CN109873134A - Iron-based chalcogenide, electrode material, the sodium-ion battery and preparation method thereof of in-situ carbon encapsulation - Google Patents
Iron-based chalcogenide, electrode material, the sodium-ion battery and preparation method thereof of in-situ carbon encapsulation Download PDFInfo
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- CN109873134A CN109873134A CN201910042548.5A CN201910042548A CN109873134A CN 109873134 A CN109873134 A CN 109873134A CN 201910042548 A CN201910042548 A CN 201910042548A CN 109873134 A CN109873134 A CN 109873134A
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of iron-based chalcogenides of in-situ carbon encapsulation, electrode material, sodium-ion battery and preparation method thereof, the preparation method prepares body MIL-88-Fe early period by simple solvent thermal process, it then realizes by the way that step pyrolysis is synchronous to the vulcanization (or selenizing) of presoma and carbon encapsulation process, successfully realizes that iron ion is converted in situ into Fe in presoma7S8Or Fe7Se8, and be encapsulated in carbon skeleton made of synchronous conversion.And electrode material is prepared as sodium-ion battery cathode using compound prepared by the present invention, present the characteristics such as height ratio capacity, long circulation life and excellent high rate performance, it is provided simultaneously with the advantage that environmental-friendly, safety coefficient is high, at low cost, has shown wide application prospect.
Description
Technical field
The present invention relates to anode material of lithium-ion battery fields, and in particular to the iron-based chalcogenide of in-situ carbon encapsulation,
Electrode material, sodium-ion battery and preparation method thereof.
Background technique
It is consumed along with the fast development and progress, a large amount of fossil fuels of human civilization, environmental pollution and energy danger
Machine has become the crisis for restricting social stability development.Develop emerging renewable energy, such as: solar energy, wind energy undoubtedly will
As the only way which must be passed of development of human civilization, and the intermittent problems needs that renewable energy is faced are settled properly.
In the development course of energy storage technology, secondary energy storage battery-lithium ion battery, performer key player, still, existing
Under the modern extensive increasingly increased background of energy storage demand, the application of lithium ion battery because lithium resource finiteness and be unevenly distributed
The problems such as even and increase cost, finding the next generation and can be used for the secondary energy storage battery of extensive energy storage becomes and solves extensive energy storage
One new challenge of industrial field.And metallic sodium is because having physicochemical properties similar with lithium metal and resource abundant
Therefore advantage, sodium-ion battery also become the focus of next-generation energy storage technology development.
The graphite material for being commercially used for negative electrode of lithium ion battery at present cannot achieve answering on sodium-ion battery cathode
With therefore the development of sodium-ion battery cathode application material also faces huge challenge, find the cathode for being suitable for sodium-ion battery
Material is extremely crucial.Transition metal chalcogenide, such as FeS, FeS2,CoS,CoS2,NiSe,Co3S4,Co3O4,Co3Se etc. exists
Application in sodium-ion battery cathode is widely studied.Although transition metal chalcogenide have specific capacity it is high, it is resourceful,
The advantages such as price is low, but its puzzlement for still suffering from the factors such as poor, the high rate performance difference of cyclical stability, such as nanosizing,
The technologies such as charcoal coats, graphene is compound are applied in the modification of transition metal chalcogenide by researcher, but still remain and receive
The problems such as rice material is easy to reunite, charcoal coats structural instability, graphene composite cost is high.
Summary of the invention
For the defects in the prior art, the main purpose of the present invention is to provide a kind of iron-based sulfur families of in-situ carbon encapsulation
Compound, electrode material, sodium-ion battery and preparation method thereof.Based on this purpose, the present invention is at least provided the following technical solutions:
The preparation method of the iron-based chalcogenide of in-situ carbon encapsulation comprising following steps:
Presoma MIL-88-Fe is prepared using solvent thermal process；
A certain amount of above-mentioned presoma MIL-88-Fe is mixed with VI race's material, is then pyrolyzed in an inert atmosphere
Obtain the iron-based chalcogenide of in-situ carbon encapsulation.
Further, VI race material is at least one of S powder or Se powder.
Further, the mass ratio of the presoma MIL-88-Fe and VI race's material is 1:1~3.
Further, further, the use solvent thermal process prepares presoma MIL-88-Fe and specifically includes, and takes matter
Amount is dissolved in the DMF solvent of 25-30mL than the ferric chloride (FeCl36H2O) and terephthalic acid (TPA) for being 1.4~1.8:1, is then added
The sodium hydroxide solution of 2~5 milliliters of 0.2~0.5mol/L, obtains mixed solution, and mixed solution is kept the temperature at 100~120 DEG C
18~for 24 hours after, be cooled to room temperature, cleaned, be dried after then precipitating solution.
Further, the actual conditions of the pyrolysis include, by presoma MIL-88-Fe and VI race's material ground and mixed
Afterwards, 500~700 DEG C are warming up to the heating rate of 1~5 DEG C/min under an inert atmosphere, then 1~3h of heat preservation pyrolysis.
Further, the mass ratio of the presoma MIL-88-Fe and the S powder is 1:1~2, the presoma MIL-
The mass ratio of 88-Fe and the Se powder is 1:1~3.
Further, the iron-based chalcogenide of the in-situ carbon encapsulation is Fe7S8@C or Fe7Se8At least one in@C
Kind.
The iron-based chalcogenide of in-situ carbon encapsulation, the compound are Fe7S8@C or Fe7Se8At least one of@C,
Wherein Fe7S8Or Fe7Se8It is uniformly encapsulated on the carbon skeleton of in-situ synchronization synthesis, forms fusiform structure.
Electrode material, the electrode material include active material, and the active material includes the iron of the in-situ carbon encapsulation
Base chalcogenide.
Sodium-ion battery, the sodium-ion battery use the electrode material as negative electrode material.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) persursor material according to the present invention is obtained by solvent thermal process, and preparation method is simple, and is easy big rule
Mould preparation.
(2) pyrolytic process of the invention realizes the vulcanization (or selenizing) to presoma, and can synchronize realization carbon
The fabricated in situ of skeleton and to sulfur product (or selenizing product) realize encapsulate, compared to existing method, carbon recombination process
More easily, operability is stronger, and generally, material preparation condition designed by the present invention is easy, advantage of lower cost, can advise greatly
Mould production.
(3) present invention is pyrolyzed by a step, the synchronous vulcanization (or selenizing) realized to precursor and carbonization, carbon skeleton
Presence effectively inhibit Fe7X8Agglomeration in forming process, the Fe being dispersed in carbon skeleton7X8Nano particle is filling
Bulk effect during electrochemical can be effectively reduced, and the bulk effect still remained is buffered, while this carbon
The Fe/Na that the presence of skeleton can generate in effective protection electrochemical process2The interface X effectively improves the reversible of electrochemical reaction
Property process.Compound-material prepared by the present invention is used for anode material of lithium-ion battery, shows stable chemical property,
Realize the advantages such as height ratio capacity, long circulation life, high rate capability.
(4) in preparation method of the invention, the sulphur source (or selenium source) for vulcanizing (either selenizing) is completed to be pyrolyzed
Cheng Hou, excessive sulphur source (or selenium source), which can be recovered, realizes secondary recycling, on the one hand can economize on resources, be effectively reduced
On the other hand cost can be substantially reduced and be polluted the environment, be it is a kind of save, environmental protection effective preparation method.
Detailed description of the invention
Fig. 1 is the iron-based chalcogenide Fe of in-situ carbon prepared by the present invention encapsulation7S8@C and Fe7Se8The XRD diagram of@C.
Fig. 2 is presoma MIL-88-Fe, Fe prepared by the present invention7S8@C and Fe7Se8The SEM of@C schemes.
Fig. 3 is Fe prepared by the present invention7S8@C and Fe7Se8The TEM of@C schemes.
Fig. 4 is Fe prepared by the present invention7S8@C is used for sodium-ion battery cathode following under 0.2A/g and 2A/g current density
Ring curve and high rate performance figure.
Fig. 5 is Fe prepared by the present invention7Se8@C is for sodium-ion battery cathode under 0.5A/g and 2A/g current density
Cyclic curve and high rate performance figure.
Specific embodiment
It to preparation method according to the present invention and its is used for specific embodiment process with reference to the accompanying drawings of the specification
Situations such as chemical property that sodium-ion battery cathode is shown, elaborates, but embodiment does not do any shape to the present invention
The restriction of formula.
The preparation of persursor material MIL-88-Fe:
The present invention prepares persursor material MIL-88-Fe by solvent thermal process, and specific preparation process is, firstly, will
0.675 gram of ferric chloride (FeCl36H2O) and 0.415 gram of terephthalic acid (TPA) are dissolved in 27mL DMF solvent；Then, then by 3 milliliters
The sodium hydroxide solution of 0.4mol/L is added in above-mentioned solution, by mixed solution on magnetic stirring apparatus strong stirring to solution
It is uniformly mixed；Then, above-mentioned uniformly mixed solution is encapsulated in the reaction kettle that volume is 50ml, in 100 DEG C of insulating boxs
Heat preservation is for 24 hours；Solution is cooled to room temperature to the end of reacting, to the precipitating deionized water and dehydrated alcohol obtained after hydro-thermal reaction into
Row cleaning, after drying process, can obtain presoma MIL-88-Fe.
The preparation of the iron-based chalcogenide of in-situ carbon encapsulation:
The presoma MIL-88-Fe and the source S that mass ratio is 1:2 are taken, the source S is S powder in the embodiment, by MIL-88-Fe and S
Powder is ground to the two in mortar and is uniformly sufficiently mixed.Then uniformly mixed powder is transferred in tube furnace, in indifferent gas
Pyrolysis processing is carried out in atmosphere, in the embodiment, inert atmosphere N2Gas, wherein the actual conditions of pyrolysis processing are: first with 2 DEG C/
The heating rate of min is warming up to 650 DEG C, and then heat preservation pyrolysis 2h, is then cooled to environment temperature, realizes the vulcanization of presoma
It is encapsulated with carbon, to make Fe7S8It is uniformly encapsulated on the carbon skeleton of in-situ synchronization synthesis, forms fusiform structure, obtain Fe7S8@
C-material.Vulcanization and carbonization to presoma, the presence of carbon skeleton effectively inhibit Fe7S8Reunion in forming process is existing
As.The carbon recombination process of this method is easy, strong operability, at low cost, can be mass produced
In another embodiment, the source S is replaced with into the source Se, concretely Se powder, that is, vulcanization is replaced with into selenizing,
The same above-described embodiment of remaining preparation condition.
The iron-based chalcogenide that the in-situ carbon of above-mentioned acquisition is encapsulated is used as electrode active material, with conductive agent acetylene
Black, binder PVDF is uniformly mixed, and lytic agent NMP is added and is dissolved, modulates uniform sizing material, is coated on copper foil, then carry out
It is dried.To obtain electrode structure.Using the electrode of acquisition as working electrode, with sodium piece electrode as a comparison, GF/F
For glass fibre membrane as diaphragm, content is the NaCF of 1mol/L3SO3It is dissolved in diethylene glycol dimethyl ether as electrolyte, is filling
2032 type button cell of CR is assembled into the super purification glove box of full argon gas.By the battery assembled in Land test macro
Upper progress constant current discharge/charging measurement, voltage range are 0.1 to 3V, select different test current densities to the invention institute
Electrochemistry of the electrode material of preparation for sodium-ion battery cathode can be carried out assessment.
The present invention is pyrolyzed by a step, the synchronous vulcanization (or selenizing) realized to precursor and carbonization, carbon skeleton
Fe is inhibited in the presence of effective7S8Or Fe7Se8Agglomeration in forming process, the Fe being dispersed in carbon skeleton7S8Or Fe7Se8
Bulk effect of the nano particle in charge and discharge electrochemical process can be effectively reduced, and the bulk effect still remained is delayed
Punching, while the Fe/Na that the presence of this carbon skeleton can generate in effective protection electrochemical process2The interface X, effectively improves electrification
Learn the reversible process of reaction.
Fig. 1 is the electrode material Fe prepared using preparation method of the present invention7S8@C and electrode Fe7Se8The XRD diagram [email protected]
In in 30.0 °, 33.9 °, 44.0 °, 53.3 °, 57.6 ° and 71.5 ° peak correspond to Fe7S8(200), (203), (206),
(220), (209) and (406) crystal face, with Fe7S8Standard card JCPDS NO.24-0220 be consistent.It is in figure
32.2 °, 41.9 °, 50.2 °, 55.1 °, 60.9 ° and 67.4 ° of peak corresponds to Fe7S8(203), (206), (220), (029),
(403) and (046) crystal face, with Fe7S8Standard card JCPDS NO.33-0676 it is corresponding.This demonstrate that set by the present invention
The electrode material of meter is successfully prepared.
Fig. 2 is presoma MIL-88-Fe, electrode material Fe7S8@C and Fe7Se8The SEM of@C schemes.A, B are presoma in Fig. 2
The SEM of MIL-88-Fe schemes, and as can be seen from the figure the pattern of fusiform is successfully prepared.C, D are electrode material Fe in Fig. 27S8@C
SEM figure, E, F be electrode material Fe7Se8The SEM of@C schemes.As shown in Figure 2, pyrolysis completes vulcanization (or selenizing) and is carbonized
Later, the electrode material being prepared inherits the fusiform pattern of presoma.
Fig. 3 is electrode material Fe7S8@C and Fe7Se8The TEM of@C schemes, and A, B are electrode material Fe in figure7S8The low power of@C with
And high magnification TEM schemes, C, D are electrode material Fe in figure7Se8The low power and high magnification TEM of@C is schemed, and shows in figure
Fe7S8@C and Fe7Se8It is fusiform pattern that@C proves that pyrolysis is formed by electrode material again, and apparent lattice fringe is again
It is secondary to prove that electrode material designed in the present invention is successfully prepared.
Fig. 4 is electrode material Fe7S8@C is used for sodium-ion battery cathode, the excellent electrochemical performance showed, by the figure
It knows under the current density of 0.2A/g, charged/discharged specific capacity is 1278/1005.3mAh/g for the first time, and coulombic efficiency is
78.7%, circulation 80 can obtain the reversible charge specific capacity of 857.7mAh/g after enclosing；As Fig. 4 B figure in, excellent times
Rate performance is also showed, available when current density, which increases to 2A/g from 0.2A/g, becomes 0.2A/g again again
791.5mAh/g high reversible specific capacity；When current density is 2A/g, electrode material Fe7S8@C is by 300 circle circulations, still
It can obtain the height ratio capacity of 654.7mAh/g.It can be seen that compound prepared by the present invention is used as anode material of lithium-ion battery
When, stable chemical property is presented, the advantages such as height ratio capacity, long circulation life and high rate capability are realized.
Fig. 5 describes electrode material Fe7Se8@C is used for sodium-ion battery cathode, shows excellent chemical property,
Under the current density of 0.5A/g, showing charged/discharged specific capacity for the first time is 552.7/445.1mAh/g, and coulombic efficiency is
80.4%, circulation 150 can obtain the reversible charge specific capacity of 400.3mAh/g after enclosing；As Fig. 5 B figure in, it is excellent
High rate performance is also showed, available when current density, which increases to 2A/g from 0.2A/g, becomes 0.2A/g again again
448.5mAh/g high reversible specific capacity；When current density is 2A/g, electrode material Fe7S8140 circle circulation of@C experience, still
It can obtain the height ratio capacity of 408.0mAh/g.
Above-described embodiment is two kinds of specific embodiments that can be for selection proposed by the present invention, but embodiment party of the invention
Formula is simultaneously not restricted to the described embodiments, other any changes made without departing from the spirit and principles of the present invention,
Modification, combination, simplifies substitution, should be equivalent substitute mode, is included within the scope of the present invention.
Claims (10)
1. the preparation method of the iron-based chalcogenide of in-situ carbon encapsulation comprising following steps:
Presoma MIL-88-Fe is prepared using solvent thermal process；
A certain amount of above-mentioned presoma MIL-88-Fe is mixed with VI race's material, is then pyrolyzed, can be obtained in an inert atmosphere
The iron-based chalcogenide of in-situ carbon encapsulation.
2. the preparation method according to claim 1, which is characterized in that VI race material be in S powder or Se powder at least
It is a kind of.
3. the preparation method according to claim 2, which is characterized in that the presoma MIL-88-Fe and VI race's material
Mass ratio is 1:1~3.
4. one of -3 preparation method according to claim 1, which is characterized in that described to prepare forerunner using solvent thermal process
Body MIL-88-Fe is specifically included, and mass ratio is taken to be dissolved in 25- for the ferric chloride (FeCl36H2O) and terephthalic acid (TPA) of 1.4~1.8:1
In the DMF solvent of 30mL, the sodium hydroxide solution of 2~5 milliliters of 0.2~0.5mol/L is then added, obtains mixed solution, it will
Mixed solution keeps the temperature 18 at 100~120 DEG C~for 24 hours after, be cooled to room temperature, cleaned, dried after then precipitating solution
Processing.
5. the preparation method according to claim 3, which is characterized in that the actual conditions of the pyrolysis include, by presoma
After MIL-88-Fe and VI race's material ground and mixed, 500 are warming up to the heating rate of 1~5 DEG C/min under an inert atmosphere~
700 DEG C, then heat preservation is pyrolyzed 1~3h.
6. the preparation method according to claim 3, which is characterized in that the matter of the presoma MIL-88-Fe and the S powder
Ratio is measured as 1:1~2, the mass ratio of the presoma MIL-88-Fe and the Se powder is 1:1~3.
7. the preparation method according to claim 2, which is characterized in that the iron-based chalcogenide of in-situ carbon encapsulation is
Fe7S8@C or Fe7Se8At least one of@C.
8. the iron-based chalcogenide of in-situ carbon encapsulation, which is characterized in that the compound is Fe7S8@C or Fe7Se8In@C extremely
Lack one kind, wherein Fe7S8Or Fe7Se8It is uniformly encapsulated on the carbon skeleton of in-situ synchronization synthesis, forms fusiform structure.
9. electrode material, which is characterized in that the electrode material includes active material, and the active material includes claim 8
The in-situ carbon encapsulation iron-based chalcogenide.
10. sodium-ion battery, which is characterized in that the sodium-ion battery uses the electrode material of claim 9 as negative
Pole material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110459766A (en) * | 2019-07-11 | 2019-11-15 | 华南师范大学 | Micro- cube of composite material, electrode slice, sodium-ion battery with hierarchical structure and preparation method thereof |
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN110743576A (en) * | 2019-11-16 | 2020-02-04 | 福州大学 | Preparation method of hollow double-pyramid structured quaternary nickel-iron-molybdenum sulfide counter electrode catalyst |
| CN111204717A (en) * | 2020-01-14 | 2020-05-29 | 龙岩学院 | One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof |
| CN113346065A (en) * | 2020-07-30 | 2021-09-03 | 广东格林赛福能源科技有限公司 | Preparation method, material and application of high-performance CoSe/C-NS composite material |
| CN113511710A (en) * | 2021-05-27 | 2021-10-19 | 安徽中科索纳新材料科技有限公司 | Electrode active material for capacitance adsorption of lead ions and preparation method and application thereof |
| CN115207344A (en) * | 2021-04-12 | 2022-10-18 | 南京工业大学 | Fe x Se y Preparation of @ CN composite material and electrochemical energy storage application thereof |
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Cited By (8)
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| CN110459766A (en) * | 2019-07-11 | 2019-11-15 | 华南师范大学 | Micro- cube of composite material, electrode slice, sodium-ion battery with hierarchical structure and preparation method thereof |
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN110743576A (en) * | 2019-11-16 | 2020-02-04 | 福州大学 | Preparation method of hollow double-pyramid structured quaternary nickel-iron-molybdenum sulfide counter electrode catalyst |
| CN110743576B (en) * | 2019-11-16 | 2021-07-13 | 福州大学 | Preparation method of hollow double-pyramid structured quaternary nickel-iron-molybdenum sulfide counter electrode catalyst |
| CN111204717A (en) * | 2020-01-14 | 2020-05-29 | 龙岩学院 | One-dimensional lithium/sodium ion battery cathode material and preparation method and application thereof |
| CN113346065A (en) * | 2020-07-30 | 2021-09-03 | 广东格林赛福能源科技有限公司 | Preparation method, material and application of high-performance CoSe/C-NS composite material |
| CN115207344A (en) * | 2021-04-12 | 2022-10-18 | 南京工业大学 | Fe x Se y Preparation of @ CN composite material and electrochemical energy storage application thereof |
| CN113511710A (en) * | 2021-05-27 | 2021-10-19 | 安徽中科索纳新材料科技有限公司 | Electrode active material for capacitance adsorption of lead ions and preparation method and application thereof |
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Application publication date: 20190611 |