CN111816456A - Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances - Google Patents

Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances Download PDF

Info

Publication number
CN111816456A
CN111816456A CN202010612865.9A CN202010612865A CN111816456A CN 111816456 A CN111816456 A CN 111816456A CN 202010612865 A CN202010612865 A CN 202010612865A CN 111816456 A CN111816456 A CN 111816456A
Authority
CN
China
Prior art keywords
electrode
supercapacitor
electrodeposition
falling
conductivity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010612865.9A
Other languages
Chinese (zh)
Other versions
CN111816456B (en
Inventor
陈元振
吕光军
柳永宁
信燕飞
薛通
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN202010612865.9A priority Critical patent/CN111816456B/en
Publication of CN111816456A publication Critical patent/CN111816456A/en
Application granted granted Critical
Publication of CN111816456B publication Critical patent/CN111816456B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses an electrode manufacturing method capable of enhancing conductivity of a supercapacitor electrode and inhibiting falling of active substances, which comprises the following steps: step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant; step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode of the super capacitor and the settled layer metal sheet into the electrodeposition solution prepared in the step (1), and performing electrodeposition to obtain the electrode of the super capacitor protected by the settled layer metal. The invention can solve the technical problems of electrode cracking and falling caused by low conductivity and serious volume expansion in the reaction process when the active substance is highly loaded in the conventional super capacitor.

Description

Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to an electrode manufacturing method capable of enhancing conductivity of a super capacitor electrode and inhibiting falling of active substances.
Background
The super capacitor is an energy storage device with high power density, high charging and discharging speed, long cycle life and wide working temperature range, and is applied to various fields such as traffic, national defense, communication and the like; however, the energy density of the super capacitor is relatively low compared with other energy storage devices, and is a great obstacle to limit the application of the super capacitor.
For activated carbon electrode materials, increasing the active material fraction by increasing the coating thickness is one of the strategies to increase the overall energy density of the supercapacitor; the thickness of the coating layer has important influence on the electrochemical performance, the bonding strength of the electrode is correspondingly reduced after the thickness is increased, and the surface of the electrode bulges and falls off in the charging and discharging process, so that the performance of the device is seriously influenced.
In addition, the adoption of a Faraday pseudo-capacitance material to replace a traditional electric double layer material is another strategy for improving the energy density of the super capacitor. The active material mainly comprises RuO2、IrO2、NiO、MnO2、Co3O4、V2O5、WO3、PbO2、SnO2、MoO3、Ni(OH)2、Co(OH)2、NiS、Ni3S2、Ni3S4、Co3S4、MoS2、NiCo2S4、Ti3C2、TiN、VN、Fe2The conductivity of metal oxides such as N and the like, hydroxides, nitrides, sulfides and the like is relatively low, and the volume expansion is relatively obvious during reaction, so that the electrode material is cracked and falls off during the reaction process, the phenomenon is particularly obvious when the electrode loading capacity is improved, and the performance of the electrode is greatly influenced.
At the present stage, electrode manufacturing methods for enhancing conductivity of a supercapacitor electrode and inhibiting falling of active substances generally focus on coating with a carbon coating, reduced graphene oxide, a carbon nanotube, three-dimensional foam or aerogel or the like, or structural design is performed, and materials are synthesized into nanoflower, nanosheet, nanocage, hollow sphere, core-shell structure and the like, but these methods are often complex in process and high in cost, cannot realize industrial production, and limit practical application thereof.
In view of the above, there is a need for a new method for manufacturing an electrode that enhances the conductivity of a supercapacitor electrode and inhibits the shedding of active materials.
Disclosure of Invention
The invention aims to provide an electrode manufacturing method capable of enhancing the conductivity of a supercapacitor electrode and inhibiting falling of an active substance, so as to solve the technical problems of electrode cracking and falling caused by severe volume expansion in the reaction process when the conductivity of the conventional supercapacitor is not high and the active substance is highly loaded.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses an electrode manufacturing method capable of enhancing conductivity of a supercapacitor electrode and inhibiting falling of active substances, which comprises the following steps:
step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant;
step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode of the super capacitor and the settled layer metal sheet into the electrodeposition solution prepared in the step (1), and performing electrodeposition to obtain the electrode of the super capacitor protected by the settled layer metal.
The invention is further improved in that in the step 2, the electrode of the super capacitor is a porous carbon electrode or a pseudocapacitive electrode.
In a further improvement of the invention, in step 1, the deposited layer metal is cobalt or nickel.
In the further improvement of the invention, in the step 1, the sedimentary deposit metal salt is sulfate, nitrate or chloride of sedimentary deposit metal;
the pH buffering agent is boric acid, sodium fluoborate, saccharin, sodium citrate or formic acid;
the surfactant is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
The invention has the further improvement that in the step 2, the electrode of the super capacitor is an electrode which is coated on a current collector after mixing porous carbon or pseudocapacitance material, conductive agent and binder according to a preset proportion;
or the electrode of the super capacitor is an electrode obtained by growing an active material on a three-dimensional conductive network.
The further improvement of the invention is that in the step 2, the total mass density of the electrodeposition is 0.5-4 mg/cm2。
The further improvement of the invention is that in the electrodeposition solution in the step 1, the concentration of the metal salt of the deposition layer is 240-300 g/L, the concentration of the pH buffering agent is 30-50 g/L, and the concentration of the surfactant is 0.1 g/L.
The invention is further improved in that in the electrodeposition in the step 2, the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min.
Compared with the prior art, the invention has the following beneficial effects:
the invention realizes the electrode manufacturing method for enhancing the conductivity of the electrode of the super capacitor and inhibiting the falling of the active substance through the electrodeposition, the electrodeposition liquid is prepared according to the preparation process of the invention, the preparation can be completed by utilizing simple electrodeposition, the preparation process does not comprise any expensive raw material, the operation is simple and rapid, the production cost is greatly reduced, and the foundation is laid for industrialized mass production; meanwhile, the conductivity of the electrode can be obviously improved by the electrodeposited metal layer, the problem of falling-off of electrode materials is solved, and the electrochemical performance of the finally prepared electrodeposited and protected supercapacitor electrode is obviously improved. The electrode manufacturing method can avoid the falling off of the electrode material in the reaction process, improve the conductivity of the electrode and greatly improve the electrochemical performance of the electrode. Compared with the traditional methods of carbon coating, graphene aerogel coating and the like, the method provided by the invention has the advantages that the electrode strength is improved, the cracking is not easy, the complex process and harsh synthesis conditions are not required, the operation is simple, and the electrode protection layer can be quickly and effectively prepared, so that the method is suitable for large-batch industrial production. Compared with graphene and carbon nanotubes, the electrodeposited metal salts have low price and large quantity, so that the production cost is low, and the requirement on the electrodeposited liquid is low, so that the cheap main salt components such as sulfate, chloride and the like can be selected; and the electrodeposition liquid can be recycled for a plurality of times, so that the production cost can be further reduced.
In the embodiment of the invention, the deposited layer metal can be cobalt, nickel and other metals which are not easily oxidized and do not react with alkali and alloys thereof, so that the deposited layer metal is ensured to be kept in the original state and not to be deteriorated in the service process of the supercapacitor.
In the embodiment of the invention, the larger the current density during electrodeposition is, the longer the electrodeposition time is, and the total mass density of electrodeposition is kept between 0.5 and 4mg/cm2If the electrodeposition is too little, the electrode cannot be completely wrapped by the deposited layer metal, and if the electrodeposition is too much, the deposited layer metal is too thick, so that the ion transmission between the electrolyte and the electrode material is influenced.
In the embodiment of the invention, the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min; the quality and thickness of the finally deposited layer metal are controlled by controlling the current and the deposition time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow chart of a process for protecting a blade coating method supercapacitor electrode by electrodeposition in an embodiment of the invention;
FIG. 2 is an SEM image of electrodeposition protection after NiS growth on carbon paper in an example of the present invention;
FIG. 3 is a schematic diagram comparing the peeling of the NiS electrode after the non-protection and the electro-deposition protection in the embodiment of the present invention;
FIG. 4 is a graph showing the comparison of the rate capability of unprotected versus electrodeposition protected NiS electrodes in an embodiment of the present invention;
FIG. 5 is a graph comparing the cycling performance of unprotected versus electrodeposition protected NiS electrodes in an embodiment of the invention;
FIG. 6 is a schematic diagram of the electrochemical impedance test of unprotected and nickel-deposited NiS electrodes in an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the following clearly and completely describes the technical solution of the embodiments of the present invention with reference to the drawings in the embodiments of the present invention; it is to be understood that the described embodiments are only some of the embodiments of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
The electrode manufacturing method capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of the active substances is an electrode manufacturing method for enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of the active substances through electrodeposition, and the specific report includes the following steps:
step 1, preparing an electrodeposition solution containing salts of sedimentary metal, a pH buffer and a surfactant;
and 2, connecting the prepared electrode (porous carbon electrode or pseudo-capacitive electrode) of the super capacitor to the cathode of the direct-current power supply, connecting the deposited layer metal sheet to the anode, and obtaining the electrode of the super capacitor protected by the deposited layer metal through electrodeposition.
In the embodiment of the invention, the larger the current density during electrodeposition is, the relative reduction of the electrodeposition time is required, the total mass density of electrodeposition is kept at 0.5-4 mg/cm2, the too little electrodeposition results in that the electrode cannot be completely wrapped by the deposited layer metal, and the too thick deposited layer metal results in that the ion transmission between the electrolyte and the electrode material is influenced if the electrodeposition is too much.
The method of the invention avoids the falling off of the electrode material in the reaction process, and improves the conductivity of the electrode, thereby greatly improving the electrochemical performance of the electrode; compared with the traditional methods of carbon coating, graphene aerogel coating and the like, the method has the advantages of improving the electrode strength, being not easy to crack, needing no complex process and harsh synthesis conditions, being simple to operate, and being capable of quickly and effectively preparing the electrode protection layer, thereby being suitable for large-batch industrial production; compared with graphene and carbon nanotubes, the electrodeposited metal salts are low in price and large in quantity, so that the production cost is low, the requirement on the electrodeposited liquid is not high, the cheap main salt components such as sulfate and chloride can be selected, the electrodeposited liquid can be recycled for multiple times, and the production cost is further reduced.
Referring to fig. 1, a method for preparing and protecting an electrode of a supercapacitor according to an embodiment of the present invention includes:
firstly, preparing a uniform and transparent electrodeposition solution: dissolving the salt of the sedimentary deposit metal in deionized water, and adding a buffer agent for adjusting the pH value of the solution and a surfactant; wherein, the concentration of the metal salt of the deposition layer is 240-300 g/L, the concentration of the buffering agent is 30-50 g/L, and the concentration of the surface active agent is 0.1 g/L.
Performing electrodeposition to obtain a pseudo-capacitor supercapacitor electrode protected by an electrodeposition layer: connecting the prepared electrode of the pseudocapacitor super capacitor to a cathode of a direct current power supply, connecting a high-purity metal sheet of the deposited layer metal to the cathode of the direct current power supply, and controlling the quality and the thickness of the final deposited layer metal by controlling the current and the deposition time, wherein the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min.
The deposited layer metal in the first step can be cobalt, nickel and other metals which are not easily oxidized and do not react with alkali and alloys thereof, so that the deposited layer metal is kept in the original state and is not deteriorated in the service process of the supercapacitor.
The salts corresponding to the deposit metal in the first step can be sulfates, nitrates, chlorides and other salts.
In the first step, the pH buffer can be boric acid, sodium fluoborate, saccharin, sodium citrate, formic acid and the like, and the surfactant can be one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide and the like.
The prepared supercapacitor electrode used in the step two can be an electrode coated on a current collector through porous carbon or pseudocapacitance material, a conductive agent and a binder which are mixed according to a certain proportion; the electrode can also be obtained by directly growing active materials on three-dimensional conductive networks such as carbon paper, carbon cloth, foamed nickel, three-dimensional graphene and the like.
The larger the current density in the electrodeposition process, the longer the electrodeposition time is, and the total mass density of the electrodeposition is kept between 0.5 and 4mg/cm2If the electrodeposition is too little, the electrode cannot be completely wrapped by the deposited layer metal, and if the electrodeposition is too much, the deposited layer metal is too thick, so that the ion transmission between the electrolyte and the electrode material is influenced.
In conclusion, the invention realizes the electrode manufacturing method for enhancing the conductivity of the electrode of the super capacitor and inhibiting the falling of the active substances through electrodeposition, prepares a proper electrodeposition solution according to the preparation process, can be completed by utilizing simple electrodeposition, does not comprise any expensive raw material in the preparation process, is simple and rapid to operate, greatly reduces the production cost, lays a foundation for industrialized mass production, simultaneously, the electrodeposited metal layer can obviously enhance the conductivity of the electrode and improve the problem of the falling of the electrode material, and the electrochemical performance of the finally prepared electrodeposition-protected super capacitor electrode is obviously enhanced.
The effect of the invention is verified by experiments with the following examples:
example 1:
the electrode manufacturing method capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of active substances in the embodiment of the invention specifically comprises the following steps:
a method for preparing a homogeneous and transparent electrodeposition solution, comprising: 12g of NiSO4·6H2O, 1.5g of boric acid and 0.05g of sodium dodecyl sulfate were added to 50mL of deionized water, and after being dissolved uniformly, the mixture was poured into an electrolytic cell shown in FIG. 1.
Performing electrodeposition to obtain a supercapacitor electrode protected by a deposited metal layer, comprising: will use the Ni (OH) produced by the hydrothermal method2PTFE and acetylene black in a weight ratio of 8: 1: 1, drying and compacting, taking the prepared electrode as a cathode and a high-purity nickel sheet as an anode, and adopting 30mA/cm under a direct current power supply2Current density of (2), after 5 minutes of electrodeposition, obtaining Ni (OH) protected by deposited nickel2And an electrode.
Example 2:
in the embodiment of the invention, the prepared electrode selected in the second step is an electrode obtained by coating activated carbon, PTFE and acetylene black on foamed nickel in a scraping manner, and the rest is the same as that in the embodiment 1, so that the supercapacitor activated carbon electrode protected by deposited nickel is obtained.
Example 3:
in the embodiment of the invention, the prepared electrode selected in the second step is NiS directly grown on the carbon fiber paper by a hydrothermal method, and the rest is the same as that in the embodiment 1, so that the NiS/carbon fiber paper composite electrode protected by electrodeposited nickel is obtained.
The SEM image of the cross section of the resulting electrode is shown in fig. 2, and it can be clearly seen that the carbon fiber of the core carbon paper, the middle NiS active material layer and the outermost electrodeposited metallic nickel protective layer are constituted by three parts, which was expected in the present invention.
In addition, in the digital photograph shown in fig. 3, it is clear that the unprotected (upper half of fig. 3) and nickel-deposited (lower half of fig. 3) NiS electrodes were peeled off during the test, and the unprotected electrodes had a large amount of active material peeled off at the bottom of the cell after the reaction, while the nickel-deposited electrodes had only a small amount of peeled off during the reaction.
FIGS. 4 and 5 are unprotectedAnd the multiplying power performance and the cycle performance diagram of the NiS electrode with the deposited nickel protection, wherein the NiS electrode with the deposited nickel protection is at 5mA/cm2The specific capacitance of 1574F/g, far exceeding 874F/g of the unprotected NiS electrode, at 100mA/cm2The NiS electrode protected by the deposited nickel still maintains 911F/g specific capacitance, while the unprotected NiS electrode only remains 353F/g, and the NiS electrode protected by the deposited nickel has the advantage of improving the conductivity after the nickel is deposited, and the specific capacitance of the NiS electrode protected by the deposited nickel is 250mA/cm2At a current density of 714F/g, a specific capacitance of F/g is still obtained. FIG. 5 is a graph showing a curve at 50mA/cm2The specific capacitance of the electrode without electroplating protection is only 329F/g (42.2%) after 472 constant current charge-discharge cycles from the initial 779F/g, while the NiS electrode with deposited nickel still maintains 778F/g (61.9%) after 2000 cycles from the maximum 1256F/g, and the performance is obviously improved.
Fig. 6 is an electrochemical impedance test of an unprotected, deposited nickel protected NiS electrode. Under the same experimental conditions, the obtained unprotected electrode has a much higher charge transfer resistance (6.6 Ω) than the electrode after nickel deposition (0.6 Ω), and the result fully shows that the conductivity of the electrode is greatly improved after nickel deposition.
Example 3:
in the embodiment of the invention, the prepared electrode selected in the second step is NiS directly grown on the carbon fiber cloth by a hydrothermal method, and the rest is the same as that in the embodiment 1, so that the NiS/carbon fiber cloth composite electrode with deposited nickel protection is obtained.
Example 4:
in the embodiment of the invention, the deposited layer metal selected in the first step is Co, and the selected main salt is CoSO 12g4·7H2O, otherwise same as in example 1, to obtain Ni (OH) protected by the deposited Co Metal layer2And an electrode.
Example 5:
in the embodiment of the invention, the metal of the deposition layer selected in the first step is nickel-cobalt alloy, and the main salt selected is 6gCoSO4·7H2O and 6g NiSO4·6H2O, otherwise and implementationIn the same manner as in example 1, Ni (OH) protected by a composite Ni/Co deposit layer was obtained2And an electrode.
Example 6:
in the embodiment of the invention, the current density adopted in the first step is 30mA/cm2Electrodeposition time 4 minutes, otherwise the same as in example 1, to obtain Ni (OH) protected by a nickel metal layer deposited2And an electrode.
Example 7:
in the embodiment of the invention, the current density adopted in the first step is 50mA/cm2Electrodeposition time 3 minutes, otherwise the same as in example 1, to obtain Ni (OH) protected by a nickel metal layer deposited2And an electrode.
Example 8:
the electrode manufacturing method capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of active substances comprises the following steps:
step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant;
step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode and the settled layer metal sheet of the supercapacitor into the electrodeposition solution prepared in the step (1) for electrodeposition to obtain the electrode of the supercapacitor protected by the settled layer metal.
Wherein, the metal of the deposition layer is cobalt; the sedimentary metal salt is nitrate of sedimentary metal; the pH buffering agent is sodium citrate; the surfactant is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
In the step 2, the electrode of the super capacitor is an electrode which is coated on a current collector after porous carbon or pseudocapacitance material, conductive agent and binder are mixed according to a preset proportion.
The total mass density of the electrodeposition is 0.5mg/cm2。
In the electro-deposition solution in the step 1, the concentration of metal salt of a deposition layer is 240g/L, the concentration of a pH buffering agent is 30g/L, and the concentration of a surfactant is 0.1 g/L.
In the electrodeposition in the step 2, the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min.
Example 9:
the electrode manufacturing method capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of active substances comprises the following steps:
step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant;
step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode and the settled layer metal sheet of the supercapacitor into the electrodeposition solution prepared in the step (1) for electrodeposition to obtain the electrode of the supercapacitor protected by the settled layer metal.
Wherein, the metal of the deposition layer is cobalt; the sedimentary metal salt is chloride salt of sedimentary metal; the pH buffering agent is sodium fluoborate; the surfactant is sodium dodecyl benzene sulfonate.
In the step 2, the electrode of the super capacitor is an electrode obtained by growing an active material on the three-dimensional conductive network.
In step 2, the total mass density of the electrodeposition is 3mg/cm2。
In the electro-deposition solution in the step 1, the concentration of metal salt of a deposition layer is 280g/L, the concentration of a pH buffering agent is 40g/L, and the concentration of a surfactant is 0.1 g/L.
In the electrodeposition in the step 2, the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min.
Example 10:
the electrode manufacturing method capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of active substances comprises the following steps:
step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant;
step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode and the settled layer metal sheet of the supercapacitor into the electrodeposition solution prepared in the step (1) for electrodeposition to obtain the electrode of the supercapacitor protected by the settled layer metal.
Wherein, the metal of the deposition layer is cobalt; the sedimentary metal salt is nitrate of sedimentary metal; the pH buffering agent is sodium citrate; the surfactant is a mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
In the step 2, the electrode of the super capacitor is an electrode which is coated on a current collector after porous carbon or pseudocapacitance material, conductive agent and binder are mixed according to a preset proportion.
In step 2, the total mass density of the electrodeposition is 4mg/cm2。
In the electro-deposition solution in the step 1, the concentration of metal salt of a deposition layer is 300g/L, the concentration of a pH buffering agent is 50g/L, and the concentration of a surfactant is 0.1 g/L.
In the electrodeposition of the step 2, the current density is 60mA/cm2The electrodeposition time was 6 min.
In summary, the present invention provides an electrode protection method for enhancing the conductivity of a supercapacitor (symmetric and asymmetric), and relates to an electrode manufacturing method for enhancing the conductivity of a supercapacitor electrode and inhibiting the falling of active materials. The invention comprises the following steps: preparing a salt solution containing metal ions of a sedimentary layer as an electrodeposition solution, and uniformly stirring; taking the electrode to be protected as a cathode and the deposited layer metal as an anode, and performing electrodeposition by adding a direct current power supply; and taking out the electrode after electrodeposition for a certain time, cleaning and drying to obtain the electrode of the supercapacitor with the electrodeposited metal protection layer. The electrode protection method for enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of the active substance has obvious effect, particularly for high-capacity electrodes, the falling phenomenon of the active material is obviously improved, the electrochemical performance is obviously improved, and the method is low in cost, simple and rapid to operate and suitable for large-scale production.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.

Claims (9)

1. A method for manufacturing an electrode capable of enhancing conductivity of a supercapacitor electrode and inhibiting falling-off of active substances is characterized by comprising the following steps:
step 1, preparing and obtaining an electrodeposition solution; wherein the electrodeposition solution contains a deposition layer metal salt, a pH buffer and a surfactant;
step 2, connecting the electrode of the super capacitor to the cathode of the direct current power supply, and connecting the deposited layer metal sheet to the anode of the direct current power supply; and (3) putting the electrode and the settled layer metal sheet of the supercapacitor into the electrodeposition solution prepared in the step (1) for electrodeposition to obtain the electrode of the supercapacitor protected by the settled layer metal.
2. The method for manufacturing an electrode capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of the active material according to claim 1, wherein in the step 2, the electrode of the supercapacitor is a porous carbon electrode or a pseudocapacitive electrode.
3. The method for manufacturing the electrode, which can enhance the conductivity of the supercapacitor electrode and inhibit the falling of the active material, according to claim 1, wherein in the step 1, the deposited layer metal is one or both of cobalt and nickel.
4. The method for manufacturing the electrode, which can enhance the conductivity of the supercapacitor electrode and inhibit the falling of active substances, according to claim 1, wherein in the step 1, the deposited layer metal salt is a sulfate, a nitrate or a chloride of the deposited layer metal;
the pH buffering agent is boric acid, sodium fluoborate, saccharin, sodium citrate or formic acid;
the surfactant is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
5. The method for manufacturing the electrode capable of enhancing the conductivity of the electrode of the supercapacitor and inhibiting the falling of the active substances according to claim 1, wherein in the step 2, the electrode of the supercapacitor is an electrode which is coated on a current collector by mixing porous carbon or pseudocapacitance material, conductive agent and binder according to a predetermined ratio;
or the electrode of the super capacitor is an electrode obtained by growing an active material on a three-dimensional conductive network.
6. The method for manufacturing the electrode capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling-off of the active substances according to claim 1, wherein in the step 2, the total mass density of the electrodeposition is 0.5-4 mg/cm2。
7. The method for manufacturing the electrode capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling-off of the active substances according to claim 1, wherein in the electrodeposition solution in the step 1, the concentration of the metal salt of the deposition layer is 240-300 g/L, the concentration of the pH buffering agent is 30-50 g/L, and the concentration of the surfactant is 0.1 g/L.
8. The method for manufacturing the electrode capable of enhancing the conductivity of the supercapacitor electrode and inhibiting the falling of the active substances according to claim 1, wherein in the electrodeposition in the step 2, the current density is 10-100 mA/cm2The electrodeposition time is 1-20 min.
9. The method as claimed in claim 1, wherein the supercapacitor is symmetrical or asymmetrical.
CN202010612865.9A 2020-06-30 2020-06-30 Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances Active CN111816456B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010612865.9A CN111816456B (en) 2020-06-30 2020-06-30 Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010612865.9A CN111816456B (en) 2020-06-30 2020-06-30 Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances

Publications (2)

Publication Number Publication Date
CN111816456A true CN111816456A (en) 2020-10-23
CN111816456B CN111816456B (en) 2021-08-13

Family

ID=72855166

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010612865.9A Active CN111816456B (en) 2020-06-30 2020-06-30 Electrode manufacturing method capable of enhancing conductivity of supercapacitor electrode and inhibiting falling of active substances

Country Status (1)

Country Link
CN (1) CN111816456B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62278293A (en) * 1986-05-26 1987-12-03 C Uyemura & Co Ltd Production of electronic parts
CN101613080A (en) * 2009-07-23 2009-12-30 重庆大学 A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array
CN102074702A (en) * 2010-12-28 2011-05-25 株洲冶炼集团股份有限公司 Lead-carbon composite material
CN102436934A (en) * 2011-09-15 2012-05-02 中国科学院苏州纳米技术与纳米仿生研究所 Composite nanometer carbon paper and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62278293A (en) * 1986-05-26 1987-12-03 C Uyemura & Co Ltd Production of electronic parts
CN101613080A (en) * 2009-07-23 2009-12-30 重庆大学 A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array
CN102074702A (en) * 2010-12-28 2011-05-25 株洲冶炼集团股份有限公司 Lead-carbon composite material
CN102436934A (en) * 2011-09-15 2012-05-02 中国科学院苏州纳米技术与纳米仿生研究所 Composite nanometer carbon paper and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
耿阳: "两种尺度碳纤维材料的电化学镀镍及其特性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Also Published As

Publication number Publication date
CN111816456B (en) 2021-08-13

Similar Documents

Publication Publication Date Title
CN110649267B (en) Composite metal lithium cathode, preparation method and metal lithium battery
Guo et al. Inhibition of zinc dendrites in zinc-based flow batteries
CN105513831B (en) A kind of hollow tubular structure electrode material and preparation method thereof
CN112151799B (en) Three-dimensional porous interconnected framework lithium metal battery negative electrode material and preparation method thereof
CN102881866B (en) A kind of lead carbon battery negative plate containing lead graphene composite material
CN101503805B (en) Super capacitor and preparation of composite anode material of battery
CN103794754B (en) Composite negative electrode and preparation method thereof as well as electrochemical power source and application thereof
CN107403968A (en) Aqoue seconary battery
CN102185131A (en) Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode
CN103779581A (en) Porous negative pole piece and preparation method thereof, and lithium ion battery
CN102290244B (en) Preparation method of asymmetrical high-power capacitor battery
Jin et al. Vertical nanoarrays with lithiophilic sites suppress the growth of lithium dendrites for ultrastable lithium metal batteries
CN108538609A (en) A kind of iron Cu oxide/copper base electrode material and preparation method thereof
CN111118908B (en) Layered double-metal hydroxide-polyaniline modified porous conductive composite material and preparation method and application thereof
CN105489872B (en) A kind of copper/CNTs tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof
CN113675365B (en) Negative plate and lithium ion battery
CN110048104A (en) A kind of water system battery and preparation method thereof based on cyaniding frame material
CN107256946A (en) Battery
CN113540402B (en) Internally lithium-philic multi-confinement/induced lithium cathode and preparation method and application thereof
CN102912174A (en) Lead and graphene composite material
CN106207091A (en) A kind of lithium ion battery flexibility positive pole, its preparation method and the super full battery of flexible lithium ion
CN104766971A (en) Positive electrode material and aqueous battery containing positive electrode material
CN105449180B (en) A kind of aluminium/copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof
CN105321725A (en) Micro-nano structure electrode material for super capacitor and preparation method of electrode plate
CN103022450B (en) Three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant