CN111470544A - Solid-phase sintering method of carbon-coated ferroferric oxide - Google Patents

Solid-phase sintering method of carbon-coated ferroferric oxide Download PDF

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CN111470544A
CN111470544A CN202010034589.2A CN202010034589A CN111470544A CN 111470544 A CN111470544 A CN 111470544A CN 202010034589 A CN202010034589 A CN 202010034589A CN 111470544 A CN111470544 A CN 111470544A
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ferroferric oxide
solid
carbon
sintering method
phase sintering
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赵强
徐飞
何泓材
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • 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
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • 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
    • 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

The invention discloses a carbon-coated ferroferric oxide, in particular relates to a simple solid-phase sintering method for preparing the ferroferric oxide, which is mainly used for a lithium ion battery cathode material and belongs to the field of battery materials. A solid-phase sintering method of carbon-coated ferroferric oxide greatly improves the cycle stability of the lithium ion battery cathode material. The method is a complete solid-phase sintering method, and the carbon-coated ferroferric oxide is prepared from ferrous iron in one step. Has the obvious advantages of simple operation, high repeatability, no pollution of raw materials, low price and the like. The carbon-coated ferroferric oxide prepared by sintering has simple steps and only needs a sintering process. By coating the carbon layer, the volume change of the ferroferric oxide material in the charging and discharging process is greatly relieved, and the cycle stability of the ferroferric oxide material is improved. The pulverization effect of ferroferric oxide in the process of lithium ion intercalation and deintercalation is slowed down, and the electrochemical performance is very stable.

Description

Solid-phase sintering method of carbon-coated ferroferric oxide
Technical Field
The invention designs carbon-coated ferroferric oxide, in particular relates to simple preparation of the ferroferric oxide by a solid-phase sintering method, which is mainly used for preparing a lithium ion battery cathode material and can also be used in other fields, and belongs to chemical products.
Background
The negative electrode material of the traditional commercial lithium ion battery is mainly made of graphite, the lithium ion battery can be embedded into the layered graphite, but the theoretical capacity of the lithium ion battery is only 372mAh/g, and the capacity can not meet the requirement of people on portable energy, particularly a new energy automobile system which is mainly developed at present, and in order to meet the requirement of people on large battery capacity and improve the capacity and high rate performance of the lithium ion battery, the search for a new high-performance negative electrode material is an important solution. The current negative electrode material of the lithium ion battery mainly comprises Si, Sn and SnO2、MnO2、Fe3O4The common characteristic of these types of negative electrode materials is that they all have high theoretical capacity, most typically silicon material, which has a theoretical capacity of 4200mAh/g, which is ten times higher than the specific capacity of conventional graphite (372 mAh/g). Although the new negative electrode material can obviously improve the capacity of the existing lithium ion battery, a serious problem exists in that the volume expansion rate of 400% of silicon after lithium intercalation is easy to cause pulverization of the active material.
In a plurality of cathode materials, ferroferric oxide has the advantages of no toxicity, abundant natural reserves, environmental friendliness and the like, has higher theoretical capacity (927mAh/g) and lower discharge voltage, and is reflected in a typical conversion reaction in the charge-discharge process of a lithium ion battery, the ferroferric oxide material reacts with lithium ions to generate elementary iron, and the lithium ions are combined with oxygen to generate lithium oxide. The process is very easy to cause electrode pulverization, so that the negative electrode material falls off from the collector, and the negative electrode material cannot participate in electrochemical cycle in the subsequent charging and discharging processes. In addition, after repeated circulation of the ferroferric oxide active substance, the active substance is easy to aggregate and agglomerate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a solid-phase sintering method capable of preparing carbon-coated ferroferric oxide by one-step sintering, which has good circulation stability, greatly improves the electrochemical performance of a lithium ion battery and improves the quality of the battery. The invention provides a solid-phase sintering method capable of preparing carbon-coated ferroferric oxide by one-step sintering, which is characterized in that raw materials are uniformly mixed by a mortar and then sintered under specific conditions to obtain the carbon-coated ferroferric oxide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a simple preparation method of solid-phase sintering of carbon-coated ferroferric oxide comprises the following steps:
1. heptahydrate and ferrous sulfate with a molar mass in the range of 1-3 mmol are first taken and ground in a mortar for ten minutes to half an hour until the powder particles are fine enough without significant large particles.
2. In the above process, D-glucose with a molar mass in the range of 5mmol-10mmol is continuously taken, and is added into a mortar for grinding for ten minutes to half an hour until the powder particles are fine enough without obvious large particles.
3. In the above process, citric acid with a molar mass in the range of 2mmol-5mmol is continuously taken, and is added into a mortar for grinding for ten minutes to half an hour until the powder particles are fine enough without obvious large particles.
4. In the above process, ammonium chloride with a molar mass in the range of 15mmol-30mmol is continuously taken, and is added into a mortar for grinding for ten minutes to half an hour until the powder particles are fine enough without obvious large particles.
5. Adding the ground mixed powder into a corundum square boat, transferring the corundum square boat into a tube furnace, introducing inert gas into the other end of the tube furnace, and introducing the inert gas for a plurality of times until the air is exhausted. And then calcining for 10 minutes to 3 hours at the temperature of 600-900 ℃ to obtain the carbon-coated ferroferric oxide material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the simple solid-phase sintering method for preparing carbon-coated ferroferric oxide, through charge and discharge tests, 500 cycles of charge and discharge circulation are carried out under the current multiplying power of 0.5C, the capacity of 470mAh/g is still maintained, and the charge and discharge efficiency is as high as 99%. This shows that we have better cycle stability by compounding with carbon, and the electrochemical performance of the material is further improved.
2. The simple solid-phase sintering method for preparing the carbon-coated ferroferric oxide, provided by the invention, has the advantages of simple preparation method, low cost and easiness in realization of large-scale production.
Drawings
FIG. 1 is a schematic diagram of XRD spectral lines of a simple carbon-coated ferroferric oxide according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a simple carbon-coated ferroferric oxide macro-morphology according to an embodiment of the present invention;
FIG. 3 is a schematic surface SEM of a simple carbon-coated ferroferric oxide according to an embodiment of the present invention;
Detailed Description
The invention is further described with reference to specific embodiments and the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
1. Preparation of Mixed sintered precursor
0.5g of heptahydrate and ferrous sulfate (purchased from Shanghai alatin) are taken and added into a mortar to be ground for ten minutes to half an hour until the powder particles are fine enough and have no obvious large particles; adding 1g D-glucose (purchased from Shanghai Aladdin) into a mortar containing heptahydrate and ferrous sulfate, and continuously grinding for ten minutes until the mixture is uniformly mixed; adding 0.5g citric acid (purchased from Shanghai Aladdin) into the system, and continuously grinding for ten minutes until the mixture is uniformly mixed; adding 1g ammonium chloride (purchased from Shanghai Aladdin) into the above system, and grinding for half an hour until uniformly mixed to obtain mixed powder.
2. Sintering
And (3) adding the sintering precursor obtained in the step (1) into a corundum square boat, transferring the corundum square boat to a tubular furnace, placing the corundum square boat in the center of the tubular furnace, and introducing nitrogen into the other end of the tubular furnace. Ventilating for half an hour till oxygen in the tube furnace is completely exhausted, then heating to 800 ℃ at 5 ℃ per minute, keeping the temperature for half an hour, and naturally cooling.
3. Collecting
After the temperature is completely reduced, taking out the blocky sinter in the corundum ark, putting the blocky sinter into a mortar for grinding until no obvious particles exist, collecting the blocky sinter, putting the collected sample into a small sample tube, waiting for preparing a battery and carrying out analysis test
4. Formulating an active material slurry
Taking acetylene black (Hefei Ke crystal materials technology Co., Ltd.), polyvinylidene fluoride (Hefei Ke crystal materials technology Co., Ltd.) and the active substances collected in the step 3, and drying in an oven at 80 ℃ for one night. Adding 3ml of N-methyl pyrrolidone (Chengdu Kelong chemical reagent factory) into a small beaker with the specification of 10ml, adding 0.1g of polyvinylidene fluoride into the beaker, magnetically stirring for 1 hour, adding 0.1g of acetylene black into the beaker, magnetically stirring for 1 hour, finally adding 0.8g of active substance into the beaker, magnetically stirring for 4 hours, and finally preparing viscous liquid.
5. Coating of
Taking a piece of 20 x 15cm glass, repeatedly wiping the surface of the glass with alcohol until the surface is clean and smooth, spreading a copper foil on the glass, fixing two edges with an adhesive tape to ensure that the copper foil is completely contacted with the surface of the glass and is flat without creases, and uniformly coating the prepared slurry on the copper foil by using a square coater.
6. Drying by baking
And (3) placing the copper foil in a blast type oven, drying at 80 ℃ overnight, cutting the copper foil into a wafer with the diameter of 12mm, and then placing the wafer in a vacuum oven for drying for 8 hours.
7. Performing battery assembly
The assembled CR2032 button cell in laboratory was completed in a glove box model L ab2000 made by ITX inert gas systems, Inc. filled with high purity argon gasThe sequence is as follows: positive electrode casing, gasket, lithium plate, (electrolyte,) diaphragm, (electrolyte,) negative pole piece, gasket, shell fragment and negative electrode casing. Wherein the purity of the lithium metal sheet>99.9% by volume, 16mm in diameter, and 1 mol/L of lithium hexafluorophosphate (L iPF) dissolved in a mixed solution of DMC/DEC/EC in a volume ratio of 1:1:16) As an electrolyte for the battery; the separator used was a polypropylene porous membrane (Celgard 2300) having a diameter of 20 mm. Finally, the battery is packaged on a manual sealing machine
In order to verify that the sintered product is ferroferric oxide, XRD analysis is performed on the sintered product, the test result is shown in fig. 1, fig. 2 is a composite material of ferroferric oxide and carbon prepared by co-firing glucose, heptahydrate, ferrous sulfate, ammonium chloride and citric acid, and fig. 1 is compared with a standard card, which shows that: the prepared sintering sample generates a characteristic peak of the ferroferric oxide, and meanwhile, the fact that a mixed peak appears in the first half of XRD is caused by the carbon material can be seen, and in addition, no other peak appears, which shows that the composite material of the ferroferric oxide and the carbon is successfully prepared by the sintering method. Fig. 3 is a SEM picture of the sintered powder, and it can be seen that ferroferric oxide forms a composite material with carbon, and fig. 2 is a macroscopic morphology thereof.
As can be seen from fig. 1: the curve of the crystal face is more zigzag, and the diffraction peak of the ferroferric oxide is sharp and the half-width peak is narrower due to the existence of carbon with various crystal forms, which indicates that the crystallinity is still acceptable. The influence of the hetero peak of carbon is removed, other peaks are not existed, the carbon composite material is obtained, and the proportion of the carbon and ferroferric oxide after the carbon and the ferroferric oxide are compounded is not researched.

Claims (8)

1. A solid-phase sintering method of carbon-coated ferroferric oxide comprises the steps of adding heptahydrate and ferrous sulfate into a mortar to be ground for ten minutes to half an hour until powder particles are fine enough and no obvious large particles exist; adding D-glucose into a mortar containing heptahydrate and ferrous sulfate, and continuously grinding for ten minutes until the D-glucose is uniformly mixed; adding citric acid into the system, and continuously grinding for ten minutes until the citric acid is uniformly mixed; and adding ammonium chloride into the system, and continuously grinding for half an hour until the ammonium chloride and the ammonium chloride are uniformly mixed to obtain mixed powder. Adding the mixed powder into a corundum square boat, transferring the corundum square boat to a tubular furnace, placing the corundum square boat in the center of the tubular furnace, and introducing nitrogen at the other end of the tubular furnace. Introducing gas into a tube furnace, completely exhausting oxygen, heating to a certain temperature, keeping the temperature for a plurality of hours, and naturally cooling.
2. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the molar mass of the heptahydrate and the ferrous sulfate is 1mmol-3 mmol.
3. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the molar mass of the D-glucose is 2mmol-6 mmol.
4. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the molar mass of the citric acid is 1mmol-3 mmol.
5. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the molar mass of the ammonium chloride is 2mmol-6 mmol.
6. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the temperature rise rate is 2 to 10 degrees per minute.
7. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the heat preservation time is 10 minutes to 60 minutes.
8. The solid-phase sintering method for preparing carbon-coated ferroferric oxide according to claim 1, wherein the heat preservation temperature is 600-900 ℃.
CN202010034589.2A 2020-01-14 2020-01-14 Solid-phase sintering method of carbon-coated ferroferric oxide Pending CN111470544A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114275824A (en) * 2022-01-18 2022-04-05 杭州幄肯新材料科技有限公司 Porous carbon-coated ferroferric oxide nano-particles and solid-phase preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102790217A (en) * 2012-07-26 2012-11-21 天津大学 Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN103647041A (en) * 2013-12-10 2014-03-19 浙江大学 Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery
CN104993126A (en) * 2015-07-28 2015-10-21 河北工业大学 Preparation method and application of carbon-coated Fe3O4 nanoparticle lithium ion battery negative electrode material
CN110212192A (en) * 2019-06-25 2019-09-06 河南大学 A kind of adjustable nano ferriferrous oxide composite material and preparation method of cladding carbon layers having thicknesses and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102790217A (en) * 2012-07-26 2012-11-21 天津大学 Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN103647041A (en) * 2013-12-10 2014-03-19 浙江大学 Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery
CN104993126A (en) * 2015-07-28 2015-10-21 河北工业大学 Preparation method and application of carbon-coated Fe3O4 nanoparticle lithium ion battery negative electrode material
CN110212192A (en) * 2019-06-25 2019-09-06 河南大学 A kind of adjustable nano ferriferrous oxide composite material and preparation method of cladding carbon layers having thicknesses and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114275824A (en) * 2022-01-18 2022-04-05 杭州幄肯新材料科技有限公司 Porous carbon-coated ferroferric oxide nano-particles and solid-phase preparation method thereof

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Application publication date: 20200731