CN109671937B - In-situ synthesis method of transition metal oxide/graphene composite material - Google Patents
In-situ synthesis method of transition metal oxide/graphene composite material Download PDFInfo
- Publication number
- CN109671937B CN109671937B CN201811572258.3A CN201811572258A CN109671937B CN 109671937 B CN109671937 B CN 109671937B CN 201811572258 A CN201811572258 A CN 201811572258A CN 109671937 B CN109671937 B CN 109671937B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal oxide
- composite material
- graphene composite
- graphene
- 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.)
- Active
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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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 an in-situ synthesis method of a transition metal oxide/graphene composite material, which comprises the following steps: dissolving soluble ferric salt, transition metal salt and cerium salt in deionized water, and mixing to obtain a uniform solution; adding a precipitator until the pH value reaches above 10, stirring until the precipitation is complete, standing and aging, carrying out hydrothermal reaction, filtering, washing with water to be neutral, and drying to obtain hydroxide compound precipitate; weighing graphite and potassium permanganate, mixing, adding mixed acid solution of concentrated sulfuric acid and phosphoric acid, stirring for reaction, adding ice-water bath, adding precipitate, and adding corresponding amount of H2O2Continuously stirring and ultrasonically dispersing; and washing, centrifuging, drying and sintering the product to obtain the transition metal oxide/graphene composite material. According to the invention, hydroxide precipitation is directly added in the process of preparing graphite oxide, so that graphene oxide grows on a hydroxide matrix in situ, and the effect of relieving volume expansion of metal oxide when the metal oxide is used for a lithium ion battery cathode is achieved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to an in-situ synthesis method of a transition metal oxide/graphene composite material.
Background
Compared with the traditional secondary battery, the lithium ion battery has the advantages of high energy density, safety, no pollution, small self-discharge, wide working temperature, long cycle life, no memory effect and the like, and therefore has attracted extensive attention. Lithium ion batteries are widely used in the fields of portable electronic devices (such as mobile phones, digital cameras, video cameras, notebook computers, and the like) and electric tools, and are gradually expanding to the fields of electric bicycles, electric vehicles, new energy storage, and the like.
At present, graphite is the most commonly used material for the negative electrode of the lithium ion battery, and although the graphite has the advantages of high electronic conductivity, long cycle life, low cost, good safety performance and the like, the theoretical specific capacity of the graphite is only 372mAh/g, and the requirements of the lithium ion battery with high performance and high capacity are difficult to meet. The energy density and specific capacity of the transition metal oxide negative electrode material are higher than those of graphite, the transition metal oxide negative electrode material is wide in source, low in price and simple to prepare, and has excellent electrochemical performance, however, the transition metal oxide negative electrode material has a serious volume expansion effect in the charging and discharging processes, the electrode material is pulverized, active species fall off, the capacity of an electrode is greatly attenuated, and the stability performance is difficult to guarantee. A large number of researches show that if a proper conductive carbon material can be selected to modify the metal oxide, the structure and the morphology are reasonably designed, the conductivity of the electrode material can be effectively enhanced, and the volume expansion effect of the electrode material is relieved. Graphene is a two-dimensional lattice structure consisting of a single layer of carbon atoms, and is sp2The honeycomb network structure formed by arranging high-density atomic layers formed by hybridized carbon atoms has excellent electric conductivity and higher specific surface area (2600 m)2/g), excellent thermal and mechanical properties, and is widely used in the fields of nano-electronics, hydrogen storage, supercapacitors and sensors.
The existing preparation method of the graphene composite material comprises the steps of placing a metal simple substance in a graphene oxide aqueous solution, and freeze-drying a black solid product generated after placing to obtain a metal oxide/graphene composite, but the method generally has the problem of volume expansion when being used for a lithium ion battery cathode.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an in-situ synthesis method of a transition metal oxide/graphene composite material, and the transition metal oxide/graphene composite material with high capacity and high performance is prepared by the in-situ synthesis method and utilizing the excellent conductivity of graphene to further relieve the volume expansion effect of the metal oxide when the metal oxide is used for a lithium ion battery cathode.
In order to achieve the purpose, the invention adopts the following technical scheme:
an in-situ synthesis method of a transition metal oxide/graphene composite material comprises the following steps:
(1) dissolving soluble ferric salt, soluble transition metal salt and soluble cerium salt according to a molar ratio of 1: (0.01-0.5): (0.01-0.1), respectively dissolving in deionized water, and uniformly mixing to form a uniform solution;
(2) dropwise adding a precipitator into the uniform solution, continuously stirring in the dropwise adding process until the pH value of the solution reaches more than 10, stopping dropwise adding, continuously stirring for 1-3h, standing at room temperature, aging for 4h, carrying out hydrothermal reaction, filtering and washing to neutrality, and drying to obtain a transition metal hydroxide compound precipitate, wherein: the hydrothermal reaction temperature is 120-180 ℃, and the time is 3-10 h;
(3) weighing graphite and potassium permanganate according to the mass ratio of 1 (3-4), uniformly mixing, adding the mixture into a three-neck flask filled with mixed acid liquid of concentrated sulfuric acid and phosphoric acid, continuously stirring and reacting for 12 hours to obtain a gray green solution, adding hydroxide for precipitation after an ice water bath is carried out for 1-5 hours, and then slowly adding H with the volume of 1/20-1/5 in the gray green solution2O2And continuously stirring for 30-40min, and then performing ultrasonic dispersion for 1-2h to obtain a suspension of the transition metal hydroxide/graphene oxide which is coated and grown mutually.
(4) Washing and centrifuging the suspension of the transition metal hydroxide/graphene oxide, and drying and roasting to obtain the transition metal composite oxide/graphene, wherein the roasting atmosphere is an oxygen-free atmosphere, the roasting temperature is 500 ℃ below zero, and the roasting time is 3-6 h.
In the step (1), the soluble ferric salt is one of ferric nitrate, ferric sulfate or ferric chloride, and the soluble ferric salt is used as a matrix.
In the step (1), the soluble transition metal salt is one of soluble nitrate, sulfate or chloride of metal cobalt, metal zinc, metal manganese or metal titanium, and one or more of the soluble transition metal salt is added.
In the step (1), the soluble cerium salt is one of cerium nitrate or cerium chloride.
In the step (1), the mass ratio of the deionized water to the soluble ferric salt is (10-25): 1.
in the step (2), the precipitator is one of sodium hydroxide, ammonia water or urea, and the dropping rate is 1-500 drops/min.
In the step (2), the hydrothermal reaction is carried out in a hydrothermal reaction kettle.
In the step (3), the concentration of the concentrated sulfuric acid is 98%, and the ratio of the concentrated sulfuric acid to the phosphoric acid is 1: 1.
In the step (3), the mass percentage of the graphite and the hydroxide precipitate is (0.01-20): 100.
in the step (3), H is added2O2After that, the solution quickly changed from grayish green to bright yellow.
In the step (3), hydroxide precipitation is added in the process of preparing the graphene oxide by adopting an improved Hummers method, so as to obtain a suspension of the transition metal hydroxide/graphene oxide.
In the step (4), the roasting atmosphere is a nitrogen atmosphere or an inert gas atmosphere.
In the step (4), the drying operation is carried out in a vacuum drying oven, and the drying temperature is 60 ℃.
In the step (4), the prepared transition metal composite oxide/graphene composite material is used as a lithium ion battery cathode, the current density is 100mA/g through detection, the specific capacity reaches 1210-1260mAh/g after 100 cycles, and the coulombic efficiency reaches more than 99.5%.
The invention has the beneficial effects that:
(1) in the method, the compound of the transition metal hydroxide is directly added in the process of synthesizing the graphene oxide by adopting an in-situ synthesis method, so that the process is simple and easy to operate, and the production cost is low;
(2) the transition metal oxide/graphene composite material prepared by the method has a porous structure, and the specific surface area reaches 100-200m2/g，CeO2Beneficial to nano-rodAnd the generated graphene is uniformly dispersed among gaps of product particles, and the structure can buffer the volume expansion effect of the metal oxide in the charge-discharge cycle process and improve the electrode reaction dynamic performance.
Description of the figures
Fig. 1 is an XRD pattern of the transition metal oxide/graphene composite material prepared in example 1 of the present invention;
fig. 2 is an SEM image of the transition metal oxide/graphene composite material prepared in example 1 of the present invention;
fig. 3 is a cycle curve diagram of the transition metal oxide/graphene composite material prepared in example 1 of the present invention used as a negative electrode of a lithium ion battery;
fig. 4 is an SEM image of the transition metal oxide/graphene composite material prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
(1) Respectively mixing iron nitrate, cobalt nitrate and cerium nitrate in a molar ratio of 1: 0.1: 0.02 is dissolved in deionized water, and a uniform solution is obtained after uniform mixing and stirring; (2) adding ammonia water into the solution at a rate of 100 drops/min until the pH value reaches 10, continuously stirring for 2 hours to completely precipitate, standing and aging at room temperature for 4 hours, placing the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 6 hours, filtering and washing the solution to be neutral, and drying the solution to obtain Fe2O3-Co2O3-CeO2Precipitating the composite hydroxide; (3) graphene oxide was prepared using a modified Hummers method: weighing a certain amount of graphite and potassium permanganate, uniformly mixing, adding the graphite and potassium permanganate into a three-neck flask filled with 98% mixed acid solution of concentrated sulfuric acid and phosphoric acid, continuously stirring for reaction for 12 hours to obtain a gray green solution, carrying out ice-water bath for 2 hours, adding hydroxide precipitate (the mass percent of the graphite is 10%), and slowly adding 10mL of H2O2At the moment, the solution is rapidly changed from grey green to bright yellow, and ultrasonic dispersion is carried out for 1h after the solution is continuously stirred for 30min, so that a suspension of transition metal hydroxide/graphene oxide which is mutually coated and grows is obtained; (4) transition metal hydrogenWashing and centrifuging the oxide/graphene oxide suspension, putting the filter cake into a vacuum drying oven at 60 ℃ for fully drying, and roasting at 400 ℃ for 4 hours under the atmosphere of nitrogen to obtain Fe2O3-Co2O3-CeO2Graphene negative electrode material with specific surface area up to 200m2The XRD pattern is shown in figure 1, and the phase is mainly Fe2O3And as shown in an SEM picture of fig. 2, a cycle curve chart of the negative electrode material used as a negative electrode of the lithium ion battery is shown in fig. 3, and after 100 cycles at a current density of 100mA/g, the specific capacity is stabilized at 1254mAh/g, and the coulombic efficiency is 99.57%.
Example 2
(1) Mixing ferric chloride, manganese sulfate and cerium chloride in a molar ratio of 1: 0.5: 0.06 is dissolved in deionized water, and a uniform solution is obtained after uniform mixing and stirring; (2) adding ammonia water into the solution at 300 drops/min until the pH value reaches 10, continuously stirring for 2 hours to completely precipitate, standing and aging at room temperature for 4 hours, placing the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 4 hours, filtering, washing with water to be neutral, and drying to obtain Fe2O3-MnO2-CeO2Precipitating the composite hydroxide; (3) graphite oxide was prepared using a modified Hummers method: weighing a certain amount of graphite and potassium permanganate, uniformly mixing, adding the graphite and potassium permanganate into a three-neck flask filled with 98% mixed acid solution of concentrated sulfuric acid and phosphoric acid, continuously stirring for reaction for 12 hours to obtain a gray green solution, carrying out ice-water bath for 2 hours, adding hydroxide precipitate (the mass percent of the graphite is 5%), and slowly adding 10mL of H2O2At the moment, the solution is rapidly changed from grey green to bright yellow, and ultrasonic dispersion is carried out for 1h after the solution is continuously stirred for 30min, so that a suspension of transition metal hydroxide/graphene oxide which is mutually coated and grows is obtained; (4) washing and centrifuging the suspension of the transition metal hydroxide/graphene oxide, putting the filter cake into a vacuum drying oven at 60 ℃ for fully drying, and roasting at 400 ℃ for 5 hours in a nitrogen atmosphere to obtain Fe2O3-MnO2-CeO2Graphene negative electrode material with specific surface area up to 150m2The specific capacity is stabilized at 1219mAh/g after 100 cycles under the current density of 100mA/g, and the coulombic efficiency is 99.53 percent.
Example 3
(1) Respectively mixing ferric sulfate, titanium sulfate and cerium chloride in a molar ratio of 1: 0.3: 0.03 is dissolved in deionized water, and a uniform solution is obtained after uniform mixing and stirring; (2) adding ammonia water into the solution at a rate of 400 drops/min until the pH value reaches 10, continuously stirring for 2 hours to completely precipitate, standing and aging at room temperature for 4 hours, placing the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 140 ℃ for 5 hours, filtering, washing with water to neutrality, and drying to obtain Fe2O3-TiO2-CeO2Precipitating the composite hydroxide; (3) graphite oxide was prepared using a modified Hummers method: weighing a certain amount of graphite and potassium permanganate, uniformly mixing, adding the graphite and potassium permanganate into a three-neck flask filled with 98% mixed acid solution of concentrated sulfuric acid and phosphoric acid, continuously stirring for reaction for 12 hours to obtain a gray green solution, carrying out ice-water bath for 2 hours, adding hydroxide precipitate (the mass percent of the graphite is 20%), and slowly adding 10mL of H2O2At the moment, the solution is rapidly changed from grey green to bright yellow, and ultrasonic dispersion is carried out for 1h after the solution is continuously stirred for 30min, so that a suspension of transition metal hydroxide/graphene oxide which is mutually coated and grows is obtained; (4) washing and centrifuging a suspension product of the transition metal hydroxide/graphene oxide, putting a filter cake into a vacuum drying oven at 60 ℃ for fully drying, and roasting at 500 ℃ for 6 hours in a nitrogen atmosphere to obtain Fe2O3-TiO2-CeO2Graphene negative electrode material with specific surface area of 160m2The specific capacity is stabilized at 1232mAh/g after 100 cycles under the current density of 100mA/g, and the coulombic efficiency is 99.55%.
Example 4
(1) Respectively mixing ferric sulfate, zinc chloride and cerium nitrate in a molar ratio of 1: 0.5: 0.1 is dissolved in deionized water, and a uniform solution is obtained after uniform mixing and stirring; (2) adding ammonia water into the solution at a rate of 500 drops/min until the pH value reaches 10, continuously stirring for 2 hours to completely precipitate, standing and aging at room temperature for 4 hours, placing the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 6 hours, filtering, washing with water to neutrality, and drying to obtain Fe2O3-ZnO2-CeO2Precipitating the composite hydroxide; (3) preparation of oxygenates using a modified Hummers processGraphite: weighing a certain amount of graphite and potassium permanganate, uniformly mixing, adding the graphite and potassium permanganate into a three-neck flask filled with 98% mixed acid solution of concentrated sulfuric acid and phosphoric acid, continuously stirring for reaction for 12 hours to obtain a gray green solution, carrying out ice-water bath for 2 hours, adding hydroxide precipitate (the mass percent of the graphite is 15%), and slowly adding 10mL of H2O2At the moment, the solution is rapidly changed from grey green to bright yellow, and ultrasonic dispersion is carried out for 1h after the solution is continuously stirred for 30min, so that a suspension of transition metal hydroxide/graphene oxide which is mutually coated and grows is obtained; (4) washing and centrifuging a suspension product of the transition metal hydroxide/graphene oxide, putting a filter cake into a vacuum drying oven at 60 ℃ for fully drying, and roasting at 400 ℃ for 3 hours in a nitrogen atmosphere to obtain Fe2O3-ZnO2-CeO2The SEM image of the graphene negative electrode material is shown in figure 4, and the specific surface area reaches 180m2The specific capacity is stabilized at 1247mAh/g after 100 cycles under the current density of 100mA/g, and the coulombic efficiency is 99.54 percent.
Claims (6)
1. An in-situ synthesis method of a transition metal oxide/graphene composite material is characterized by comprising the following steps:
(1) dissolving soluble ferric salt, soluble transition metal salt and soluble cerium salt according to a molar ratio of 1: (0.01-0.5): (0.01-0.1), respectively dissolving in deionized water, and uniformly mixing to form a uniform solution;
(2) dropwise adding a precipitator into the uniform solution, continuously stirring in the dropwise adding process until the pH value of the solution reaches more than 10, stopping dropwise adding, continuously stirring for 1-3h, standing at room temperature, aging for 4h, carrying out hydrothermal reaction, filtering and washing to neutrality, and drying to obtain a transition metal hydroxide compound precipitate, wherein: the precipitator is one of sodium hydroxide, ammonia water or urea, the hydrothermal reaction temperature is 120-180 ℃, and the time is 3-10 h;
(3) weighing graphite and potassium permanganate according to the mass ratio of 1 (3-4), uniformly mixing, adding the mixture into a three-neck flask filled with mixed acid liquid of concentrated sulfuric acid and phosphoric acid, continuously stirring and reacting for 12 hours to obtain a gray green solution, then carrying out ice water bath for 1-5 hours, and addingThe transition metal hydroxide complex is precipitated, followed by slow addition of H in a gray-green solution volume of 1/20-1/52O2Continuously stirring for 30-40min, and then performing ultrasonic dispersion for 1-2h to obtain a suspension of transition metal hydroxide/graphene oxide which is coated and grown mutually;
(4) washing and centrifuging the suspension of the transition metal hydroxide/graphene oxide, and drying and roasting to obtain the transition metal composite oxide/graphene, wherein the roasting atmosphere is an oxygen-free atmosphere, the roasting temperature is 500 ℃ below zero, and the roasting time is 3-6 h.
2. The in-situ synthesis method of the transition metal oxide/graphene composite material according to claim 1, wherein in the step (1), the soluble iron salt is one of ferric nitrate, ferric sulfate or ferric chloride, and the soluble iron salt is used as a matrix.
3. The in-situ synthesis method of a transition metal oxide/graphene composite material according to claim 1, wherein in the step (1), the soluble transition metal salt is one of soluble nitrate, sulfate or chloride salts of cobalt, zinc, manganese or titanium, and one or more of the soluble transition metal salts are added.
4. The in-situ synthesis method of a transition metal oxide/graphene composite material according to claim 1, wherein in the step (1), the soluble cerium salt is one of cerium nitrate or cerium chloride.
5. The in-situ synthesis method of a transition metal oxide/graphene composite material according to claim 1, wherein in the step (4), the calcination atmosphere is a nitrogen atmosphere or an inert gas atmosphere.
6. The in-situ synthesis method of the transition metal oxide/graphene composite material as claimed in claim 1, wherein in the step (4), the prepared transition metal oxide/graphene composite material is used as a negative electrode of a lithium ion battery, and the current density is 100mA/g through detection, the specific capacity reaches 1210-1260mAh/g after 100 cycles, and the coulombic efficiency reaches more than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811572258.3A CN109671937B (en) | 2018-12-21 | 2018-12-21 | In-situ synthesis method of transition metal oxide/graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811572258.3A CN109671937B (en) | 2018-12-21 | 2018-12-21 | In-situ synthesis method of transition metal oxide/graphene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109671937A CN109671937A (en) | 2019-04-23 |
| CN109671937B true CN109671937B (en) | 2021-06-22 |
Family
ID=66145761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811572258.3A Active CN109671937B (en) | 2018-12-21 | 2018-12-21 | In-situ synthesis method of transition metal oxide/graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109671937B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113577271A (en) * | 2021-07-28 | 2021-11-02 | 苏州广林皓医药科技有限公司 | Preparation method of graphene-ferroferric oxide composite magnetic carrier |
| CN115651696B (en) * | 2022-10-24 | 2023-07-18 | 滨州乾坤化工机械有限公司 | Desulfurizing agent for liquefied petroleum gas and preparation method thereof |
| CN116139690B (en) * | 2023-02-20 | 2023-07-25 | 无锡红旗除尘设备有限公司 | Iron-smelting blast furnace waste gas treatment system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831102A (en) * | 2014-03-14 | 2014-06-04 | 哈尔滨工业大学 | Preparation method of graphene catalyst |
| CN104528833A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of metal oxide/nitrogen doped graphene composite material |
| CN106611843A (en) * | 2016-12-26 | 2017-05-03 | 东北大学 | Preparation method for porous silicon/graphene compounded lithium ion battery anode material |
| CN108231427A (en) * | 2018-01-09 | 2018-06-29 | 湘潭大学 | A kind of 3D porous graphenes/transition metal oxide composite material and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101945818B1 (en) * | 2011-10-04 | 2019-02-08 | 성균관대학교산학협력단 | Composite containing metal component supported on graphene, preparing method of the same, and uses of the same |
-
2018
- 2018-12-21 CN CN201811572258.3A patent/CN109671937B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831102A (en) * | 2014-03-14 | 2014-06-04 | 哈尔滨工业大学 | Preparation method of graphene catalyst |
| CN104528833A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of metal oxide/nitrogen doped graphene composite material |
| CN106611843A (en) * | 2016-12-26 | 2017-05-03 | 东北大学 | Preparation method for porous silicon/graphene compounded lithium ion battery anode material |
| CN108231427A (en) * | 2018-01-09 | 2018-06-29 | 湘潭大学 | A kind of 3D porous graphenes/transition metal oxide composite material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109671937A (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102130334B (en) | Graphene-based nano iron oxide composite material and preparation method thereof | |
| CN109244427B (en) | Preparation method of carbon-coated zinc sulfide loaded graphene as potassium ion battery cathode | |
| CN107808958B (en) | Preparation method of ferroferric oxide/nitrogen-doped graphene composite material, product and application thereof | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN109671937B (en) | In-situ synthesis method of transition metal oxide/graphene composite material | |
| CN103855385B (en) | A kind of preparation method with the micro nano structure cobaltosic oxide of high rate capability | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN109935818B (en) | Ferroferric oxide/rGO nano anode material and preparation method thereof | |
| CN101916854A (en) | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery | |
| CN112850690A (en) | Preparation method and sodium storage application of graphene-loaded double-transition metal sulfide composite material | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN108400296B (en) | Heterogeneous element doped ferroferric oxide/graphene negative electrode material | |
| CN110504447A (en) | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof | |
| CN102259933A (en) | Preparation method and application of rice-grain alpha-iron trioxide | |
| CN109950523A (en) | Lithium ion battery negative material transition metal oxide/carbon preparation method | |
| CN111924864A (en) | MnO/MgO composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
| CN108400299B (en) | Preparation method of CuFe2O4/C composite anode material for sodium-ion battery | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN104183827A (en) | Lithium iron phosphate nanorods and preparation method thereof | |
| CN113753963A (en) | Tin cobalt disulfide nano-particles and preparation method and application thereof | |
| CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
| CN109768233B (en) | NiCo of lithium ion battery2S4Preparation method of/graphene composite negative electrode material | |
| CN112694104A (en) | Prussian blue analogue, preparation method thereof, negative electrode material and application |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210715 Address after: Diaomayang village, Sunwu street, Huimin County, Binzhou City, Shandong Province Patentee after: HUIBO NEW MATERIALS Co.,Ltd. Address before: 110819 No. 3 lane, Heping Road, Heping District, Shenyang, Liaoning 11 Patentee before: Northeastern University |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Diaomayang village, Sunwu street, Huimin County, Binzhou City, Shandong Province Patentee after: Huibo New Materials Co.,Ltd. Address before: Diaomayang village, Sunwu street, Huimin County, Binzhou City, Shandong Province Patentee before: HUIBO NEW MATERIALS CO.,LTD. |