CN108615618B - Preparation method and application of high-voltage composite material electrode - Google Patents
Preparation method and application of high-voltage composite material electrode Download PDFInfo
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- CN108615618B CN108615618B CN201810418838.0A CN201810418838A CN108615618B CN 108615618 B CN108615618 B CN 108615618B CN 201810418838 A CN201810418838 A CN 201810418838A CN 108615618 B CN108615618 B CN 108615618B
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- prussian blue
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- 238000013329 compounding Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 17
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 5
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- -1 cyanate ions Chemical class 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CWZOMTYLSNXUEL-UHFFFAOYSA-N cobalt(ii) cyanide Chemical compound [Co+2].N#[C-].N#[C-] CWZOMTYLSNXUEL-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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
- H01G11/30—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
- H01G11/46—Metal oxides
-
- 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
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- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of composite materials, and discloses a high-voltage electrode composite material which is formed by compounding a Prussian blue analogue and a metal oxide, wherein the Prussian blue analogue is a complex of transition metal ions and metal cyanate ions. The invention aims to provide a prussian blue analogue and metal oxide composite material, a preparation method and a method for constructing a water system super capacitor with an ultra-wide potential window (more than 2.0V) by using the composite material, wherein the water system super capacitor has the characteristics of high power characteristic, excellent cycle life, ultra-wide working potential window, high energy density, low cost, good safety performance and the like.
Description
Technical Field
The invention relates to the field of composite preparation, in particular to a preparation method and application of a high-voltage composite material electrode.
Background
The super capacitor is a novel efficient secondary power supply between a battery and a traditional capacitor, and has the advantages of long service life, high power density, safety, environmental friendliness and the like. The power density of the battery is 10-100 times higher than that of a battery, and the battery can instantly release extra large current, so that the battery is very suitable for electric vehicles. For example, the super capacitor can be used in cooperation with a high-energy battery such as a lithium secondary battery as an electric vehicle, and the performance of the electric vehicle can be greatly improved by using the super capacitor under the conditions of high-power output such as starting, climbing, accelerating and the like. In addition, the super capacitor can also be widely applied to the fields of communication, industry and the like as a standby power supply and an independent power supply. Therefore, supercapacitors have been the focus of research.
The water-based super capacitor has the main defect of low energy density, which seriously limits the wide application of the super capacitor, so the current primary task is to improve the energy density of the super capacitor. According to the formula of energy density E-1/2 CV2The energy density (E) is related to the working potential window (V) and the capacity (C), wherein the energy density and the working potential window have an exponential relationship as can be seen from a formula, so that the improvement of the working potential window is particularly important.
Because the Prussian blue analogue has larger specific capacitance and higher oxygen evolution potential (1V), and the metal oxides such as manganese dioxide also have larger specific capacitance and higher oxygen evolution potential (1V), the Prussian blue analogue is very suitable for being used as an electrode material of a high-potential super capacitor. However, the currently reported working potential window of the water-based supercapacitor is generally lower than 2.0V, and the potential window is low, so that the further improvement of the energy density is limited.
Disclosure of Invention
In order to overcome the current situation that the current water system supercapacitor is narrow in potential window and low in energy density, the invention aims to provide a prussian blue analogue and metal oxide composite material, a preparation method and a method for constructing a water system asymmetric supercapacitor with an ultra-wide potential window (larger than 2.0V) by using the composite material, and the water system asymmetric supercapacitor has the characteristics of high power characteristic, excellent cycle life, ultra-wide working potential window (larger than 2.0V), high energy density, low cost, good safety performance and the like.
In order to achieve the purpose, the invention provides the following technical scheme: the composite material is formed by compounding a Prussian blue analogue and a metal oxide, wherein the Prussian blue analogue is a complex of transition metal ions and metal cyanide.
In the composite material, the prussian blue analog is one or more of iron ferricyanide, copper ferricyanide, cobalt ferricyanide, nickel ferricyanide, manganese ferricyanide, iron manganoceyanide, copper manganoceyanide, iron cobaltoceyanide, copper cobaltoceyanide, iron nickelous cyanidde, and copper nickelous cyanidde.
In the composite material, the metal oxide is one or more of manganese dioxide, titanium dioxide, mangano-manganic oxide and vanadium pentoxide.
In the prussian blue analogue and metal oxide composite material, the prussian blue analogue content is 10-90 wt%, and the metal oxide content is 10-90 wt%.
Meanwhile, the invention also discloses a preparation method of the composite material, which comprises the following steps:
step 1: preparing a prussian blue analogue on a carrier;
step 2: and (3) depositing a metal oxide on the carrier obtained in the step (1).
In the above method for preparing the composite material, the carrier is carbon cloth.
In the above method for preparing the composite material, the method for depositing the metal oxide in step 2 comprises: one of electrodeposition, hydrothermal method and self-assembly reaction.
Meanwhile, the invention also discloses application of the composite material, which is used for the electrode material of the super capacitor.
In the application of the composite material, the composite material is used for constructing a high-voltage (more than 2.0V) water system super capacitor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the Prussian blue analogue @ metal oxide composite material has excellent electrochemical properties, including an ultra-wide potential window of-0.2-1.4V (vs. Ag/AgCl), and high specific capacitance 315.3F g-1And excellent rate capability.
(2) The Prussian blue analogue @ metal oxide composite material// the active carbon water system asymmetric supercapacitor has an ultra-wide working potential window of 2.4V and an ultra-high energy density of 46.13Wh kg-1Wherein the potential window of 2.4V is higher than that of all the reported water-based supercapacitors. This invention is important to promote the further development of water-based supercapacitorsWhat is meant is that.
(3) The electrode material is directly prepared on the carbon cloth, the carbon fiber paper, the graphite paper and the metal foil, no adhesive or conductive agent is used, the preparation process is short, and the large-scale production is facilitated. And the assembled super capacitor has a good bendable folding type, and is very suitable for flexible wearable electronic equipment.
Drawings
Fig. 1 is a scanning electron micrograph of the prussian blue analog @ metal oxide composite material in example 1.
Fig. 2 is a charge-discharge curve of the prussian blue analog @ metal oxide composite electrode in example 1.
Fig. 3 is a charge-discharge curve of the prussian blue analogue @ metal oxide composite// active carbohydrate-based asymmetric supercapacitor in example 1.
Fig. 4 is a graph of the cycle life of the prussian blue analog @ metal oxide composite// active carbohydrate based asymmetric supercapacitor of example 1.
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.
Example 1
Example 1 an electrodeposition process was used to synthesize a prussian blue analog @ metal oxide composite with 20 wt% ferrous ferricyanide and 80 wt% manganese dioxide as specific examples.
The first step is as follows: and (3) pretreating the carbon cloth, namely treating the carbon cloth by using nitric acid at 90 ℃ for 6 hours, removing surface impurities, and storing the carbon cloth in absolute ethyl alcohol for later use.
The second step is that: at 0.01M K3[Fe(CN)6And 0.5M Na2SO4The mixed solution is used as electrolyte, and three electrodes are used in electrodepositionThe electrode system uses carbon cloth as a working electrode, a platinum electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode. In the voltage range of-0.2-1.6V and in 100mV s-1The scanning rate of (a) is used for cyclic voltammetric electrodeposition, so that ferrous ferricyanide is prepared in situ on the surface of the carbon cloth.
The third step: after the iron ferricyanide is prepared in situ on the surface of the carbon cloth, the electrolyte is replaced by 0.1M manganese acetate solution electrolyte, and the manganese dioxide is electrodeposited at a continuous working voltage of 1.8V (vs. Ag/AgCl). Finally obtaining the ferricyanide/manganese dioxide composite material. Fig. 1 is a scanning electron microscope image of the prussian blue analog @ metal oxide composite material obtained in this example, and tests show that the composite material prepared in situ on carbon cloth can be completely obtained in this example. FIG. 2 is a charge-discharge curve of a Prussian blue analogue @ metal oxide composite electrode, wherein the abscissa is the time of charge-discharge and the ordinate is the voltage, and the value is calculated from the data in the graph and is 1A g-1The specific capacitance of the Prussian blue analogue @ metal oxide composite material electrode can reach 315.3F g under the condition of the current density-1(ii) a The current density is even 15A g-1The electrode can also maintain 41.7% of the initial specific capacitance at the current density of (2). In addition, the working potential of the Prussian blue analogue @ metal oxide composite material electrode is up to 1.4V as can be seen from the ordinate.
The fourth step: the Prussian blue analogue @ metal oxide composite material is used as a positive electrode, the carbon cloth loaded with activated carbon is used as a negative electrode, and the asymmetric supercapacitor is assembled. Subsequently, the supercapacitor separator was replaced with 1M Na2SO4The method comprises the following steps of soaking in electrolyte, sandwiching the Prussian blue analogue @ metal oxide composite material electrode and the activated carbon electrode in a sandwich mode, and taking a plastic film as an encapsulation film. Thus, a water-based asymmetric supercapacitor is assembled. FIG. 3 is a charging and discharging curve of the Prussian blue analogue @ metal oxide composite material// active carbohydrate system asymmetric supercapacitor, the abscissa is charging and discharging time, the ordinate is voltage, and the data in the graph can be calculated when the voltage is 1A g-1At a current density of (a), the Prussian blue analogue @ metal oxide composite// active carbohydrateIs an asymmetric supercapacitor exhibiting 57.7F g-1High specific capacitance of (2); even if the current density is increased to 15A g-143.15% of the initial specific capacitance can still be maintained. Furthermore, it can be seen from the ordinate (voltage) in the figure that this supercapacitor has a stable operating potential window of 2.4V and has a very high coulomb efficiency. Fig. 4 is a life cycle diagram of the prussian blue analogue @ metal oxide composite// active carbohydrate asymmetric supercapacitor in this example, and the ordinate is specific capacitance retention rate, and the abscissa is the number of charge and discharge tests, and it can be seen from the diagram that after 20000 charge and discharge tests, 85.5% of capacity retention rate still remains, and extremely stable electrochemical stability is shown.
Example 2
Example 2 an electrodeposition process was used to synthesize a prussian blue analog @ metal oxide composite with 30 wt% cobalt ferricyanide and 70 wt% manganous manganic oxide as specific examples.
The first step is as follows: the pretreatment of the graphite paper comprises the steps of treating the graphite paper by nitric acid at 90 ℃ for 6 hours, removing surface impurities, and storing in absolute ethyl alcohol for later use.
The second step is that: at 0.01M K3[Co(CN)6The solution is used as electrolyte, a three-electrode system is used in electrodeposition, graphite paper is used as a working electrode, a platinum electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. In the voltage range of-0.2-1.6V and at 1000mV s-1The scanning rate of (a) is used for cyclic voltammetric electrodeposition, so that ferrous ferricyanide is prepared in situ on the surface of the graphite paper.
The third step: after cobalt cobaltous cyanide is prepared in situ on the surface of the graphite paper, the electrolyte is replaced by a manganese acetate solution electrolyte with the concentration of 1M, and the electrolytic deposition of manganous manganic oxide is carried out at the continuous working voltage of-1.8V (vs. Ag/AgCl). Finally obtaining the cobaltosite/manganous manganic oxide composite material.
Example 3
Example 3 an electrodeposition process was used to synthesize prussian blue analog @ metal oxide composite with 50 wt% copper ferricyanide and 50 wt% manganese dioxide as specific examples.
The first step is as follows: the carbon cloth is pretreated by treating the carbon cloth with nitric acid at 90 ℃ for 6 hours, removing surface impurities, and storing in absolute ethyl alcohol for later use.
The second step is that: at 0.01M K4[Cu(CN)6]And 0.5M Na2SO4The mixed solution is used as electrolyte, a three-electrode system is used during electrodeposition, carbon cloth is used as a working electrode, a platinum electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. In the voltage range of-0.2-1.6V and in 100mV s-1The scanning rate of the carbon cloth is adopted to carry out cyclic voltammetry electrodeposition, so that copper cyanide is prepared on the surface of the carbon cloth in situ.
The third step: after copper cyanide was prepared in situ on the surface of the carbon cloth, the electrolyte was replaced with 0.1M manganese acetate solution electrolyte and manganese dioxide was electrodeposited at a continuous operating voltage of 1.8V (vs. ag/AgCl). Finally, the copper cyanide @ manganese dioxide composite material is obtained.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. The high-voltage electrode composite material is characterized in that the composite material is formed by compounding a Prussian blue analogue and a metal oxide, the metal oxide is deposited by an electrodeposition method and tightly covers the surface of Prussian blue analogue particles in a composite form, and the Prussian blue analogue is a complex of transition metal ions and metal cyanide; the Prussian blue analogue is a coordination compound formed by coordination of metal cyanide ions and transition metal ions, wherein the mass concentration of the Prussian blue analogue is 0.01-3M, and the Prussian blue analogue is ferrous ferricyanide; in the Prussian blue analogue and metal oxide composite material, the content of the Prussian blue analogue is 20 wt%, and the content of the metal oxide is 80 wt%; the metal oxide is manganese dioxide; the metal oxide is prepared with 0.1-3M of a corresponding metal salt solution.
2. A method of making the composite material of claim 1, comprising the steps of:
step 1: preparing a prussian blue analogue on a carrier;
step 2: and (3) depositing a metal oxide on the carrier obtained in the step (1).
3. The method of claim 2, wherein the carrier is selected from the group consisting of carbon cloth, carbon fiber paper, graphite paper, and metal foil.
4. The method for preparing the composite material according to claim 2, wherein the method for depositing the metal oxide in the step 2 is as follows: one of electrodeposition, hydrothermal method and self-assembly reaction.
5. Use of the composite material of claim 1 for the construction of high voltage aqueous supercapacitor energy storage devices > 2.0V.
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| CN101546650A (en) * | 2009-04-10 | 2009-09-30 | 中南大学 | Electrode material of super capacitor and its preparation method |
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2018
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546650A (en) * | 2009-04-10 | 2009-09-30 | 中南大学 | Electrode material of super capacitor and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| Bendable tube-shaped supercapacitor based on reduced grapheme oxide and Prussian blue coated carbon fiber yarns for energy storage;Mohd. Khalid等;《Journal of Energy Chemistry》;20170701;第866-873页 * |
| Dual-Layer-Structured Nickel Hexacyanoferrate/MnO2 Composite as a High-Energy Supercapacitive Material Based on the Complementarity and Interlayer Concentration Enhancement Effect;Yu Wang等;《Applied Materials & Interfaces》;20140501;第6卷;第6196-6201页 * |
| Yu Wang等.Dual-Layer-Structured Nickel Hexacyanoferrate/MnO2 Composite as a High-Energy Supercapacitive Material Based on the Complementarity and Interlayer Concentration Enhancement Effect.《Applied Materials & Interfaces》.2014,第6卷 * |
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