CN109686943A - A kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon - Google Patents
A kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon Download PDFInfo
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- CN109686943A CN109686943A CN201811572984.5A CN201811572984A CN109686943A CN 109686943 A CN109686943 A CN 109686943A CN 201811572984 A CN201811572984 A CN 201811572984A CN 109686943 A CN109686943 A CN 109686943A
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- negative electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon, belongs to battery technology field.Source of iron is mixed in proportion with the source S；Mixed-powder is placed in mortar and is ground, it is uniformly mixed；Mixed-powder after grinding is placed in porcelain boat, is put into atmosphere furnace, high-temperature process is carried out, is down to room temperature and obtains FeSx@C negative electrode material.The FeSx@C-material of the method synthesis is demonstrated by good chemical property, has high specific capacity；For lithium ion battery, especially under high power charging-discharging, after 100 circle of circulation, capacity can also keep 1000mAh/g, be demonstrated by good cyclicity；For sodium-ion battery, first circle discharge capacity is up to 816mAh/g, and high specific capacity is belonged in sode cell.
Description
Technical field
The invention belongs to battery technology fields, especially a kind of metal sulfide in-stiu coating of FeSx lithium (sodium) ion battery
The preparation method of the negative electrode material of carbon.
Background technique
Electrochemical cell is a kind of energy storage system of efficient stable, and wherein lithium ion battery is since specific energy is high, follows
The advantages that ring service life is long, specific discharge capacity is high, voltage is steady, consumption is low, nuisanceless, cryogenic property is excellent, is widely used in
The field of mobile equipment such as electric car, battery of mobile phone.And the price of lithium metal is higher, to reduce production cost, finds other
Electrode material always is that the hot spot of research, sodium and lithium are congeners, has similar chemical property, and opposing metallic lithium valence
Lattice are cheap, rich reserves.Therefore, sodium-ion battery is considered to be the new direction of electrochemical cell development.
Negative electrode material is one of the critical material for influencing lithium (sodium) ion battery performance, at present lithium (sodium) ion secondary battery
Negative electrode material mainly has graphite carbon material, transition metal oxide, sulfide and nano metal etc., wherein lithium (sodium) metal sulphur
Compound battery has very wide market prospects, and being primarily due to (1) lithium (sodium) metal sulfide battery is to have height in secondary cell
Theoretical specific capacity；(2) inexpensive, nature rich content；(3) stable operating voltage, the open circuit of lithium-metal sulfide cell
Voltage is in 2.8~3.2V or so, and the open-circuit voltage platform of sodium is relatively low；(4) it has a safety feature.
For lithium (sodium) although metal sulfide battery has the advantages that a series of, it is not perfect.For example, electric
Pond puts that high rate capability is poor, electric conductivity is poor, there are serious Study of Volume Expansion in charge and discharge process[1].Wherein volume expansion is existing
Application as having seriously affected lithium-metal sulfide cell.People change metal sulfide battery by different methods
Journal of Sex Research.Min-Jae Choi etc. obtains Fe by colloid synthetic method7S8The negative electrode material of@C NCs core-shell structure, is demonstrated by
Good cycle performance[2].Xun Wen etc.[3]The FeS2/RGO composite material of synthesis, special conductive web frame make electrode and electricity
Solution liquid comes into full contact with, and high rate performance and cycle performance significantly improve, and shows as following in the case where current density is 0.2c discharging condition
After ring 100 encloses, FeS2/RGO capacity is also positively retained at 1080.3mAh/g, compared to original FeS2Negative electrode material, in identical electricity
Under current density, after 100 circle of circulation, capacity only remains 60.9mAh/g.Above-mentioned improved method improves FeSx@C to a certain extent
The performance of battery, but experimental method is relative complex.Therefore, easy experimental method, the inexpensive raw material property prepared are found
Can good negative electrode material, be realize industrialization there is an urgent need to.
Bibliography:
[1]Xu Z,Shen X,Zhang Q,et al.Synthesis of Structurally Stable3D
MoS2Architectures as High Performance Lithium-Ion Battery Anodes[J].Particle&
Particle Systems Characterization,2016,33(6):311-315.
[2]Choi M J,Kim J,Yoo J K,et al.Extremely Small pyrrhotite
Fe7S8Nanocrystals with Simultaneous Carbon-Encapsulation for High-Performance
Na–Ion Batteries[J].Small,2018,14(2):1702816.
[3]Wen X,Wei X,Yang L,et al.Self-assembled FeS2cubes anchored on
reduced graphene oxide as an anode material for lithium ion batteries[J]
.Journal of Materials Chemistry A,2015,3(5):2090-2096.
Summary of the invention
It is an object of the invention to use simple experimental method, it is prepared for the lithium-ion electric with excellent electrochemical performance
Pond negative electrode material FeSx C (wherein FeSx represents sulphur iron compound, and the ratio of two elements is uncertain or does not limit), skill of the invention
Art scheme is as follows.
A kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon, which comprises the following steps:
(1) source of iron is mixed in proportion with the source S；
(2) mixed-powder is placed in mortar and is ground, be uniformly mixed it；
(3) mixed-powder after grinding is placed in porcelain boat, is put into atmosphere furnace, carried out high-temperature process, be down to room temperature and obtain
To FeSx@C negative electrode material.
Source of iron is selected from ferrocene, ferric acetate, ferric carbonate etc.；The source S is selected from S powder, thiocarbamide, L-cysteine, thioacetamide
Deng, general ferric carbonate and S powder not simultaneously as source of iron and the source S.
The mass ratio in source of iron and the source S is 1:(1-10).
High-temperature process condition described in step (3) are as follows: N2Or the inert atmospheres such as Ar, it is warming up to the speed of 5 DEG C/min
500-800 DEG C of constant temperature carries out 3h calcining to mix powder in the process of constant temperature.
Gained negative electrode material of the invention is used for lithium sode cell.
The invention has the following advantages that
(1) preparation method of FeSx@C-material of the present invention is simple, and raw material are not noxious materials, and to environment without
Evil.
(2) the FeSx@C-material of the method synthesis is demonstrated by good chemical property, has high specific capacity；Especially
Under high power charging-discharging, 100 circle left and right of circulation, moreover it is possible to keep high specific capacity.Because the invention can use simple method, at
Function has synthesized the good lithium ion battery negative material of chemical property, has very big potentiality to be exploited and application prospect.
Detailed description of the invention
Fig. 1 is that embodiment 1 synthesizes FeSx@C (1:6) material XRD curve graph.As shown in Figure 1, there is Fe in XRD7S8's
Diffractive features peak, but deviated to high angle direction.By XRD diagram it is found that the peak intensity of sample generated is very low, illustrate to synthesize
FeSx@C crystallinity it is low.
Fig. 2 is the figure of the HRTEM for the FeSx C (1:6) that embodiment 1 synthesizes, and as seen from the figure, FeSx and C have formed cladding knot
Structure, FeSx have one layer of C shell outside, further demonstrate the method by HRTEM figure and synthesized carbon coating in situ.
For Fig. 3 embodiment 1 in charge and discharge process, lithium secondary battery prepared by the present invention has high specific discharge capacity, (a)
It is electric discharge figure of the FeSx@C (1:6) under conditions of current density 100mA/g shown in figure；It (b) is in high magnification shown in figure
Electric discharge figure under conditions of current density 1000mA/g also maintains high specific capacity, this illustrates the present invention after circulation 100 is enclosed
FeSx@C battery performance is excellent.
For Fig. 4 in charge and discharge process, sode cell prepared by the present invention has higher specific discharge capacity, first circle discharge capacity
Up to 816mAh/g belongs to high specific capacity in sode cell.
Specific embodiment
The present invention is further illustrated with comparative example combined with specific embodiments below, but the present invention is not limited to following
Embodiment.
Embodiment 1:
(1) ferrocene and S powder are mixed in a certain ratio.
(2) mixed-powder is placed in mortar and is ground, be uniformly mixed it.
(3) mixed-powder after grinding is placed in porcelain boat, is put into atmosphere furnace, carried out high-temperature process, be down to room temperature and obtain
To FeSx@C negative electrode material.
Above-mentioned preparation method is illustrated below:
The ratio of ferrocene and S in step 1 of the present invention is 1:6.
High-temperature process condition described in step 3 are as follows: N2Atmosphere is warming up to 650 DEG C of constant temperature with the speed of 5 DEG C/min,
The calcining of 3h is carried out during constant temperature to mix powder.
It is conductive agent for binder, acetylene black that FeSx@C-material made of embodiment 1, which is used, as negative electrode material, PVDF,
(active material: conductive agent: binder=8:1:1) weighs it after a certain amount of negative electrode material and acetylene black according to a certain percentage
It pours into mortar and grinds uniformly, the PVDF of addition a certain amount of 10% continues grinding and obtains uniform thick dark slurry, by it
Even being coated on copper foil paper prepares electrode slice.Lithium battery is assembled in vacuum glove box, according to negative electrode casing, lithium piece, diaphragm, just
Pole, steel disc, spring leaf, anode cover sequence assembled (before putting anode pole piece drip 5-6 drop electrolyte, electrolyte 1mol/
L LiPF6, then by the lithium battery of assembling discharge test under the conditions of (a) 25 DEG C of room temperature, 100mA/g respectively, first circle specific volume
It measures up to 2095mAh/g.(b) discharge test is carried out under the conditions of 25 DEG C of room temperature, 1000mA/g, after circulation 100 is enclosed, capacity can also be protected
1000mAh/g is held, good cyclicity is showed, as a result such as Fig. 3.
Embodiment 2:
(1) ferrocene and S powder are mixed in a certain ratio.
(2) mixed-powder is placed in mortar and is ground, be uniformly mixed it.
(3) mixed-powder after grinding is placed in porcelain boat, is put into atmosphere furnace, carried out high-temperature process, be down to room temperature and obtain
To FeSx@C negative electrode material.
Above-mentioned preparation method is illustrated below:
The ratio of ferrocene and S in step 1 of the present invention is 1:4.
High-temperature process condition described in step 3 are as follows: N2Atmosphere is warming up to 650 DEG C of constant temperature with the speed of 5 DEG C/min,
The calcining of 3h is carried out during constant temperature to mix powder.
It is conductive agent for binder, acetylene black that FeSx@C-material made of embodiment 1, which is used, as negative electrode material, PVDF,
(active material: conductive agent: binder=8:1:1) weighs it after a certain amount of negative electrode material and acetylene black according to a certain percentage
It pours into mortar and grinds uniformly, the PVDF of addition a certain amount of 10% continues grinding and obtains uniform thick dark slurry, by it
Even being coated on copper foil paper prepares electrode slice.Lithium battery is assembled in vacuum glove box, according to negative electrode casing, sodium piece, diaphragm, just
Pole, steel disc, spring leaf, anode cover sequence assembled (before putting anode pole piece drip 4-5 drop electrolyte, electrolyte 1mol/
L NaClO4.Then by the sode cell of assembling discharge test under the conditions of 25 DEG C of room temperature, 100mA/g respectively, first circle specific capacity
Up to 816mAh/g, the sodium metal sulfide battery of height ratio capacity can get by the method, as a result as shown in Figure 3.
Claims (6)
1. a kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon, which comprises the following steps:
(1) source of iron is mixed in proportion with the source S；
(2) mixed-powder is placed in mortar and is ground, be uniformly mixed it；
(3) mixed-powder after grinding is placed in porcelain boat, is put into atmosphere furnace, carried out high-temperature process, be down to room temperature and obtain
FeSx@C negative electrode material.
2. a kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon described in accordance with the claim 1, feature
It is, source of iron is selected from ferrocene, ferric acetate, ferric carbonate etc.；The source S is selected from S powder, thiocarbamide, L-cysteine, thioacetamide；Carbon
Sour iron and S powder be not simultaneously as source of iron and the source S.
3. a kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon described in accordance with the claim 1, feature
It is, the mass ratio in source of iron and the source S is 1:(1-10).
4. a kind of preparation method of the negative electrode material of metal sulfide in-stiu coating carbon described in accordance with the claim 1, feature
It is, high-temperature process condition described in step (3) are as follows: N2Or the inert atmospheres such as Ar, 500- is warming up to the speed of 5 DEG C/min
800 DEG C of constant temperature carry out 3h calcining to mix powder in the process of constant temperature.
5. according to the cathode material for the metal sulfide in-stiu coating carbon that the described in any item methods of claim 1-4 are prepared
Material.
6. according to the negative electrode material for the metal sulfide in-stiu coating carbon that the described in any item methods of claim 1-4 are prepared
It must apply, be used for lithium sode cell.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112418A (en) * | 2019-06-12 | 2019-08-09 | 河北师范大学 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries meterial additive |
| CN111785967A (en) * | 2020-06-30 | 2020-10-16 | 北京高压科学研究中心 | Core-shell structure chalcogenide negative electrode material and preparation method thereof |
| CN112607792A (en) * | 2020-12-17 | 2021-04-06 | 中国科学技术大学 | Sodium-ion battery negative electrode material, and preparation method and application thereof |
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| US20030113632A1 (en) * | 2001-07-30 | 2003-06-19 | Brown W. Richard | Oxidized titanium as a cathodic current collector |
| CN108987718A (en) * | 2018-07-24 | 2018-12-11 | 西南科技大学 | High performance lithium ionic cell cathode material, that is, core-shell structure FeS2The preparation method of@C nano ring |
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| ZHENXIAO LU ET AL.: ""Metal-Organic Framework-Derived Sea-Cucumber-like FeS2@C nanorods with outstanding Pseudocapactive Na-Ion Storage Properties"", 《ACS APP. ENERGY MATER.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112418A (en) * | 2019-06-12 | 2019-08-09 | 河北师范大学 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries meterial additive |
| CN111785967A (en) * | 2020-06-30 | 2020-10-16 | 北京高压科学研究中心 | Core-shell structure chalcogenide negative electrode material and preparation method thereof |
| CN112607792A (en) * | 2020-12-17 | 2021-04-06 | 中国科学技术大学 | Sodium-ion battery negative electrode material, and preparation method and application thereof |
| CN112607792B (en) * | 2020-12-17 | 2022-07-15 | 中国科学技术大学 | Sodium-ion battery negative electrode material, and preparation method and application thereof |
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