CN109888262B - Double-layer coated graphite composite material and preparation method and application thereof - Google Patents

Double-layer coated graphite composite material and preparation method and application thereof Download PDF

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CN109888262B
CN109888262B CN201910296809.6A CN201910296809A CN109888262B CN 109888262 B CN109888262 B CN 109888262B CN 201910296809 A CN201910296809 A CN 201910296809A CN 109888262 B CN109888262 B CN 109888262B
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graphite
pan
double
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feo
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CN109888262A (en
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姜付义
康利涛
杜伟
周艳丽
孙学勤
张潇予
孙建超
闫鑫升
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Yantai University
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a double-layer coated graphite composite material and a preparation method and application thereof. The method comprises the following steps: A. preparation of FeOxFeO having a solids content of 2.5 to 20% by weightxEthanol dispersion, B. preparation of Polyvinylatrile (PAN) coated graphite Material, C. preparation of graphite @ PAN @ FeOxMaterial, D, graphite @ C @ FeOxDouble-layer clad composite material. The graphite @ C @ FeOxThe material is applied as a negative electrode material in a lithium ion battery. The graphite @ C @ FeOx double-layer coating material prepared by the invention solves the problems that solvent molecules of a lithium ion battery and lithium ions are co-inserted into graphite layers when the battery is charged, so that the graphite structure is changed and the capacity is greatly attenuated. Therefore, the graphite @ C @ FeOx double-layer coating material prepared by the invention has more excellent electrical cycle stability on the premise of not reducing specific capacity, and the graphite @ C @ FeOx double-layer coating structure has the advantages of good chemical stability, excellent full electrical cycle stability, high conductivity, full raw material supply, low price, greenness and no pollution.

Description

Double-layer coated graphite composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a carbon and iron oxide double-layer coated graphite composite material and application of the carbon and iron oxide double-layer coated graphite composite material in a battery.
Background
The lithium ion battery has the advantages of high specific energy, long sufficient electricity life, little environmental pollution, high charging speed, low self-discharge rate and the like, and is applied to portable electronic equipment, electric workers/toys, green traffic and largeThe method has wide application prospect in the fields of large-scale energy storage and the like. From the viewpoint of the material composition of the battery, the negative electrode material is one of the important components of the lithium ion battery. In the development process of lithium ion batteries, Li is contained+The successful development of graphite cathode materials with an intercalation reaction mechanism is the key of large-scale application of lithium ion batteries and is also the most widely applied cathode material product of the lithium ion batteries at present. Even in some other types of battery products, graphite is incorporated in an amount as a conductive additive to improve the conductivity and utilization efficiency of the electrode. The graphite material can be widely applied to the field of batteries, and has the outstanding advantages of good chemical stability, excellent sufficient electrical cycle stability, high conductivity, abundant natural reserves, sufficient raw material supply, low price, greenness, no pollution and the like. However, the graphite material also has a drawback that it is not negligible when used as a negative electrode material for a lithium ion battery. For example, the lithium storage capacity of the graphite negative electrode is low (320-350 mAh g)-1) And the capacity improvement space is small (the theoretical capacity is only 372mAh g-1) (ii) a During charging of the battery, solvent molecules of the lithium ion battery and lithium ions are intercalated between graphite layers, so that the structural change and capacity attenuation of the graphite are caused.
Oxide materials are another class of electrode active materials that are widely used. Among lithium ion batteries, lithium cobaltate, lithium iron phosphate and lithium cobalt manganese nickelate (ternary) positive electrode materials are currently commercially applied. On the negative electrode side, oxide-based negative electrode materials such as iron oxide based on conversion reaction also exhibit high reversible lithium storage capacity. However, the iron oxide material is an insulator material and has poor electrical conductivity. The use of pure iron oxide as the negative electrode material can cause the capacity of the battery to drop sharply under the conditions of large-current charging and discharging, and the rate characteristic (namely, the high-power output characteristic) of the lithium ion battery is obviously reduced. In addition, the iron oxide negative electrode material can undergo a reciprocating severe volume change due to a lithium ion intercalation-deintercalation reaction during charging and discharging, so that material pulverization, resistance increase and capacity rapid attenuation are caused, and the capacity improvement of the lithium ion battery is seriously restricted.
From the viewpoint of material performance, the iron oxide negative electrode material and the graphite negative electrode material have strong complementarity. Therefore, in order to further improve the battery performance, researchers propose an experimental idea of compounding an iron oxide material with a graphite material. For example: the chinese patent application No. 201711044838.0 discloses a method for preparing a nano iron oxide particle/expanded microcrystalline graphite composite material for a lithium ion battery, which comprises subjecting a microcrystalline graphite material to primary high temperature expansion to obtain primary expanded microcrystalline graphite; and then ball-milling and mixing the primary expanded microcrystalline graphite and the ferrocene serving as raw materials, and performing secondary high-temperature expansion to obtain the nano iron oxide particle/expanded microcrystalline graphite composite material. The modification means can improve the electrochemical performance of the graphite, but the modification method is complex and needs three steps of treatment; and the expanded graphite has low density and small volume capacity, and is very not beneficial to the improvement of the volume energy density of the battery. The chinese patent application No. 201611009344.4 discloses a preparation method of a 3D iron oxide/graphene composite electrode material, which comprises reacting an iron source compound with an imidazole compound to form an iron-imidazole framework compound, and then calcining in air to obtain iron oxide microspheres. Ultrasonically dispersing the iron oxide microspheres and graphite oxide in water, introducing a reducing agent to reduce graphene oxide, preparing iron oxide/graphite oxide aerogel by adopting a freeze drying method, and then calcining at high temperature in an inert atmosphere to obtain the 3D iron oxide/graphene composite electrode material. The preparation method disclosed by the patent adopts a freeze-drying process, and has the problems of high cost, long production period, small yield and the like. Moreover, the graphite aerogel-state product has low density, and the specific volume capacity of the graphite aerogel-state product is necessarily low.
Disclosure of Invention
The invention discloses a preparation method of a novel graphite/oxide composite material, which aims to solve the problems of low capacity of a graphite cathode material, solvent co-intercalation, low conductivity and poor rate characteristic of an iron oxide cathode material.
In order to realize one of the purposes of the invention, the technical scheme of the invention is as follows:
a preparation method of a carbon and iron oxide double-layer coated graphite composite negative electrode material comprises the following steps:
A. preparation of FeOxThe solid content is 2.5-20% (by weight)) FeO (e) ofxEthanol dispersion:
FeO is added into a ball milling tankxGrinding balls and ethanol, and ball milling for 1-24 hours at the rotating speed of 200-xEthanol dispersion;
B. preparation of a polyvinyl nitrile (PAN) coated graphite material:
preparing N, N-Dimethylformamide (DMF) solution with polyvinyl nitrile concentration of 10-100g/L, adding graphite powder into the DMF solution for dispersion, wherein the weight ratio of the graphite powder to the DMF solution is 1:1-100, stirring for 1-4 hours, centrifuging after the graphite powder is fully dispersed, filtering, and separating the graphite powder from the solution to obtain a PAN-coated graphite material;
C. preparation of graphite @ PAN @ FeOxMaterials:
adding the PAN-coated graphite material separated in the step B into the FeO prepared in the step AxStirring in ethanol dispersion for 10-30 min to form FeO on the surface of the graphite material coated by PANxCoating the graphite layer, centrifuging and filtering to obtain graphite @ PAN @ FeOxA material;
D. graphite @ C @ FeOxDouble-layer coating of the composite material:
the graphite @ PAN @ FeO obtained in the step C is processedxThe material is treated for 1 to 5 hours at the high temperature of 1500 ℃ under the protection of inert atmosphere and 500-xDouble-layer clad composite material.
Preferably, the inert gas in step D is one or more of nitrogen, argon, helium, hydrogen, methane, and acetylene.
In order to achieve the second purpose of the invention, the technical scheme of the invention is as follows:
graphite @ C @ FeO prepared by the methodxA material.
In order to achieve the third purpose of the invention, the technical scheme of the invention is as follows:
the graphite @ C @ FeOxThe material is applied as a negative electrode material in a lithium ion battery.
The key point of the invention is that the inventionPrepared graphite @ C @ FeOxThe C layer of the material enhances the binding property of graphite and ferric oxide, prevents solvent molecules from being co-inserted into the graphite during battery charging, and improves the cycling stability of the material, and the FeOxThe layer as a high capacity active material can significantly enhance the lithium storage capacity of the resulting material.
Because the DMF solution of PAN has viscosity, a solution coating layer can be formed on the surface of graphite, DMF adhered to the surface of graphite is mutually soluble with ethanol, and PAN on the surface of graphite loses DMF solvent to be separated out to form a PAN coating layer (namely graphite @ PAN); meanwhile, iron oxide particles with Lewis acidity in the iron oxide ethanol dispersion liquid migrate to the surface of Lewis basic PAN and are adsorbed, the iron oxide particles and the Lewis basic PAN interact with each other to quickly load an iron oxide coating layer (graphite @ PAN @ FeOx) on the surface of the graphite @ PAN, and after the graphite @ PAN @ FeOx is dried and carbonized at high temperature, the PAN is carbonized and converted into a pyrolytic carbon coating layer to form a graphite @ C @ FeOx double-layer coating structure.
The graphite @ C @ FeOx double-layer coating material prepared by the invention solves the problems that solvent molecules of a lithium ion battery and lithium ions are co-inserted into graphite layers when the battery is charged, so that the graphite structure is changed and the capacity is greatly attenuated. Therefore, the graphite @ C @ FeOx double-layer coating material prepared by the invention has more excellent electrical cycle stability on the premise of not reducing specific capacity, and the graphite @ C @ FeOx double-layer coating structure has the advantages of good chemical stability, excellent full electrical cycle stability, high conductivity, full raw material supply, low price, greenness and no pollution.
Drawings
FIG. 1 is an SEM photograph of graphite @ C @ Fe3O4 prepared in example 1.
FIG. 2 is an SEM photograph of a sample of Fe3O4 prepared in comparative example 1-1.
FIG. 3 is an SEM photograph of a spherical graphite sample of comparative examples 1-2.
FIG. 4 is a graph of the cycling stability of the Fe3O4 sample, the spheroidal graphite sample, and the graphite @ C @ Fe3O4 prepared in example 1.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
Example 1:
step A: 2.5g of Fe3O420g of alumina grinding balls (diameter 5mm) and 50ml of ethanol are added into a 150ml ball milling tank, ball milling is carried out for 24 hours under the condition of 500 revolutions per minute, the grinding balls are filtered out, and Fe is obtained3O4And (3) ethanol dispersion.
And B: another 50g of PAN was added to 1000ml of DMF and stirred for 3 hours to dissolve the PAN sufficiently, and then 15g of graphite powder was added to the solution and stirred for another 1 hour. Then, the graphite was separated from the DMF solution of PAN by centrifugation to obtain a slurry-like graphite material (DMF solution with PAN coated on the surface).
And C: uniformly dispersing the slurry-like graphite material separated in the step B into the Fe prepared in the step A under the stirring condition3O4Dispersing in ethanol; the dispersion is continuously stirred for 2 hours and then fully dried at the temperature of 60 ℃ to obtain graphite @ PAN @ Fe3O4A material.
Step D: the graphite @ PAN @ Fe obtained in the step C is subjected to3O4Heating to 900 ℃ in nitrogen atmosphere, preserving heat for 3h, and naturally cooling to room temperature to obtain graphite @ C @ Fe3O4And (3) compounding the negative electrode material.
The graphite @ C @ Fe prepared in this example was added3O4The composite cathode material is used as a cathode to assemble a symmetrical battery to test electrochemical performance, and the material is 0.01-3V (vs.Li/Li)+) Within the potential range, the specific capacity is about 560mAh/g (current density is 200mA/g), the capacity is still 560mAh/g after 200 cycles, and the capacity is kept 100 percent of the initial value.
Comparative example 1-1:
step A: 10g of ferric nitrate, 2 g of oxalic acid and 2 g of ammonium nitrate are dissolved in 40mL of deionized water, stirred for 15 minutes and fully dissolved, and then the dispersion is transferred to an alumina crucible and evaporated to dryness at 105 ℃.
And B: putting the dried sample into a 400-degree electric furnace to be heated for 30 minutes,initiating the oxidation-reduction reaction between ferric nitrate and oxalic acid, and obtaining Fe after the sample is cooled to room temperature3O4And (3) sampling.
Fe prepared in this example3O4The material is used as a negative electrode to assemble a symmetrical battery to test the electrochemical performance, and the material is 0.01-3V (vs+) Within the potential range, the specific capacity is about 1190mAh/g (current density is 200mA/g), the capacity is attenuated to 786mAh/g after 200 cycles, and the capacity is kept 66 percent of the initial value.
Comparative examples 1 to 2:
the purchased spherical graphite is directly used as a negative electrode material, and the graphite is used as a negative electrode to assemble a symmetrical battery to test the electrochemical performance, wherein the electrochemical performance is 0.01-3V (vs+) Within the potential range, the specific capacity of the spherical graphite is measured to be about 420mAh/g (the current density is 200mA/g), the capacity is attenuated to 300mAh/g after 200 cycles, and the capacity is kept to be 71 percent of the initial value.
Graphite @ PAN @ Fe prepared in example 13O4Composite negative electrode material and comparative example Fe3O4Or compared with the graphite cathode material, the specific capacity is about 560mAh/g (current density is 200mA/g), the capacity is basically kept unchanged after 200 cycles, and the graphite @ PAN @ Fe prepared in example 13O4The composite cathode material solves the problems of low capacity and solvent co-intercalation of the graphite cathode material, namely Fe3O4The negative electrode material has low conductivity and poor rate characteristics,
example 2:
step A: mixing 8g of Fe3O440g of alumina grinding balls (diameter 5mm) and 50ml of ethanol are added into a 150ml ball milling tank, ball milling is carried out for 5 hours under the condition of 1000 revolutions per minute, the grinding balls are filtered out, and Fe is obtained3O4And (3) ethanol dispersion.
And B: 100g of PAN is added into 1000ml of DMF, and after stirring for 3 hours to fully dissolve the PAN, 24g of graphite powder is added into the solution and stirring is continued for 1 hour. Then, the graphite was separated from the DMF solution of PAN by centrifugation to obtain a slurry-like graphite material (DMF solution with PAN coated on the surface).
And C: stirring the slurry stone separated in the step BThe ink material was uniformly dispersed in the Fe prepared in step A3O4Dispersing in ethanol; the dispersion liquid is continuously stirred for 2 hours and then is fully dried at the temperature of 60 ℃ to obtain graphite @ PAN @ Fe3O4A material.
Step D: the graphite @ PAN @ Fe obtained in the step C is subjected to3O4Heating to 1300 ℃ in argon atmosphere, preserving the heat for 1h, and naturally cooling to room temperature to obtain graphite @ C @ Fe3O4And (3) compounding the negative electrode material.
The graphite @ C @ Fe prepared in this example was added3O4The composite cathode material is used as a cathode to assemble a symmetrical battery to test electrochemical performance, and the material is 0.01-3V (vs.Li/Li)+) Within the potential range, the specific capacity is about 640mAh/g (current density is 200mA/g), the capacity is still 598mAh/g after 200 cycles, and the capacity is kept 93 percent of the initial value.
Example 3:
step A: mixing 1g of Fe3O420g of alumina grinding balls (diameter 5mm) and 50ml of ethanol are added into a 100ml ball milling tank, ball milling is carried out for 3 hours under the condition of 800 r/min, the grinding balls are filtered out, and Fe is obtained3O4And (3) ethanol dispersion.
And B: another 25g of PAN was added to 1000ml of DMF and stirred for 3 hours to dissolve the PAN sufficiently, and then 10g of graphite was added to the solution and stirring was continued for 1 hour. Then, the graphite was separated from the DMF solution of PAN by centrifugation to obtain a slurry-like graphite material (DMF solution with PAN coated on the surface).
And C: uniformly dispersing the slurry-like graphite material separated in the step B into the Fe prepared in the step A under the stirring condition3O4Dispersing in ethanol; the dispersion liquid is continuously stirred for 2 hours and then is fully dried at the temperature of 60 ℃ to obtain graphite @ PAN @ Fe3O4A material.
Step D: the graphite @ PAN @ Fe obtained in the step C is subjected to3O4Heating to 600 ℃ in argon atmosphere, preserving the heat for 5 hours, and naturally cooling to room temperature to obtain graphite @ C @ Fe3O4And (3) compounding the negative electrode material.
The graphite @ C @ Fe prepared in this example was added3O4The composite cathode material is used as a cathode to assemble a symmetrical battery to test electrochemical performance, and the material is 0.01-3V (vs.Li/Li)+) Within the potential range, the specific capacity is about 410mAh/g (current density is 200mA/g), the capacity is still 404mAh/g after 200 cycles, and the capacity is kept to be 98 percent of the initial value.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be interchanged with other features disclosed in this application, but not limited to those having similar functions.

Claims (4)

1. A preparation method of a carbon and iron oxide double-layer coated graphite composite negative electrode material is characterized by comprising the following steps:
A. preparation of Fe3O4Fe with a solid content of 2.5-20 wt%3O4Ethanol dispersion:
adding Fe into a ball milling tank3O4Grinding ball and ethanol, ball milling for 1-24 hours at the rotating speed of 200-3O4Ethanol dispersion;
B. preparing a polyvinyl nitrile PAN-coated graphite material:
preparing an N, N-dimethylformamide solution with polyvinyl nitrile concentration of 10-100g/L, adding graphite powder into the N, N-dimethylformamide solution for dispersion, wherein the weight ratio of the graphite powder to the N, N-dimethylformamide solution is 1:1-100, stirring for 1-4 hours, centrifuging after the graphite powder is fully dispersed, filtering, and separating the graphite powder from the solution to obtain a graphite material coated with PAN;
C. preparation of graphite @ PAN @ Fe3O4Materials:
adding the PAN-coated graphite material separated in the step B to the Fe prepared in the step A3O4Stirring in ethanol dispersion for 10-30 min to form Fe on the surface of PAN-coated graphite material3O4Coating, centrifuging and filtering to obtain graphite @ PAN @ Fe3O4A material;
D. preparation of graphite @ C @ Fe3O4Double-layer coating of the composite material:
the graphite @ PAN @ Fe obtained in the step C is3O4The material is treated at the high temperature of 500-1500 ℃ for 1-5 hours under the protection of inert atmosphere and then cooled to room temperature to obtain graphite @ C @ Fe3O4Double-layer clad composite material.
2. The method according to claim 1, wherein the inert gas atmosphere in step D is any one of nitrogen, argon, helium, hydrogen, methane, and acetylene.
3. Graphite @ C @ Fe prepared by the process of claim 1 or 23O4A composite material.
4. Graphite @ C @ Fe as claimed in claim 33O4The application of the composite material is characterized in that the graphite @ C @ Fe3O4The composite material is applied as a negative electrode material in a lithium ion battery.
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CN112563510A (en) * 2020-12-10 2021-03-26 烟台大学 Spherical graphite/manganese dioxide lithium battery negative electrode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764546A (en) * 2011-06-30 2014-04-30 康奈尔大学 Hybrid materials and nanocomposite materials, methods of making same, and uses thereof
CN104009237A (en) * 2014-06-09 2014-08-27 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 Ultrahigh-capacity spherical graphite cathode material and production method thereof
CN107093745A (en) * 2017-03-23 2017-08-25 华南理工大学 A kind of class nucleocapsid elctro-catalyst of porous carbon coating Nanoalloy aoxidized for alcohol and preparation method and application
WO2017147623A1 (en) * 2016-02-24 2017-08-31 Green Nanotech Labs, Llc A Method to Manufacture Carbon Fibers through Graphene Composites and the Use Thereof
CN109468701A (en) * 2018-10-19 2019-03-15 南通纺织丝绸产业技术研究院 Electrostatic spinning apparatus, orientation Fe3O4/ Gr/PAN composite conducting nanofiber and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764546A (en) * 2011-06-30 2014-04-30 康奈尔大学 Hybrid materials and nanocomposite materials, methods of making same, and uses thereof
CN104009237A (en) * 2014-06-09 2014-08-27 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 Ultrahigh-capacity spherical graphite cathode material and production method thereof
WO2017147623A1 (en) * 2016-02-24 2017-08-31 Green Nanotech Labs, Llc A Method to Manufacture Carbon Fibers through Graphene Composites and the Use Thereof
CN107093745A (en) * 2017-03-23 2017-08-25 华南理工大学 A kind of class nucleocapsid elctro-catalyst of porous carbon coating Nanoalloy aoxidized for alcohol and preparation method and application
CN109468701A (en) * 2018-10-19 2019-03-15 南通纺织丝绸产业技术研究院 Electrostatic spinning apparatus, orientation Fe3O4/ Gr/PAN composite conducting nanofiber and preparation method thereof

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