CN112582616A - FeSz-FexOyCore-shell structure composite material and preparation method and application thereof - Google Patents
FeSz-FexOyCore-shell structure composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112582616A CN112582616A CN202011439583.XA CN202011439583A CN112582616A CN 112582616 A CN112582616 A CN 112582616A CN 202011439583 A CN202011439583 A CN 202011439583A CN 112582616 A CN112582616 A CN 112582616A
- Authority
- CN
- China
- Prior art keywords
- fes
- composite material
- core
- shell structure
- structure composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of material synthesis and electrochemistry, and particularly relates to FeSz‑FexOyCore-shell structure composite material, preparation method and application thereof, and FeSzCalcining in oxygen atmosphere, quenching, and controlling calcining time and/or temperature to obtain FeS with different coating thicknessesz‑FexOyCore-shell structure composite material. Then FeS is put intoz‑FexOyThe core-shell structure composite material, a conductive agent and a binder are fully mixed and then coated on a current collector, the obtained current collector is dried to obtain a positive plate, and the obtained positive plate, a negative plate, electrolyte and a diaphragm are assembled into a battery.
Description
Technical Field
The invention belongs to the technical field of material synthesis and electrochemistry, and particularly relates to FeSz-FexOyA core-shell structure composite material, a preparation method and application thereof.
Background
To date, most commercial Lithium Ion Batteries (LIBs) have been based on graphite negative electrodes and intercalated LiMO2(M is a transition metal) positive electrode. However, these systems do not meet the increasing demand for large grid energy storage and high energy density of Electric Vehicles (EV). In order to increase the energy density, enormous research has been carried out for decades. However, while various potential negative electrode materials are available today, this is not the case for the positive electrode.
Transition metal sulfides are expected to replace traditional embedded oxide positive electrode materials, with iron sulfide (FeS), which is abundant and environmentally friendly in nature, being particularly attractive due to its reasonable Li storage capacity (in comparison to FeS)2Compared) and high theoretical capacity based on complete lithiation
609mAh·g-1(FeS+2Li++2e-→Fe+Li2S), much higher than the Ni-rich LiNi prevalent in the prior art0.8Co0.15Al0.05O2Positive electrode (C)<200mAh g-1). However, FeS due to low conductivityzThe volume expansion during the intercalation/deintercalation of lithium and the conversion reaction of lithium during the intercalation process involving Li2SxFormation of mesophase, and Li2SxEasily dissolved in the liquid electrolyte, resulting in a decline in the battery capacity, deteriorating the cycle performance of the battery. Therefore, it is necessary to treat FeSzThe material is modified.
The coating measure can inhibit the volume expansion of the electrode material in the lithium intercalation/lithium removal process and the dissolution and erosion of the electrode material by electrolyte to a certain extent, and is beneficial to the cycle performance of the anode material; however, since the general coating material has better stability in the battery than the electrode material, the coating material may prevent lithium ions in the electrolyte from being inserted into the positive electrode material during the discharge of the battery, which may also reduce the specific discharge capacity of the battery. How to reduce the influence of the coating on the specific discharge capacity of the battery as much as possible is a direction explored in the industry.
Disclosure of Invention
In order to solve the technical problem, the invention provides a FeSz-FexOyCore-shell structured composite material, FeSz-FexOyComposite material with core-shell structure and FeSzIs a core coated with FexOy，FeSzIs FeS, FeS2Or a mixture of the two, FexOyIs Fe2O3、Fe3O4Or the mixture of the two, the inner core is connected with the shell layer through a transition layer, the thickness of the shell layer is 30 to 90 percent of the diameter of the inner core,
the preparation method comprises the following steps: for FeSzCalcining in the presence of oxygen atmosphere, quenching after calcining, and controlling the calcining time and/or temperature to obtain FeS with different coating thicknessesz-FexOyThe calcination temperature of the core-shell structure composite material is controlled to be 400-600 ℃, the calcination time is controlled to be 0.5-2 hours, the cooling rate of the quenching treatment is 80-200 ℃/min,
preferably, the method comprises the following steps: in the core-shell structure formed by calcination, the thickness of the shell is 30% -90% of the diameter of the core.
The invention also provides FeS prepared by the methodz-FexOyThe application of the core-shell structure composite material as the lithium ion battery anode material is as follows:
FeS is preparedz-FexOyThe core-shell structure composite material is used as a battery anode active material, is fully mixed with a conductive agent and a binder and then is coated on a current collector, and the core-shell structure composite material is prepared byAnd drying the obtained current collector to obtain a positive plate, and assembling the obtained positive plate, the negative plate, the electrolyte and the diaphragm into the lithium battery.
FeS used in the inventionzRich resources, no pollution to environment, and can be directly purified from nature, and the characteristics are favorable for FeSzAnd FeS, andz-FexOythe preparation method of the core-shell structure composite material is relatively simple, the energy consumption in the preparation process is less, and the core-shell structure composite material is suitable for large-scale production; the coating effect is good, and when the coated material is applied to a high-performance lithium ion battery, the problems of electrode structure degradation and intermediate product Li caused by large volume change of iron-based sulfide in the charging and discharging processes can be solved2SxThe capacity is rapidly reduced and the like due to easy dissolution in liquid electrolyte; meanwhile, through the in-situ coating preparation process, the influence of the coating layer on the specific capacity of the battery is effectively reduced.
In conclusion, the electrode material prepared by coating in the scheme has less capacity attenuation and improved stability, has high specific capacity, excellent cycling stability and high rate performance as the lithium ion battery anode material, and has certain commercial value.
Drawings
FIG. 1 is FeS-Fe prepared in example 12O3A TEM image of the composite material is taken,
FIG. 2 is an XRD pattern of FeS powder as a precursor raw material in example 1,
FIG. 3 is FeS-Fe prepared in example 12O3The XRD pattern of the composite material,
figure 4 is a test chart of electrochemical properties of the battery prepared in example 1,
figure 5 is a test chart of electrochemical properties of the battery prepared in comparative example 1,
FIG. 6 shows Fe in comparative example 12O3-test pattern of electrochemical performances of FeS composite 1,
FIG. 7 shows pure Fe in comparative example 12O3The electrochemical performance test chart of the material is shown,
FIG. 8 is a graph showing electrochemical performance tests of a battery fabricated using the material of comparative example 2,
figure 9 is a test chart of electrochemical properties of the battery prepared in example 2,
fig. 10 is an XRD pattern of the composite material prepared in example 3.
Detailed Description
Example 1
Calcining FeS powder at 600 deg.C under high-purity oxygen atmosphere for 1h (oxygen is in full excess), and immediately transferring the calcined product to dry nitrogen environment to quench at cooling rate of 150 deg.C/min to normal temperature (25 deg.C, the same below), to obtain FeS-Fe2O3Composite material, FeS-Fe2O3The composite material has uniform particle size of about 2 μm.
The FeS-Fe2O3The TEM image of the composite material is shown in FIG. 1, and from FIG. 1, it can be seen that FeS-Fe is prepared2O3The outer surface of FeS particles of the composite material is coated with a layer of Fe2O3A core-shell structure is formed, the thickness of the coating layer is about 0.5 mu m,
the XRD pattern of the FeS powder as the precursor material in this example is shown in FIG. 2. from FIG. 2, it can be seen that the precursor material is relatively pure FeS, which conforms to the standard card PDF #37-0477,
FeS-Fe prepared in this example2O3The XRD pattern of the composite material is shown in FIG. 3, and it can be seen from FIG. 3 that the calcined composite material has one more diffraction peak compared with FIG. 2, and the comparison with the PDF standard card proves that the FeS surface coating layer is Fe2O3。
FeS-Fe prepared in this example2O3The composite material, SuperP and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8: 1: dispersing the mixture in a solvent N-methylpyrrolidone (NMP) according to the proportion of 1, mixing the mixture by using a defoaming machine, uniformly coating the obtained slurry on an Al foil current collector after uniform mixing, transferring the Al foil current collector to a vacuum oven at 120 ℃ for drying for 6 hours to obtain a lithium battery positive plate, and dissolving the obtained positive plate, a metal lithium plate serving as a counter electrode, and lithium bistrifluoromethanesulfonylimide LiTFSI in a mixed solvent of DOL and DME (v: v is 1:1) according to the concentration of 1mol/LThe obtained electrolyte and the PP/PE diaphragm are assembled into a button cell in an argon atmosphere glove box with water and oxygen content lower than 1 ppm. Testing the electrical property of the obtained battery test system for the battery, setting the charge-discharge current density to be 100mA/g, setting the charge-discharge cut-off voltage limit to be 1.0-3.0V,
the test result is shown in fig. 4, and as can be seen from # 2 in fig. 4, the specific discharge capacity of the first circle of the battery is 535.2mAh/g, and the button cell only replaces FeS-Fe with equal-quality pure FeS material2O3In the case of the composite material, as shown in figure 4 # 1, the first-turn specific discharge capacity of the battery is 543.9 mAh/g. In contrast, the first-turn specific discharge capacity of the battery of the present embodiment is reduced because the cladding material is an iron-based oxide with a relatively low specific capacity; however, after 100 cycles, the specific discharge capacity of the battery of the embodiment is 505.8mAh/g, the capacity retention rate is 94.5%, and FeS-Fe is shown2O3The core-shell structure of the composite material exhibits good cycling stability because the shell coating layer inhibits the formation of Li internally due to lithium intercalation2SxThe intermediate product of (a) is in contact with the electrolyte, preventing the dissolution reaction from occurring, thereby alleviating the capacity fade.
Comparative example 1
The quenching measure is cancelled, and the preparation raw materials and other preparation processes are the same as those in the example 1:
calcining FeS powder for 1h (full excess of oxygen) at the temperature of 600 ℃ under the condition of high-purity oxygen atmosphere, immediately transferring the calcined product to a constant-temperature dry nitrogen environment at the temperature of 25 ℃ to naturally cool the calcined product to normal temperature, and obtaining FeS-Fe2O3Composite material, FeS-Fe2O3The composite material has uniform particle size of about 2 μm.
With FeS-Fe prepared in comparative example 12O3The composite material is used as an active substance of a positive electrode material to prepare a battery positive electrode and a button cell, and the preparation operation is the same as that of the embodiment 1:
FeS-Fe prepared in comparative example 12O3The composite material, SuperP and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8: 1:1 in a proportion dispersed in N-methylpyrroleUniformly coating the obtained slurry on an Al foil current collector after uniform mixing, transferring the Al foil current collector to a vacuum oven at 120 ℃ for drying for 6 hours to obtain a lithium battery positive plate, dissolving a metal lithium plate serving as a counter electrode and lithium bistrifluoromethanesulfonylimide (LiTFSI) in a mixed solvent of DOL and DME (v: v ═ 1:1) to obtain an electrolyte and a PP/PE diaphragm by matching the obtained positive plate, and assembling the electrolyte and the PP/PE diaphragm into a button cell in an argon atmosphere glove box with water and oxygen contents lower than 1 ppm. The resulting battery test system for batteries was tested for electrical properties in the same manner as in example 1.
The test results of the electrochemical performance of the battery of comparative example 1 are shown as # 2 in fig. 5 (1 in fig. 5 is also # 1 in fig. 4): compared to FeS-Fe in example 12O3The battery cycle performance of the composite material (i.e., # 2 in fig. 4) is basically equal: after 100 cycles, the specific discharge capacity of the battery is 483mAh/g, namely the capacity retention rate is 94.2%, so that the comprehensive stability of the coating in the comparative example 1 is basically equal to that of the battery in the example 1, and according to the conventional knowledge, the difficulty of the electrolyte contacting the electrode material in the core layer is basically equal, so that the difficulty of lithium ions in the electrolyte being inserted into the cathode material is also basically equal, but the specific discharge capacity of the first cycle of the battery in the comparative example 1 is 512.8mAh/g (2 # in figure 5), and the detection data obviously slide down compared with the battery (535.2mAh/g) in the example 1.
It can be seen that in example 1, the coating layer obtained by rapid cooling after calcination significantly reduces the influence on the specific capacitance of the anode material while improving the coating stability. In this regard, applicants understand that: the scheme obtains the coating layer through in-situ calcination, and the coating layer and the kernel form a transition joint part (as shown in figure 1) due to in-situ generation, the transition effect plays a certain role in promoting the conduction and the insertion of the lithium ions, or the transition effect has no great obstruction to the conduction and the insertion of the lithium ions,
in a reverse view of the conventional calcination process with natural cooling after calcination (comparative example 1), the applicant believes that, although the coating layer and the inner layer are presentA transitional bonding layer is formed between the cores, but the transitional bonding layer is mainly formed by FeS and Fe under the action of high-temperature afterheat of calcination2O3The reaction is carried out: such as FeS +10Fe2O3＝7Fe3O4+SO2A part of FeS is further generated into iron oxide, and the newly generated Fe3O4Like Fe2O3Mainly plays a role of coating and stabilizing FeS, does not help the conduction and the insertion of lithium ions, and further generates a barrier on the contrary,
the scheme is shock-cooling treatment immediately after calcination, and basically is not influenced by high-temperature waste heat after calcination, so that the transition layer obtained by the scheme is different from that obtained by the comparative example 1, and from the view point of cycle performance, the scheme can be basically equal to that obtained by the comparative example 1, and the transition layer formed by shock cooling is equivalent to increase the coating thickness and stability under the condition of little influence or no influence on the specific discharge capacity.
Comparative example 1
Mixing Fe2O3Calcining the powder at 600 deg.C under hydrogen sulfide atmosphere for 1h (hydrogen sulfide gas is excessive), and immediately transferring the calcined product to dry nitrogen environment, and quenching at 150 deg.C/min to normal temperature to obtain Fe2O3FeS composite 1(FeS coated Fe)2O3Composite 1) having a particle size of about 2 μm.
With Fe prepared in comparative example 12O3The FeS composite 1 is used as a positive electrode material active material to prepare a battery positive electrode and a button cell, and the preparation operation is the same as that of example 1:
fe prepared in comparative example 12O3The mass ratio of the FeS composite material 1 to the SuperP and the polyvinylidene fluoride (PVDF) is 8: 1:1 in proportion, dispersing in N-methylpyrrolidone (NMP) solvent, mixing by using a defoaming machine, uniformly coating the obtained slurry on an Al foil current collector after uniform mixing, transferring the Al foil current collector to a vacuum oven at 120 ℃ for drying for 6 hours to obtain a lithium battery positive plate, and dissolving a metal lithium plate and lithium bistrifluoromethanesulfonylimide LiTFSI which are matched as a counter electrode in DOL and DME (v) according to the concentration of 1mol/LV ═ 1:1) of the electrolyte obtained in the mixed solvent, a PP/PE separator, were assembled into a button cell in an argon atmosphere glove box having both water and oxygen contents lower than 1 ppm. The resulting battery test system for batteries was tested for electrical properties in the same manner as in example 1.
The test results of the electrochemical performance of the cell of comparative example 1 are shown in fig. 6, while the button cell of comparative example 1 only contains equal mass of pure Fe2O3Material for replacing Fe2O3The results of the test of electrochemical properties in the case of the FeS composite 1 are shown in FIG. 7.
In contrast, Fe2O3After FeS is coated on the surface in situ, the specific discharge capacity of the first circle of the battery is increased, because the specific discharge capacity of FeS is higher than that of Fe on lithium ion2O3。
Comparative example 2
The quenching measure is cancelled, and the preparation raw materials and other preparation processes are the same as those in the comparative example 1:
mixing Fe2O3Calcining the powder at 600 deg.C under hydrogen sulfide atmosphere for 1h (hydrogen sulfide gas is excessive), and immediately transferring the calcined product to 25 deg.C dry nitrogen environment to naturally cool to normal temperature to obtain Fe2O3-FeS composite 2(FeS coated Fe)2O3Composite 2) having a particle size of about 2 μm.
With Fe prepared in comparative example 22O3The FeS composite 2 was used as a positive electrode active material to prepare a battery positive electrode and a button cell, and the preparation operation was the same as that of example 1:
fe prepared in comparative example 22O3The mass ratio of the FeS composite material 2 to the SuperP and the polyvinylidene fluoride (PVDF) is 8: 1: dispersing the raw materials in the proportion of 1 in an N-methylpyrrolidone (NMP) solvent, mixing the raw materials by using a defoaming machine, uniformly coating the obtained slurry on an Al foil current collector after uniform mixing, transferring the Al foil current collector to a vacuum oven at 120 ℃ for drying for 6 hours to obtain a lithium battery positive plate, matching the obtained positive plate with a metal lithium plate serving as a counter electrode and lithium bistrifluoromethanesulfonylimide (LiTFSI) and dissolving the lithium bistrifluoromethanesulfonylimide (LiTFSI) in DOL and DME (v: v ═ at the concentration of 1mol/L1:1) and a PP/PE diaphragm in an argon atmosphere glove box with water and oxygen content lower than 1 ppm. The resulting battery test system for batteries was tested for electrical properties in the same manner as in example 1.
The results of testing the electrochemical performance of the cell of comparative example 2 are shown in fig. 8: compared with Fe in comparative example 12O3The FeS composite material 1 has no improvement in the first-cycle specific discharge capacity compared with the natural cooling of the comparative example 2 after the quenching treatment is adopted in the comparative example 1.
It can be seen that comparative example 1 does not have a transition layer due to the quenching treatment, so that lithium ions in the electrolyte can be more easily inserted into the positive electrode material. In this regard, the reason why lithium ions are actually inserted into the positive electrode material from the electrolyte during the discharge of the battery is that: the transfer of electrons from the external circuit to the positive electrode material charges the positive electrode material negatively, thereby attracting the positively charged lithium ions in the electrolyte, so that the "intercalation" corresponds to an absorption effect, and the lithium ions reach the cladding layer before being absorbed into the core layer. On the basis of this, the applicant believes that in comparative example 1, FeS has a higher lithium ion specific capacity than Fe in the core layer due to the clad layer2O3That is, the coating layer FeS has more advantages in the absorption capacity for lithium ions, so that after the lithium ions in the electrolyte reach the outer layer FeS first during discharging, the FeS cannot easily release the lithium ions to enter the nuclear layer; the difference in example 1 is that FeS is core, Fe2O3For the cladding, the FeS core pair reaches the Fe cladding2O3The lithium ions in the lithium ion battery have stronger absorption effect, and the effect of the transition layer is shown under the absorption effect.
Comparative example 2
FeS powder with the particle size of about 1.5 mu m is prepared by mixing FeS powder with the following components in a material-liquid ratio of 1: 6g/mL of iron (Fe) Nitrate (NO) was dispersed in water and added thereto at a concentration of 0.5mol/L3)3Aqueous solution, FeS powder and ferric nitrate Fe (NO)3)3The mass and dosage ratio of (1): 1, slowly dropwise adding hydrogen with the concentration of 0.5mol/L into the solution under the stable stirring stateThe sodium oxide aqueous solution is filtered, the filter cake is washed and then is thermally treated at 120 ℃ under inert atmosphere until the mass of the filter cake is not reduced, the calcined product is transferred to a dry nitrogen environment and is quenched to normal temperature at the cooling rate of 100 ℃/min, and then Fe is obtained2O3A composite material coating FeS particles.
With Fe prepared in comparative example 22O3The coated FeS particle composite material was used as an active material of a positive electrode material to prepare a battery positive electrode and a button cell, and the preparation operations were the same as in example 1. The electrical performance of the obtained battery test system for the battery was tested by the same test method as in example 1, and the specific discharge capacity of the first coil was found to be 529.4 mAh/g.
Comparative example 3
The quenching measure is cancelled, and the preparation raw materials and other preparation processes are the same as those in the comparative example 2:
FeS powder with the particle size of about 1.5 mu m is prepared by mixing FeS powder with the following components in a material-liquid ratio of 1: 6g/mL of iron (Fe) Nitrate (NO) was dispersed in water and added thereto at a concentration of 0.5mol/L3)3Aqueous solution, FeS powder and ferric nitrate Fe (NO)3)3The mass and dosage ratio of (1): 1, slowly dropwise adding a sodium hydroxide aqueous solution with the concentration of 0.5mol/L into the mixture under a stable stirring state until the precipitation amount in the reaction system is not increased any more, filtering, washing a filter cake, then carrying out heat treatment at 120 ℃ under an inert atmosphere until the mass of the filter cake is not reduced any more, transferring a calcined product to a constant-temperature dry nitrogen environment at 25 ℃ to naturally cool the calcined product to the normal temperature, and obtaining Fe2O3A composite material coating FeS particles.
With Fe prepared in comparative example 32O3The coated FeS particle composite material was used as an active material of a positive electrode material to prepare a battery positive electrode and a button cell, and the preparation operations were the same as in example 1. The electrical performance of the obtained battery test system for the battery was tested by the same test method as in example 1, and the specific discharge capacity of the first coil was found to be 531.1 mAh/g.
Both comparative example 2 and comparative example 3, which had been coated with foreign substances to give shells, did not involve high-temperature calcination unlike in-situ conversion, and thus did not form an effective transition region between the core and the shell, and did not contribute to the extent of lithium ion introduction into the core FeS even though comparative example 2 used a quenching measure compared to comparative example 3.
Example 2
FeS-Fe with calcination time modified to 1.5 hours only2O3The remaining operations for preparing the composite material and the process for manufacturing the battery were the same as in example 1. Fe coated on the outer surface of FeS due to increased sintering time2O3The layer thickness is increased correspondingly, the stability is improved (to 95.6%) and the specific capacity is reduced to a certain extent, as shown in fig. 9. As can be seen from FIG. 9, 1# is FeS-Fe in example 12O3 Composite material # 2 was the material synthesized in example 2, and increasing the calcination time caused a thickening of the shell, resulting in a change in properties.
Example 3
Only the calcination preparation process is modified as follows: firstly calcining for 0.5h (oxygen is fully excessive) under the condition of high-purity oxygen atmosphere, and then calcining for 0.5h under the condition of oxygen-free inert atmosphere.
The XRD pattern of the prepared composite material is shown in figure 10, and as can be seen from figure 10, the composite material has a new diffraction peak which is Fe compared with a PDF standard card3O4Characteristic peaks of # PDF26-1136, which indicates that the FeS surface is coated with Fe3O4。
Example 4
Only the calcination preparation process is modified as follows: FeS is prepared2Calcining the powder at 400 ℃ under a high-purity oxygen atmosphere for 0.5h (with sufficient excess oxygen), and introducing inert gas instead of oxygen atmosphere to calcine the powder at 400 ℃ for 0.5h under an oxygen-free condition. The composite material obtained by the method contains Fe in the outer layer3O4。
Example 5
Only the calcination preparation process is modified as follows: FeS is prepared2Calcining the powder for 1h (with sufficient excess oxygen) at 400 ℃ under the condition of high-purity oxygen atmosphere. The composite material obtained by the method has an outer layer mainly containing Fe2O3。
Claims (7)
1. FeSz-FexOyThe core-shell structure composite material is characterized in that: the FeSz-FexOyComposite material with core-shell structure and FeSzIs an inner core and coated with Fe on the surfacexOyAnd the inner core is connected with the shell layer through a transition layer.
2. The FeS of claim 1z-FexOyThe core-shell structure composite material is characterized in that: the thickness of the shell layer is 30% -90% of the diameter of the inner core.
3. The FeS of claim 1z-FexOyThe core-shell structure composite material is characterized in that: the FeSzIs FeS, FeS2Or a mixture of both, said FexOyIs Fe2O3、Fe3O4Or a mixture of both.
4. FeS according to any one of claims 1 to 3z-FexOyThe preparation method of the core-shell structure composite material is characterized by comprising the following steps: the preparation method comprises the steps of preparing FeSzCalcining in the presence of oxygen atmosphere, and quenching to obtain FeSz-FexOyA core-shell structure composite material.
5. The FeS of claim 4z-FexOyThe preparation method of the core-shell structure composite material is characterized by comprising the following steps: the calcining time is 0.5-2 hours, and the calcining temperature is 400-600 ℃.
6. The FeS of claim 4z-FexOyThe preparation method of the core-shell structure composite material is characterized by comprising the following steps: in the quenching treatment, the cooling rate is 80-200 ℃/min.
7. FeS according to any one of claims 1 to 3z-FexOyThe application of the core-shell structure composite material is characterized in that: the application is that the FeS is usedz-FexOyThe core-shell structure composite material, a conductive agent and a binder are fully mixed and then coated on a current collector, the obtained current collector is dried to obtain a positive plate, and the obtained positive plate, a negative plate, electrolyte and a diaphragm are assembled into the lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011439583.XA CN112582616B (en) | 2020-12-11 | 2020-12-11 | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011439583.XA CN112582616B (en) | 2020-12-11 | 2020-12-11 | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112582616A true CN112582616A (en) | 2021-03-30 |
| CN112582616B CN112582616B (en) | 2022-03-15 |
Family
ID=75130688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011439583.XA Active CN112582616B (en) | 2020-12-11 | 2020-12-11 | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112582616B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB374486A (en) * | 1930-03-05 | 1932-06-06 | Horace Freeman | Process of making iron oxide and sulphur dioxide from iron sulphide ores |
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| JP2008091219A (en) * | 2006-10-02 | 2008-04-17 | Sony Corp | Positive electrode material for lithium/iron disulfide primary battery, and manufacturing method therefor, and the lithium/iron disulfide primary battery |
| CN103515596A (en) * | 2013-09-11 | 2014-01-15 | 广州鹏辉能源科技股份有限公司 | Sulfur-iron-containing positive electrode material and lithium battery |
| CN107507978A (en) * | 2017-07-28 | 2017-12-22 | 齐鲁工业大学 | A kind of sodium-ion battery FeS2/Fe3O4/ C negative materials and preparation method thereof |
| CN107658459A (en) * | 2017-09-30 | 2018-02-02 | 哈尔滨工业大学 | A kind of preparation method and application of iron oxide, ferrous disulfide and sulphur composite |
| KR20190090496A (en) * | 2018-01-25 | 2019-08-02 | 한국전기연구원 | Anode Active Material Comprising Self-binded Composites Coating On the Carbon Materials, Manufacturing Method Thereof, And Lithium Secondary Battery Comprising the Same |
| CN110357168A (en) * | 2019-05-14 | 2019-10-22 | 江西师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN111129469A (en) * | 2019-12-31 | 2020-05-08 | 天目湖先进储能技术研究院有限公司 | FexOy-FeS2-zComposite material and preparation method and application thereof |
| CN111302403A (en) * | 2020-03-04 | 2020-06-19 | 井冈山大学 | Preparation method and application of ferroferric oxide @ iron disulfide nanocomposite |
| CN111320212A (en) * | 2020-03-13 | 2020-06-23 | 西安交通大学 | Ferrous selenide/ferric oxide nanoparticle heterojunction, preparation method and application thereof |
-
2020
- 2020-12-11 CN CN202011439583.XA patent/CN112582616B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB374486A (en) * | 1930-03-05 | 1932-06-06 | Horace Freeman | Process of making iron oxide and sulphur dioxide from iron sulphide ores |
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| JP2008091219A (en) * | 2006-10-02 | 2008-04-17 | Sony Corp | Positive electrode material for lithium/iron disulfide primary battery, and manufacturing method therefor, and the lithium/iron disulfide primary battery |
| CN103515596A (en) * | 2013-09-11 | 2014-01-15 | 广州鹏辉能源科技股份有限公司 | Sulfur-iron-containing positive electrode material and lithium battery |
| CN107507978A (en) * | 2017-07-28 | 2017-12-22 | 齐鲁工业大学 | A kind of sodium-ion battery FeS2/Fe3O4/ C negative materials and preparation method thereof |
| CN107658459A (en) * | 2017-09-30 | 2018-02-02 | 哈尔滨工业大学 | A kind of preparation method and application of iron oxide, ferrous disulfide and sulphur composite |
| KR20190090496A (en) * | 2018-01-25 | 2019-08-02 | 한국전기연구원 | Anode Active Material Comprising Self-binded Composites Coating On the Carbon Materials, Manufacturing Method Thereof, And Lithium Secondary Battery Comprising the Same |
| CN110357168A (en) * | 2019-05-14 | 2019-10-22 | 江西师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN111129469A (en) * | 2019-12-31 | 2020-05-08 | 天目湖先进储能技术研究院有限公司 | FexOy-FeS2-zComposite material and preparation method and application thereof |
| CN111302403A (en) * | 2020-03-04 | 2020-06-19 | 井冈山大学 | Preparation method and application of ferroferric oxide @ iron disulfide nanocomposite |
| CN111320212A (en) * | 2020-03-13 | 2020-06-23 | 西安交通大学 | Ferrous selenide/ferric oxide nanoparticle heterojunction, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| GUO QIAN ET AL.: "In situ construction of Z-scheme FeS2/Fe2O3 photocatalyst via structural transformation of pyrite for photocatalytic degradation of carbamazepine and the synergistic reduction of Cr(VI)", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
| WANG JIE ET AL.: "Controllable construction of flower-like FeS/Fe2O3 composite for lithium storage", 《JOURNAL OF POWER SOURCES》 * |
| 何欢: "钴、铁基金属氧化物结构调控及其储锂性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅱ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112582616B (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107732205B (en) | Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material | |
| CN109119624B (en) | Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN103456939A (en) | Method for preparing cathode material carbon-coated lithium titanate for lithium ion battery from metatitanic acid | |
| CN114944476B (en) | MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof | |
| CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| JP2024516477A (en) | Method for producing ferroboron alloy-coated lithium iron phosphate | |
| CN111129449A (en) | Graphene/carbon/ferroferric oxide nanocomposite and preparation method and application thereof | |
| CN111697204A (en) | Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN113066988B (en) | Negative pole piece and preparation method and application thereof | |
| CN114204002A (en) | Composite coating method of high-compaction high-nickel layered cathode material for solid-state battery | |
| CN113772718A (en) | SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof | |
| CN113571681A (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
| Li et al. | Effect of Nb 5+ doping on LiNi 0.5 Co 0.25 Mn 0.25 O 2 cathode material | |
| CN114715936B (en) | Negative electrode NaSbS of lithium or sodium ion battery 2 Preparation method of @ C composite material | |
| WO2023060992A1 (en) | Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application | |
| CN110931726A (en) | Lithium titanate negative electrode composite material, preparation method thereof and lithium ion battery | |
| CN116895744A (en) | Preparation method of long-cycle sodium-ion battery positive electrode material and sodium-ion battery | |
| CN113968590B (en) | Alkali metal ion intercalation SnS 2 And preparation method thereof, and application of battery anode material and preparation method thereof | |
| CN112582616B (en) | FeSz-FexOyCore-shell structure composite material and preparation method and application thereof | |
| CN114864894A (en) | High-pressure-resistant coating-layer-modified lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN113506867A (en) | MoS for lithium ion battery2N/N doped composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |