CN1925076A - High-power electrochemical electrode - Google Patents

High-power electrochemical electrode Download PDF

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CN1925076A
CN1925076A CNA2005100990799A CN200510099079A CN1925076A CN 1925076 A CN1925076 A CN 1925076A CN A2005100990799 A CNA2005100990799 A CN A2005100990799A CN 200510099079 A CN200510099079 A CN 200510099079A CN 1925076 A CN1925076 A CN 1925076A
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electrode
metal
electrochemical
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sediment
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吴乃立
郭信良
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    • 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
    • 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

Abstract

This invention provides one electron chemical electrode, which comprises electron chemical parts, electrode coating layer and its process method, wherein, the coating comprises at least one iron oxidation with chemical component as M<1+x>Fe<2-x>O<4> with -0.2<=x<=0.2 and M represents one non Fe transient metal element. This invention part is of high ability of power output and is suitable for super capacitor.

Description

High-power electrochemical electrode
Technical field
The present invention relates to a kind of electrochemical electrode and the formed capacitor of its combination and preparation method thereof, the electrode of particularly a kind of application ferriferous oxide (ferrite) and the formed ultra-high capacity device of its combination and preparation method thereof.
Background technology
For a long time, battery is the most normal energy storage device that is used, though secondary cell can provide preferable energy density, and its high power that is not enough to load too frequent output.Known under the situation that high power discharges and recharges, battery is easily impaired and cause cycle life sharply to reduce.This shortcoming will cause battery to satisfy to need moment that the electricity needs of the machinery of big electric current is provided, and as electric automobile, therefore be badly in need of exploitation one be enough to the to arrange in pairs or groups high power energy-storage travelling wave tube of battery.
Ultra-high capacity device (supercapacitor) is called electrochemical capacitor (electrochemical capacitor) again.Since nineteen ninety, the ultra-high capacity device just like has been regarded as a kind of novel energy-storing element between battery and traditional ceramics capacitor, it can store the capacitance up to thousands of farads in limited bulk, and has the characteristic of high power density, high charge-discharge cycle and high coulomb efficiency.Owing to have both above-mentioned characteristic, the ultra-high capacity device is except the direct stand-by power supply as compact electric apparatus, and main is the instantaneous large-current supply that can be used as portable electronic product, motor starter and electric motor car.This notion is derived from the AC-battery power source that ultra-high capacity device and battery are formed, and uses down when both are in parallel, provides any required immediate current by the ultra-high capacity device, and battery then can discharge under specific currents; This all carries the useful life that effect can prolong battery.
According to the difference of Charge Storage mechanism, the ultra-high capacity device can roughly be divided into two kinds, and one is double-layer capacitor, and another then is pseudo-capacitor.Wherein, the accumulate mode of double-layer capacitor is to be derived from electrode and electrolyte interface to carry out electrostatic separation of charge, and its start only involves a simple physical property absorption behavior.Usually, double-layer capacitor mainly makes the carbon material of apparatus high-specific surface area as electrode material.On the other hand, pseudo-capacitor (pseudocapacitor) then has an accumulate mechanism inequality.The capacitance of pseudo-capacitor except small part from the Electric double-layer capacitor, it mainly is derived from active material and carries out electricity absorption or faraday's reaction at electrode surface, owing to only there is the material that is positioned near surf zone to participate in reaction, therefore its charge-discharge velocity is fast more than battery, and still can satisfy the characteristic of electric capacity and be employed widely.In addition, because the specific capacitance amount of pseudo-electric capacity exceeds Electric double-layer capacitor far away, the many stakes of recent ultra-high capacity device correlative study are at the category of pseudo-electric capacity.
The electrode material that prior art discloses pseudo-capacitor mainly concentrates on transition metal oxide and conducting polymer, and wherein maximum is the transition metal oxide development.In recent years, ruthenium-oxide (RuO 2) studied and be applied in the category of ultra-high capacity device widely, Journal of theElectrochemical Society, 142, pp.2699-2703 (1995) paper discloses, and armorphous ruthenium-oxide can provide a specific capacitance up to 720F/g in sulfuric acid electrolyte.But, do not have the benefit of substantial commercialization because ruthenium-oxide is very expensive.Prior art comprises Journal of Solid State Chemistry, 144, and pp.220-223 (1999) paper and United States Patent (USP) also disclose for the 6th, 616, No. 875 and the 6th, 339, No. 538 and disclose armorphous (amorphous) manganese dioxide (MnO 2) then be the pseudo-capacitor electrode material of a potentialization, except low price and to the characteristic of environment friendliness, the neutral water of its collocation is that electrolyte also can not pollute environment.Yet, maximum shortcoming is that the electron conduction degree of armorphous manganese dioxide is not good, therefore the many upward uses of carrier (substrate) that are coated on conduction with the form of film of this material, therefore and be not suitable for the process technique product of traditional thick membrane electrode can obtain higher capacitance and discharge and recharge power.
Disclose iron oxide (Fe No. 89323 at No. the 6th, 762,926, prior art United States Patent (USP) and TaiWan, China patent xO yH z) as the electrode material of ultra-high capacity device, wherein the preferably is tri-iron tetroxide (Fe 3O 4) present higher capacitance.Yet Fe 3O 4Electron conduction degree difference and its pseudo-electric capacity are that reaction speed is slower from anionic redox reaction, and therefore capacitance sharply descends under high charge-discharge speed, is unsuitable for the application of high charge-discharge power.
Fe 3O 4Belong to spinel structure, this structure is to form a face-centred cubic framework by oxygen atom, and has two kinds of locus for metal cation, and wherein 1/3 iron ion occupies other iron ions of 2/3 of tetrahedron center and then occupies octahedral center.The present invention discloses and to replace about 1/3rd iron ion number with other metal ion and still can obtain one and keep spinel structure, be commonly called as the multicomponent oxide into ferrite (ferrite), and its capacitance characteristic comprises capacitance and discharges and recharges power, purer Fe 3O 4Significantly promote.
The objective of the invention is to, exploitation is compared to the cheap ultra-high capacity device electrode material of ruthenium-oxide.Another object of the present invention is that then this electrode material has preferable electron conduction degree and is enough to provide high power output.
Summary of the invention
A first aspect of the present invention is to provide a kind of electrochemical electrode, and it comprises a base material and an electrode coating, and this electrode coating is to coat on this base material, and contains a ferriferous oxide at least, and its chemical composition is M 1+xFe 2-xO 4, wherein-0.2≤x≤0.2, and M is non-iron (Fe) transition metal.
In a preferred embodiment, wherein this base material is a sheet metal.
In a preferred embodiment, this ferriferous oxide tool one spinel structure wherein.
In a preferred embodiment, wherein M be selected from the group that constituted by manganese (Mn), cobalt (Cu), nickel (Ni), copper (Cu) and combination thereof one of them.
A second aspect of the present invention is to provide a kind of electrochemical element, and it comprises the electrochemical electrode with above-mentioned feature.
In a preferred embodiment, this electrochemical element is an electrochemical energy storage element.
In a preferred embodiment, this electrochemical element also comprises an electrolyte, this electrolyte be a metal inorganic salt and a metal organic salt class one of them.
In a preferred embodiment, wherein this metal inorganic salt and this metal organic salt class also comprise an alkali metal group metallic element and an alkaline earth metal element one of them.
In a preferred embodiment, wherein this alkali metal group metallic element comprises lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) and combination thereof.
In a preferred embodiment, wherein this alkaline earth metal element comprises beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and combination thereof.
In a preferred embodiment, wherein this metal inorganic salt also comprises chloride, sulfate, sulphite, nitrate and combination thereof.
In a preferred embodiment, wherein this metal organic salt class also comprises hexafluorophosphate, tetrafluoroborate, perchlorate, trifluoromethyl sulfonic acid and combination thereof.
The 3rd conception of the present invention is to provide a kind of preparation method of electrode coating, and it comprises the following steps: (a) preparation one solution, and this solution contains Fe 3+Ion and M 2+Ion, and Fe 3+Ion and M 2+The concentration ratio of ion is 2: 1; (b) this solution is added in the alkaline solution, to form a sediment; (c) this sediment of heat treatment is to form a ferriferous oxide powder; (d) add an adhesive and a solvent in this ferriferous oxide body, to form a mixed slurry; And (e) this mixed slurry is coated on the sheet metal base material.
In a preferred embodiment, wherein M be selected from the group that constituted by manganese (Mn), cobalt (Cu), nickel (Ni), copper (Cu) and combination thereof one of them.
In a preferred embodiment, wherein also comprise a porousness conductive material in this alkaline solution.
In a preferred embodiment, this preparation method also comprises after step (b): (b1) continue to stir this solution so that react completely; (b2) with this sediment of excessive washed with de-ionized water; And (b3) dry this sediment.
In a preferred embodiment, in its step (c) in an oxygen-free environment this sediment of heat treatment.
In a preferred embodiment, in the step (c) with this sediment of temperature range heat treatment of 350 ℃ ~ 600 ℃.
In a preferred embodiment, wherein this adhesive agent be selected from a poly-difluoroethylene resin (PVdF), one polystyrene-butadiene rubber (Styrene-Butadiene-Rubber) and an acrylic resin (Acrylic resin) one of them.
In a preferred embodiment, wherein this solvent be a positive methyl pyrrolidone (NMP) with water one of them.
Accompanying drawing is further illustrated the present invention below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is a method flow diagram, in order to electrode coating preparation method's of the present invention key step to be described;
Fig. 2 is an X-ray diffracting spectrum, and its diffraction maximum that confirms the powder that the present invention is prepared is the structure that belongs to spinelle (spinel), and the Si in collection of illustrative plates (111) peak is the standard that includes (internal standard) material that comes from interpolation.
Fig. 3 is the prepared MnFe of preferred embodiment according to the present invention 2O 4Three electric pole type systemic circulation volt-ampere analysis result, wherein MnFe of electrode 2O 4Heat treatment temperature be 350 ℃;
Fig. 4 is the prepared MnFe of comparative example according to the present invention 2O 4The cyclic voltammetric analysis result of electrode, wherein MnFe 2O 4Heat treatment temperature be 200 ℃;
Fig. 5 is the prepared MnFe of preferred embodiment according to the present invention 2O 4Two electric pole type systemic circulation volt-ampere analysis results of electrode, wherein electric potential scanning speed is 20mV/s;
Fig. 6 is the prepared MnFe of preferred embodiment according to the present invention 2O 4Two electric pole type systemic circulation volt-ampere analysis results of electrode wherein are with 0.5mA/cm 2The electric current of deciding of current density discharges and recharges; And
Fig. 7 is according to the prepared Mn of another preferred embodiment of the present invention 1.2Fe 1.8O 4Three electric pole type systemic circulation volt-ampere analysis results of electrode.
Embodiment
Below will describe electrode coating of the present invention and the detailed preparation process that comprises the electrochemical electrode of this electrode coating in detail, and correlation analysis be the results are shown in the accompanying drawing, with feature and the advantage that further specifies electrochemical electrode of the present invention and electrochemical element.
See also Fig. 1, it is a method flow diagram, in order to electrode coating preparation method's of the present invention key step to be described.At first, preparation one contains Fe 3+Ion and M 2+The ion solution system, shown in step 11, this Fe wherein 3+Ion and this M 2+The concentration ratio of ion is 2: 1.Then, this solution is added in the alkaline solution, shown in step 12, in solution, promptly form a sediment this moment.Continue to stir this solution so that react completely and with this sediment of excessive washed with de-ionized water, respectively as step 13 with shown in the step 14; With after this drying precipitate, this sediment of heat treatment in an oxygen-free environment is to form a ferriferous oxide powder, respectively shown in step 15 and step 16 then.Add an adhesive agent and a solvent (shown in step 17) at last in this ferriferous oxide body, promptly become the slurry of this electrode coating, it can further be coated on the base material, to form an electrochemical electrode, shown in step 18.
Below will describe the preparation process and the analysis result of various embodiments of the present invention in detail:
[embodiment 1]
With 0.024 mole of FeCl 36H 2O and 0.012 mole of MCl 2, wherein M is Fe, Co, Ni or Cu, or 0.012 mole of MnSO 4H 2O is dissolved in the deoxidized water solution of 20 milliliters of 1M HCl, at this moment solution Fe 3+With other another metal (Co, Ni, Cu or Mn) ion concentration be 2: 1.
Then this bisalt solution is dropwise added in 200 milliliters the 1.5M NaOH aqueous solution, produce the brownish black precipitation immediately, and continue to stir 30 minutes so that precipitation reaction is complete.Through precipitating with after removing unnecessary ion,, wherein remove Fe with the sediment taking-up and in 50 ℃ of air dryings with this brownish black of excessive washed with de-ionized water 3O 4Be outside the crystalline phase, all the other MFe 2O 4Powder is noncrystalline phase; In nitrogen environment with this sediment of 600 ℃ of heat treatments 2 hours so that its crystallization.
Its diffraction maximum from synthetic powder of X-ray diffracting spectrum susceptible of proof by each crystallization powder of Fig. 2 is the structure that belongs to spinelle (spinel).
The first adding of the above-mentioned powder percentage by weight that is synthesized is 10% electrical conductivity Carbon black and adds suitable amount of adhesive and solvent thereupon, wherein adhesive promptly forms an electrode coating slurry for poly-difluoroethylene resin (PVdF) solvent is positive methyl pyrrolidone (NMP); This slurry is uniformly coated on the making of promptly finishing electrochemical electrode on the titanium plate substrate.At last with this electrode in 120 ℃ of vacuum dry 6 hours to remove solvent.
This experiment uses cyclic voltammetry (CV) to carry out the electrochemical analysis of electrode, and this analyzes the three electric pole type systems of employing and measures in 1M NaCl electrolyte; In this measuring system, work electrode, auxiliary electrode and reference electrode are respectively MnFe 2O 4The saturated KCl solution of electrode, platinum guaze and Ag/AgCl/ (its current potential is 0.197V with respect to standard hydrogen electrode).
The capacitor C of electrode material can be assessed by following formula (1):
C = &Integral; Vi Vf i / s dV / w - - - ( 1 )
Wherein i is electric current (unit is ampere), and s is electric potential scanning speed (unit is volt/second), and w is weight (unit is gram), V iAnd V f(unit is volt, V at this moment to be respectively voltage range iAnd V fBe respectively 0.0V and 0.7V).
Contribution according to formula (1) calculates and deduct carbon black can obtain various MFe 2O 4The capacitance of powder.Table (one) more different MFe 2O 4The capacitance that electrode is showed in 1M NaCl electrolyte.By table () as can be known, with the crystallization MFe of disclosed different Transition metal substituted 2O 4Capacitance all than existing Fe 3O 4Height is wherein again with MnFe 2O 4And CoFe 2O 4Best results.
Table (one)
Become phase-splitting Capacitance (F/g)
Fe 3O 4 1.2
MnFe 2O 4 14.9
CoFe 2O 4 7.1
NiFe 2O 4 2.0
CuFe 2O 4 3.0
In addition, in order further to promote the capacitance of MFe2O4, in following embodiment, powder crystallization temperature and synthetic method are done preferable selection.
[embodiment 2]
With 0.024 mole of FeCl 36H 2O and 0.012 mole of MnSO 4H 2O is dissolved in 20 milliliters the 1M HCl aqueous solution in order, Fe in this moment solution 3+With Mn 2+Ion concentration is 2: 1.Carbon black with 2.76 grams adds aforesaid solution and continues stirring 30 minutes after grinding again, so that carbon black can be dispersed in the solution.Then this solution is dropwise added in 200 milliliters the 1.5M NaOH aqueous solution, produce the brownish black precipitation immediately, and continue to stir 30 minutes so that precipitation reaction is complete.Through with this brownish black of excessive washed with de-ionized water precipitation with after removing unnecessary ion, sediment taken out and in 50 ℃ of air dryings, subsequently in nitrogen environment with 350 ℃ of heat treatments 2 hours.X light diffracting analysis discloses and comprises a MnFe in this composite granule 2O 4Crystalline phase.
Will be through heat treated MnFe 2O 4/ carbon black composite granule grinds and also to add suitable amount of adhesive and solvent, and wherein adhesive is that PVdF, solvent are NMP, this slurry is uniformly coated on the titanium plate substrate finishing electrode, and with this electrode in 120 ℃ of vacuumizes 6 hours to remove solvent.
Same, utilize cyclic voltammetry (CV) to carry out the electrochemical analysis of electrode, prepared MnFe 2O 4Electrode in the 1M NaCl aqueous solution be with the sweep speed gained under the 20mV/s condition the cyclic voltammetric analysis result as shown in Figure 3.This analyzes the three electric pole type systems that still adopt.As shown in Figure 3, this CV curve almost presents a rectangle except the redox peak that a broadness is arranged, and when voltage reversal, electric current reaches reverse stationary value very soon, convergence one typical capacitor.In addition, under many different voltage scan rate, this electrode is kept and is close to identical characteristic, and this discloses MnFe 2O 4Characteristic with good capacitance characteristic, reaction invertibity and high power output.Calculate according to formula (1) and to learn, after the capacitance of deduction carbon black composition, but clear MnFe wherein 2O 4The capacitance of being contributed is 102F/g.
[comparative example 1]
MnFe with embodiment 2 2O 4Powder, difference are to change its heat-treat condition, make its in nitrogen environment with 200 ℃ of heat treatments 2 hours.
Equally to carrying out the cyclic voltammetric analysis by the prepared electrode of above-mentioned powder, its in the 1MNaCl aqueous solution be with the sweep speed under the 20mV/s condition the cyclic voltammetric analysis result as shown in Figure 4, this analyzes the three electric pole type systems that still adopt.A tangible irreversible oxidation reduction reaction only appears in this electrode in this operating condition as shown in Figure 4, but not presents a typical electric capacity behavior.This phenomenon discloses low excessively as heat treatment temperature, the MnFe of then formed non-spinel structure crystal formation 2O 4Do not have potentiality as ultra-high capacity device electrode material.
[embodiment 3]
Make a ultra-high capacity device according to embodiment 2, wherein electrolyte is used the 1M KCl aqueous solution instead.According to analysis, its capacitance is 94F/g.
[embodiment 4]
With embodiment 2 preparation MnFe 2O 4Electrode, difference are to use instead two electric pole type systems and carry out the cyclic voltammetric analysis.This analysis is to form identical electrode with two to be opposite to mutually in the 1MNaCl electrolyte.Figure 5 shows that these electrodes are the cyclic voltammetric test result of 20mV/s with electric potential scanning speed in the 1M NaCl aqueous solution.Use because two utmost point formula systems can be considered two capacitors in series, its equivalent capacity is expressed as follows:
1/Ce＝1/C+1/C＝2/C (2)
C＝2Ce (3)
The capacitance of unit electrode is the twice of actual measured value, learns MnFe according to formula (1) and (3) calculating 2O 4The contribution capacitance is 100F/g.When electric potential scanning speed was brought up to 200mV/s, capacitance was reduced to about 78F/g, estimated wherein MnFe 2O 4The power that discharges and recharges be about 15kW/kg.This power output is existing Fe 3O 4More than 10 times of electrode.
Fig. 6 then be these electrodes in the 1M NaCl aqueous solution with fixing 0.5mA/cm 2Current density decide the result schematic diagram that electric current discharges and recharges, it is disclosed in charging and discharging curve in the 1.0V voltage range near straight line and there is not tangible IR potential drop, is a typical capacitor.
[embodiment 5]
Make an electrochemical capacitor according to embodiment 2, wherein electrolyte is used 1M Na instead 2SO 4The aqueous solution.By analysis, this MnFe 2O 4The capacitance of capacitor is 63F/g-MnFe 2O 4
[embodiment 6]
With 0.024 mole of FeCl 36H 2O and 0.012 mole of CoCl 26H 2O is dissolved in 20 milliliters the 1M HCl aqueous solution in regular turn, Fe in this moment solution 3+With Co 2+Ion concentration be 2: 1; Then the carbon black with 2.815 grams adds aforesaid solution and continues stirring 30 minutes after grinding, so that carbon black can be dispersed in this solution.Then this solution is dropwise added in 200 milliliters the 1.5M NaOH aqueous solution, produce the brownish black precipitation immediately, and continue to stir 30 minutes so that precipitation reaction is complete.With after removing unnecessary ion, be about to that sediment takes out and with this brownish black of excessive washed with de-ionized water precipitation in 50 ℃ of air dryings, subsequently in nitrogen environment with 400 ℃ of heat treatments 2 hours.
Then carry out the preparation of electrode, and still adopt two utmost point formula systems that this electrode is carried out electro-chemical test (being the cyclic voltammetric analysis) according to embodiment 2.Reach the calculating of (3) by analysis with formula (1), as can be known CoFe 2O 4The contribution capacitance is 45F/g.
[embodiment 8]
With 0.0216 mole of FeCl 36H 2O and 0.0144 mole of MnSO 4H 2O is dissolved in 20 milliliters the 1M HCl aqueous solution in regular turn, Fe in this moment solution 3+With Mn 2+Ion concentration be 1.8: 1.2.The carbon black of 2.815 grams is added aforesaid solution and continues stirring 30 minutes after grinding, so that carbon black can be dispersed in the solution, then this solution is dropwise added in 200 milliliters of 1.5M NaOH aqueous solution that are heated to 80 ℃ in advance, produce the brownish black precipitation immediately, and continue to stir 30 minutes so that precipitation reaction is complete.Through precipitating with after removing unnecessary ion with this brownish black of excessive washed with de-ionized water, with the sediment taking-up and in 50 ℃ of air dryings, this moment, this powder had Mn 1.2Fe 1.8O 4Chemical composition.
Carry out the making of electrode according to embodiment 2 disclosed methods equally, and adopt the three-pole system to carry out the cyclic voltammetric analysis; Fig. 7 is and utilizes the three-pole system to test the cyclic voltammogram of this electrode in the 1M NaCl aqueous solution, and by analysis, the electric capacity of prepared electrode material is 40F/g in this embodiment.
Because the prepared various MFe of the present invention 2O 4Therefore powder all has the structure of spinelle, and the solid-state mutual solubility height between each metal ion can be with different M, M ' metal ion, and wherein M, M '=Mn, Co, Ni, Cu or Fe are combined to form (MM ') with different ratios 1+xFe 2-xO 4, wherein-0.2≤x≤0.2; When x fell within-0.2 ~ 0.2 the scope, the capacitance of prepared electrode material was best, if beyond this scope, then capacitance will reduce fast.
Compared to existing ruthenium-oxide material, the invention provides the cheaper novel ultra-high capacity device capacitance electrode material of a series of prices, and compared to existing tri-iron tetroxide (Fe 3O 4), the M of the crystal formation of signing an undertaking provided by the present invention 1+xFe 2-xO 4Have more the preferable power that discharges and recharges.
Comprehensive above-mentioned explanation, the present invention are the invention of a novelty, progress and tool industrial applicability in fact, dark tool dynamogenetic value.
Those skilled in the art can make the change or the modification of various equivalences to the present invention, and these equivalent modification fall within the application's appended claims institute restricted portion equally.

Claims (10)

1. electrochemical electrode, it comprises:
One base material;
One electrode coating, it is coated on the described base material, and described electrode coating contains a ferriferous oxide at least, and its chemical composition is M 1+xFe 2-xO 4, wherein-0.2≤x≤0.2, and M is non-iron (Fe) transition metal.
2. electrochemical electrode as claimed in claim 1 is characterized in that,
Described base material is a sheet metal; And/or
Described ferriferous oxide tool one spinel structure.
3. electrochemical electrode as claimed in claim 1 is characterized in that, M is selected from manganese (Mn), cobalt (Cu), nickel (Ni), copper (Cu) and combination thereof.
4. an electrochemical element is characterized in that, it comprises each the described electrochemical electrode as claim 1 to 4.
5. electrochemical element as claimed in claim 4 is characterized in that, it is an electrochemical energy storage element; And/or
Described electrochemical element also comprises an electrolyte, described electrolyte be a metal inorganic salt and a metal organic salt class one of them, wherein:
Described metal inorganic salt and described metal organic salt class also comprise an alkali metal group metallic element and an alkaline earth metal element one of them;
Described alkali metal group metallic element comprises lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) and combination thereof;
Described alkaline earth metal element comprises beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and combination thereof;
Described metal inorganic salt also comprises chloride, sulfate, sulphite, nitrate and combination thereof; And/or
Described metal organic salt class also comprises hexafluorophosphate, tetrafluoroborate, perchlorate, trifluoromethyl sulfonic acid and combination thereof.
6. the preparation method of an electrode coating comprises the following steps:
(a) preparation one solution, described solution contains Fe 3+Ion and M 2+Ion, and Fe 3+Ion and M 2+The concentration ratio of ion is 2: 1;
(b) described solution is added in the alkaline solution, to form a sediment;
(c) the described sediment of heat treatment is to form a ferriferous oxide powder;
(d) add an adhesive and a solvent in described ferriferous oxide body, to form a mixed slurry; And
(e) described mixed slurry is coated on the sheet metal base material.
7. preparation method as claimed in claim 6 is characterized in that:
Also wrap a porousness conductive material in the described alkaline solution; And/or
Described porousness conductive material is to be selected from a carbon black, a metal oxide and to make up one of them.
8. preparation method as claimed in claim 6 is characterized in that, step (b) back is further comprising the steps of:
(b1) continue to stir described solution so that react completely;
(b2) with the described sediment of excessive washed with de-ionized water; And
(b3) dry described sediment.
9. preparation method as claimed in claim 6 is characterized in that, in the step (c):
It is the described sediment of heat treatment in an oxygen-free environment; And/or
It is the described sediment of temperature range heat treatment with 350 ℃ ~ 600 ℃.
10. preparation method as claimed in claim 6 is characterized in that:
Described adhesive agent be selected from a poly-difluoroethylene resin, one polystyrene-butadiene rubber and an acrylic resin one of them; And/or
Described solvent be a positive methyl pyrrolidone and water one of them.
CNA2005100990799A 2005-09-01 2005-09-01 High-power electrochemical electrode Pending CN1925076A (en)

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Publication number Priority date Publication date Assignee Title
CN101847522A (en) * 2009-03-23 2010-09-29 阿维科斯公司 Double layer capacitor
CN102208637A (en) * 2010-11-09 2011-10-05 广州市香港科大***研究院 ZnFe2O4/C composite cathode material with hollow sphere structure and one-step preparation method thereof
CN104134788A (en) * 2014-07-22 2014-11-05 南方科技大学 Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof
CN104332625A (en) * 2014-08-27 2015-02-04 山东大学 Cobalt ferrite-nitrogen doped carbon composite negative electrode material for dynamic lithium battery and preparation method thereof
CN105826550A (en) * 2016-05-26 2016-08-03 广西师范大学 Preparation method of lithium manganate cathode material with ferri-containing compound coating
CN105826550B (en) * 2016-05-26 2018-02-16 广西师范大学 A kind of preparation method of iron containing compoundses coating manganate cathode material for lithium
CN109243856A (en) * 2018-11-09 2019-01-18 天津工业大学 A kind of preparation method of iron-cobalt-nickel oxide/carbon cloth composite and flexible electrode
CN113511732A (en) * 2021-04-09 2021-10-19 安徽中科索纳新材料科技有限公司 Capacitive deionization selective adsorption electrode, capacitive deionization device and application

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