CN109037623B - Positive electrode material of magnesium secondary battery and preparation method thereof - Google Patents

Positive electrode material of magnesium secondary battery and preparation method thereof Download PDF

Info

Publication number
CN109037623B
CN109037623B CN201810776325.7A CN201810776325A CN109037623B CN 109037623 B CN109037623 B CN 109037623B CN 201810776325 A CN201810776325 A CN 201810776325A CN 109037623 B CN109037623 B CN 109037623B
Authority
CN
China
Prior art keywords
secondary battery
ferrous disulfide
carbon
magnesium secondary
positive electrode
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
Application number
CN201810776325.7A
Other languages
Chinese (zh)
Other versions
CN109037623A (en
Inventor
路金林
李卓
张晓伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Liaoning USTL
Original Assignee
University of Science and Technology Liaoning USTL
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Liaoning USTL filed Critical University of Science and Technology Liaoning USTL
Priority to CN201810776325.7A priority Critical patent/CN109037623B/en
Publication of CN109037623A publication Critical patent/CN109037623A/en
Application granted granted Critical
Publication of CN109037623B publication Critical patent/CN109037623B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 positive electrode material is a ferrous disulfide/nano carbon composite material formed by coating ferrous disulfide in situ with a carbon nano material, and is applied to the magnesium secondary battery, wherein the weight percentages of the carbon material and the ferrous disulfide in the ferrous disulfide/nano carbon composite material are as follows: 2 to 5 percent of carbon material and 98 to 95 percent of ferrous disulfide. The invention adopts ferrous disulfide as a base material, adopts a doped nano carbon material to carry out in-situ carbon coating, and obtains the final composite material by a one-step hydrothermal method. When the material is used as the magnesium secondary battery anode material, more channels can be provided for the reversible diffusion of magnesium ions, so that the battery has higher charge-discharge specific capacity and excellent cycle performance. The synthesis of the substrate material only needs two elements, the step method is simple and convenient, high-temperature calcination is not needed, the substrate material can be directly applied after preparation, the preparation raw materials are rich, the cost is low, and the large-scale production is easy.

Description

Positive electrode material of magnesium secondary battery and preparation method thereof
Technical Field
The invention relates to the field of secondary batteries, in particular to a positive electrode material of a magnesium secondary battery and a preparation method thereof.
Background
With the increasing energy consumption and the increasing environmental pollution all over the world, people generally realize the importance of developing and utilizing green renewable energy sources. Therefore, some new environmental-friendly, large-capacity secondary batteries have received much attention from researchers, including lithium ion batteries, lead acid batteries, nickel cadmium batteries, and the like. However, lithium ion batteries have the problems of high cost and poor safety, and lead-acid batteries and nickel-cadmium batteries contain harmful elements and can cause environmental pollution.
Magnesium metal and lithium metal are diagonal elements, so that the characteristics of the magnesium metal, such as chemical property, ionic radius and the like, have many similarities with lithium. In addition, magnesium is abundant in the earth's crust, approximately 10 of lithium4The metal magnesium has higher stability and higher melting point than lithium, so that the metal magnesium is safer than lithium and is considered as a metal cathode with good application prospect and high specific capacity densityA material. Although the theoretical specific capacity is not as good as that of lithium (3862mAh g)-1) But also relatively observable (2205mAh g)-1). The magnesium secondary battery is widely researched and developed as a novel green battery, and compared with a lithium ion battery which is researched well, although the magnesium secondary battery is not developed on portable equipment at present, the magnesium secondary battery is expected to get a further breakthrough in the aspects of price, use safety performance, large-load energy storage and the like. However, magnesium ions have a larger charge density and a more severe solvation phenomenon than lithium ions, and thus magnesium ions are more difficult to intercalate into a matrix material than lithium ions, and thus finding a matrix material from which magnesium ions can be reversibly deintercalated and intercalated is a major issue in the research of magnesium secondary batteries.
Currently, research on positive electrode materials for magnesium secondary batteries has been mainly focused on compounds such as transition metal oxides, transition metal sulfides, polyanionic compounds, and the like. Among them, transition metal sulfides have considerable research prospects as a positive electrode material of a magnesium secondary battery, and transition metal sulfides are considered as a typical reversible intercalation/deintercalation matrix material. Compared with transition metal oxides, the crystal structure of the transition metal sulfide is not easy to capture magnesium ions, and the reversible deintercalation degree of the magnesium ions can be improved. The sulfide positive electrode material of the magnesium secondary battery mainly comprises a Scherfrel (Chevrel) phase compound (Mo)6S8) And binary metal sulfides (MoS)2、TiS2Etc.). Chevrel phase compound (Mo)6S8) The Chevrel phase compound serving as the positive electrode material of the magnesium secondary battery has good cycle performance and diffusion kinetic properties, but the preparation conditions of the material are harsh, the compound containing three elements (copper, molybdenum and sulfur) needs to be prepared by reacting for a long time under a specific atmosphere and temperature, and the reaction process is complicated. Binary metal sulfide (MoS)2、TiS2Etc.) have also been widely studied and achieved certain results as positive electrode materials for magnesium secondary batteries. Researchers have prepared MoS with different structural characteristics by chemical reaction between liquids2The lithium ion battery is applied to a magnesium secondary battery as a positive electrode material, however, the specific discharge capacity of the batteryOnly 2-25 mAh g-1The circulation efficiency is 10-40%. TiS with layered structure2Ions can be inserted into the gaps of the sheets, and researchers compared two-dimensional sheets (1-TiS)2)TiS2And the three-dimensional cube (c-TiS)2)TiS2At 0.2mol L-1The chemical magnesium intercalation property in the dibutyl magnesium electrolyte respectively obtains Mg0.25TiS2And Mg0.22TiS2The reversible deintercalation of magnesium ions can be realized, but the capacity attenuation of the battery is serious.
Ferrous disulfide (FeS)2) Is an important transition metal sulfide, has attracted wide attention of researchers due to the characteristics of high theoretical energy, environmental protection and the like, and FeS2But the application range of the cathode material is wide, but the cathode material is not applied to the sulfide cathode material of the magnesium secondary battery.
Disclosure of Invention
The invention aims to provide a positive electrode material of a magnesium secondary battery and a preparation method thereof, wherein a binary metal sulfide FeS is selected2As a substrate material, a certain amount of nano carbon material is doped in situ to synthesize a composite material as a positive electrode material of the magnesium secondary battery, so as to expand the application of disulfide in the magnesium secondary battery and improve the performance of the magnesium secondary battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the positive electrode material is a ferrous disulfide/nano carbon composite material formed by coating ferrous disulfide in situ with a carbon nano material, and is applied to the magnesium secondary battery, wherein the weight percentages of the carbon material and the ferrous disulfide in the ferrous disulfide/nano carbon composite material are as follows: 2 to 5 percent of carbon material and 98 to 95 percent of ferrous disulfide.
A preparation method of a positive electrode material of a magnesium secondary battery comprises the following specific steps:
a. preparing a composite material ferrous disulfide/nano carbon:
mixing an iron source and a sulfur source according to a molar ratio, adding the mixture into 150-170 mL of deionized water, violently stirring until the mixture is completely dissolved, adding an acid-treated carbon material into the mixed solution, fully stirring for 0.5-1 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, keeping rapid stirring in the hydrothermal reaction process, naturally cooling to room temperature after the hydrothermal reaction, performing centrifugal separation at a rotating speed of 8000-10000 r/min, repeatedly washing the product with absolute ethyl alcohol and deionized water, and finally performing freeze drying to obtain the ferrous disulfide composite material coated with the carbon nanomaterial in situ;
b. preparing an electrode slice:
fully grinding the composite material obtained in the step a and a conductive agent, adding the composite material and the conductive agent into an organic solvent for dissolving a binder, stirring, uniformly coating slurry on a copper current collector by using a coating machine, drying, and tabletting to obtain a positive plate; and selecting the metal magnesium polished by sand paper as the negative plate.
The iron source is ferrous sulfate.
The sulfur source is L-cysteine.
The molar ratio of the iron source to the sulfur source is 1-1.2: 4-4.2.
The hydrothermal reaction temperature is 160-170 ℃, and the water reaction time is as follows: 10-12 h.
The carbon material is a multi-wall carbon nanotube or a single-wall carbon nanotube or graphene.
The mass ratio of the composite material, the conductive agent and the binder in the step b is 6-8: 1-2.
And the drying condition in the step b is vacuum drying for 8-10 h at 70-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a positive electrode material of a magnesium secondary battery and a preparation method thereof. When the material is used as the magnesium secondary battery anode material, more channels can be provided for the reversible diffusion of magnesium ions, so that the battery has higher charge-discharge specific capacity and excellent cycle performance.
The synthesis of the substrate material only needs two elements, the step method is simple and convenient, high-temperature calcination is not needed, the substrate material can be directly applied after preparation, the preparation raw materials are rich, the cost is low, and the large-scale production is easy.
Drawings
Fig. 1 is a schematic view of a reaction apparatus for a positive electrode material of a magnesium secondary battery.
FIG. 2 shows that the amount of the ferrous disulfide/MWCNTs positive electrode material is 20mA g-1Constant current charge and discharge curves at current density (example 1).
FIG. 3 shows the ferrous disulfide/Graphene anode material at 20mA g-1Constant current charge and discharge curves at current density (example 2).
In the figure: 1-reaction kettle, 2-sample stirrer, 3-silicon oil, 4-heating tube, 5-oil bath, 6-reaction solution and 7-thermistor.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples described below.
The positive electrode material of the magnesium secondary battery is a ferrous disulfide/nano carbon composite material (FeS) formed by coating ferrous disulfide on a carbon nano material in situ2and/C) and applying the composite material to a magnesium secondary battery, wherein the weight percentage of the carbon material and the ferrous disulfide in the ferrous disulfide/nano carbon composite material is as follows: 2 to 5 percent of carbon material and 98 to 95 percent of ferrous disulfide. The material has high charge-discharge specific capacity, excellent cycle performance and rate capability.
A preparation method of a positive electrode material of a magnesium secondary battery comprises the following specific steps:
a. preparing a composite material ferrous disulfide/nano carbon:
mixing an iron source and a sulfur source according to a molar ratio, adding the mixture into 150-170 mL of deionized water, violently stirring until the mixture is completely dissolved, adding an acid-treated carbon material into the mixed solution, fully stirring for 0.5-1 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, keeping rapid stirring in the hydrothermal reaction process, naturally cooling to room temperature after the hydrothermal reaction, performing centrifugal separation at a rotating speed of 8000-10000 r/min, repeatedly washing the product with absolute ethyl alcohol and deionized water, finally performing freeze drying, pre-freezing at-70 ℃, and finally cooling to room temperature to finish the freeze drying process to obtain the ferrous disulfide composite material coated with the carbon nano material in situ.
As shown in figure 1, the synthesis method in the reaction kettle 1 is a 'one-step hydrothermal method', the closed reaction kettle 1 filled with the mixture is heated and stirred through an oil bath pot 5, the stirring speed is 600-800 rpm, and the composite material is synthesized in one step. The method can realize FeS product2Nanocrystallization of/C and making two components FeS2And C, mixing more uniformly and fully.
b. Preparing an electrode slice:
fully grinding the composite material obtained in the step a and a conductive agent, adding the composite material and the conductive agent into an organic solvent for dissolving a binder, stirring, uniformly coating slurry on a copper current collector by using a coating machine, drying, and tabletting to obtain a positive plate; and selecting the metal magnesium polished by sand paper as the negative plate.
The iron source is ferrous sulfate (FeSO)4·7H2O)。
The sulfur source is L-cysteine (C)3H7NO2S)。
The molar ratio of the iron source to the sulfur source is 1-1.2: 4-4.2.
The hydrothermal reaction temperature is 160-170 ℃, and the water reaction time is as follows: 10-12 h.
The carbon material is multi-wall carbon nanotubes (MWCNTs) or single-wall carbon nanotubes (SWCNTs) or Graphene (Graphene).
The mass ratio of the composite material, the conductive agent and the binder in the step b is 6-8: 1-2.
And the drying condition in the step b is vacuum drying for 8-10 h at 70-80 ℃.
The invention adopts an iron source and a sulfur source to develop a one-step hydrothermal method for preparing FeS2a/C nanocomposite material. The method can lead the hydrothermal reaction to be carried out under the conditions of high temperature, high pressure and rapid stirring, and lead the two components of FeS to be simultaneously existed2The mixture is more uniformly and fully mixed with C to realize the FeS product2Nanocrystallization of/C.
Example 1: the weight percentages of the carbon material and the ferrous disulfide in the ferrous disulfide/nanocarbon composite material of the embodiment are as follows: 2 percent of carbon material and 98 percent of ferrous disulfide
The multi-walled carbon nanotubes (MWCNTs) are required to be subjected to acid washing, a certain amount of MWCNTs are placed in a mixed solution of hydrochloric acid (with the concentration of 98%) and nitric acid (with the concentration of 98%) in a volume ratio of 3: 1, ultrasonic dispersion is carried out, repeated washing is carried out after uniform dispersion is carried out until the solution is neutral, finally, filtration is carried out, and the MWCNTs after acid washing are subjected to vacuum drying at the temperature of 60 ℃. 40mg of MWCNTs after acid washing are placed in 40mL of deionized water for ultrasonic dispersion, and after uniform dispersion, the MWCNTs are transferred to 2.22g of FeSO4·7H2O and 3.87g C3H7NO2In the S mixed solution (molar ratio is 1: 4), the total amount of deionized water in the solution is 160mL, and the solution is fully stirred. The mixed solution was transferred to a reaction vessel (200 mL capacity) having a clean, smooth polytetrafluoroethylene liner. Heating and stirring (as shown in figure 1) a closed reaction kettle filled with the mixture through an oil bath kettle at 160 ℃, wherein the stirring speed is 600-800 rpm, the hydrothermal reaction time is 12 hours, cooling to room temperature is carried out, separating the obtained product by using a centrifugal machine, repeatedly washing by using deionized water and absolute ethyl alcohol, finally freeze-drying, pre-freezing at minus 70 ℃, and finally cooling to room temperature to finish the freeze-drying process to obtain the ferrous disulfide/MWCNTs composite material.
Fully grinding the prepared ferrous disulfide/MWCNTs, weighing the ferrous disulfide/MWCNTs, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 1, and dripping 1.2mL of 0.2mol L-1Magnetically stirring N-methylpyrrolidone (NMP) until PVDF is completely dissolved, mixing and fully grinding ferrous disulfide/MWCNTs and Super P, adding the mixture into the solution, continuously stirring the mixture into paste, and uniformly stirring the paste by using a coating machineUniformly coating the copper foil with a clean surface, drying the coated copper current collecting sheet in a vacuum drying oven at 80 ℃ for 10 hours, cutting the copper current collecting sheet into a wafer with the diameter of 1.0cm as a positive plate, and controlling the quality of an active substance to be 1.5-2.0 mg.
The example is applied to button cells with good development prospect.
Assembling and testing the performance of the battery: selecting sand paper polished bright metal magnesium as a negative plate, transferring the prepared positive plate and negative plate into a glove box with argon atmosphere (oxygen content and water content are controlled to be less than or equal to 0.1ppm), and adding 0.25M Mg (AlCl)2EtBu)2The type of the battery is CR2032, the magnesium secondary battery with the type is selected because the magnesium secondary battery has the advantages of small volume, convenient operation and the like, and the material prepared by the method has higher discharge capacity when being applied to the magnesium secondary battery with the type, and has good application prospect as an environment-friendly energy source.
As shown in FIG. 2, the current embodiment is operated at 20mA g-1Constant current charge and discharge curve diagram under current density. The first discharge specific capacity of the battery reaches up to 167mAh g-1And after circulating for 50 circles, the specific discharge capacity can still be maintained at 148mAh g-1The composite material prepared by in-situ coating of the nano carbon material is used as the magnesium secondary battery anode material, so that the conductivity of the electrode material is improved, more channels are provided for the transmission of magnesium ions, and the electrode material has higher initial specific capacity, good cycle stability and structural stability.
Example 2: the weight percentages of the carbon material and the ferrous disulfide in the ferrous disulfide/nanocarbon composite material of the embodiment are as follows: 2% of carbon material and 98% of ferrous disulfide.
40mg of graphene is placed in 40mL of deionized water for ultrasonic dispersion, and after uniform dispersion, the graphene is transferred to 2.22g of FeSO4·7H2O and 3.87g C3H7NO2In the S mixed solution, the total amount of deionized water in the solution is 160mL, and the solution is fully stirred. After the mixed solution is transferred to the polymer with clean and smooth polymerTetrafluoroethylene-lined reactor (volume 200 mL). Heating and stirring (shown in figure 1) a closed reaction kettle filled with the mixture through an oil bath kettle at 160 ℃, wherein the stirring speed is 600-800 rpm, the hydrothermal reaction is carried out for 12 hours, the reaction kettle is cooled to room temperature, the obtained product is separated by a centrifugal machine, then deionized water and absolute ethyl alcohol are repeatedly washed, finally freeze drying is carried out, pre-freezing is carried out at minus 70 ℃, and finally the reaction kettle is cooled to room temperature, so that the freeze drying process is completed, and the ferrous disulfide/Graphene composite material is obtained.
Fully grinding the prepared ferrous disulfide/Graphene, weighing the ferrous disulfide/Graphene, the conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 1, and firstly, dropwise adding 1.2mL of 0.2mol L-1N-methylpyrrolidone (NMP) is magnetically stirred until PVDF is completely dissolved, then ferrous disulfide/MWCNTs and Super P are mixed and fully ground, the mixture is added into the solution, the mixture is continuously stirred into paste, slurry is uniformly coated on copper foil with a clean surface by a coating machine, a coated copper current collecting sheet is placed in a vacuum drying oven to be dried for 10 hours at the temperature of 80 ℃, the copper current collecting sheet is cut into a wafer with the diameter of 1.0cm and is used as a positive electrode sheet, and the quality of active substances (ferrous disulfide/Graphene) is controlled to be 1.5-2.0 mg.
Assembling and testing the performance of the battery: selecting sand paper polished bright metal magnesium as a negative plate, transferring the prepared positive plate and negative plate into a glove box with argon atmosphere (oxygen content and water content are controlled to be less than or equal to 0.1ppm), and adding 0.25M Mg (AlCl)2EtBu)2The type of the battery is CR2032, the magnesium secondary battery with the type is selected because the magnesium secondary battery has the advantages of small volume, convenient operation and the like, and the material prepared by the method has higher discharge capacity when being applied to the magnesium secondary battery with the type, and has good application prospect as an environment-friendly energy source.
As shown in FIG. 3, the current embodiment is operated at 20mA g-1Constant current charge and discharge curve diagram under current density. The first discharge specific capacity of the battery reaches 50mAh g-1。

Claims (5)

1. The positive electrode material of the magnesium secondary battery is characterized in that the positive electrode material is a ferrous disulfide/nano carbon composite material formed by coating ferrous disulfide on a carbon nano material in situ and is applied to the magnesium secondary battery, and the weight percentages of the carbon material and the ferrous disulfide in the ferrous disulfide/nano carbon composite material are as follows: 2% -5% of carbon material and 98% -95% of ferrous disulfide;
the preparation method of the cathode material of the magnesium secondary battery comprises the following steps:
mixing an iron source and a sulfur source according to a molar ratio, adding the mixture into 150-170 mL of deionized water, violently stirring until the mixture is completely dissolved, adding an acid-treated carbon material into the mixed solution, fully stirring for 0.5-1 h, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, keeping rapid stirring in the hydrothermal reaction process, naturally cooling to room temperature after the hydrothermal reaction, performing centrifugal separation at a rotating speed of 8000-10000 r/min, repeatedly washing the product with absolute ethyl alcohol and deionized water, and finally performing freeze drying to obtain a ferrous disulfide/nano carbon composite material formed by coating ferrous disulfide on a carbon nano material in situ;
the sulfur source is L-cysteine.
2. The positive electrode material for a magnesium secondary battery as claimed in claim 1, wherein the iron source is ferrous sulfate.
3. The positive electrode material for a magnesium secondary battery according to claim 1, wherein the molar ratio of the iron source to the sulfur source is 1-1.2: 4-4.2.
4. The positive electrode material for a magnesium secondary battery according to claim 1, wherein the hydrothermal reaction temperature is 160 to 170 ℃, and the hydrothermal reaction time is: 10-12 h.
5. The positive electrode material for a magnesium secondary battery as claimed in claim 1, wherein the carbon material is multi-walled carbon nanotube or single-walled carbon nanotube or graphene.
CN201810776325.7A 2018-07-16 2018-07-16 Positive electrode material of magnesium secondary battery and preparation method thereof Active CN109037623B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810776325.7A CN109037623B (en) 2018-07-16 2018-07-16 Positive electrode material of magnesium secondary battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810776325.7A CN109037623B (en) 2018-07-16 2018-07-16 Positive electrode material of magnesium secondary battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109037623A CN109037623A (en) 2018-12-18
CN109037623B true CN109037623B (en) 2021-10-29

Family

ID=64643176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810776325.7A Active CN109037623B (en) 2018-07-16 2018-07-16 Positive electrode material of magnesium secondary battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109037623B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817950A (en) * 2019-03-15 2019-05-28 贵州梅岭电源有限公司 A kind of C cladding MoxCo1-xS2The preparation method of composite positive pole
WO2021166280A1 (en) * 2020-02-21 2021-08-26 パナソニックＩｐマネジメント株式会社 Positive electrode active material and magnesium secondary battery
CN111960477A (en) * 2020-08-20 2020-11-20 辽宁科技大学 Preparation method of all-solid-state supercapacitor electrode material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8211578B2 (en) * 2009-06-09 2012-07-03 The Gillette Company Magnesium cell with improved electrolyte
CN106532111B (en) * 2015-09-15 2019-01-08 中国科学院上海硅酸盐研究所 A kind of magnesium cell of the high-energy density based on conversion reaction

Also Published As

Publication number Publication date
CN109037623A (en) 2018-12-18

Similar Documents

Publication Publication Date Title
CN104332616B (en) Graphene coated graphite composite lithium ion battery negative material and its preparation method
CN108269982B (en) Composite material, preparation method thereof and application thereof in lithium ion battery
CN109817918B (en) Sulfur-doped MXene composite material and preparation method and application thereof
CN106207171B (en) A kind of preparation method of molybdenum disulfide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery
CN108321378B (en) Preparation method of metal oxide @ metal compound/graphene core-shell semiconductor material with heterojunction interface effect
CN109037623B (en) Positive electrode material of magnesium secondary battery and preparation method thereof
CN106252628A (en) The preparation method of a kind of manganese oxide/graphene nanocomposite material, lithium ion battery negative, lithium ion battery
CN111211273A (en) Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof
CN107579250A (en) A kind of complex carbon material conductive agent
Liu et al. 3D nanoflower-like MoS2 grown on wheat straw cellulose carbon for lithium-ion battery anode material
CN110165190A (en) A kind of nanocarbon/metal sulfide composite material and preparation method and application
CN105000545A (en) Method for preparing lithium ion battery artificial graphite/coke anode material
CN106058193A (en) Novel negative electrode material of sodium-ion battery as well as preparation method and application thereof
CN109950503B (en) CoMoOxPreparation method of/carbon/sulfur composite nano material, lithium ion battery cathode and lithium ion half battery
CN110085823B (en) Nano composite negative electrode material and preparation method and application thereof
CN109755535B (en) Tin-manganese sulfide/carbon composite material and preparation method and application thereof
CN105591107B (en) A kind of ultra-thin stratiform V5S8And preparation method thereof with the application in lithium ion/sodium-ion battery
CN104852042A (en) Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material
CN107959024B (en) Flaky Sb for sodium ion battery cathode2Se3Method for preparing nanocrystalline
CN113506860A (en) Carbon nanotube-in-tube @ selenium composite material and preparation method and application thereof
CN115188936A (en) Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof
CN103208624A (en) Preparation method of Fe3O4@C nano composite lithium battery negative electrode materials of monodisperse core-shell structure
CN114243007A (en) Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof
CN109786728B (en) NbOPO4 nanosheet/rGO composite material and preparation method and application thereof
WO2018195837A1 (en) Metal-sulfur battery and preparation method therefor

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