CN110854354A - Composite electrode, manufacturing method thereof and battery - Google Patents

Composite electrode, manufacturing method thereof and battery Download PDF

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Publication number
CN110854354A
CN110854354A CN201810953175.2A CN201810953175A CN110854354A CN 110854354 A CN110854354 A CN 110854354A CN 201810953175 A CN201810953175 A CN 201810953175A CN 110854354 A CN110854354 A CN 110854354A
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Prior art keywords
transition metal
composite electrode
metal substrate
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
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/628—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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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 following steps: providing a transition metal substrate; and forming a transition metal sulfide layer on the surface of the transition metal substrate by a hydrothermal method. The composite electrode is manufactured by applying the manufacturing method of the composite electrode. The composite electrode, the manufacturing method thereof and the battery are used for inhibiting the capacity attenuation of the battery in the charging and discharging processes.

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 a hydrothermal method.
Compared with the prior art, in the preparation method of the composite electrode, the transition metal sulfide layer is formed on the surface of the transition metal substrate by a hydrothermal method, so that when the composite electrode manufactured by 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 an example of the formation of a transition metal sulfide layer on a surface of a transition metal substrate by a hydrothermal method according to the present invention;
FIG. 3 is a flowchart of an anticorrosion coating treatment of a transition metal sulfide layer formed on a surface of a transition metal substrate;
FIG. 4 is a schematic structural diagram of a composite electrode according to an embodiment of the present invention;
fig. 5 is a performance 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. 2, a method for manufacturing a composite electrode according to an embodiment of the present invention includes: 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 a hydrothermal 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 a hydrothermal method, so that when the composite electrode manufactured by 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 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 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 hydrothermal method:
step S200: the transition metal substrate is pickled until bubbles are generated on the surface of the transition metal substrate. This indicates that the transition metal oxide contained on the surface of the transition metal substrate has been completely removed, and the surface of the transition metal substrate has good metal characteristics. Whether bubbles are generated on the surface can be used for judging whether the transition metal oxide on the surface of the transition metal substrate is completely removed or not, and the corrosion of an acid solution used for pickling on the transition metal substrate can be reduced to the greatest extent. 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 specific method for forming a transition metal sulfide layer on the surface of a transition metal substrate by using a hydrothermal method includes the following steps:
step S310: adding a transition metal substrate and a sulfide solution capable of releasing hydrogen sulfide gas into a reaction container, so that the transition metal substrate is immersed in the sulfide solution to obtain a treatment system;
step S330: controlling the decomposition of sulfide in a sulfide solution contained in a treatment system in a sealed environment to release hydrogen sulfide gas;
step S340: the hydrogen sulfide gas reacts 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.
It is understood that the transition metal sulfide layer formed on the surface of the transition metal substrate covers all surfaces of the transition metal substrate since the transition metal substrate is immersed in a sulfide solution that can release hydrogen sulfide gas.
For example, the sulfide contained in the sulfide solution may be thioacetamide or thiourea; when the sulfide contained in the sulfide solution is thioacetamide, after obtaining the treatment system, and before controlling the sulfide contained in the sulfide solution contained in the treatment system to decompose in a sealed environment, the forming of the transition metal sulfide layer on the surface of the transition metal substrate by using the hydrothermal method further comprises:
step S320: and adding an acidic solution into the treatment system to make the pH value of the treatment system be 4.5-6.5 so that thioacetamide can decompose hydrogen sulfide gas under the acidic addition condition. The acidic solution may be hydrochloric acid or dilute sulfuric acid, etc.
The concentration of the sulfide solution is 0.1-0.5 mmoL/L, the decomposition temperature of sulfide contained in the sulfide solution is 60-150 ℃, and the reaction time is 5-20 h. When the hydrogen sulfide gas in the reaction vessel reacts with the transition metal atoms on the surface of the transition metal substrate at 60 ℃ to 150 ℃ for 5h to 20h, the thickness of the formed transition metal sulfide layer is about 1 μm to 100 μm.
Step S350: 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 can be seen from the above process of forming a transition metal sulfide layer on the surface of a transition metal substrate by a hydrothermal method, 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. Furthermore, controlling the decomposition of sulfides in the sulfide solution contained in the treatment system in a sealed environment can provide hydrogen sulfide gas that reacts with the transition metal substrate, so that the resulting transition metal sulfide can form on the surface of the transition metal 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 is relatively compact, the contact area of the foam type transition metal substrate and hydrogen sulfide gas is relatively large, so that the deposition amount of the transition metal sulfide can be increased under the condition that the contact area of a subsequent transition metal sulfide layer and the foam type transition metal substrate is relatively large, and the transition metal sulfide layer and the foam type transition metal substrate are relatively compact.
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 hydrothermal method, the method for manufacturing the composite electrode further includes:
step S400: and carrying out anti-corrosion coating treatment on the transition metal sulfide layer formed on the surface of the transition metal substrate to form an anti-corrosion layer on the surface of the transition metal sulfide layer, wherein the anti-corrosion layer is made of a conductive anti-corrosion 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.
Further, as shown in fig. 3, the above-mentioned corrosion-preventive 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 the transition metal substrate to ensure that the anti-corrosion material contained in the anti-corrosion material dispersion liquid is attached to the surface of the transition metal sulfide layer to obtain 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, since the transition metal sulfide layer covers the entire surface of the transition metal substrate, the anticorrosive material contained in the anticorrosive material dispersion is adhered to the entire surface of the transition metal sulfide layer.
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 to enable the anti-corrosion material in the composite electrode to be sintered on the surface of the transition metal sulfide layer, and obtaining 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 lead, 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, the nickel metal on the surface of the Ni substrate contacting the NiS layer loses electrons at the moment, and the NiS obtained electrons on the surface of the NiS layer contacting the Ni substrate 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. 4, 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 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. The foamed Ni disks had a porosity of 50% and a thickness of 200 μm.
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 pickled foam Ni wafer by a hydrothermal method. Specifically, the step of forming the NiS layer on the surface of the pickled foam Ni wafer by a hydrothermal method comprises the following steps:
step S310: and adding the pickled foamed Ni wafer and a thioacetamide aqueous solution of 0.1mmoL/L into a hydrothermal reaction kettle, so that the pickled foamed Ni wafer is immersed in the thioacetamide aqueous solution to obtain a treatment system.
Step S320: hydrochloric acid was added to the treatment system so that the pH of the treatment system was 5.
Step S330: screwing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying box, and heating the hydrothermal reaction kettle by the electric heating constant-temperature air blowing drying box until the thioacetamide aqueous solution contained in the treatment system reaches 80 ℃, wherein the thioacetamide aqueous solution is decomposed and hydrogen sulfide gas is released.
Step S340: the hydrogen sulfide gas reacts with Ni atoms contained on the surface of the foam Ni wafer for 10h, so that a NiS layer is formed on the surface of the foam Ni wafer.
Step S350: 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, 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, 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 pickled foamed Cu wafer by a hydrothermal method. Specifically, the step of forming the CuS layer on the surface of the pickled foamed Cu wafer by a hydrothermal method comprises the following steps:
step S310: and adding the foamed Cu wafer subjected to acid washing and a thioacetamide aqueous solution of 0.3mmoL/L into a hydrothermal reaction kettle, so that the foamed Cu wafer subjected to acid washing is immersed in the thioacetamide aqueous solution to obtain a treatment system.
Step S320: hydrochloric acid was added to the treatment system so that the pH of the treatment system was 4.5.
Step S330: screwing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying box, and heating the hydrothermal reaction kettle by the electric heating constant-temperature air blowing drying box until the thioacetamide aqueous solution contained in the treatment system reaches 60 ℃, wherein the thioacetamide aqueous solution is decomposed and hydrogen sulfide gas is released.
Step S340: and reacting the hydrogen sulfide gas with Cu atoms contained on the surface of the foamed Cu wafer for 20 hours to form a CuS layer on the surface of the foamed Cu wafer.
Step S350: 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: putting the foam 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, 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, 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 hydrothermal method. Specifically, the step of forming the FeS layer on the surface of the pickled foam Fe wafer by adopting a hydrothermal method comprises the following steps:
step S310: and adding the pickled foam Fe wafer and a thioacetamide aqueous solution of 0.3mmoL/L into a hydrothermal reaction kettle, so that the pickled foam Fe wafer is immersed in the thioacetamide aqueous solution to obtain a treatment system.
Step S330: hydrochloric acid was added to the treatment system so that the pH of the treatment system was 6.5.
Step S340: screwing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying box, and heating the hydrothermal reaction kettle by the electric heating constant-temperature air blowing drying box until the thioacetamide aqueous solution contained in the treatment system reaches 120 ℃, wherein the thioacetamide aqueous solution is decomposed and hydrogen sulfide gas is released.
Step S332: and reacting the hydrogen sulfide gas with Fe atoms contained on the surface of the foamed Fe wafer for 7h to form a FeS layer 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 a nanocarbon dispersion liquid with the concentration of 230mg/L, stirring for 12min, and stirring the nanocarbon dispersion liquid to enable nanocarbon contained in the nanocarbon dispersion liquid to be attached to the surface of the FeS layer, 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 2h at 90 ℃.
Step S430: and heating the dried composite electrode preform at 180 ℃ for 4h in an air atmosphere to sinter the nanocarbon in the composite electrode on the surface of the FeS 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.
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 sulfide nickel layer on the surface of the foamed nickel-cobalt alloy wafer subjected to acid cleaning by adopting a hydrothermal method. Specifically, the step of forming the cobalt sulfide nickel layer on the surface of the pickled foam nickel-cobalt alloy wafer by adopting a hydrothermal method comprises the following steps:
step S310: and adding the foamed nickel-cobalt alloy wafer after the acid washing and 0.5mmoL/L thiourea aqueous solution into a hydrothermal reaction kettle, so that the foamed nickel-cobalt alloy wafer after the acid washing is immersed in the thiourea aqueous solution, and obtaining a treatment system.
Step S330: screwing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an electric heating constant-temperature air blowing drying box, and heating the hydrothermal reaction kettle by the electric heating constant-temperature air blowing drying box until the thiourea aqueous solution contained in the treatment system reaches 70 ℃, wherein the thiourea aqueous solution is decomposed and releases hydrogen sulfide gas.
Step S340: and reacting the hydrogen sulfide gas with nickel-cobalt atoms contained on the surface of the foam nickel-cobalt alloy wafer for 5 hours to form a cobalt-nickel sulfide layer on the surface of the foam nickel-cobalt alloy wafer.
Step S350: 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 foam 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, 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. 5 shows a performance test curve of the pouch aluminum ion battery. As can be seen from fig. 5: the first discharge capacity of the soft-coated aluminum ion battery reaches 202mAhg-1After 22 cycles, the mixture gradually stabilized to about 250mAh g-1(ii) a In addition, the first charge capacity of the soft package aluminum ion battery reaches 219mAh g-1Gradually stabilizes to about 270mAh g after 22 cycles-1(ii) a And the charging and discharging coulombic efficiency in the circulation process is always kept above 92%, so that when the composite electrode provided by the embodiment of the invention is applied to a battery, the performance of the battery can be effectively improved. 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 (14)

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 a hydrothermal method.
2. The method for manufacturing a composite electrode according to claim 1, wherein after the providing the transition metal substrate and before the hydrothermal method is used to form the transition metal sulfide layer on the surface of the transition metal substrate, 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 layer on the surface of the transition metal substrate by a hydrothermal process comprises:
adding the transition metal substrate and a sulfide solution capable of releasing hydrogen sulfide gas into a reaction container, so that the transition metal substrate is immersed in the sulfide solution to obtain a treatment system;
controlling the decomposition of sulfides in a sulfide solution contained in the treatment system in a sealed environment to release hydrogen sulfide gas;
reacting the hydrogen sulfide gas with transition metal atoms contained on the surface of the transition metal substrate to form a transition metal sulfide layer 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.
5. The method for manufacturing a composite electrode according to claim 4, wherein the sulfide contained in the sulfide solution is thioacetamide or thiourea;
when the sulfide contained in the sulfide solution is thioacetamide, after the obtaining of the treatment system, before controlling the sulfide contained in the sulfide solution contained in the treatment system to decompose in a sealed environment, the forming of the transition metal sulfide layer on the surface of the transition metal substrate by using a hydrothermal method further comprises:
and adding an acidic solution into the treatment system to ensure that the pH value of the treatment system is 4.5-6.5.
6. The method for manufacturing a composite electrode according to claim 4, wherein the concentration of the sulfide solution is 0.1 to 0.5mmoL/L, the decomposition temperature of the sulfide contained in the sulfide solution is 60 to 150 ℃, and the reaction time is 5 to 20 hours.
7. The method for manufacturing a composite electrode according to any one of claims 1 to 6, 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%.
8. The method for manufacturing a composite electrode according to any one of claims 1 to 6, 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.
9. The method for manufacturing a composite electrode according to any one of claims 1 to 6, wherein after the formation of the transition metal sulfide layer on the surface of the transition metal substrate by a hydrothermal method, the method for manufacturing a composite electrode further comprises:
and carrying out anti-corrosion coating treatment on the transition metal sulfide layer formed on the surface of the transition metal substrate to form an anti-corrosion layer on the surface of the transition metal sulfide layer, wherein the anti-corrosion layer is made of a conductive anti-corrosion material.
10. The method of manufacturing a composite electrode according to claim 9, wherein the subjecting of 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 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.
11. The method for producing a composite electrode according to claim 10, wherein the anticorrosive material contained in the anticorrosive material dispersion liquid is graphene oxide and/or nanocarbon.
12. A composite electrode manufactured by the method for manufacturing a composite electrode according to any one of claims 1 to 11, comprising a transition metal substrate and a transition metal sulfide layer formed on a surface of the transition metal substrate.
13. A composite electrode according to claim 12, wherein the surface of the transition metal sulphide layer is formed with a corrosion protection layer.
14. A battery comprising the composite electrode of claim 12 or 13.
CN201810953175.2A 2018-08-21 2018-08-21 Composite electrode, manufacturing method thereof and battery Pending CN110854354A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106917105A (en) * 2017-01-13 2017-07-04 太原理工大学 A kind of water decomposition preparation method of self-supporting transient metal sulfide foam electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106917105A (en) * 2017-01-13 2017-07-04 太原理工大学 A kind of water decomposition preparation method of self-supporting transient metal sulfide foam electrode

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