CN104134788A - Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof - Google Patents

Three dimensional gradient metal hydroxide/oxide electrode material and manufacture method and application thereof Download PDF

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CN104134788A
CN104134788A CN201410351118.9A CN201410351118A CN104134788A CN 104134788 A CN104134788 A CN 104134788A CN 201410351118 A CN201410351118 A CN 201410351118A CN 104134788 A CN104134788 A CN 104134788A
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metal
electrode material
dimensional gradient
oxide electrode
water
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CN104134788B (en
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卢周广
杨明阳
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Southwest University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Abstract

The invention provides a three dimensional gradient metal hydroxide/oxide electrode material and a manufacturing method and application thereof. The three dimensional gradient metal hydroxide/oxide electrode material consists of a conductive substrate and a metal compound layer, wherein the metal compound layer is arranged or formed on the surface of the conductive substrate, and the metal compound layer is made of metal hydroxide or oxide; the metal is transition metal, and the content of the metal ions in the metal compound layer decreases or increases in a gradient manner towards the conductive substrate. The three dimensional gradient metal hydroxide/oxide electrode material has the advantages of good cycling performance and good rate capability. The method for manufacturing the three-dimensional gradient metal hydroxide/oxide electrode material is easy and convenient, and the three dimensional gradient metal hydroxide/oxide electrode material can be used for manufacturing electrodes and batteries directly and shows good electrochemical activity.

Description

A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application
Technical field
The present invention relates to electrode material preparation field, be specifically related to a kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application.
Background technology
Along with the development of World Economics, green novel energy more and more comes into one's own, and Novel energy storage apparatus and energy conversion apparatus become the mankind and make full use of the key technology of new forms of energy.Wherein, electrochemical energy storage and conversion equipment, as ultracapacitor, lithium ion battery, lithium-oxygen battery and metal-air cell etc. by people's broad research.
Ultracapacitor has the advantages such as high-energy-density, fast charging and discharging and long circulation life due to it, receive more and more researchers' concern.But the energy density of ultracapacitor is still not high enough, it is applied in the key factor of power vehicle aspect to become restriction.In recent years, the fast development of Asymmetric Supercapacitor research, for the practical application of high-energy-density and high-capacity super capacitor provides possibility.Lithium ion battery, because it has the energy density higher than ultracapacitor, has been obtained immense success in commercialization, and is widely used in portable electric appts, cell phone, notebook computer etc.Lithium-oxygen battery and metal-air cell be because it has the theoretical energy density higher than lithium ion battery far away, and enjoy researcher's favor, but because key issue fails effectively to be solved, its actual energy density is well below its theoretical energy density at present.
Transition metal hydroxide and oxide, because it is rich in multiple valence state, and wide material sources, cheap, aspect energy storage, there is using value very widely.For example, transition metal hydroxide and oxide can be on oxide electrode surfaces and the Reversible redox reaction that occurs mutually of body and produce very high specific capacity, thereby in ultracapacitor and the lithium ion battery value that has a wide range of applications; In addition, transition metal hydroxide and oxide have high-specific surface area and oxygen room, and effectively the oxygen in catalytic air participates in the reaction of lithium-oxygen battery and metal-air cell and goes, and has improved greatly the energy density of battery.But transition metal hydroxide and oxide be due to its poor electric conductivity and ion dynamics, cause in charge and discharge process cycle performance and high rate performance not good, limit its practical application at energy source device.
Therefore, be necessary to provide a kind of cycle performance, the good three-dimensional gradient metal hydroxides/oxide electrode material of high rate performance and its preparation method and application.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application.Three-dimensional gradient metal hydroxides/oxide electrode material cycle performance provided by the invention, high rate performance are better.The preparation method of three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention is simple, convenient, three-dimensional gradient metal hydroxides/the oxide electrode material obtaining can be directly used in prepares electrode and battery, and demonstrates good electro-chemical activity.
First aspect present invention provides a kind of three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, and the surface of described conductive substrates is located at or is formed to described metal compound layer; The material that described metal compound layer adopts is hydroxide or the oxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
Preferably, described transition metal comprises at least one in Mn, Fe, Co, Ni, Cu and Zn.
The content of metal of the present invention calculates with molal quantity, every metal ion species concentration gradients to conductive substrates direction in metal compound layer changes, described graded shows as: the molal quantity gradient of the metal ion having raises, and the molal quantity gradient of some metal ions reduces.
Preferably, described metal compound layer to the each tenor of conductive substrates direction is: have at least the concentration gradients of a metal ion species to raise, have at least the concentration gradients of a metal ion species to reduce.
Preferably, described transition metal is Me and M, and wherein, described Me and M are all independently selected from the one in Mn, Fe, Co, Ni, Cu and Zn, and Me is different with M.
Further preferably, described transition metal is Me and M, and wherein, described Me is selected from the one in Mn, Fe, Ni, Co, Cu and Zn, and described M is selected from Co, Fe or Mn, and Me is different with M.
Further preferably, described metal compound layer to the each tenor of conductive substrates direction is: the concentration gradients of transition metal M e reduces, and the concentration gradients of M raises.
" independently " of the present invention refers to that Me and M are all selected from the one in Mn, Fe, Co, Ni, Cu and Zn, and do not interfere with each other, and when Me is specific certain metal, can't affect the kind of M, and vice versa.
Preferably, the molecular formula of the hydroxide of described metal is Me xm y(OH) 2, wherein, the span of x is 0<x<1, the span of y is 0<y<1, x+y=1; Me and M are all selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, Me and M are different metal ions.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Further preferably, described Me is selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one, described M is selected from Co 2+, Fe 2+or Mn 2+, and Me is different with M.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material makes by the mode of electro-deposition.
Further preferably, the mode of described electro-deposition adopts galvanostatic method or potentiostatic method, taking the solution of many parts of water-soluble metal salts that is concentration-graded as electrolyte, successively in conductive substrates electro-deposition a period of time, obtain three-dimensional gradient metal hydroxides/oxide electrode material.
Further preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is more than or equal to 2.
Still more preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 2～30.
Still more preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 4～10.
Further preferably, in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～5mol/L.
Further preferably, in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.5mol/L.
Still more preferably, in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.02mol/L.
Preferably, the molecular formula of the oxide of described metal is Me xm yo 4, wherein, M is doped metal ion, and the span of x is 0<x<4, and the span of y is 0<y<8/3,2x+3y=8; Me and M are all selected from Mn 2+, Fe 3+, Co 3+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Me is selected from Ni 2+, Cu 2+, Fe 2+, Co 2+and Zn 2+in one, M is selected from Mn 3+, Fe 3+and Co 3+in one.
Preferably, the molecular formula of the oxide of described metal is Me xm yo, wherein, M is doped metal ion, and the span of x is 0<x<1, and the span of y is 0<y<1, x+y=1; Me and M are all selected from Ni 2+, Fe 2+, Co 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Preferably, the molecular formula of the oxide of described metal is Me 2xm 2yo 3, wherein, M is doped metal ion, and the span of x is 0<x<1, and the span of y is 0<y<1, x+y=1, x+y=1; Me and M are all selected from Mn 3+, Fe 3+and Co 3+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material makes by the preparation method described in inventor's second aspect.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material makes by the preparation method described in inventor's third aspect.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material makes by the mode of electro-deposition and calcining.
The present invention first adopts the mode of electro-deposition first to prepare conductive substrates/transistion metal compound presoma, then conductive substrates/transistion metal compound presoma is calcined and prepared described three-dimensional gradient metal hydroxides/oxide electrode material.
Further preferably, the step that the mode of described employing electro-deposition and calcining is prepared three-dimensional gradient metal hydroxides/oxide electrode material comprises: first adopt galvanostatic method or potentiostatic method, taking the solution of many parts of water-soluble metal salts that is concentration-graded as electrolyte, in conductive substrates electro-deposition a period of time, obtain conductive substrates/transistion metal compound presoma successively; Then calcine conductive substrates/transistion metal compound forerunner of gained, obtain described three-dimensional gradient metal hydroxides/oxide electrode material.
Still more preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is more than or equal to 2.
Still more preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 2～30.
Still more preferably, described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 4～10.
Still more preferably, described in be in the solution of many parts of water-soluble metal salts of concentration-graded, the metal ion total concentration in the solution of every part of water-soluble metal salt is 0.01～5mol/L.
Still more preferably, described in be in the solution of many parts of water-soluble metal salts of concentration-graded, the metal ion total concentration in the solution of every part of water-soluble metal salt is 0.01～0.5mol/L.
Still more preferably, described in be in the solution of many parts of water-soluble metal salts of concentration-graded, the metal ion total concentration in the solution of every part of water-soluble metal salt is 0.01～0.02mol/L.
Still more preferably, in each part of described water-soluble metal salting liquid, the concentration gradients of metal ions M e reduces, and the concentration gradients of M raises.
Still more preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is k, and except only containing respectively two parts of solution of metal ions M e or M, the absolute value of the difference of the k value of other any adjacent two parts of solution is not more than 1.
Still more preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 1:0,2:1,1:1,1:2 and 0:1.
Still more preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 3:1,2:1,1:1,1:2 and 1:3.
Still more preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 4:1,3:1,2:1 and 1:2.
Preferably, described conductive substrates includes but not limited to three-dimensional conducting base, stainless steel substrates, titanium sheet, nickel sheet or the electro-conductive glass such as nickel foam, foam copper, carbon fiber paper, carbon cloth.
Preferably, the gross thickness of described metal compound layer is 0.5 μ m～50 μ m.
Three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention is three-dimensional, the network structure that the nanometer dendritic morphology frameworks such as nano wire, nano strip, nano-pillar, nanometer blocks, nanometer taper, hollow nanometer tubular or nanometer sheet form, three-dimensional, the network structure that are preferably that nanometer sheet forms; This three-dimensional, network structure has the netted pattern of spatial intersecting, between nano-micro structure, mutually intersects, thickness is homogeneous comparatively, has great surface area and higher porosity, therefore has good chemical property.
The not simple gradient layer forming of piling up layer by layer of the metal hydroxides of gained or metal oxide gradient on three-dimensional gradient metal hydroxides/oxide electrode material electrically-conductive backing plate provided by the invention, from microstructure, on electrically-conductive backing plate, the metal hydroxides of gained or metal oxide show as: the network structure that the nanometer dendritic morphology framework being interlocked by three dimensions forms, and described Nanostructure Network is polycrystalline sedimentary deposit; From metal ion content gradient, on electrically-conductive backing plate, the metal hydroxides of gained or metal oxide show as: described metal compound layer (being layers of metal hydroxides or metal oxide layer) reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction; In addition, between each metallic compound gradient layer of gained of the present invention, have between the transition region of mutually inlaying, between this transition region, be during due to electro-deposition, crystal growth gained, while adopting variable concentrations liquid deposition due to front and back, the new nanometer dendritic morphology forming is grown between the gap of original nanometer dendritic morphology, and has been staggered to form the transitional region layer of mesh nanometer pattern; This interval structure can well reduce the stress between each gradient layer, makes the structure of whole layers of metal hydroxides more excellent.
Second aspect present invention provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the following steps:
(1) the water-soluble metal salting liquid of configuration concentration-graded
The water-soluble metal salting liquid of at least 2 parts of variable concentrations of configuration, obtains at least 2 parts of water-soluble metal salting liquids that are concentration-graded; Wherein, described metal is transition metal, and in each part of described water-soluble metal salting liquid, the molar concentration of every metal ion species raises by part or reduces;
(2) get reference electrode and to electrode, assemble three-electrode system taking conductive substrates as work electrode;
(3) with galvanostatic method or potentiostatic method, get the water-soluble metal salting liquid of concentration-graded that step (1) makes, according to the molar concentration of a certain metal order from high to low or from low to high, the water-soluble metal salting liquid that described three-electrode system is placed in to concentration-graded that step (1) makes by part carries out electro-deposition, washing, after dry, obtain three-dimensional gradient metal hydroxides/oxide electrode material, wherein, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, the surface of described conductive substrates is located at or is formed to described metal compound layer, the material that described metal compound layer adopts is the hydroxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
Preferably, in described step (1), described water-soluble metal salt comprises at least one in the nitrate of metal, sulfate, acetate and chloride.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, described metal ion comprises Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, and Zn 2+in at least one.
In " the water-soluble metal salting liquid of variable concentrations " of the present invention, the molar concentration that " concentration " is metal ion, " concentration difference " refers to that the concentration of every kind of metal in each part of water-soluble metal salting liquid changes by part.
Preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～5mol/L.
Preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.5mol/L.
Further preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.02mol/L.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is more than or equal to 2.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 2～30.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 4～10.
" concentration-graded " of the present invention refers to that the molar concentration gradient of any metal ion in each part of water-soluble metal salting liquid raises or gradient reduces.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, have at least the molal quantity gradient of a metal ion species to raise, have at least the molal quantity gradient of a metal ion species to reduce.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, described metal ion is Me and M, and wherein, described Me and M are all selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, and Zn 2+in one, and Me is different with M.
Further preferably, described metal ion is Me and M, and wherein, described Me is selected from Mn 2+, Fe 2+, Ni 2+, Cu 2+, and Zn 2+in one, described M is selected from Co 2+, Fe 2+or Mn 2+, and Me is different with M.
Further preferably, in each part of water-soluble metal salting liquid, the concentration gradients of metal ions M e reduces, and the concentration gradients of M raises.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is k, and except only containing respectively two parts of solution of metal ions M e or M, the absolute value of the difference of the k value of other any adjacent two parts of solution is not more than 1.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 1:0,2:1,1:1,1:2 and 0:1.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 3:1,2:1,1:1,1:2 and 1:3.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 4:1,3:1,2:1 and 1:2.
Preferably, in described step (2), described reference electrode and electrode is all adopted to conventional electrodes while assembling three-electrode system in industry, such as adopting saturated calomel electrode as reference electrode, platinum plate electrode is as to electrode.
The inventor adopts three-electrode system plated metal compound layer in conductive substrates, the hydroxide that the material of described metal compound layer is metal in water-soluble metal salting liquid; Those skilled in the art according to specific needs, can adopt other electrode systems in conductive substrates, to deposit metal compound layer of the present invention.
Preferably, in described step (2), described conductive substrates includes but not limited to nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet or electro-conductive glass.
Preferably, in described step (2), described conductive substrates is the pretreated conductive substrates of hydrochloric acid.
Nickel foam, foam copper, carbon fiber paper, carbon cloth conductive substrates that the present invention adopts are three-dimensional conducting base, can make three-dimensional gradient metal hydroxides/oxide electrode material.
Preferably, in described step (3), the condition of described electro-deposition is: with the electric current of 0.5～100mA, deposit 60～600 seconds by part is each.
Further preferably, in described step (3), the condition of described electro-deposition is: with the electric current of 0.5～20mA, deposit 100～300 seconds by part is each.
Preferably, in described step (3), the condition of described electro-deposition is: to bear the electric current of 1.3～negative 0.5V, deposit 60～600 seconds by part is each.
Preferably, in described step (3), the condition of described electro-deposition is: to bear the electric current of 1.0～negative 0.8V, deposit 100～300 seconds by part is each.
Preferably, in described step (3), described electro-deposition is to carry out under the condition of 15～65 DEG C.
Preferably, in described step (3), the mode of described washing is the three-dimensional gradient metal hydroxides/oxide electrode material that adopts deionized water and absolute ethanol washing gained.
The mode of washing that the present invention adopts is the conventional washing methods of metal electrode material in industry, and the cleaning solvent of employing is preferably at least one in deionized water, methyl alcohol, ethanol, isopropyl alcohol.
Preferably, in described step (3), 60～120 DEG C of described dry conditions.
The drying mode that the present invention adopts is metal electrode material conventional drying method in industry, such as adopting drying baker to be dried or vacuumize.
Preferably, in described step (3), described transition metal comprises at least one in Mn, Fe, Co, Ni, Cu and Zn.
Preferably, in described step (3), described transition metal is Me and M, and wherein, described Me and M are all selected from the one in Mn, Fe, Co, Ni, Cu and Zn, and Me is different with M.
Further preferably, in described step (3), described transition metal is Me and M, and wherein, described Me is selected from the one in Mn, Fe, Ni, Co, Cu and Zn, and described M is selected from Co, Fe or Mn, and Me is different with M.
Preferably, in described step (3), described metal compound layer to the content of the each metal ion of conductive substrates direction is: have at least the molal quantity gradient of a metal ion species to raise, have at least the molal quantity gradient of a metal ion species to reduce.
Further preferably, in described step (3), described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of transition metal M e ion reduces, and the concentration gradients of M ion raises.
Preferably, in described step (3), the molecular formula of the hydroxide of described metal is Me xm y(OH) 2, wherein, the span of x is 0<x<1, the span of y is 0<y<1, x+y=1; Me and M are all selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, Me and M are different metal ions.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Further preferably, described Me is selected from Mn 2+, Fe 2+, Ni 2+, Cu 2+and Zn 2+in one, described M is selected from Co 2+, Fe 2+or Mn 2+, and Me is different with M.
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Preferably, in described step (3), the gross thickness of described metal compound layer is 0.5 μ m～50 μ m.
Third aspect present invention provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the following steps:
(1) the water-soluble metal salting liquid of configuration concentration-graded
The water-soluble metal salting liquid of at least 2 parts of variable concentrations of configuration, obtains at least 2 parts of water-soluble metal salting liquids that are concentration-graded; Wherein, described metal is transition metal, and in each part of described water-soluble metal salting liquid, the molar concentration of every metal ion species raises by part or reduces;
(2) get reference electrode and to electrode, assemble three-electrode system taking conductive substrates as work electrode;
(3) with galvanostatic method or potentiostatic method, get the water-soluble metal salting liquid of concentration-graded that step (1) makes, according to the molar concentration of a certain metal order from high to low or from low to high, the water-soluble metal salting liquid that described three-electrode system is placed in to concentration-graded that step (1) makes by part carries out electro-deposition, washing, after dry, obtain conductive substrates/transition metal hydroxide presoma, described conductive substrates/transition metal hydroxide presoma comprises conductive substrates and is deposited on the transition metal hydroxide presoma on conductive substrates surface,
(4), under inert gas shielding, conductive substrates/transition metal hydroxide presoma that step (3) is made is calcined 1～6 hour at 300～600 DEG C of temperature, obtains three-dimensional gradient metal hydroxides/oxide electrode material; Wherein, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, and the surface of described conductive substrates is located at or is formed to described metal compound layer; The material that described metal compound layer adopts is the oxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
Preferably, in described step (1), described water-soluble metal salt comprises at least one in the nitrate of metal, sulfate, acetate and chloride.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, described metal ion comprises Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in at least one.
In " the water-soluble metal salting liquid of variable concentrations " of the present invention, the molar concentration that " concentration " is metal ion, " concentration difference " refers to that the concentration of every kind of metal in each part of water-soluble metal salting liquid changes by part.
Preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～5mol/L.
Preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.5mol/L.
Further preferably, in described step (1), in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01～0.02mol/L.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is more than or equal to 2.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 2～30.
Preferably, in described step (1), described in be many parts of water-soluble metal salts of concentration-graded solution be the solution of n part water-soluble metal salt, wherein, n is 4～10.
" concentration-graded " of the present invention refers to that the molar concentration gradient of any metal ion in each part of water-soluble metal salting liquid raises or gradient reduces.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, have at least the molal quantity gradient of a metal ion species to raise, have at least the molal quantity gradient of a metal ion species to reduce.
Preferably, in described step (1), in each part of water-soluble metal salting liquid, described metal ion is Me and M, and wherein, described Me and M are all selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one, and Me is different with M.
Further preferably, described metal ion is Me and M, and wherein, described Me is selected from Mn 2+, Fe 2+, Ni 2+, Co 2+, Cu 2+and Zn 2+in one, described M is selected from Co 2+, Fe 2+or Mn 2+, and Me is different with M.
Further preferably, in each part of water-soluble metal salting liquid, the concentration gradients of metal ions M e reduces, and the concentration gradients of M raises.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is k, and except only containing two parts of solution of metal ions M e or M, the absolute value of the difference of the k value of other any adjacent two parts of solution is not more than 1.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 1:0,2:1,1:1,1:2 and 0:1.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 3:1,2:1,1:1,1:2 and 1:3.
Further preferably, in each part of described water-soluble metal salting liquid, the ratio of Me molar concentration and M molar concentration is respectively 4:1,3:1,2:1 and 1:2.
Preferably, in described step (2), described reference electrode and electrode is all adopted to conventional electrodes while assembling three-electrode system in industry, such as adopting saturated calomel electrode as reference electrode, platinum plate electrode is as to electrode.
The inventor adopts three-electrode system plated metal compound layer in conductive substrates, the hydroxide that the material of described metal compound layer is metal in water-soluble metal salting liquid; Those skilled in the art according to specific needs, can adopt other electrode systems in conductive substrates, to deposit metal compound layer of the present invention.
Preferably, in described step (2), described conductive substrates includes but not limited to nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet or electro-conductive glass.
Preferably, in described step (2), described conductive substrates is the pretreated conductive substrates of hydrochloric acid.
Nickel foam, foam copper, carbon fiber paper, carbon cloth conductive substrates that the present invention adopts are three-dimensional conducting base, can make three-dimensional three-dimensional gradient metal hydroxides/oxide electrode material.
Preferably, in described step (3), the condition of described electro-deposition is: with the electric current of 1～100mA, deposit 60～600 seconds by part is each.
Further preferably, in described step (3), the condition of described electro-deposition is: with the electric current of 0.5～20mA, deposit 100～300 seconds by part is each.
Preferably, in described step (3), the condition of described electro-deposition is: to bear the electric current of 1.3～negative 0.5V, deposit 60～600 seconds by part is each.
Preferably, in described step (3), the condition of described electro-deposition is: to bear the electric current of 1.0～negative 0.8V, deposit 100～300 seconds by part is each.
Preferably, in described step (3), described electro-deposition is to carry out under the condition of 15～65 DEG C.
Preferably, in described step (3), the mode of described washing is the three-dimensional gradient metal hydroxides/oxide electrode material that adopts deionized water and absolute ethanol washing gained.
The mode of washing that the present invention adopts is the conventional washing methods of metal electrode material in industry, and the cleaning solvent of employing is preferably at least one in deionized water, methyl alcohol, ethanol, isopropyl alcohol.
Preferably, in described step (3), 60～120 DEG C of described dry conditions.
The drying mode that the present invention adopts is metal electrode material conventional drying method in industry, such as adopting drying baker to be dried or vacuumize.
Preferably, in described step (4), conductive substrates/transition metal hydroxide presoma that step (3) is made is calcined 2～3 hours at 300～600 DEG C of temperature.
Preferably, in described step (4), described transition metal comprises at least one in Mn, Fe, Co, Ni, Cu and Zn.
Preferably, in described step (4), described transition metal is Me and M, and wherein, described Me and M are all selected from the one in Mn, Fe, Co, Ni, Cu and Zn, and Me is different with M.
Further preferably, in described step (4), described transition metal is Me and M, and wherein, described Me is selected from the one in Mn, Fe, Ni, Co, Cu and Zn, and described M is selected from Co, Fe or Mn, and Me is different with M.
Preferably, in described step (4), described metal compound layer to the content of the each metal ion of conductive substrates direction is: have at least the molal quantity gradient of a metal ion species to raise, have at least the molal quantity gradient of a metal ion species to reduce.
Further preferably, in described step (4), described metal compound layer to the each tenor of conductive substrates direction is: the concentration gradients of transition metal M e reduces, and the concentration gradients of M raises.
Preferably, in described step (4), the molecular formula of the oxide of described metal is Me xm yo 4, wherein, M is doped metal ion, and the span of x is 0<x<4, and the span of y is 0<y<8/3,2x+3y=8; Me and M are all selected from Mn 2+, Fe 3+, Co 3+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Further preferably, described Me is selected from Ni 2+, Fe 2+, Co 2+, Cu 2+and Zn 2+in one, M is selected from Mn 3+, Fe 3+and Co 3+in one.
Further preferably, the span of described x is 0.3≤x≤0.8.
Further preferably, the span of described y is 0.3≤y≤0.8.
Preferably, the molecular formula of the oxide of described metal is Me xm yo, wherein, M is doped metal ion, and the span of x is 0<x<1, and the span of y is 0<y<1, x+y=1; Me and M are all selected from Ni 2+, Fe 2+, Co 2+, Cu 2+and Zn 2+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.
Preferably, the molecular formula of the oxide of described metal is Me 2xm 2yo 3, wherein, M is doped metal ion, and the span of x is 0<x<1, and the span of y is 0<y<1, x+y=1, x+y=1; Me and M are all selected from Mn 3+, Fe 3+and Co 3+in one.
Under this optimum condition:
Further preferably, the span of described x is 0.1≤x≤0.9.
Further preferably, the span of described y is 0.1≤y≤0.9.
Further preferably, described metal compound layer to the content of the each metal ion of conductive substrates direction is: the concentration gradients of Me reduces, and the concentration gradients of M raises.Preferably, in described step (4), the gross thickness of described layers of metal hydroxides is 0.5 μ m～50 μ m.
Preparation method provided by the invention adopts concentration-gradient solution, and the order that reduces or raise by part according to certain metal concentration, deposits by part.At every turn in the time of rear deposition, the nanometer dendritic morphology of the nanometer dendritic morphologies such as new nano-tube/nano-wire, nano strip, nano-pillar, nanometer blocks, nanometer taper, hollow nanometer tubular or the nanometer sheet forming and front primary depositing gained is interlaced, forms Nanostructure Network new, that specific area is larger.The nanometer dendritic morphology of preparation method's electro-deposition gained of the present invention is preferably nanometer sheet.Three-dimensional gradient metal hydroxides/oxide electrode material prepared by the present invention is preferably interlaced three-dimensional, the network structure forming of nanometer sheet.
The present invention preferably adopts two kinds of different metal ion combinations, be conducive to posterior deposition and break the growth tendency that formerly deposits original nanometer dendritic morphology, form new nanowire growth point, and from forming new nanometer dendritic morphology between the gap of original nanometer dendritic morphology, thereby form three-dimensional, the gradient nano network structure of spatial intersecting, greatly provide specific area, for high specific capacitance provides important pattern basis.The electro-deposition method that the present invention adopts is simple, convenient, and can obtain nano material rule, spatial intersecting pattern by controlling the condition of electro-deposition; In addition, the present invention directly by transition metal ions Direct precipitation in three-dimensional conductive substrates, without adding binding agent and conductive agent, both eliminated the obstruction of binding agent to ion transfer, shorten the ion transfer distance of electrode in charge and discharge process, also greatly improved the energy density of its unit volume simultaneously.
Three-dimensional gradient metal hydroxides/oxide electrode material prepared by the present invention has special space three-dimensional structure, by the combination of different transition metal, prepare the nano-electrode material on macroscopical each concentration of metal ions graded, microcosmic with the staggered netted pattern of nano-micro structure, the inside of this nano-electrode material is mainly high Energy Density Materials, top layer is mainly the component of stability and high rate performance excellence, thereby makes on the whole whole electrode obtain high-energy-density, high stable performance and excellent high rate performance.
Fifth aspect present invention provide three-dimensional gradient metal hydroxides/oxide electrode material as described in first aspect in the application of preparing in electrode material and battery.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material as described in first aspect in the application of preparing in electrode of super capacitor, lithium ion battery negative, lithium-oxygen battery and metal-air cell catalyst.
Sixth aspect present invention provide three-dimensional gradient metal hydroxides/oxide electrode material as described in second aspect in the application of preparing in electrode material and battery.
Preferably, described three-dimensional gradient metal hydroxides/oxide electrode material as described in second aspect in the application of preparing in electrode of super capacitor, lithium ion battery negative, lithium-oxygen battery and metal-air cell catalyst.
The beneficial effect of three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention and its preparation method and application:
(1) electro-deposition method that the present invention adopts is simple, convenient, and can obtain nano material rule, spatial intersecting pattern by controlling the condition of electro-deposition;
(2) the present invention directly by transition metal hydroxide (oxide) three-dimensional gradient nano material Direct precipitation in three-dimensional conductive substrates, without adding binding agent and conductive agent, both eliminated the obstruction of binding agent to ion transfer, shorten the ion transfer distance of electrode in charge and discharge process, also greatly improved the energy density of its unit volume simultaneously;
(3) three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention combines along in substrate upward direction, the premium properties of various different components: inside is mainly high Energy Density Materials, top layer is mainly the component of stability and high rate performance excellence, thereby makes whole electrode obtain high-energy-density, high stable performance and excellent high rate performance.
Brief description of the drawings
Fig. 1 is the SEM figure of the three-dimensional gradient metal hydroxides/oxide electrode material of preparation in example 1;
Fig. 2 is the XRD figure of the three-dimensional gradient metal hydroxides/oxide electrode material of preparation in example 1;
Fig. 3 is the XPS depth analysis figure of the three-dimensional gradient metal hydroxides/oxide electrode material of preparation in example 1;
Fig. 4 is the cyclic voltammetry curve figure under electrode material for super capacitor different scanning speed in effect example 1;
Fig. 5 is the constant current charge-discharge curve chart under the different current densities of electrode material for super capacitor in effect example 1;
Fig. 6 is the cyclic voltammetry curve figure under Asymmetric Supercapacitor different scanning speed in effect example 2;
Fig. 7 is the energy density-power density diagram of Asymmetric Supercapacitor in effect example 2;
Fig. 8 is the cycle life figure of Asymmetric Supercapacitor in effect example 2.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Ni 2+: Co 2+molar concentration rate is respectively 1:0,2:1, and 1:1,1:2, the ratio of 0:1, configures 5 parts of metal ion total concentrations and is the nitrate solution of 0.01mol/L; Nickel foam is cut into 1 × 1cm 2size, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, remove its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the nickel foam processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.0005A on CHI660E electrochemical workstation, successively at Ni 2+: Co 2+mol ratio is 1:0,2:1, and 1:1,1:2, in the nitrate solution of 0:1, electro-deposition 2 minutes respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (nickel foam) and is deposited on the nickel cobalt hydroxide layer on nickel foam surface, the material of described nickel cobalt hydroxide layer is nickel cobalt hydroxide, thickness is 900nm, and the molecular formula of described nickel cobalt hydroxide is Ni xco y(OH) 2, wherein, the span of x is 0<x<1, the span of y is 0<y<1, x+y=1; Wherein, described x is about 0.35, and described y is about 0.65; In described nickel cobalt hydroxide layer, the content of cobalt element upwards constantly increases along base, and the content of nickel element constantly reduces.
In order to absolutely prove beneficial effect of the present invention, the invention provides SEM figure, XRD figure and the XPS depth analysis figure of three-dimensional gradient metal hydroxides/oxide electrode material prepared by embodiment 1, respectively as shown in Figure 1, Figure 2 and Figure 3, the each down scale in Fig. 1 is 50nm.
As shown in Figure 1, the nickel cobalt hydroxide layer of three-dimensional gradient metal hydroxides/oxide electrode material that the embodiment of the present invention 1 provides is nanofiber web structure, this special construction has the netted pattern of spatial intersecting, between nanometer sheet, mutually intersect, thickness is homogeneous comparatively, there is great surface area, therefore there is good chemical property.Each dendritic morphology of nanometer web frame of three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention represents a crystal grain, is polycrystalline sedimentary deposit.
Preparation method provided by the invention adopts concentration-gradient solution, taking described in the present embodiment as example, according to Ni 2+concentration is by part reduction, Co 2+the order that concentration raises by part, deposits by part.After adopting first part of solution to deposit for the first time, Nanostructure Network is in nickel foam superficial growth, and nickel foam surface microstructure becomes Nanostructure Network from the nickel dam of opposed flattened; When the solution of second part of variable concentrations of employing carries out the second deposition, on the one hand, new nanometer sheet continues or regrows based on original nanostructure, on the other hand, nanometer sheet is more prone to grow from the gap of Nanostructure Network, this is due to the Nanostructure Network with respect to formed, the resistance of the nickel foam at gap place is less, be conducive to the deposition growing of new nanometer sheet, the nanometer sheet of this stylish formation is interlaced with the nanometer sheet that deposits for the first time gained, forms Nanostructure Network new, that specific area is larger; In addition, because the embodiment of the present invention adopts two kinds of different metal ion combinations, be conducive to posterior deposition and break the growth tendency that formerly deposits original nanometer sheet, form new nanowire growth point, and form new nanometer sheet between the gap of original nanometer sheet, thereby the nanofiber web structure that forms spatial intersecting, provides specific area, greatly for high specific capacitance provides important pattern basis.
By comparison standard card, as shown in Figure 2, the main active substances of three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention is α-Ni (OH) 2and α-Co (OH) 2.
From the XPS depth analysis figure of Fig. 3, from the top layer of three-dimensional gradient metal hydroxides/oxide electrode material to nickel foam substrate direction (corresponding diagram 3 curve) from down to up, different depth Ni2p 3/2peak intensity obviously raise gradually, and Co2p 3/2peak intensity obviously gradually reduce.This explanation Ni (OH) 2content constantly increased to nickel foam conductive substrates by electrode surface, Co (OH) 2content constantly reduce.
From layer structure, although the present invention adopts the solution of 5 parts of concentration-gradients to carry out deposition 5 times, but Fig. 3 show result be, in the time that different depth between 60nm～480nm carries out XPS analysis, Ni2p in three-dimensional gradient metal hydroxides/oxide electrode material 3/2and Co2p 3/2more than 5 layers of the variable gradients of peak intensity, this has also verified the spatial intersecting pattern of Fig. 1, illustrate between the different sedimentary deposits of three-dimensional gradient metal hydroxides provided by the invention/oxide electrode material and have transition zone, when this transition zone adopts variable concentrations liquid deposition before and after being, the new nanometer sheet forming is by original nanometer sheet interstital growth, and is staggered to form the transitional region layer of mesh nanometer pattern.
In order to further illustrate beneficial effect of the present invention, the invention provides the effect embodiment of three-dimensional gradient metal hydroxides/oxide electrode material prepared by embodiment 1:
Effect embodiment 1
Three-dimensional gradient metal hydroxides/oxide electrode material prepared by embodiment 1 is directly as work electrode, taking mercury oxidation mercury and platinum plate electrode as reference electrode with to electrode, be assembled into the electrochemical property test that three-electrode system carries out ultracapacitor, wherein electrolyte is 6M KOH solution.
Adopt electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) cyclic voltammetry curve of the ultracapacitor assembled of test effect embodiment 1, test is under different scanning rates, electric current is with the Changing Pattern of current potential, and Fig. 4 is the cyclic voltammetry curve figure under electrode material for super capacitor different scanning speed; Abscissa is current density (current density, A/g), and ordinate is current potential (potential, V).
In Fig. 4, arrow across 5 curve correspondences go back virgin curve, the corresponding oxidation of 5 curves curve that arrow does not stride across, wherein, arrow across the from top to bottom sweep speed of corresponding 2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s successively of 5 curves, from bottom to top corresponding sweep speed of answering 2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s successively of 5 curves that arrow does not stride across.
As can be seen from Figure 4, every CV curve all has a pair of redox peak, and this is due to Co (OH) 2and Ni (OH) 2redox reaction occurs and cause, faraday's reaction that its electrode surface occurs is shown below:
The electric capacity of tested electrode material for super capacitor mainly comes from the fake capacitance that above-mentioned redox reaction produces.Anode peak is owing to Co (OH) 2and Ni (OH) 2be oxidized to the process of CoOOH and NiOOH, negative electrode peak is corresponding its inverse process.The shape of CV curve shows, tested electrode material for super capacitor to discharge and recharge invertibity better.The shape of the cyclic voltammetry curve of electrode material for super capacitor under different scanning rates there is no marked change with the variation of sweep speed, this mass transfer and electric charge that illustrates that the structure of this electrode material is conducive in electrochemical reaction faster shifts, and has reduced polarization phenomena.
Adopt electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) the constant current charge-discharge curve of the ultracapacitor assembled of test effect embodiment 1, the specific capacity of test electrode material under different current densities, Fig. 5 is the constant current charge-discharge curve chart under the different current densities of electrode material for super capacitor, abscissa is specific capacity (specific capacitance, F/g), ordinate is current potential (V).
In Fig. 5, by arrow direction, the curve successively current density of correspondence is 100A/g, 50A/g, 20A/g, 10A/g, 5A/g, 2A/g, 1A/g.
As shown in Figure 5, when putting, a current density is respectively 1,2,5,10,20,50, when 100A/g, corresponding single electrode than capacitance be respectively 1759,1712,1646,1619,1480,1260,1100F/g.The ultracapacitor of three-dimensional gradient metal hydroxides provided by the invention as can be seen here ,/oxide electrode material assembling still has very high specific capacitance on larger discharge current density.Illustrate that three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention has higher large current ratio volumetric properties.Fig. 4 and Fig. 5 illustrate that the prepared three-dimensional gradient metal hydroxides/oxide electrode material of the present invention has good invertibity and high specific capacity and the good high rate performance of discharging and recharging.
Effect embodiment 2
1) by even to 0.04g Ketjen black and 2mL absolute ethyl alcohol mechanical mixture in mortar, in the process of constantly grinding, be slowly added in that under continuous grinding, to add 0.2g mass fraction be 5% polytetrafluoroethylsolution solution, continuing to be ground to ethanol volatilizees completely, obtain the composite material of plasticine shape, evenly roll and be pressed into thickness and be about after 0.5mm, be cut into the pole piece of 10mm × 10mm, roll extrusion on roll squeezer together with the nickel foam of handling well in advance, 80 DEG C of vacuumize 12h.
2) pole piece of being prepared by step (1) is as negative pole, three-dimensional gradient metal hydroxides/oxide electrode material prepared by embodiment 1 is as positive pole, be assembled into the electrochemical property test that two electrode systems carry out Asymmetric Supercapacitor, wherein electrolyte is 6M KOH solution.
Adopt electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) cyclic voltammetry curve of the ultracapacitor assembled of test effect embodiment 1, test is under different scanning rates, electric current is with the Changing Pattern of current potential, the cyclic voltammetry curve figure under the different scanning speed that Fig. 6 is Asymmetric Supercapacitor; Abscissa is current density (current density, A/g), and ordinate is current potential (potential, V).
In Fig. 6, arrow across the corresponding oxidation of 5 curves curves, 5 curve correspondences that arrow does not stride across are gone back virgin curve, wherein, arrow across the from bottom to top sweep speed of corresponding 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s successively of 5 curves, the from top to bottom sweep speed of corresponding 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s successively of 5 curves that arrow does not stride across.
Adopt electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) the constant current charge-discharge curve of the ultracapacitor assembled of test effect embodiment 1, the specific capacity of test electrode material under different current densities, Fig. 7 be Asymmetric Supercapacitor different current densities under constant current charge-discharge curve chart, abscissa is energy density (energy density, Wh/kg), ordinate is power density (power density, W/kg).
Adopt electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) cycle life of the ultracapacitor assembled of test effect embodiment 1, the specific capacity of test electrode material after charge and discharge cycles test changes, test condition: current density is 5A/g, potential window is 0～1.5V; Fig. 8 be Asymmetric Supercapacitor cycle life figure, abscissa is specific capacity (specific capacitance, F/g), ordinate is period; The abscissa of the medium and small figure of Fig. 8 is current potential (V), and ordinate is time (s).
Fig. 6～Fig. 8 illustrates and adopts the prepared Asymmetric Supercapacitor of three-dimensional gradient metal hydroxides/oxide electrode material provided by the invention to have high-energy-density, the high rate performance of excellence and stable cycle life.
Embodiment 2
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Ni 2+: Co 2+molar concentration rate be respectively 4:1,3:1,2:1, the ratio of 1:1, configures 4 parts of metal ion total concentrations and is the sulfate liquor of 0.02mol/L; Foam copper is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the foam copper processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Ni 2+: Co 2+mol ratio is 4:1,3:1, and 2:1, in the nitrate solution of 1:1, electro-deposition 2 minutes respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 300 DEG C of nitrogen atmospheres, calcine 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the nickel cobalt oxide layer on foam copper surface, the material of described nickel cobalt oxide layer is nickel cobalt oxide, and the molecular formula of described nickel cobalt oxide is Ni xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described nickel cobalt oxide layer, the content of cobalt element upwards constantly increases along substrate, and the content of nickel element constantly reduces.
In order to absolutely prove beneficial effect of the present invention, the present embodiment also provides gained three-dimensional gradient metal hydroxides/oxide electrode material in the application of preparing in battery: will prepare three-dimensional gradient metal hydroxides/oxide electrode material directly as work electrode, adopt metal lithium sheet to do electrode, polypropylene porous film makees barrier film, 1.0mol/L LiPF 6the mixed solution of EC:DMC=1:1 (volume ratio) do electrolyte, in anhydrous and oxygen-free control box, be assembled into 2016 type button cells.
Embodiment 3
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Ni 2+: Co 2+mol ratio be respectively 4:1,3:1,2:1, the ratio of 1:1, configures 4 parts of metal ion total concentrations and is the chloride salt solution of 0.02mol/L; Foam copper is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the foam copper processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Ni 2+: Co 2+mol ratio is 4:1,3:1, and 2:1, in the nitrate solution of 1:1, electro-deposition 2 minutes respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 300 DEG C of nitrogen atmospheres, calcine 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the nickel cobalt hydroxide layer on foam copper surface, the material of described nickel cobalt hydroxide layer is nickel cobalt hydroxide, and the molecular formula of described nickel cobalt hydroxide is Ni xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described nickel cobalt oxide layer, the content of cobalt element upwards constantly increases along foam copper substrate, and the content of nickel element constantly reduces.
In order to absolutely prove beneficial effect of the present invention, the present embodiment also provides gained three-dimensional gradient metal hydroxides/oxide electrode material in the application of preparing in battery: will prepare three-dimensional gradient metal hydroxides/oxide electrode material directly as work electrode, adopt metal lithium sheet to do electrode, glass fibre membrane makees barrier film, two (fluoroform sulfimide) lithium/tetraethyleneglycol dimethyl ether mixed solutions of 1.0mol/L do electrolyte, are assembled into 2032 type porous button cells in anhydrous and oxygen-free control box.
Embodiment 4
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Mn 2+: Co 2+molar concentration rate be respectively the ratio of 3:1,2:1,1:1,1:2,1:3, configure respectively metal ion total concentration and be the nitrate solution of 0.02mol/L; Foam copper is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the foam copper processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Mn 2+: Co 2+mol ratio is in the nitrate solution of 3:1,2:1,1:1,1:2,1:3, respectively electro-deposition 2 minutes; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 400-600 DEG C of air atmosphere, calcine 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the nickel cobalt hydroxide layer on foam copper surface, the material of described nickel cobalt hydroxide layer is nickel cobalt hydroxide, and the molecular formula of described nickel cobalt hydroxide is Mn xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described manganese cobalt/cobalt oxide layer, the content of cobalt element upwards constantly increases along foam copper substrate, and the content of manganese element constantly reduces.
In order to absolutely prove beneficial effect of the present invention, the present embodiment also provides gained three-dimensional gradient metal hydroxides/oxide electrode material in the application of preparing in battery: will prepare three-dimensional gradient metal hydroxides/oxide electrode material directly as work electrode, adopt metal lithium sheet to do electrode, polypropylene porous film makees barrier film, 1.0mol/L LiPF 6the mixed solution of EC:DMC=1:1 (volume ratio) do electrolyte, in anhydrous and oxygen-free control box, be assembled into 2016 type button cells.
Embodiment 5
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Mn 2+: Co 2+molar concentration rate be respectively the ratio of 3:1,2:1,1:1,1:2,1:3, configure respectively 5 parts of metal ion total concentrations and be the nitrate solution of 0.02mol/L; Nickel foam is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the nickel foam processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Mn 2+: Co 2+mol ratio is in the nitrate solution of 3:1,2:1,1:1,1:2,1:3, respectively electro-deposition 2 minutes; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 400-600 DEG C of air atmosphere, calcine 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the nickel cobalt hydroxide layer on foam copper surface, the material of described magnesium cobalt hydroxide layer is magnesium cobalt hydroxide, and the molecular formula of described magnesium cobalt hydroxide is Mn xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described manganese cobalt/cobalt oxide layer, the content of cobalt element upwards constantly increases along foam copper substrate, and the content of manganese element constantly reduces.
In order to absolutely prove beneficial effect of the present invention, the present embodiment also provides gained three-dimensional gradient metal hydroxides/oxide electrode material in the application of preparing in battery: will prepare three-dimensional gradient metal hydroxides/oxide electrode material directly as work electrode, adopt metal lithium sheet to do electrode, glass fibre membrane makees barrier film, two (fluoroform sulfimide) lithium/tetraethyleneglycol dimethyl ether mixed solutions of 1.0mol/L do electrolyte, are assembled into 2032 type porous button cells in anhydrous and oxygen-free control box.
Embodiment 6
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
1) according to Fe 2+: Co 2+molar concentration rate is respectively 1:0,2:1, and 1:1,1:2, the ratio of 0:1,5 parts of configuration metal ion total concentrations are the nitrate solution of 5mol/L respectively; Nickel foam is cut into 1 × 1cm 2size, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, remove its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the nickel foam processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.1A on CHI660E electrochemical workstation, successively at Fe 2+: Co 2+mol ratio is 1:0,2:1, and 1:1,1:2, in the nitrate solution of 0:1, electro-deposition 60 seconds respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (nickel foam) and is deposited on the iron cobalt hydroxide layer on nickel foam surface, the material of described iron cobalt hydroxide layer is iron cobalt hydroxide, and the molecular formula of described iron cobalt hydroxide is Fe xco y(OH) 2, the span of x is 0<x<1, the span of y is 0<y<1, x+y=1; In described iron cobalt hydroxide layer, the content of cobalt element upwards constantly increases along base, and the content of ferro element constantly reduces.
2) further the three-dimensional gradient metal hydroxides/oxide electrode material of step (1) gained is calcined 3 hours under 600 DEG C of nitrogen atmospheres, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the iron cobalt/cobalt oxide layer on foam copper surface, the material of described iron cobalt/cobalt oxide layer is iron cobalt/cobalt oxide, and the molecular formula of described iron cobalt/cobalt oxide is Fe xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described iron cobalt/cobalt oxide, the content of cobalt element upwards constantly increases along substrate, and the content of ferro element constantly reduces.
Embodiment 7
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Cu 2+: Co 2+molar concentration rate is respectively 4:1,3:1, and 2:1, the ratio of 1:1, configures respectively 4 parts of metal ion total concentrations and is the nitrate solution of 0.5mol/L; Foam copper is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the foam copper processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Cu 2+: Co 2+mol ratio is 4:1,3:1, and 2:1, in the nitrate solution of 1:1, electro-deposition 300 seconds respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 300 DEG C of nitrogen atmospheres, calcine 1 hour, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the copper cobalt/cobalt oxide layer on foam copper surface, the material of described copper cobalt/cobalt oxide layer is copper cobalt/cobalt oxide, and the molecular formula of described copper cobalt/cobalt oxide is Cu xco yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described copper cobalt/cobalt oxide layer, the content of cobalt element upwards constantly increases along substrate, and the content of copper constantly reduces.
Embodiment 8
The present embodiment provides a kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material, comprises the steps:
According to Ni 2+: Fe 2+molar concentration rate is respectively 4:1,3:1, and 2:1, the ratio of 1:1, configures respectively 4 parts of metal ion total concentrations and is the nitrate solution of 0.02mol/L; Foam copper is cut into the circular pole piece that diameter is 1.8cm, and through ultrasonic 10 minutes of 3mol/L hydrochloric acid solution, removes its surperficial oxidation film, then wash successively 3 times with deionized water and absolute ethyl alcohol; Using the foam copper processed as work electrode, saturated calomel and platinized platinum respectively as reference electrode with to electrode, assembling three-electrode system, constant current 0.001A on CHI660E electrochemical workstation, successively at Ni 2+: Fe 2+mol ratio is 4:1,3:1, and 2:1, in the nitrate solution of 1:1, electro-deposition 600 seconds respectively; The foam nickel electrode obtaining after deposition is washed three times successively with deionized water and absolute ethyl alcohol respectively, and in the baking oven of 110 DEG C, dry 12 hours; Under 300 DEG C of nitrogen atmospheres, calcine 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises three-dimensional conductive substrates (foam copper) and is deposited on the ferronickel hydroxide layer on foam copper surface, the material of described ferronickel hydroxide layer is ferronickel hydroxide, and the molecular formula of described ferronickel hydroxide is Ni xfe yo 4, the span of x is 0<x<4, the span of y is 0<y<8/3,2x+3y=8; In described iron-doped nickel oxide layer, the content of ferro element upwards constantly increases along foam copper substrate, and the content of nickel element constantly reduces.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (15)

1. three-dimensional gradient metal hydroxides/oxide electrode material, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, the surface of described conductive substrates is located at or is formed to described metal compound layer; The material that described metal compound layer adopts is hydroxide or the oxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
2. three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 1, is characterized in that, described transition metal comprises at least one in Mn, Fe, Co, Ni, Cu and Zn.
3. three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 1, is characterized in that, the molecular formula of the hydroxide of described metal is Me xm y(OH) 2, wherein, the span of x is 0<x<1, the span of y is 0<y<1, x+y=1; Me and M are all selected from Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
4. three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 3, the molecular formula that it is characterized in that the oxide of described metal is Me xm yo 4, wherein, M is doped metal ion, and the span of x is 0<x<4, and the span of y is 0<y<8/3,2x+3y=8; Me and M are all selected from Mn 2+, Fe 3+, Co 3+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in one.
5. a preparation method for three-dimensional gradient metal hydroxides/oxide electrode material, comprises the following steps:
(1) the water-soluble metal salting liquid of configuration concentration-graded
The water-soluble metal salting liquid of at least 2 parts of variable concentrations of configuration, obtains at least 2 parts of water-soluble metal salting liquids that are concentration-graded; Wherein, described metal is transition metal, and in each part of described water-soluble metal salting liquid, the molar concentration of every metal ion species raises by part or reduces;
(2) get reference electrode and to electrode, assemble three-electrode system taking conductive substrates as work electrode;
(3) with galvanostatic method or potentiostatic method, get the water-soluble metal salting liquid of concentration-graded that step (1) makes, according to the molar concentration of a certain metal order from high to low or from low to high, the water-soluble metal salting liquid that described three-electrode system is placed in to concentration-graded that step (1) makes by part carries out electro-deposition, washing, after dry, obtain three-dimensional gradient metal hydroxides/oxide electrode material, wherein, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, the surface of described conductive substrates is located at or is formed to described metal compound layer, the material that described metal compound layer adopts is the hydroxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
6. the preparation method of three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 5, is characterized in that, in described step (1), in each part of water-soluble metal salting liquid, described metal ion comprises Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in at least one.
7. the preparation method of three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 5, is characterized in that, in described step (1), the metal ion total concentration in every part of water-soluble metal salting liquid is 0.01～5mol/L.
8. the preparation method of three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 5, it is characterized in that, in described step (2), described conductive substrates be selected from nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet and electro-conductive glass one.
9. the preparation method of three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 5, is characterized in that, in described step (3), the condition of described electro-deposition is: with the electric current of 0.5～100mA, deposit 60～600 seconds by part is each.
10. a preparation method for three-dimensional gradient metal hydroxides/oxide electrode material, comprises the following steps:
(1) the water-soluble metal salting liquid of configuration concentration-graded
The water-soluble metal salting liquid of at least 2 parts of variable concentrations of configuration, obtains at least 2 parts of water-soluble metal salting liquids that are concentration-graded; Wherein, described metal is transition metal, and in each part of described water-soluble metal salting liquid, the molar concentration of every metal ion species raises by part or reduces;
(2) get reference electrode and to electrode, assemble three-electrode system taking conductive substrates as work electrode;
(3) with galvanostatic method or potentiostatic method, get the water-soluble metal salting liquid of concentration-graded that step (1) makes, according to the molar concentration of a certain metal order from high to low or from low to high, the water-soluble metal salting liquid that described three-electrode system is placed in to concentration-graded that step (1) makes by part carries out electro-deposition, washing, after dry, obtain conductive substrates/transition metal hydroxide presoma, described conductive substrates/transition metal hydroxide presoma comprises conductive substrates and is deposited on the transition metal hydroxide on conductive substrates surface,
(4), under inert gas shielding, conductive substrates/transition metal hydroxide presoma that step (3) is made is calcined 1～6 hour at 300～600 DEG C of temperature, obtains three-dimensional gradient metal hydroxides/oxide electrode material; Wherein, described three-dimensional gradient metal hydroxides/oxide electrode material comprises conductive substrates and metal compound layer, and the surface of described conductive substrates is located at or is formed to described metal compound layer; The material that described metal compound layer adopts is the oxide of metal, and described metal is transition metal, and described metal compound layer reduces or raises to the concentration gradients of the each metal ion of conductive substrates direction.
The preparation method of 11. three-dimensional gradient metal hydroxides/oxide electrode materials as claimed in claim 10, is characterized in that, in described step (1), in each part of water-soluble metal salting liquid, described metal ion comprises Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+and Zn 2+in at least one.
The preparation method of 12. three-dimensional gradient metal hydroxides/oxide electrode materials as claimed in claim 10, is characterized in that, in described step (1), the metal ion total concentration in every part of water-soluble metal salting liquid is 0.01～5mol/L.
The preparation method of 13. three-dimensional gradient metal hydroxides/oxide electrode materials as claimed in claim 10, it is characterized in that, in described step (2), described conductive substrates be selected from nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet and electro-conductive glass one.
The preparation method of 14. three-dimensional gradient metal hydroxides/oxide electrode materials as claimed in claim 10, it is characterized in that, in described step (3), the condition of described electro-deposition is: with the electric current of 0.5～100mA, deposit 60～600 seconds by part is each.
15. 1 kinds of three-dimensional gradient metal hydroxides/oxide electrode materials as claimed in claim 1 are in the application of preparing in electrode material and battery.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104787809A (en) * 2015-04-16 2015-07-22 电子科技大学 Preparation method for nickel cobaltite material adopting rattan-shaped three-dimensional nano-structure
CN105513831A (en) * 2015-11-23 2016-04-20 北京化工大学 Electrode material in hollow tubular structure, and preparation method for electrode material
CN105575671A (en) * 2016-03-03 2016-05-11 哈尔滨工程大学 Preparation method of supercapacitor electrode material comprising porous nickel hydroxide
CN106011926A (en) * 2016-07-07 2016-10-12 江苏大学 Electrocatalyst with cobalt-based multi-stage nano-composite structure for oxygen production by electrolysis of water and preparation method of electrocatalyst
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US20200273631A1 (en) * 2017-09-25 2020-08-27 National University Corporation Chiba University Porous conductor having conductive nanostructure and electricity storage device using same
CN112467069A (en) * 2020-12-11 2021-03-09 燕山大学 Battery negative electrode material and preparation method and application thereof
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CN114582636A (en) * 2022-04-12 2022-06-03 桂林电子科技大学 Sea urchin-shaped microsphere cobalt-nickel-based electrode material and preparation method and application thereof
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CN115159590A (en) * 2022-07-21 2022-10-11 江苏电子信息职业学院 High-entropy transition metal oxyhydroxide and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1734689A (en) * 2004-08-13 2006-02-15 中国人民解放军63971部队 Electrochemical capacitor with composite oxide electrode and preparation method thereof
CN1925076A (en) * 2005-09-01 2007-03-07 吴乃立 High-power electrochemical electrode
CN101503805A (en) * 2009-01-24 2009-08-12 燕山大学 Super capacitor and preparation of composite anode material of battery
CN101752554A (en) * 2010-01-04 2010-06-23 北京航空航天大学 Method for preparing Sn-Zn alloy cathode material of lithium ion battery
CN101937989A (en) * 2010-08-13 2011-01-05 上海中科深江电动车辆有限公司 Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1734689A (en) * 2004-08-13 2006-02-15 中国人民解放军63971部队 Electrochemical capacitor with composite oxide electrode and preparation method thereof
CN1925076A (en) * 2005-09-01 2007-03-07 吴乃立 High-power electrochemical electrode
CN101503805A (en) * 2009-01-24 2009-08-12 燕山大学 Super capacitor and preparation of composite anode material of battery
CN101752554A (en) * 2010-01-04 2010-06-23 北京航空航天大学 Method for preparing Sn-Zn alloy cathode material of lithium ion battery
CN101937989A (en) * 2010-08-13 2011-01-05 上海中科深江电动车辆有限公司 Three-dimensional nanoporous metal-oxide electrode material of lithium ion battery and preparation method thereof

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CN106011926A (en) * 2016-07-07 2016-10-12 江苏大学 Electrocatalyst with cobalt-based multi-stage nano-composite structure for oxygen production by electrolysis of water and preparation method of electrocatalyst
CN106011926B (en) * 2016-07-07 2019-04-02 江苏大学 A kind of cobalt-based multi-stage nano composite construction electrolysis water oxygen elctro-catalyst and preparation method thereof
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US20200273631A1 (en) * 2017-09-25 2020-08-27 National University Corporation Chiba University Porous conductor having conductive nanostructure and electricity storage device using same
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