccentric cleaning；
（2）Prepare FeS2@FeSe2Core-shell particles electrode material:
By 1 mmol Fe (NH4)2(SO4)2.6H2O and 3 mmol Se are dissolved in 40 ml deionized water, and stir 40
Minute.Then 8 ml hydrazine hydrate is added in above-mentioned solution and is stirred 30 minutes, by 1 mmol steps（1）Obtained FeS2It is micro-
Rice ball is added in above-mentioned solution and stirred 30 minutes.Finally above-mentioned suspension is transferred in 100 ml autoclave,
Put it into 150 DEG C of 20 hours of reaction of air dry oven.Secondary, anhydrous second finally is washed with deionized in products therefrom
Alcohol eccentric cleaning is once.
Embodiment 4
With the FeS prepared in embodiment 12@FeSe2Electrode material makes sodium-ion battery and the test of gained battery correlated performance
FeS made from Example 12@FeSe2Electrode material and acetylene black, CMC binding agents in mass ratio 60:30:10 mixing,
Appropriate deionized water is added, pasty state is ground in agate mortar, on the copper foil coated in a diameter of 13 mm, then will
Copper foil is dried in vacuo 12h in 120 DEG C, so as to obtain the negative plate of sodium-ion battery, then transfers them to the hand full of argon gas
The assembling of button cell is carried out in casing, button cell model is CR2032, and metallic sodium piece is used as to electrode, and barrier film is polypropylene
Microporous barrier Celgard 2400 or glass fibre, electrolyte are 1mol/L NaCF3SO3Solution（Solvent is diethylene glycol diformazan
Ethereal solution）.After the battery assembled is placed into 6 more than h, electrochemical property test, voltage model are carried out in Land test systems
Enclose for 0.5 ~ 2.9 V.
Fig. 1 is FeS2ESEM, transmission electron microscope and the energy spectrum diagram of micron ball.By scanning electron microscope (SEM) photograph it can be seen that big scale
The smooth uniform FeS of but pattern in face2Micron ball is packed together, and each micron bulb diameter is about in 2 um.By FeS2Micron ball
Energy spectrum diagram shows that the material includes Fe and S elements, 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 Emission in Cubic crystalline texture,
And the presence of other miscellaneous peaks is not detected, illustrate synthesized FeS2Micron ball has higher purity.
Fig. 3 is FeS2@FeSe2ESEM, transmission electron microscope and the energy spectrum diagram of nucleocapsid micron ball.Can be with by scanning electron microscope (SEM) photograph
Find out that exhibiting high surface is coarse but the uniform micron ball of pattern is packed together, and each microsphere diameter remains within a 2 um left sides
It is right.And the presence of core shell structure is clearly observed 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 elements, 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 is by standing
The FeS of square phase2With the FeSe of orthorhombic phase2Form and they have good crystal structure, do not detect other miscellaneous peaks in addition
In the presence of illustrating synthesized FeS2@FeSe2Nucleocapsid micron ball has higher purity.
Fig. 5 is FeS2@FeSe2The x-ray photoelectron energy spectrum diagram 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 cyclic voltammetric under speed in difference（CV）Test.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 0.1 A g-1Change procedure in, its discharge capacity is by 203 mAh g-1Increase to 596 mAh g-1, explanation
FeS2@FeSe2Core-shell material has excellent high rate performance.
Fig. 8 is FeS2@FeSe2Core-shell particles electrode material is in 1 A g-1Cyclical stability test, as seen from the figure, electricity
Its specific discharge capacity still has 350 mAh g after the circle of pole circulation 2700-1, capacity retention rate is 97%, and it is outstanding to illustrate that the material is shown
Cycle performance.
Fig. 9 is FeS2@FeSe2Core-shell particles electrode material is in 5 A g-1Cyclical stability test, as seen from the figure, electricity
Its specific discharge capacity still has 301.5 mAh g after the circle of pole circulation 3850-1, capacity retention rate is 105.5%, illustrates that the material shows
Go out outstanding cycle performance.
It should be noted that in the present invention, the either corresponding dripping quantity of selection, the reaction temperature of source of iron, sulphur source and selenium source
The parameters such as degree, reaction time can be made corresponding adjustment by common knowledge.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art 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, it is characterised in that comprise the following steps：
（1）XS is prepared using solvent-thermal method2Micron ball intermediate product is as stock；
（2）By step（1）The intermediate product of middle gained is added in the precursor solution containing X or Y sources and selenium source, and by molten
The hot method of agent obtains XS2@YSe2Core-shell particles electrode material；
Wherein, described X and Y is each independently transition metal, preferably Fe, Co, Ni, Sb or Sn, and X and Y can be with identical
It is or different.
2. preparation method as claimed in claim 1, it is characterised in that described X, Y are Fe.
3. preparation method as claimed in claim 2, it is characterised in that comprise 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 suspends
Liquid is transferred in pyroreaction kettle, is put into air dry oven and is carried out pyroreaction, its relief reactor natural cooling, by reactor
In FeS2Micron ball is washed with deionized water and absolute ethyl alcohol, and is dried in vacuum drying chamber；
（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, is then added dropwise one
Quantitative hydrazine hydrate (N2H4.H2O) in above-mentioned solution and continue to stir, then by step（1）A certain amount of FeS prepared2It is micro-
Rice ball is added in above-mentioned mixed solution and stirred, and finally suspension is transferred in pyroreaction kettle, air dry oven is put into and enters
Row pyroreaction, its relief reactor natural cooling, by the FeS in reactor2@FeSe2Core-shell particles deionized water and anhydrous
Ethanol washs, and is then dried in vacuum drying chamber.
4. preparation method according to claim 3, it is characterised in that the step（1）Middle source of iron is ferrous sulfate
(FeSO4.7H2O), iron ammonium sulfate (Fe (NH4)2(SO4)2.6H2) and frerrous chloride (FeCl O2.4H2O2) in one kind or more
Kind, sulphur source is ferrous sulfate (FeSO4.7H2O), thiocarbamide (CH4N2S), sublimed sulfur or thioacetamide (CH3CSNH2) a kind of or more
Kind.
5. preparation method according to claim 3, it is characterised in that the step（1）Source of iron, sulphur source and the urine of middle addition
The mol ratio of element is 1：（1~3）:（1~7）.
6. preparation method according to claim 3, it is characterised in that the step（1）In organic mixed solution be N, N bis-
NMF (C3H7) and ethylene glycol ((CH NO2OH)2)。
7. preparation method according to claim 3, it is characterised in that the step（1）It is middle suspension is transferred to 10 ~
150 ~ 200 DEG C of high temperature reacts 8 ~ 12 hours in 100 ml reactor.
8. preparation method according to claim 3, it is characterised in that the step（2）Middle source of iron is iron ammonium sulfate (Fe
(NH4)2(SO4)2.6H2O), ferrous sulfate (FeSO4.7H2) and frerrous chloride (FeCl O2.4H2O2) in one or more, selenium
Source is selenium powder (Se).
9. preparation method according to claim 3, it is characterised in that the step（2）The selenium source and hydrazine hydrate of middle addition
Ratio be 1g:(2.5~62.5) ml.
10. preparation method according to claim 3, it is characterised in that the step（2）The source of iron of middle addition, selenium source and
FeS2The mol ratio of microballoon is 1:（2~4）：（1~3）.
11. preparation method according to claim 3, it is characterised in that the step（2）It is middle suspension is transferred to 10 ~
150 ~ 200 DEG C of high temperature reacts 10 ~ 24 hours in 100ml reactor.
12. using XS made from any one of claim 1~11 methods described2@YSe2Core-shell particles electrode material is in sodium ion
Application in battery.
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|---|---|---|---|---|
| CN108172406A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material |
| CN109148864A (en) * | 2018-09-06 | 2019-01-04 | 欣旺达电子股份有限公司 | Ferrous disulfide composite negative pole material, preparation method and battery |
| CN109437123A (en) * | 2018-10-16 | 2019-03-08 | 中山高容新能源科技有限公司 | The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes |
| CN109461902A (en) * | 2018-09-29 | 2019-03-12 | 大连理工大学 | A kind of preparation method and applications of two ferrous selenides/honeycomb carbon composite |
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN113130851A (en) * | 2021-04-22 | 2021-07-16 | 长江师范学院 | ASx/BSyComposite heterogeneous electrode material and preparation method and application thereof |
| CN113745475A (en) * | 2021-08-23 | 2021-12-03 | 哈尔滨工程大学 | Graphene/iron diselenide composite material for lithium ion battery cathode material and preparation method thereof |
| CN114023931A (en) * | 2021-09-28 | 2022-02-08 | 多助科技(武汉)有限公司 | Iron diselenide coated nitrogen-carbon doped FeS core-shell structure composite material and preparation and application thereof |
| CN115911286A (en) * | 2022-10-27 | 2023-04-04 | 哈尔滨理工大学 | Preparation method and application of iron selenide/molybdenum selenide heterostructure electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424248A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Synthesis of nano hollow balls of zinc selenide |
| US20060088785A1 (en) * | 2004-10-22 | 2006-04-27 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material, thermal development method of the same, and thermal development apparatus for the same |
| CN106876676A (en) * | 2017-03-29 | 2017-06-20 | 武汉理工大学 | NiS classification micron balls of carbon shell cladding and its preparation method and application |
-
2017
- 2017-08-11 CN CN201710686776.7A patent/CN107452951B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424248A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Synthesis of nano hollow balls of zinc selenide |
| US20060088785A1 (en) * | 2004-10-22 | 2006-04-27 | Konica Minolta Medical & Graphic, Inc. | Silver salt photothermographic dry imaging material, thermal development method of the same, and thermal development apparatus for the same |
| CN106876676A (en) * | 2017-03-29 | 2017-06-20 | 武汉理工大学 | NiS classification micron balls of carbon shell cladding and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HONGBO GENG 等: "Co9S8/MoS2 yolk-shell spheres for advanced Li/Na storage", 《SMALL》 * |
| NGUYEN XUAN CA等: "Type-2 CdS/ZnSe core/shell heterostructures；UV-vis absorption, photoluminescence and Raman scattering studies", 《NANOTECHNOLOGY 》 * |
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| CN108172406B (en) * | 2017-12-29 | 2020-04-21 | 山东大学 | FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material |
| CN108172406A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material |
| CN109148864A (en) * | 2018-09-06 | 2019-01-04 | 欣旺达电子股份有限公司 | Ferrous disulfide composite negative pole material, preparation method and battery |
| CN109461902A (en) * | 2018-09-29 | 2019-03-12 | 大连理工大学 | A kind of preparation method and applications of two ferrous selenides/honeycomb carbon composite |
| CN109437123B (en) * | 2018-10-16 | 2022-05-31 | 中山高容新能源科技有限公司 | Selenium-doped ferrous disulfide carbon-coated composite material and preparation method and application thereof |
| CN109437123A (en) * | 2018-10-16 | 2019-03-08 | 中山高容新能源科技有限公司 | The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes |
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN113130851A (en) * | 2021-04-22 | 2021-07-16 | 长江师范学院 | ASx/BSyComposite heterogeneous electrode material and preparation method and application thereof |
| CN113130851B (en) * | 2021-04-22 | 2022-03-25 | 长江师范学院 | ASx/BSyComposite heterogeneous electrode material and preparation method and application thereof |
| CN113745475A (en) * | 2021-08-23 | 2021-12-03 | 哈尔滨工程大学 | Graphene/iron diselenide composite material for lithium ion battery cathode material and preparation method thereof |
| 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 |
| CN114023931A (en) * | 2021-09-28 | 2022-02-08 | 多助科技(武汉)有限公司 | Iron diselenide coated nitrogen-carbon doped FeS core-shell structure composite material and preparation and application thereof |
| CN115911286A (en) * | 2022-10-27 | 2023-04-04 | 哈尔滨理工大学 | Preparation method and application of iron selenide/molybdenum selenide heterostructure electrode material |
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