CN110854355A - Composite electrode, manufacturing method thereof and battery - Google Patents

Composite electrode, manufacturing method thereof and battery Download PDF

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Publication number
CN110854355A
CN110854355A CN201810953577.2A CN201810953577A CN110854355A CN 110854355 A CN110854355 A CN 110854355A CN 201810953577 A CN201810953577 A CN 201810953577A CN 110854355 A CN110854355 A CN 110854355A
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transition metal
metal substrate
composite electrode
layer
sulfide layer
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范卫超
王俊明
孟垂舟
朱晓军
房金刚
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ENN Science and Technology Development Co Ltd
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ENN Science and Technology Development Co Ltd
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • H01M4/136—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
    • H01M4/13—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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a composite electrode, a manufacturing method thereof and a battery, and relates to the technical field of batteries, in order to inhibit capacity fading of the battery in the charging and discharging processes. The manufacturing method of the composite electrode comprises the steps of providing a transition metal substrate; and forming a transition metal sulfide layer on the surface of the transition metal substrate by adopting a vapor deposition method. The composite electrode is manufactured by the method. The composite electrode, the manufacturing method thereof and the battery provided by the invention are used for inhibiting capacity fading in the charging and discharging processes of the battery.

Description

Composite electrode, manufacturing method thereof and battery
Technical Field
The invention relates to the technical field of batteries, in particular to a composite electrode, a manufacturing method thereof and a battery.
Background
Aluminum ion batteries are a new type of energy storage device with high theoretical capacity, good safety characteristics, low flammability, and low cost, and are considered as a promising energy storage of the new generation. Since the positive electrode material is a key component of the aluminum ion battery, which is a main factor determining the electrochemical performance of the aluminum ion battery, the preparation and performance improvement of the positive electrode material will become important points of research.
A large number of research results prove that the transition metal sulfide has excellent electrical characteristics of good conductivity, large capacitance and the like, which enables the transition metal sulfide to be used in a positive electrode material of an aluminum ion battery. Although transition metal sulfides have a high capacity, Al generated in the electrode reaction is generated in the transition metal sulfides2S3And the intermediate products can be dissolved in the electrolyte, so that the performance of the aluminum ion battery is seriously attenuated in the charging and discharging process.
Disclosure of Invention
The invention aims to provide a composite electrode, a manufacturing method thereof and a battery, so as to inhibit capacity fading of the battery in the charging and discharging processes.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method of making a composite electrode, comprising:
providing a transition metal substrate;
and forming a transition metal sulfide layer on the surface of the transition metal substrate by adopting a vapor deposition method.
Compared with the prior art, in the manufacturing method of the composite electrode, the transition metal sulfide layer is formed on the surface of the transition metal substrate by adopting a vapor deposition method, so that when the composite electrode manufactured by adopting the manufacturing method of the composite electrode is used as a positive electrode and applied to a battery, if the battery generates a discharge reaction, electrons transmitted by an external lead can be conducted to the transition metal sulfide layer by the transition metal substrate contained in the composite electrode used as the positive electrode, and an electrochemical reaction is generated on the contact surface of the transition metal substrate and the transition metal sulfide layer; in the process, transition metal atoms on the surface of the transition metal substrate contacting the transition metal sulfide layer lose electrons to become transition metal ions, and are transferred to the surface of the transition metal sulfide layer contacting the transition metal substrate; and because the transition metal sulfide layer contacts the transition metal ions contained on the surface of the transition metal substrate, electrons are obtained to form transition metal atoms and transition metal sulfides with lower valence states of the transition metal ions. If the battery is charged, a part of transition metal sulfide contained in the transition metal sulfide layer loses electrons, so that the transition metal sulfide with lower transition metal ion valence state obtained in the discharging reaction is oxidized to form transition metal sulfide with higher transition metal ion valence state, and partial transition metal is deposited.
Therefore, in the process of charging and discharging, the gain-loss electrons occur at the contact surface of the transition metal substrate and the transition metal sulfide layer; and because the transition metal sulfide layer has a certain thickness, ions contained in the electrolyte contained in the battery are difficult to enter the contact surface of the transition metal substrate and the transition metal sulfide layer, when the composite electrode manufactured by the manufacturing method of the composite electrode provided by the invention is used as a positive electrode for the battery, the transition metal sulfide layer contained in the composite electrode is difficult to react with the electrolyte, so that the capacity attenuation of the battery is greatly inhibited.
In addition, in the process of charging and discharging the battery, the transition metal sulfide layer generates oxidation-reduction reaction, so that the transition metal sulfide layer can be used as a carrier for storing electrons, and the transmission speed of the electrons is increased.
The invention also provides a composite electrode which is manufactured by applying the manufacturing method of the composite electrode, and the composite electrode comprises a transition metal substrate and a transition metal sulfide layer formed on the surface of the transition metal substrate.
Compared with the prior art, the beneficial effects of the composite electrode provided by the invention are the same as those of the manufacturing method of the composite electrode provided by the technical scheme, and are not repeated herein.
The invention also provides a battery, which comprises the composite electrode in the technical scheme.
Compared with the prior art, the beneficial effects of the battery provided by the invention are the same as those of the manufacturing method of the composite electrode in the technical scheme, and are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flowchart of a method for manufacturing a composite electrode according to an embodiment of the present invention;
FIG. 2 is a flow chart of a vapor deposition process for forming a transition metal sulfide layer on a surface of a transition metal substrate according to an embodiment of the present invention;
FIG. 3 is a flow chart illustrating the reaction of hydrogen sulfide gas in the reaction vessel with the surface transition metal atoms of the transition metal substrate according to an embodiment of the present invention;
FIG. 4 is a flowchart of an anticorrosion coating treatment of at least a transition metal sulfide layer formed on a surface of the transition metal substrate;
FIG. 5 is a schematic structural diagram of a composite electrode according to an embodiment of the present invention;
fig. 6 is a cycle charge and discharge test curve of the soft package aluminum ion battery.
Reference numerals:
1-transition metal substrate, 2-transition metal sulfide layer;
3-anti-corrosion layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, a method for manufacturing a composite electrode according to an embodiment of the present invention includes the following steps:
step S100: providing a transition metal substrate; the transition metal substrate can be tailored to the actual size and shape requirements.
Step S300: and forming a transition metal sulfide layer on the surface of the transition metal substrate by adopting a vapor deposition method.
In the manufacturing method of the composite electrode provided by the embodiment of the invention, the transition metal sulfide layer is formed on the surface of the transition metal substrate by adopting a vapor deposition method, so that when the composite electrode manufactured by adopting the manufacturing method of the composite electrode is used as a positive electrode and applied to a battery, if the battery generates a discharge reaction, the transition metal substrate contained in the composite electrode used as the positive electrode can conduct electrons transmitted by an external lead to the transition metal sulfide layer, and the electrochemical reaction is generated on the contact surface of the transition metal substrate and the transition metal sulfide layer; in the process, transition metal atoms on the surface of the transition metal substrate contacting the transition metal sulfide layer lose electrons to become transition metal ions, and are transferred to the surface of the transition metal sulfide layer contacting the transition metal substrate; and because the transition metal sulfide layer contacts the transition metal ions contained on the surface of the transition metal substrate, electrons are obtained to form transition metal atoms and transition metal sulfides with lower valence states of the transition metal ions. If the battery is charged, a part of transition metal sulfide contained in the transition metal sulfide layer loses electrons, so that the transition metal sulfide with lower transition metal ion valence state obtained in the discharging reaction is oxidized to form transition metal sulfide with higher transition metal ion valence state, and partial transition metal is deposited.
Therefore, in the process of charging and discharging, the gain-loss electrons occur at the contact surface of the transition metal substrate and the transition metal sulfide layer; and because the transition metal sulfide layer has a certain thickness, ions contained in the electrolyte contained in the battery are difficult to enter the contact surface of the transition metal substrate and the transition metal sulfide layer, when the composite electrode manufactured by the manufacturing method of the composite electrode provided by the embodiment of the invention is used as a positive electrode for the battery, the transition metal sulfide layer contained in the composite electrode is not easy to react with the electrolyte, so that the capacity attenuation of the battery is greatly inhibited, and the stability of the battery can be improved.
In addition, in the process of charging and discharging the battery, the transition metal sulfide layer generates oxidation-reduction reaction, so that the transition metal sulfide layer can be used as a carrier for storing electrons, and the transmission speed of the electrons is increased.
In order to prevent the transition metal oxide from being formed on the surface of the transition metal substrate, which may result in poor electrical conductivity of the fabricated composite electrode, as shown in fig. 1, after providing the transition metal substrate, the fabrication method of the composite electrode further includes, before forming a transition metal sulfide layer on the surface of the transition metal substrate by a vapor deposition method:
step S200: the transition metal substrate is pickled until bubbles are generated on the surface of the transition metal substrate. At this time, it is explained that the transition metal oxide contained in the surface of the transition metal substrate is completely removed, and whether or not the transition metal oxide on the surface of the transition metal substrate is completely removed can be judged by whether or not the surface generates bubbles, and corrosion of the transition metal substrate by the acidic solution used for pickling can be minimized. Wherein, the acid solution used for acid cleaning is generally a nitric acid aqueous solution with the mass concentration of 2-10%.
In order to avoid the transition metal substrate from being corroded by the residual acidic solution on the surface of the transition metal substrate after the transition metal substrate is subjected to acid cleaning, the acid-cleaned transition metal substrate can be put into absolute ethyl alcohol for ultrasonic cleaning, so that the residual acidic solution on the surface of the acid-cleaned transition metal substrate can be removed. Meanwhile, after the transition metal substrate after acid washing is cleaned by absolute ethyl alcohol, the absolute ethyl alcohol attached to the surface of the transition metal substrate can be quickly volatilized, so that unnecessary drying processes are reduced.
As shown in fig. 2, the above-mentioned specific method for forming a transition metal sulfide layer on the surface of a transition metal substrate by vapor deposition includes the following steps:
step S310: introducing hydrogen sulfide gas into the reaction container in an oxygen-free environment; the reaction vessel may be purged with an inert gas such as nitrogen or argon to evacuate the reaction vessel of air, resulting in an oxygen-free environment within the reaction vessel. The reaction may be performed by a tubular furnace, or may be performed by other reaction equipment, and is not limited herein.
Step S320: and (3) conveying the transition metal substrate into a reaction container filled with hydrogen sulfide gas.
Step S330: controlling the hydrogen sulfide gas in the reaction container to react with transition metal atoms contained on the surface of the transition metal substrate, so that a transition metal sulfide layer is formed on the surface of the transition metal substrate. In this case, the transition metal contained in the transition metal substrate is the same as the transition metal contained in the transition metal sulfide layer.
Illustratively, as shown in fig. 3, controlling the hydrogen sulfide gas in the reaction vessel to react with the transition metal atoms on the surface of the transition metal substrate so that the transition metal sulfide layer is formed on the surface of the transition metal substrate includes:
step S331: controlling a reaction vessel to heat the transition metal substrate to 400-700 ℃; controlling the reaction vessel to heat the transition metal substrate to 400 ℃ to 700 ℃ comprises:
controlling the reaction vessel to heat the transition metal substrate to 400-700 ℃ according to the heating rate of 200-600 ℃/h.
Step S332: the hydrogen sulfide gas in the reaction vessel reacts with the transition metal atoms contained in the surface of the transition metal substrate at 400 ℃ to 700 ℃ to obtain a transition metal sulfide layer formed on the surface of the transition metal substrate.
Considering that the temperature in the reaction vessel is higher after the reaction is finished, for this reason, inert gas can be blown into the reaction vessel after the reaction is finished, so that the temperature in the reaction vessel is reduced to room temperature, and then the transition metal substrate with the transition metal sulfide layer formed on the surface is taken out; meanwhile, after the reaction is finished, the transition metal substrate which is temporarily not taken out and has a transition metal sulfide layer formed on the surface can be protected by blowing the reaction container, so that the transition metal substrate with the transition metal sulfide layer formed on the surface is prevented from being oxidized due to the contact with air.
Step S340: and vacuum drying the transition metal substrate with the transition metal sulfide layer formed on the surface to remove moisture, thereby preventing the contained moisture from affecting the performance of the composite electrode. The temperature of vacuum drying is 60-80 ℃, and the vacuum drying time is 1-6 h.
As is apparent from the above-described process of forming a transition metal sulfide layer on the surface of a transition metal substrate by vapor deposition, the transition metal contained in the transition metal substrate can be used as a source of the transition metal forming the transition metal sulfide layer. And reacting the transition metal substrate with hydrogen sulfide gas in an oxygen-free environment at 400 to 700 ℃ to form a transition metal sulfide on the surface of the transition metal substrate.
As for the thickness of the transition metal sulfide layer formed on the surface of the transition metal substrate, the thickness can be set according to the application requirement, the reaction time can be set according to the actual situation, and is generally set to be 2h to 4h, and the thickness of the formed metal sulfide layer is thinner as the reaction time is shorter at the same temperature. When the hydrogen sulfide gas in the reaction vessel reacts with the transition metal atoms on the surface of the transition metal substrate at 400 to 700 ℃ for 2 to 4 hours, the thickness of the formed transition metal sulfide layer is about 1 to 100 μm.
Optionally, the flow rate of the hydrogen sulfide gas is controlled so that the formed transition metal sulfide uniformly covers the surface of the transition metal sulfide substrate. When the flow rate of the hydrogen sulfide gas is 50mL/min-150mL/min, the transition metal sulfide can be more uniformly covered on the surface of the transition metal sulfide substrate.
Optionally, in order to increase a contact area between the transition metal substrate and the hydrogen sulfide gas, the transition metal substrate is a foam-type transition metal substrate. The foam type transition metal substrate is loose and porous, and in an oxygen-free environment at 400-700 ℃, the contact area between the foam type transition metal substrate and hydrogen sulfide gas is large, so that the deposition amount of the transition metal sulfide can be increased under the condition that the contact area between a subsequent transition metal sulfide layer and the foam type transition metal substrate is large, and the transition metal sulfide layer is compact with the foam type transition metal substrate.
Illustratively, the foamed transition metal substrate has a porosity of 20 to 97% and a thickness of 50 to 500. mu.m. The greater the porosity of the foamed transition metal substrate, the greater its surface area, and the better the contact with the formed transition metal sulfide layer.
Optionally, as shown in fig. 1, after the transition metal sulfide layer is formed on the surface of the transition metal substrate by using a vapor deposition method, the method for manufacturing the composite electrode further includes:
step S400: and performing corrosion prevention coating treatment on at least the transition metal sulfide layer formed on the surface of the transition metal substrate to form a corrosion prevention layer on at least the surface of the transition metal sulfide layer, wherein the material of the corrosion prevention layer is a conductive corrosion prevention material. The anticorrosive material contained in the anticorrosive material dispersion is graphene oxide and/or nanocarbon, but is not limited thereto. When the anti-corrosion layer is formed on the surface of the transition metal sulfide layer, the transition metal fluidized layer is not easily corroded by electrolyte during redox reaction in the charging and discharging process, so that the side reaction of the transition metal sulfide layer and the electrolyte is further inhibited, and the capacity attenuation of the sound quality battery can be effectively realized when the composite electrode is applied to the battery.
As shown in fig. 4, the anti-corrosion coating treatment of the transition metal sulfide layer formed on the surface of the transition metal substrate includes:
step S410: placing the transition metal substrate with the transition metal sulfide layer formed on the surface into the anti-corrosion material dispersion liquid and stirring, so that the anti-corrosion material contained in the anti-corrosion material dispersion liquid is at least attached to the surface of the transition metal sulfide layer, and obtaining a composite electrode preform; the concentration of the anti-corrosion material dispersion liquid is 0.1 mg/L-500 mg/L; the solvent of the anticorrosive material dispersion liquid is water, ethanol or N-methyl pyrrolidone.
Of course, the anticorrosive material contained in the anticorrosive material dispersion may be attached not only to the surface of the transition metal sulfide layer but also to the exposed surface of the transition metal substrate.
Step S420: and (3) performing vacuum drying on the composite electrode preform to remove the solvent of the anticorrosive material dispersion liquid attached to the surface of the composite electrode preform. The equipment used for vacuum drying is generally a vacuum drying oven. The temperature of vacuum drying can be selected to be 80-100 ℃, and the vacuum drying time is 1-6 h.
Step S430: heating the dried composite electrode preform at 100-300 ℃ in the air atmosphere, so that the anti-corrosion material in the composite electrode is sintered at least on the surface of the transition metal sulfide layer and can also be sintered on the surface of the transition metal substrate exposed outside to obtain the composite electrode; wherein the heating time is set according to the actual situation, for example, 1h-6 h.
Step S440: and flattening the composite electrode to enable the transition metal substrate, the transition metal sulfide layer and the anti-corrosion layer included in the composite electrode to be further tightly combined together.
The transition metal contained in the transition metal substrate is one or more of nickel, cobalt, iron, and copper, but is not limited thereto. The transition metal contained in the transition metal sulfide layer is one or more of nickel, cobalt, iron, and copper, but is not limited thereto.
For example: in the composite electrode manufactured by the manufacturing method of the composite electrode, the transition metal substrate is a Ni substrate, and the transition metal sulfide layer is a NiS layer. The composite electrode is applied to an aluminum ion battery and is used as a positive electrode of the aluminum ion battery.
During the discharging process of the aluminum ion battery, electrons flow from the negative electrode to the positive electrode through the conducting wire, the Ni substrate of the positive electrode conducts the electrons to the NiS layer, so that the contact surface of the Ni substrate and the NiS layer generates electrochemical reaction, and the Ni substrate contacts the nickel gold on the surface of the NiS layer at the momentThe NiS layer contacts the NiS electron on the surface of the Ni substrate to form Ni3S2. During the charging process of the aluminum ion battery, the contact surface of the nickel substrate and the NiS layer generates electrochemical reaction, and Ni is generated at the moment3S2Losing electrons to generate NiS, and depositing partial nickel and gold on the contact surface of the NiS layer and the Ni substrate.
From the above, it can be seen that the Ni substrate provides a nickel source during the formation of the NiS layer; when the formed composite electrode is used in an aluminum ion battery, the NiS layer provides a carrier for storing electrons in the oxidation-reduction (charge-discharge) process and increases the transmission speed of the electrons. In addition, in the process of charging and discharging the aluminum ion battery, the gain and loss electrons of the composite electrode serving as the positive electrode all occur on the contact surface of the Ni substrate and the NiS layer; the NiS layer has a certain thickness, so that Al in electrolyte contained in the aluminum ion battery is ensured3+Is isolated outside the contact surface between the Ni substrate and the NiS layer, so that the composite electrode as the positive electrode is not easy to generate Al by side reaction with the electrolyte during the repeated charge and discharge of the aluminum ion battery2S3Thereby greatly inhibiting the capacity attenuation of the aluminum ion battery.
As shown in fig. 5, an embodiment of the present invention further provides the composite electrode, which is manufactured by applying the manufacturing method of the composite electrode, and the composite electrode includes a transition metal substrate 1 and a transition metal sulfide layer 2 formed on a surface of the transition metal substrate 1.
Compared with the prior art, the beneficial effects of the composite electrode provided by the embodiment of the invention are the same as those of the manufacturing method of the composite electrode, and are not repeated herein.
Further, an anti-corrosion layer 3 is formed on at least the surface of the transition metal sulfide layer to further protect the transition metal sulfide layer 2 and prevent the transition metal sulfide layer 2 from side reactions.
The embodiment of the invention also provides a battery, which comprises the composite electrode provided by the embodiment.
Compared with the prior art, the beneficial effects of the battery provided by the embodiment of the invention are the same as those of the manufacturing method of the composite electrode, and are not repeated herein.
In order to better explain the method for manufacturing the composite electrode provided by the embodiment of the invention, several embodiments are given below.
Example one
Step S100: and cutting the foam Ni by using a cutting machine to obtain a foam Ni wafer serving as a transition metal substrate, wherein the porosity of the foam Ni wafer is 50%, and the thickness of the foam Ni wafer is 200 mu m.
Step S200: and (3) carrying out acid washing on the foam Ni wafer for 5min by adopting dilute nitric acid with the mass concentration of 2%, wherein bubbles are generated on the surface of the foam Ni wafer. The pickled foamed Ni discs were then immersed in ethanol for ultrasonic cleaning and then weighed.
Step S300: and forming a NiS layer on the surface of the foamed Ni wafer after acid cleaning by adopting a vapor deposition method. Specifically, the step of forming the NiS layer on the surface of the foamed Ni wafer after acid cleaning by adopting a vapor deposition method comprises the following steps:
step S310: and introducing nitrogen into the tube furnace, so that the nitrogen sweeps the furnace chamber of the tube furnace to exhaust the air in the furnace chamber of the tube furnace. Then introducing hydrogen sulfide gas into the furnace chamber of the tubular furnace, wherein the flow rate of the hydrogen sulfide gas is 50 mL/min.
Step S320: and (3) feeding the pickled foamed Ni wafer into a furnace chamber of a tubular furnace filled with hydrogen sulfide gas, wherein the foamed Ni wafer is positioned in the middle of the furnace chamber.
Step S330: and controlling hydrogen sulfide gas in the tubular furnace to react with Ni atoms contained on the surface of the pickled foamed Ni wafer, so that a NiS layer is formed on the surface of the foamed Ni wafer. Specifically, the step of controlling hydrogen sulfide gas in the tubular furnace to react with Ni atoms contained on the surface of the pickled foamed Ni wafer so as to form a NiS layer on the surface of the foamed Ni wafer comprises the following steps:
step S331: controlling a tube furnace to heat the foamed Ni wafer after acid washing to 400 ℃ according to the heating rate of 200 ℃/h.
Step S332: the hydrogen sulfide in the tube furnace reacted with the Ni atoms contained on the surface of the pickled Ni foam wafer at 400 ℃ for 4 hours to obtain an NiS layer formed on the surface of the Ni foam wafer.
Step S340: the foamed Ni discs with the NiS layer formed on the surface were vacuum dried at 80 ℃ for 1 h.
Step S400: and carrying out anti-corrosion coating treatment on the NiS layer formed on the surface of the foam Ni wafer, so that graphene oxide layers are formed on the surface of the NiS layer and the exposed surface of the foam Ni wafer. The method for performing the anticorrosion coating treatment on the NiS layer formed on the surface of the foamed Ni wafer comprises the following steps:
step S410: putting the foam Ni wafer with the NiS layer formed on the surface into graphene oxide dispersion liquid with the concentration of 0.1mg/L, stirring for 20min, and stirring in the graphene oxide dispersion liquid to enable graphene oxide contained in the graphene oxide dispersion liquid to be attached to the surface of the NiS layer and the exposed surface of the foam Ni wafer, so as to obtain a composite electrode preform; the solvent of the graphene oxide dispersion liquid is water.
Step S420: and (3) carrying out vacuum drying on the composite electrode preform for 6h at 80 ℃.
Step S430: and heating the dried composite electrode preform at 100 ℃ for 6h in an air atmosphere to enable graphene oxide in the composite electrode to be sintered on the surface of the NiS layer and the surface of the transition metal substrate exposed outside, so as to obtain the composite electrode.
Step S440: the composite electrode was flattened using a shaft press to obtain a composite electrode having a thickness of 100 μm.
Example two
Step S100: and cutting the foamed Cu by using a cutting machine to obtain a foamed Cu wafer serving as a transition metal substrate. The foamed Ni disks had a porosity of 20% and a thickness of 500 μm.
Step S200: and (3) pickling the foam Cu wafer for 3min by using dilute nitric acid with the mass concentration of 10%, wherein bubbles are generated on the surface of the foam Cu wafer. The pickled Cu foam discs were then ultrasonically cleaned by immersing in ethanol and then weighed.
Step S300: and forming a CuS layer on the surface of the foamed Cu wafer after acid cleaning by adopting a vapor deposition method. Specifically, the step of forming the CuS layer on the surface of the pickled foamed Cu wafer by adopting a vapor deposition method comprises the following steps:
step S310: and introducing nitrogen into the tube furnace, so that the nitrogen sweeps the furnace chamber of the tube furnace to exhaust the air in the furnace chamber of the tube furnace. Then introducing hydrogen sulfide gas into the furnace chamber of the tube furnace, wherein the flow rate of the hydrogen sulfide gas is 120 mL/min.
Step S320: and (3) conveying the pickled foamed Cu wafer into a furnace chamber of a tubular furnace filled with hydrogen sulfide gas, wherein the foamed Cu wafer is positioned in the middle of the furnace chamber.
Step S330: and controlling the hydrogen sulfide gas in the tubular furnace to react with Cu atoms contained on the surface of the pickled foamed Cu wafer, so that a CuS layer is formed on the surface of the foamed Cu wafer. Specifically, the step of controlling hydrogen sulfide gas in the tubular furnace to react with Cu atoms contained on the surface of the pickled Cu foam wafer so as to form a CuS layer on the surface of the Cu foam wafer comprises the following steps:
step S331: controlling a tube furnace to heat the foamed Cu wafer after acid washing to 600 ℃ according to the heating rate of 350 ℃/h.
Step S332: the hydrogen sulfide in the tube furnace reacted with the Ni atoms contained on the surface of the foamed Cu wafer after acid washing at 600 ℃ for 3 hours to obtain a CuS layer formed on the surface of the foamed Cu wafer.
Step S340: the foamed Cu wafers with the CuS layer formed on the surface were vacuum dried at 60 ℃ for 6 h.
Step S400: and (3) carrying out anti-corrosion coating treatment on the CuS layer formed on the surface of the foamed Cu wafer, so that a nano carbon layer is formed on the surface of the CuS layer and the exposed surface of the foamed Cu wafer. The anticorrosion coating treatment of the CuS layer formed on the surface of the foamed Cu wafer comprises the following steps:
step S410: placing the foamed Cu wafer with the CuS layer formed on the surface into nano-carbon dispersion liquid with the concentration of 100mg/L, stirring for 18min, and stirring the nano-carbon dispersion liquid to enable nano-carbon contained in the nano-carbon dispersion liquid to be attached to the surface of the CuS layer and the surface of the foamed Cu wafer exposed outside, so as to obtain a composite electrode preform; the solvent of the nano carbon dispersion liquid is ethanol.
Step S420: and (3) carrying out vacuum drying on the composite electrode preform for 1h at 100 ℃.
Step S430: and heating the dried composite electrode preform at 300 ℃ for 1h in an air atmosphere to enable the nanocarbon in the composite electrode to be sintered on the surface of the CuS layer and the surface of the transition metal substrate exposed outside, so as to obtain the composite electrode.
Step S440: the composite electrode was flattened using a shaft press to obtain a composite electrode having a thickness of 100 μm.
EXAMPLE III
Step S100: and cutting the foam Fe by using a cutting machine to obtain a foam Fe wafer serving as a transition metal substrate. The foamed Ni disks had a porosity of 75% and a thickness of 100 μm.
Step S200: and (3) pickling the foam Fe wafer for 0.5min by using dilute nitric acid with the mass concentration of 5%, wherein bubbles are generated on the surface of the foam Fe wafer. The pickled foamed Fe disks were then immersed in ethanol for ultrasonic cleaning and then weighed.
Step S300: and forming a FeS layer on the surface of the pickled foam Fe wafer by adopting a vapor deposition method. Specifically, the step of forming the FeS layer on the surface of the pickled foamed Fe wafer by adopting a vapor deposition method comprises the following steps:
step S310: and introducing nitrogen into the tube furnace, so that the nitrogen sweeps the furnace chamber of the tube furnace to exhaust the air in the furnace chamber of the tube furnace. Then, hydrogen sulfide gas is introduced into the furnace chamber of the tubular furnace, and the flow rate of the hydrogen sulfide gas is 150 mL/min.
Step S320: and (3) feeding the pickled foam Fe wafer into a furnace chamber of a tubular furnace filled with hydrogen sulfide gas, wherein the foamed Fe wafer is positioned in the middle of the furnace chamber.
Step S330: and controlling the hydrogen sulfide gas in the tubular furnace to react with Fe atoms contained on the surface of the pickled foamed Fe wafer, so that an FeS layer is formed on the surface of the foamed Fe wafer. Specifically, the step of controlling the hydrogen sulfide gas in the tubular furnace to react with the Fe atoms contained on the surface of the pickled foamed Fe wafer to form the FeS layer on the surface of the foamed Fe wafer comprises the following steps:
step S331: controlling a tube furnace to heat the pickled foam Fe wafer to 700 ℃ according to the heating rate of 600 ℃/h.
Step S332: the hydrogen sulfide in the tube furnace reacts with the Ni atoms contained on the surface of the pickled foamed Fe wafer at 700 ℃ for 2h to obtain the FeS layer formed on the surface of the foamed Fe wafer.
Step S340: the foamed Fe disks with the FeS layer formed on the surface were dried in vacuum at 60 ℃ for 6 h.
Step S400: and carrying out anti-corrosion coating treatment on the FeS layer formed on the surface of the foamed Fe wafer, so that the nano carbon layers are formed on the surface of the FeS layer and the exposed surface of the foamed Fe wafer. The anticorrosion coating treatment of the FeS layer formed on the surface of the foamed Fe wafer comprises the following steps:
step S410: placing the foam Fe wafer with the FeS layer formed on the surface into the nano-carbon dispersion liquid with the concentration of 230mg/L, stirring for 12min, and stirring the nano-carbon dispersion liquid to enable nano-carbon contained in the nano-carbon dispersion liquid to be attached to the surface of the FeS layer and the exposed surface of the foam Fe wafer to obtain a composite electrode preform; the solvent of the nano carbon dispersion liquid is ethanol.
Step S420: and (3) carrying out vacuum drying on the composite electrode preform for 2h at 90 ℃.
Step S430: and heating the dried composite electrode preform at 180 ℃ for 4h in an air atmosphere to enable the nanocarbon in the composite electrode to be sintered on the surface of the FeS layer and the surface of the transition metal substrate exposed outside, so as to obtain the composite electrode.
Step S440: the composite electrode was flattened using a shaft press to obtain a composite electrode having a thickness of 100 μm.
Example four
Step S100: and cutting the foam nickel-cobalt alloy by using a cutting machine to obtain a foam nickel-cobalt alloy wafer serving as a transition metal substrate. The foamed Ni disks had a porosity of 97% and a thickness of 50 μm.
Step S200: and (3) pickling the foam nickel-cobalt alloy wafer for 2min by using dilute nitric acid with the mass concentration of 7%, wherein bubbles are generated on the surface of the foam nickel-cobalt alloy wafer. The pickled foamed Fe disks were then immersed in ethanol for ultrasonic cleaning and then weighed.
Step S300: and forming a cobalt nickel sulfide layer on the surface of the foamed nickel-cobalt alloy wafer subjected to acid cleaning by adopting a vapor deposition method. Specifically, the step of forming the cobalt sulfide nickel layer on the surface of the foamed nickel-cobalt alloy wafer after acid cleaning by adopting a vapor deposition method comprises the following steps:
step S310: and introducing nitrogen into the tube furnace, so that the nitrogen sweeps the furnace chamber of the tube furnace to exhaust the air in the furnace chamber of the tube furnace. Then introducing hydrogen sulfide gas into the furnace chamber of the tubular furnace, wherein the flow rate of the hydrogen sulfide gas is 90 mL/min.
Step S320: and (3) feeding the foamed nickel-cobalt alloy wafer after acid washing into a furnace chamber of a tubular furnace filled with hydrogen sulfide gas, wherein the foamed nickel-cobalt alloy wafer is positioned in the middle of the furnace chamber.
Step S330: and controlling the hydrogen sulfide gas in the tubular furnace to react with nickel-cobalt atoms contained on the surface of the pickled nickel-cobalt alloy wafer, so that a cobalt-nickel sulfide layer is formed on the surface of the nickel-cobalt alloy wafer. Specifically, controlling hydrogen sulfide gas in the tubular furnace to react with nickel-cobalt atoms contained on the surface of the pickled nickel-cobalt alloy wafer, so that the cobalt-nickel sulfide layer formed on the surface of the foamed nickel-cobalt alloy wafer comprises the following steps:
step S331: controlling a tube furnace to heat the foamed nickel-cobalt alloy wafer after acid washing to 600 ℃ according to the heating rate of 500 ℃/h.
Step S332: and reacting hydrogen sulfide in the tubular furnace with nickel and cobalt atoms contained on the surface of the pickled nickel-cobalt alloy wafer at 600 ℃ for 4h to obtain the cobalt-nickel sulfide layer formed on the surface of the foamed nickel-cobalt alloy wafer.
Step S340: and (3) carrying out vacuum drying on the foamed nickel-cobalt alloy wafer with the cobalt-nickel sulfide layer formed on the surface for 2h at 70 ℃.
Step S400: and carrying out anti-corrosion coating treatment on the cobalt sulfide nickel layer formed on the surface of the foam nickel-cobalt alloy wafer, so that nano carbon layers are formed on the surface of the cobalt sulfide nickel layer and the exposed surface of the foam nickel-cobalt alloy wafer. The method for performing the anticorrosion coating treatment on the cobalt sulfide nickel layer formed on the surface of the foam nickel-cobalt alloy wafer comprises the following steps:
step S410: placing the foamed nickel-cobalt alloy wafer with the cobalt sulfide nickel layer formed on the surface into nano-carbon dispersion liquid with the concentration of 500mg/L, stirring for 5min, and stirring the nano-carbon dispersion liquid to enable nano-carbon contained in the nano-carbon dispersion liquid to be attached to the surface of the cobalt sulfide nickel layer, the exposed surface of the foamed nickel-cobalt alloy wafer and the exposed surface of the transition metal substrate, so as to obtain a composite electrode preform; the solvent of the nano-carbon dispersion liquid is N-methyl pyrrolidone.
Step S420: the composite electrode preform was vacuum dried at 85 ℃ for 4 h.
Step S430: and heating the dried composite electrode preform at 240 ℃ for 2h in an air atmosphere to sinter the nanocarbon in the composite electrode on the surface of the cobalt sulfide nickel layer, thereby obtaining the composite electrode.
Step S440: the composite electrode was flattened using a shaft press to obtain a composite electrode having a thickness of 100 μm.
In order to prove the effect of the composite electrode manufactured by the manufacturing method of the composite electrode provided by the embodiment of the invention, the composite electrode manufactured by the manufacturing method of the composite electrode provided by the embodiment is applied to a soft package aluminum ion battery and used as a positive electrode of the aluminum ion battery, a negative electrode of the aluminum ion battery is aluminum alloy, and an electrolyte is 1-ethyl-3-methylimidazolium chloride aluminum salt.
Fig. 6 shows a cyclic charge and discharge test curve for a pouch aluminum ion battery. As can be seen from fig. 6: the first discharge capacity of the soft-coated aluminum ion battery reaches 222mAhg-1After 20 cycles, the efficiency gradually stabilized to about 260mAhg-1(ii) a When the nickel sulfide electrode directly made of NiS powder is used as the positive electrode of the soft package aluminum ion battery at present, the cycle capacity of the soft package aluminum ion battery is seriously attenuated, and only 70mAhg is left after 20 cycles-1. Therefore, the composite electrode manufactured by the manufacturing method of the composite electrode can effectively inhibit the problem of cycle capacity attenuation of the battery.
In addition, a NiS layer grows on the surface of the foamed nickel wafer serving as the current collector, so that the NiS layer can be in close contact with the foamed nickel wafer serving as the current collector. In a battery performance test, the NiS layer is not easy to fall off from the surface of a foam nickel wafer serving as a current collector; therefore, the cycle life of the battery is high.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (15)

1. A method of making a composite electrode, comprising:
providing a transition metal substrate;
and forming a transition metal sulfide layer on the surface of the transition metal substrate by adopting a vapor deposition method.
2. The method for manufacturing a composite electrode according to claim 1, wherein after the providing the transition metal substrate and before the forming the transition metal sulfide layer on the surface of the transition metal substrate by using the vapor deposition method, the method for manufacturing a composite electrode further comprises:
pickling the transition metal substrate until bubbles are generated on the surface of the transition metal substrate.
3. The method of making a composite electrode according to claim 1, wherein the transition metal substrate comprises the same transition metal as the transition metal sulfide layer.
4. The method of claim 1, wherein the forming a transition metal sulfide thin film on the surface of the transition metal substrate by vapor deposition comprises:
introducing hydrogen sulfide gas into the reaction container in an oxygen-free environment;
sending the transition metal substrate into a reaction container filled with hydrogen sulfide gas;
and controlling hydrogen sulfide gas in the reaction container to react with the surface transition metal atoms of the transition metal substrate, so that a transition metal sulfide layer is formed on the surface of the transition metal substrate.
5. The method of claim 4, wherein the flow rate of the hydrogen sulfide gas is 50-150 mL/min.
6. The method for manufacturing a composite electrode according to claim 4, wherein the controlling hydrogen sulfide gas in the reaction vessel to react with the transition metal atoms on the surface of the transition metal substrate so that a transition metal sulfide layer is formed on the surface of the transition metal substrate comprises:
controlling the reaction vessel to heat the transition metal substrate to 400-700 ℃;
reacting hydrogen sulfide gas in the reaction container with transition metal atoms contained on the surface of the transition metal substrate at 400-700 ℃ to obtain a transition metal sulfide layer formed on the surface of the transition metal substrate;
and vacuum drying the transition metal substrate with the transition metal sulfide layer formed on the surface.
7. The method of claim 6, wherein the controlling the reaction vessel to heat the transition metal substrate to 400 ℃ to 700 ℃ comprises:
controlling the reaction vessel to heat the transition metal substrate to 400-700 ℃ according to the heating rate of 200-600 ℃/h.
8. The method for manufacturing a composite electrode according to any one of claims 1 to 7, wherein the transition metal substrate is a foam-type transition metal substrate, and the porosity of the foam-type transition metal substrate is 20% to 97%.
9. The method for manufacturing a composite electrode according to any one of claims 1 to 7, wherein the transition metal contained in the transition metal substrate is one or more of nickel, cobalt, iron, and copper, and the transition metal contained in the transition metal sulfide layer is one or more of nickel, cobalt, iron, and copper.
10. The method for manufacturing a composite electrode according to any one of claims 1 to 7, wherein after the transition metal sulfide layer is formed on the surface of the transition metal substrate by the vapor deposition method, the method for manufacturing a composite electrode further comprises:
and at least carrying out anti-corrosion coating treatment on the transition metal sulfide layer formed on the surface of the transition metal substrate, so that an anti-corrosion layer is formed on the surface of at least the transition metal sulfide layer, wherein the anti-corrosion layer is made of a conductive anti-corrosion material.
11. The method of manufacturing a composite electrode according to claim 10, wherein the subjecting at least the transition metal sulfide layer formed on the surface of the transition metal substrate to the anticorrosion coating treatment comprises:
placing the transition metal substrate with the transition metal sulfide layer formed on the surface into the anti-corrosion material dispersion liquid and stirring, so that the anti-corrosion material contained in the anti-corrosion material dispersion liquid is at least attached to the surface of the transition metal sulfide layer, and obtaining a composite electrode preform; the concentration of the anticorrosive material dispersion liquid is 0.1 mg/L-500 mg/L;
carrying out vacuum drying on the composite electrode preform;
heating the dried composite electrode preform at 100-300 ℃ in an air atmosphere to enable an anti-corrosion material in the composite electrode to be sintered on the surface of the transition metal sulfide layer, so as to obtain a composite electrode;
and flattening the composite electrode.
12. The method for producing a composite electrode according to claim 11, wherein the anticorrosive material contained in the anticorrosive material dispersion liquid is graphene oxide and/or nanocarbon.
13. A composite electrode produced by the method for producing a composite electrode according to any one of claims 1 to 12, comprising a transition metal substrate and a transition metal sulfide layer formed on a surface of the transition metal substrate.
14. A composite electrode according to claim 13, wherein at least the surface of the transition metal sulphide layer is formed with a corrosion protection layer.
15. A battery comprising the composite electrode of claim 13 or 14.
CN201810953577.2A 2018-08-21 2018-08-21 Composite electrode, manufacturing method thereof and battery Pending CN110854355A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105244173A (en) * 2015-11-04 2016-01-13 南京大学 Preparation method of super-capacitor transition metal sulfide electrode material with specific microstructure
CN106784719A (en) * 2017-01-05 2017-05-31 山东理工大学 A kind of preparation method of the flower-shaped nickel sulfide/foam nickel materials of graphene coated 3D

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105244173A (en) * 2015-11-04 2016-01-13 南京大学 Preparation method of super-capacitor transition metal sulfide electrode material with specific microstructure
CN106784719A (en) * 2017-01-05 2017-05-31 山东理工大学 A kind of preparation method of the flower-shaped nickel sulfide/foam nickel materials of graphene coated 3D

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