CN104134788B - A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application - Google Patents

A kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application Download PDF

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CN104134788B
CN104134788B CN201410351118.9A CN201410351118A CN104134788B CN 104134788 B CN104134788 B CN 104134788B CN 201410351118 A CN201410351118 A CN 201410351118A CN 104134788 B CN104134788 B CN 104134788B
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metal
electrode material
dimensional gradient
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conductive substrates
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CN104134788A (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 kind of three-dimensional gradient metal hydroxides/oxide electrode material and its preparation method and application, three-dimensional gradient metal hydroxides/the oxide electrode material includes conductive substrates and metal compound layer, and the metal compound layer is located at or be formed at the surface of the conductive substrates；The material that the metal compound layer is used is the hydroxide or oxide of metal, and the metal is transition metal, and the metal compound layer is reduced or raised to the concentration gradients of each metal ion in conductive substrates direction.Three-dimensional gradient metal hydroxides/oxide electrode material cycle performance that the present invention is provided, high rate performance are preferable.The preparation method for three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided is simple, convenient, obtained three-dimensional gradient metal hydroxides/oxide electrode material can be directly used for preparing electrode and battery, and show good electro-chemical activity.

Description

A kind of three-dimensional gradient metal hydroxides/oxide electrode material and preparation method thereof And application
Technical field
The present invention relates to electrode material preparation field, and in particular to a kind of three-dimensional gradient metal hydroxides/oxide electricity Pole material and its preparation method and application.
Background technology
With continuing to develop for World Economics, green novel energy is increasingly taken seriously, novel energy storage apparatus and the energy Conversion equipment then turns into the key technology that the mankind make full use of new energy.Wherein, electrochemical energy storage and conversion equipment, as super Level capacitor, lithium ion battery, lithium-oxygen battery and metal-air battery etc. are widely studied by people.
Ultracapacitor has the advantages that high-energy-density, fast charging and discharging and long circulation life due to it, by more next The concern of more researchers.But the energy density of ultracapacitor is still not high enough, applied as it is restricted in power vehicle The key factor of aspect.In recent years, the fast development of Asymmetric Supercapacitor research, is high-energy-density and high-capacity super The practical application of capacitor is provided may.Lithium ion battery has the energy density higher than ultracapacitor due to it, Commercialization has been achieved for immense success, and is widely used in portable electric appts, cell phone, notebook computer etc.. Lithium-oxygen battery and metal-air battery enjoy researcher due to its theoretical energy density with significantly larger than lithium ion battery Favor, but be due to that key issue fails effectively to be solved, its current actual energy density is well below its theoretical energy Density.
Transition metal hydroxide and oxide, because it is rich in a variety of valence states, and it is wide material sources, cheap, in storage Energy aspect has extremely wide application value.For example, transition metal hydroxide and oxide can be in oxide electrode tables Reversible redox reaction that face and body phase occur and produce very high specific capacity so that in ultracapacitor and lithium-ion electric Pond has a wide range of applications value；In addition, transition metal hydroxide and oxide have high-specific surface area and Lacking oxygen, can Oxygen in effective catalytic air is participated in the reaction of lithium-oxygen battery and metal-air battery, greatly improves battery Energy density.But, transition metal hydroxide and oxide are caused due to its poor electric conductivity and ion dynamics Cycle performance and high rate performance be not good in charge and discharge process, limits its practical application in energy source device.
Therefore, it is necessary to provide a kind of cycle performance, high rate performance preferable three-dimensional gradient metal hydroxides/oxide Electrode material and its preparation method and application.
The content of the invention
To overcome 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 that the present invention is provided is followed Ring performance, high rate performance are preferable.The preparation method for three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided Simply, convenient, obtained three-dimensional gradient metal hydroxides/oxide electrode material can be directly used for preparing electrode and electricity Pond, and show good electro-chemical activity.
First aspect present invention provides a kind of three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional Graded metal hydroxide/oxide electrode material includes conductive substrates and metal compound layer, and the metal compound layer is set In or be formed at the surfaces of the conductive substrates；The material that the metal compound layer is used for metal hydroxide or oxygen Compound, the metal is transition metal, and the metal compound layer drops to the concentration gradients of each metal ion in conductive substrates direction Low or rise.
Preferably, the transition metal includes at least one of Mn, Fe, Co, Ni, Cu and Zn.
The content of metal of the present invention is calculated with molal quantity, per metal ion species to conduction in metal compound layer The concentration gradients change in substrate direction, the graded is shown as：The molal quantity gradient rise of some metal ions, some gold Belong to the molal quantity gradient reduction of ion.
Preferably, the metal compound layer is to each tenor in conductive substrates direction：An at least metal ion species Concentration gradients rise, an at least metal ion species concentration gradients reduction.
Preferably, the transition metal is Me and M, wherein, the Me and M independently selected from Mn, Fe, Co, Ni, Cu and One kind in Zn, and Me is different with M.
It is further preferred that the transition metal is Me and M, wherein, the Me is in Mn, Fe, Ni, Co, Cu and Zn One kind, the M is selected from Co, Fe or Mn, and Me is different with M.
It is further preferred that the metal compound layer is to each tenor in conductive substrates direction：Transition metal M e's Concentration gradients are reduced, M concentration gradients rise.
" independently " of the present invention refers to that Me and M are selected from one kind in Mn, Fe, Co, Ni, Cu and Zn, and mutually not Interference, i.e. when Me is certain specific metal, can't influence M species, vice versa.
Preferably, the molecular formula of the hydroxide of the metal is MexMy(OH)2, wherein, x span is 0<x<1, Y span is 0<y<1, x+y=1；Me and M are selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that Me and M is different metal ion.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
It is further preferred that the Me is selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind, the M is selected from Co2+、Fe2+Or Mn2+, and Me is different with M.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material is made by way of electro-deposition.
It is further preferred that the mode of the electro-deposition uses galvanostatic method or potentiostatic method, with concentration-graded Many parts of water-soluble metal salts solution be electrolyte, successively in conductive substrates electro-deposition for a period of time, obtain three-dimensional gradient gold Belong to hydroxide/oxide electrode material.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts of water-soluble gold Belong to the solution of salt, wherein, n is more than or equal to 2.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts water-soluble The solution of metal salt, wherein, n is 2~30.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts water-soluble The solution of metal salt, wherein, n is 4~10.
It is further preferred that in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01~ 5mol/L。
It is further preferred that in the solution of every part of described water-soluble metal salt, metal ion total concentration is 0.01~ 0.5mol/L。
It is further preferred that 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 the metal is MexMyO4, wherein, M is doped metal ion, x value Scope is 0<x<4, y span is 0<y<8/3,2x+3y=8；Me and M are selected from Mn2+、Fe3+、Co3+、Fe2+、Co2+、Ni2 +、Cu2+And Zn2+In one kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
Me is selected from Ni2+、Cu2+、Fe2+、Co2+And Zn2+In one kind, M be selected from Mn3+、Fe3+And Co3+In one kind.
Preferably, the molecular formula of the oxide of the metal is MexMyO, wherein, M is doped metal ion, x value model Enclose for 0<x<1, y span is 0<y<1, x+y=1；Me and M are selected from Ni2+、Fe2+、Co2+、Cu2+And Zn2+In one Kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
Preferably, the molecular formula of the oxide of the metal is Me2xM2yO3, wherein, M is doped metal ion, x value Scope is 0<x<1, y span is 0<y<1, x+y=1, x+y=1；Me and M are selected from Mn3+、Fe3+And Co3+In one Kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material passes through the present inventor's second aspect institute The preparation method stated is made.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material passes through the present inventor's third aspect institute The preparation method stated is made.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material is by way of electro-deposition and calcining It is made.
The present invention first first prepares conductive substrates/transistion metal compound presoma by the way of electro-deposition, then by conduction Substrate/transistion metal compound presoma carries out calcining and prepares the three-dimensional gradient metal hydroxides/oxide electrode Material.
It is further preferred that described prepare three-dimensional gradient metal hydroxides/oxidation by the way of electro-deposition and calcining The step of thing electrode material, includes：Galvanostatic method or potentiostatic method are first used, with many parts of water-soluble gold of concentration-graded The solution for belonging to salt is electrolyte, successively in conductive substrates electro-deposition for a period of time, is obtained before conductive substrates/transistion metal compound Drive body；Then calcining obtained by conductive substrates/transistion metal compound forerunner, obtain the three-dimensional gradient metal hydroxides/ Oxide electrode material.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts water-soluble The solution of metal salt, wherein, n is more than or equal to 2.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts water-soluble The solution of metal salt, wherein, n is 2~30.
It is further preferred that the solution of many parts of water-soluble metal salts in concentration-graded is n parts water-soluble The solution of metal salt, wherein, n is 4~10.
It is further preferred that in the solution of many parts of water-soluble metal salts in concentration-graded, every part water-soluble Property metal salt solution in metal ion total concentration be 0.01~5mol/L.
It is further preferred that in the solution of many parts of water-soluble metal salts in concentration-graded, every part water-soluble Property metal salt solution in metal ion total concentration be 0.01~0.5mol/L.
It is further preferred that in the solution of many parts of water-soluble metal salts in concentration-graded, every part water-soluble Property metal salt solution in metal ion total concentration be 0.01~0.02mol/L.
It is further preferred that in described each part water-soluble metal salting liquid, metal ions M e concentration gradients drop It is low, M concentration gradients rise.
It is further preferred that in described each part water-soluble metal salting liquid, Me molar concentrations and M molar concentrations Ratio is k, in addition to two parts of solution for comprising only metal ions M e or M respectively, the difference of the k values of other any adjacent two parts of solution Absolute value is not more than 1.
It is further preferred that in described each part water-soluble metal salting liquid, Me molar concentrations and M molar concentrations Ratio is respectively 1:0、2:1、1:1、1:2 and 0:1.
It is further preferred that in described each part water-soluble metal salting liquid, Me molar concentrations and M molar concentrations Ratio is respectively 3:1、2:1、1:1、1:2 and 1:3.
It is further preferred that in described each part water-soluble metal salting liquid, Me molar concentrations and M molar concentrations Ratio is respectively 4:1、3:1、2:1 and 1:2.
Preferably, the conductive substrates include but is not limited to the three-dimensional conductives such as nickel foam, foam copper, carbon fiber paper, carbon cloth Matrix, stainless steel substrates, titanium sheet, nickel sheet or electro-conductive glass.
Preferably, the gross thickness of the metal compound layer is 0.5 μm~50 μm.
Three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided is nano wire, nano strip, nanometer Three-dimensional, the netted knot of the nanometer dendritic morphology frameworks such as post, nanometer blocks, nanometer taper, hollow nanometer tubular or nanometer sheet Three-dimensional, network structure that structure, preferably nanometer sheet are constituted；The three-dimensional, network structure there is the netted pattern of spatial intersecting, Intersected between nano-micro structure, thickness is more homogeneous, with great surface area and higher porosity, therefore with compared with Good chemical property.
The metallic hydrogen of gained on three-dimensional gradient metal hydroxides/oxide electrode material electrically-conductive backing plate that the present invention is provided The gradient layer of oxide or the not simple layer upon layer of metal oxide gradient, from microstructure, on electrically-conductive backing plate The metal hydroxides or metal oxide of gained are shown as：The net of the nanometer dendritic morphology framework interlocked by three dimensions Shape structure, and described Nanostructure Network is polycrystalline sedimentary；From metal ion content gradient, gained on electrically-conductive backing plate Metal hydroxides or metal oxide show as：(i.e. layers of metal hydroxides or metal are aoxidized the metal compound layer Nitride layer) reduce or raise to the concentration gradients of each metal ion in conductive substrates direction；In addition, each metal compound obtained by the present invention Have the transition mutually inlayed interval between thing gradient layer, when the transition interval is due to electro-deposition, obtained by crystal growth, due to During front and rear use various concentrations liquid deposition, the nanometer dendritic morphology newly formed is raw between the gap of original nanometer of dendritic morphology It is long, and it has been staggered to form the transitional region layer of mesh nanometer pattern；The interval structure can be reduced between each gradient layer well Stress so that the structure of whole layers of metal hydroxides is more excellent.
Second aspect of the present invention provides a kind of preparation side of three-dimensional gradient metal hydroxides/oxide electrode material Method, 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 various concentrations is configured, at least 2 parts water in concentration-graded is obtained Solube metallic salting liquid；Wherein, the metal is transition metal, in described each part water-soluble metal salting liquid, every kind of metal The molar concentration of ion is raised and lowered portionwise；
(2) take reference electrode and to electrode, three-electrode system is assembled by working electrode of conductive substrates；
(3) galvanostatic method or potentiostatic method are used, takes the water-soluble metal salt of concentration-graded made from step (1) molten Liquid, according to the molar concentration order from high to low or from low to high of a certain metal, the three-electrode system is placed in portionwise Electro-deposition is carried out in the water-soluble metal salting liquid of concentration-graded made from step (1), three-dimensional is obtained after washing, drying Graded metal hydroxide/oxide electrode material, wherein, the three-dimensional gradient metal hydroxides/oxide electrode material Including conductive substrates and metal compound layer, the metal compound layer is located at or is formed at the surface of the conductive substrates；Institute Material that metal compound layer used is stated for the hydroxide of metal, the metal is transition metal, the metallic compound Layer is reduced or raised to the concentration gradients of each metal ion in conductive substrates direction.
Preferably, in the step (1), described water-soluble metal salt includes nitrate, sulfate, the acetate of metal At least one of with chloride.
Preferably, in the step (1), in each part water-soluble metal salting liquid, the metal ion includes Mn2+、Fe2+、 Co2+、Ni2+、Cu2+And Zn2+At least one of.
In " the water-soluble metal salting liquids of various concentrations " of the present invention, " concentration " is mole dense for metal ion Degree, " concentration is different " refer to that concentration of every kind of metal in each part water-soluble metal salting liquid changes portionwise.
Preferably, in the step (1), in the solution of described every part of water-soluble metal salt, metal ion total concentration is 0.01~5mol/L.
Preferably, in the step (1), in the solution of described every part of water-soluble metal salt, metal ion total concentration is 0.01~0.5mol/L.
It is further preferred that in the step (1), in the solution of described every part of water-soluble metal salt, metal ion is total Concentration is 0.01~0.02mol/L.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is more than or equal to 2.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is 2~30.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is 4~10.
" concentration-graded " of the present invention refers to any metal ion in each part water-soluble metal salting liquid In molar concentration gradient rise or gradient reduction.
Preferably, in the step (1), in each part water-soluble metal salting liquid, at least mole of a metal ion species Number gradient rise, the molal quantity gradient reduction of an at least metal ion species.
Preferably, in the step (1), in each part water-soluble metal salting liquid, the metal ion is Me and M, wherein, The Me and M are selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind, and Me is different with M.
It is further preferred that the metal ion is Me and M, wherein, the Me is selected from Mn2+、Fe2+、Ni2+、Cu2+And Zn2+In one kind, the M be selected from Co2+、Fe2+Or Mn2+, and Me is different with M.
It is further preferred that in each part water-soluble metal salting liquid, metal ions M e concentration gradients reduction, M content Gradient is raised.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Be worth for k, in addition to two parts of solution for comprising only metal ions M e or M respectively, the difference of the k values of other any adjacent two parts of solution it is exhausted 1 is not more than to value.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 1:0、2:1、1:1、1:2 and 0:1.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 3:1、2:1、1:1、1:2 and 1:3.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 4:1、3:1、2:1 and 1:2.
Preferably, in the step (2), described reference electrode and to electrode using assembling three-electrode system in industry When conventional electrodes, such as using saturated calomel electrode as reference electrode, platinum plate electrode is as to electrode.
The present inventor uses three-electrode system depositing metallic compounds in conductive substrates in water-soluble metal salting liquid Layer, the material of the metal compound layer is the hydroxide of metal；Those skilled in the art according to specific needs, can use Other electrode systems deposit metal compound layer of the present invention in conductive substrates.
Preferably, in the step (2), described conductive substrates include but is 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 the step (2), described conductive substrates are the pretreated conductive substrates of hydrochloric acid.
Nickel foam that the present invention is used, foam copper, carbon fiber paper, carbon cloth conductive substrates can be made for three-dimensional conductive matrix Three-dimensional gradient metal hydroxides/oxide electrode material.
Preferably, in the step (3), the condition of the electro-deposition is：It is each portionwise to deposit with 0.5~100mA electric current 60~600 seconds.
It is further preferred that in the step (3), the condition of the electro-deposition is：With 0.5~20mA electric current, portionwise Each deposition 100~300 seconds.
Preferably, in the step (3), the condition of the electro-deposition is：With minus 1.3~negative 0.5V electric current, portionwise respectively Deposition 60~600 seconds.
Preferably, in the step (3), the condition of the electro-deposition is：With minus 1.0~negative 0.8V electric current, portionwise respectively Deposition 100~300 seconds.
Preferably, in the step (3), the electro-deposition is carried out under conditions of 15~65 DEG C.
Preferably, in the step (3), the mode of the washing is using obtained by deionized water and absolute ethyl alcohol washing Three-dimensional gradient metal hydroxides/oxide electrode material.
The mode of washing that the present invention is used is metal electrode material conventional laundry process in industry, and the cleaning solvent of use is excellent Elect at least one of deionized water, methanol, ethanol, isopropanol as.
Preferably, in the step (3), 60~120 DEG C of the condition of the drying.
The drying mode that the present invention is used such as is done for metal electrode material conventional drying methods in industry using drying baker Dry or vacuum drying.
Preferably, in the step (3), the transition metal includes at least one of Mn, Fe, Co, Ni, Cu and Zn.
Preferably, in the step (3), the transition metal be Me and M, wherein, the Me and M be selected from Mn, Fe, One kind in Co, Ni, Cu and Zn, and Me is different with M.
It is further preferred that in the step (3), the transition metal is Me and M, wherein, the Me be selected from Mn, Fe, One kind in Ni, Co, Cu and Zn, the M is selected from Co, Fe or Mn, and Me is different with M.
Preferably, in the step (3), content from the metal compound layer to each metal ion in conductive substrates direction For：The molal quantity gradient rise of an at least metal ion species, the molal quantity gradient reduction of an at least metal ion species.
It is further preferred that in the step (3), the metal compound layer is to each metal ion in conductive substrates direction Content is：The concentration gradients reduction of transition metal M e ions, the concentration gradients rise of M ions.
Preferably, in the step (3), the molecular formula of the hydroxide of the metal is MexMy(OH)2, wherein, x's takes It is 0 to be worth scope<x<1, y span is 0<y<1, x+y=1；Me and M are selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+ In one kind.
Under this optimum condition：
It is further preferred that Me and M is different metal ion.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
It is further preferred that the Me is selected from Mn2+、Fe2+、Ni2+、Cu2+And Zn2+In one kind, the M be selected from Co2+、 Fe2+Or Mn2+, and Me is different with M.
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
Preferably, in the step (3), the gross thickness of the metal compound layer is 0.5 μm~50 μm.
Third aspect present invention provides a kind of preparation side of three-dimensional gradient metal hydroxides/oxide electrode material Method, 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 various concentrations is configured, at least 2 parts water in concentration-graded is obtained Solube metallic salting liquid；Wherein, the metal is transition metal, in described each part water-soluble metal salting liquid, every kind of metal The molar concentration of ion is raised and lowered portionwise；
(2) take reference electrode and to electrode, three-electrode system is assembled by working electrode of conductive substrates；
(3) galvanostatic method or potentiostatic method are used, takes the water-soluble metal salt of concentration-graded made from step (1) molten Liquid, according to the molar concentration order from high to low or from low to high of a certain metal, the three-electrode system is placed in portionwise Electro-deposition is carried out in the water-soluble metal salting liquid of concentration-graded made from step (1), conduction is obtained after washing, drying Substrate/transition metal hydroxide presoma, the conductive substrates/transition metal hydroxide presoma include conductive substrates and It is deposited on the transition metal hydroxide presoma on conductive substrates surface；
(4) under inert gas shielding, by conductive substrates/transition metal hydroxide presoma made from step (3) 300 Calcining 1~6 hour is carried out at a temperature of~600 DEG C, three-dimensional gradient metal hydroxides/oxide electrode material is obtained；Wherein, institute Stating three-dimensional gradient metal hydroxides/oxide electrode material includes conductive substrates and metal compound layer, the metal compound Nitride layer is located at or is formed at the surface of the conductive substrates；The material that the metal compound layer is used for metal oxidation Thing, the metal is transition metal, and the metal compound layer is reduced to the concentration gradients of each metal ion in conductive substrates direction Or rise.
Preferably, in the step (1), described water-soluble metal salt includes nitrate, sulfate, the acetate of metal At least one of with chloride.
Preferably, in the step (1), in each part water-soluble metal salting liquid, the metal ion includes Mn2+、Fe2+、 Co2+、Ni2+、Cu2+And Zn2+At least one of.
In " the water-soluble metal salting liquids of various concentrations " of the present invention, " concentration " is mole dense for metal ion Degree, " concentration is different " refer to that concentration of every kind of metal in each part water-soluble metal salting liquid changes portionwise.
Preferably, in the step (1), in the solution of described every part of water-soluble metal salt, metal ion total concentration is 0.01~5mol/L.
Preferably, in the step (1), in the solution of described every part of water-soluble metal salt, metal ion total concentration is 0.01~0.5mol/L.
It is further preferred that in the step (1), in the solution of described every part of water-soluble metal salt, metal ion is total Concentration is 0.01~0.02mol/L.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is more than or equal to 2.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is 2~30.
Preferably, in the step (1), the solution of many parts of water-soluble metal salts in concentration-graded is n parts The solution of water-soluble metal salt, wherein, n is 4~10.
" concentration-graded " of the present invention refers to any metal ion in each part water-soluble metal salting liquid In molar concentration gradient rise or gradient reduction.
Preferably, in the step (1), in each part water-soluble metal salting liquid, at least mole of a metal ion species Number gradient rise, the molal quantity gradient reduction of an at least metal ion species.
Preferably, in the step (1), in each part water-soluble metal salting liquid, the metal ion is Me and M, wherein, The Me and M are selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind, and Me is different with M.
It is further preferred that the metal ion is Me and M, wherein, the Me is selected from Mn2+、Fe2+、Ni2+、Co2+、Cu2+ And Zn2+In one kind, the M be selected from Co2+、Fe2+Or Mn2+, and Me is different with M.
It is further preferred that in each part water-soluble metal salting liquid, metal ions M e concentration gradients reduction, M content Gradient is raised.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations It is worth for k, in addition to two parts of solution for comprising only metal ions M e or M, the absolute value of the difference of the k values of other any adjacent two parts of solution No more than 1.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 1:0、2:1、1:1、1:2 and 0:1.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 3:1、2:1、1:1、1:2 and 1:3.
It is further preferred that in described each part water-soluble metal salting liquid, the ratio of Me molar concentrations and M molar concentrations Value is respectively 4:1、3:1、2:1 and 1:2.
Preferably, in the step (2), described reference electrode and to electrode using assembling three-electrode system in industry When conventional electrodes, such as using saturated calomel electrode as reference electrode, platinum plate electrode is as to electrode.
The present inventor uses three-electrode system depositing metallic compounds in conductive substrates in water-soluble metal salting liquid Layer, the material of the metal compound layer is the hydroxide of metal；Those skilled in the art according to specific needs, can use Other electrode systems deposit metal compound layer of the present invention in conductive substrates.
Preferably, in the step (2), described conductive substrates include but is 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 the step (2), described conductive substrates are the pretreated conductive substrates of hydrochloric acid.
Nickel foam that the present invention is used, foam copper, carbon fiber paper, carbon cloth conductive substrates can be made for three-dimensional conductive matrix Three-dimensional three-dimensional gradient metal hydroxides/oxide electrode material.
Preferably, in the step (3), the condition of the electro-deposition is：It is each portionwise to deposit 60 with 1~100mA electric current ~600 seconds.
It is further preferred that in the step (3), the condition of the electro-deposition is：With 0.5~20mA electric current, portionwise Each deposition 100~300 seconds.
Preferably, in the step (3), the condition of the electro-deposition is：With minus 1.3~negative 0.5V electric current, portionwise respectively Deposition 60~600 seconds.
Preferably, in the step (3), the condition of the electro-deposition is：With minus 1.0~negative 0.8V electric current, portionwise respectively Deposition 100~300 seconds.
Preferably, in the step (3), the electro-deposition is carried out under conditions of 15~65 DEG C.
Preferably, in the step (3), the mode of the washing is using obtained by deionized water and absolute ethyl alcohol washing Three-dimensional gradient metal hydroxides/oxide electrode material.
The mode of washing that the present invention is used is metal electrode material conventional laundry process in industry, and the cleaning solvent of use is excellent Elect at least one of deionized water, methanol, ethanol, isopropanol as.
Preferably, in the step (3), 60~120 DEG C of the condition of the drying.
The drying mode that the present invention is used such as is done for metal electrode material conventional drying methods in industry using drying baker Dry or vacuum drying.
Preferably, in the step (4), conductive substrates/transition metal hydroxide presoma made from step (3) is existed Calcining 2~3 hours is carried out at a temperature of 300~600 DEG C.
Preferably, in the step (4), the transition metal includes at least one of Mn, Fe, Co, Ni, Cu and Zn.
Preferably, in the step (4), the transition metal be Me and M, wherein, the Me and M be selected from Mn, Fe, One kind in Co, Ni, Cu and Zn, and Me is different with M.
It is further preferred that in the step (4), the transition metal is Me and M, wherein, the Me be selected from Mn, Fe, One kind in Ni, Co, Cu and Zn, the M is selected from Co, Fe or Mn, and Me is different with M.
Preferably, in the step (4), content from the metal compound layer to each metal ion in conductive substrates direction For：The molal quantity gradient rise of an at least metal ion species, the molal quantity gradient reduction of an at least metal ion species.
It is further preferred that in the step (4), the metal compound layer is to each tenor in conductive substrates direction For：Transition metal M e concentration gradients reduction, M concentration gradients rise.
Preferably, in the step (4), the molecular formula of the oxide of the metal is MexMyO4, wherein, M is doping gold Belong to ion, x span is 0<x<4, y span is 0<y<8/3,2x+3y=8；Me and M are selected from Mn2+、Fe3+、 Co3+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind.
Under this optimum condition：
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
It is further preferred that the Me is selected from Ni2+、Fe2+、Co2+、Cu2+And Zn2+In one kind, M be selected from Mn3+、Fe3+With Co3+In one kind.
It is further preferred that the span of the x is 0.3≤x≤0.8.
It is further preferred that the span of the y is 0.3≤y≤0.8.
Preferably, the molecular formula of the oxide of the metal is MexMyO, wherein, M is doped metal ion, x value model Enclose for 0<x<1, y span is 0<y<1, x+y=1；Me and M are selected from Ni2+、Fe2+、Co2+、Cu2+And Zn2+In one Kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.
Preferably, the molecular formula of the oxide of the metal is Me2xM2yO3, wherein, M is doped metal ion, x value Scope is 0<x<1, y span is 0<y<1, x+y=1, x+y=1；Me and M are selected from Mn3+、Fe3+And Co3+In one Kind.
Under this optimum condition：
It is further preferred that the span of the x is 0.1≤x≤0.9.
It is further preferred that the span of the y is 0.1≤y≤0.9.
It is further preferred that the content of the metal compound layer to each metal ion in conductive substrates direction is：Me's contains Measure gradient reduction, M concentration gradients rise.Preferably, in the step (4), the gross thickness of the layers of metal hydroxides is 0.5 μm~50 μm.
The preparation method that the present invention is provided uses concentration-gradient solution, reduces or raises portionwise according to certain metal concentration Order, deposit portionwise.Each nano-tube/nano-wire in rear deposition, newly formed, nano strip, nano-pillar, nanometer blocks, nanocone The nanometer dendritic morphologies such as shape, hollow nanometer tubular or nanometer sheet and nanometer dendritic morphology obtained by preceding primary depositing are interlaced, Form the new, Nanostructure Network that specific surface area is bigger.Nanometer dendritic morphology obtained by preparation method electro-deposition of the present invention is excellent Elect nanometer sheet as.Three-dimensional gradient metal hydroxides/oxide electrode material prepared by the present invention is preferably that nanometer sheet is mutually handed over Three-dimensional, the network structure of mistake.
Present invention preferably employs two kinds of different metal ions combinations, be conducive to posterior deposition break formerly deposit it is original Nanometer dendritic morphology growth tendency, form new nanowire growth point, and formed between the gap of original nanometer of dendritic morphology New nanometer dendritic morphology, so that the three-dimensional of spatial intersecting, gradient nano network structure are formed, significantly there is provided specific surface area, Important pattern basis is provided for high specific capacitance.The electro-deposition method that the present invention is used is simple, convenient, and can pass through control The condition of electro-deposition is come the nano material of spatial intersecting pattern that is obtaining rule；In addition, the present invention is directly by transition metal ions It is deposited directly in three-dimensional conductive substrate, without adding binding agent and conductive agent, had both eliminated the resistance that binding agent is transmitted to ion Hinder, ion transmission range of the electrode in charge and discharge process is shortened, while the energy for also substantially increasing its unit volume is close Degree.
Three-dimensional gradient metal hydroxides/oxide electrode material prepared by the present invention has special space three-dimensional knot Structure, by the combination of different transition metal, being prepared for macroscopically each concentration of metal ions graded, microcosmic go up has nanometer micro- The nano-electrode material for the netted pattern that structure is interlocked, the inside of the nano-electrode material is mainly high Energy Density Materials, table Layer is mainly stability and the excellent component of high rate performance, so as to make whole electrode obtain high-energy-density, high stable on the whole Performance and excellent high rate performance.
Fifth aspect present invention provides three-dimensional gradient metal hydroxides/oxide electrode material as described in relation to the first aspect The application in electrode material and battery is prepared of material.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material as described in relation to the first aspect system Application in standby electrode of super capacitor, negative electrode of lithium ion battery, lithium-oxygen battery and metal-air battery catalyst.
Sixth aspect present invention provides three-dimensional gradient metal hydroxides/oxide electrode material as described in second aspect The application in electrode material and battery is prepared of material.
Preferably, the three-dimensional gradient metal hydroxides/oxide electrode material as described in second aspect system Application in standby electrode of super capacitor, negative electrode of lithium ion battery, lithium-oxygen battery and metal-air battery catalyst.
Three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided and its preparation method and application has Beneficial effect：
(1) electro-deposition method that the present invention is used is simple, convenient, and can be by controlling the condition of electro-deposition to be advised Then, the nano material of spatial intersecting pattern；
(2) transition metal hydroxide (oxide) three-dimensional gradient nano material is directly deposited directly to three-dimensional by the present invention In conductive substrates, without adding binding agent and conductive agent, the obstruction that binding agent is transmitted to ion was both eliminated, electrode has been shortened and exists Ion transmission range in charge and discharge process, while also substantially increasing the energy density of its unit volume；
(3) three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided is combined along substrate upward Upwards, the premium properties of various different components：Inside is mainly high Energy Density Materials, and top layer is mainly stability and forthright again The excellent component of energy, so that whole electrode obtains high-energy-density, high stability energy and excellent high rate performance.
Brief description of the drawings
Fig. 1 is the SEM figures of the three-dimensional gradient metal hydroxides/oxide electrode material prepared in example 1；
Fig. 2 is the XRD of the three-dimensional gradient metal hydroxides/oxide electrode material prepared in example 1；
Fig. 3 is the XPS depth analysis figures of the three-dimensional gradient metal hydroxides/oxide electrode material prepared in example 1；
Fig. 4 is the cyclic voltammetry curve figure under electrode material for super capacitor different scanning speed in example effects 1；
Fig. 5 is the constant current charge-discharge curve map under the different current densities of electrode material for super capacitor in example effects 1；
Fig. 6 is the cyclic voltammetry curve figure under Asymmetric Supercapacitor different scanning speed in example effects 2；
Fig. 7 is energy density-power density diagram of Asymmetric Supercapacitor in example effects 2；
Fig. 8 is the cycle life figure of Asymmetric Supercapacitor in example effects 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 carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Ni2+:Co2+Molar concentration rate is respectively 1:0,2:1,1:1,1:2,0:1 ratio, configures 5 parts of metal ions Total concentration is 0.01mol/L nitrate solution；Nickel foam is cut into 1 × 1cm2Size, and pass through 3mol/L hydrochloric acid solutions Ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；With what is treated Nickel foam, respectively as reference electrode and to electrode, assembles three-electrode system as working electrode, saturation calomel and platinized platinum, Constant current 0.0005A on CHI660E electrochemical workstations, successively in Ni2+:Co2+Mol ratio is 1:0,2:1,1:1,1:2,0: In 1 nitrate solution, electro-deposition 2 minutes respectively；The foam nickel electrode obtained after deposition is used to deionized water respectively and anhydrous Ethanol is washed three times successively, and is dried 12 hours in 110 DEG C of baking oven, obtains three-dimensional gradient metal hydroxides/oxide electricity Pole material, the three-dimensional gradient metal hydroxides/oxide electrode material includes three-dimensional conductive substrate (nickel foam) and heavy Product is in the nickel cobalt hydroxide layer of foam nickel surface, and the material of the nickel cobalt hydroxide layer is nickel cobalt hydroxide, and thickness is 900nm, the molecular formula of the nickel cobalt hydroxide is NixCoy(OH)2, wherein, x span is 0<x<1, y value model Enclose for 0<y<1, x+y=1；Wherein, the x is about 0.35, and the y is about 0.65；Cobalt element in the nickel cobalt hydroxide layer Content be continuously increased upwards along base, the content of nickel element is constantly reduced.
In order to absolutely prove beneficial effects of the present invention, the invention provides three-dimensional gradient metallic hydrogen prepared by embodiment 1 SEM figures, XRD and the XPS depth analysis figures of oxide/oxide electrode material, respectively as shown in Figure 1, Figure 2 and Figure 3, Fig. 1 In each down scale be 50nm.
As shown in Figure 1, the nickel for three-dimensional gradient metal hydroxides/oxide electrode material that the embodiment of the present invention 1 is provided Cobalt hydroxide layer is nanofiber web structure, and the special construction has mutually to be handed between the netted pattern of spatial intersecting, nanometer sheet Fork, thickness is more homogeneous, with great surface area, therefore with preferable chemical property.The three-dimensional ladder that the present invention is provided Each dendritic morphology of the nanometer web frame of degree metal hydroxides/oxide electrode material represents a crystal grain, is that polycrystalline sinks Lamination.
The preparation method that the present invention is provided uses concentration-gradient solution, exemplified by described in the present embodiment, according to Ni2+ Concentration is reduced portionwise, Co2+Concentration elevated order portionwise, is deposited portionwise.Carried out after first time deposition, received using first part of solution Rice network structure is in nickel foam superficial growth, and nickel foam surface microstructure is changed into mesh nanometer knot from opposed flattened nickel dam Structure；When carrying out the second deposition using the solution of second part of various concentrations, on the one hand, new nanometer sheet is based on original nanostructured Continue or regrow, on the other hand, nanometer sheet is more likely to grow from the gap of Nanostructure Network, and this is due to relative The resistance of nickel foam at the Nanostructure Network formed, gap is smaller, is conducive to the deposition growing of new nanometer sheet, this The nanometer sheet of stylish formation is interlaced with nanometer sheet obtained by first time deposition, forms the new, nanometer that specific surface area is bigger Network structure；Further, since the embodiment of the present invention is conducive to posterior deposition to break using two kinds of different metal ion combinations The growth tendency of original nanometer sheet is formerly deposited, new nanowire growth point is formed, and formed between the gap of original nanometer sheet New nanometer sheet, so as to form the nanofiber web structure of spatial intersecting, significantly there is provided specific surface area, is provided for high specific capacitance Important pattern basis.
By comparing standard card, as shown in Figure 2, three-dimensional gradient metal hydroxides/oxide electrode that the present invention is provided The main active substances of material are α-Ni (OH)2With α-Co (OH)2。
From Fig. 3 XPS depth analysis figures, from the top layer of three-dimensional gradient metal hydroxides/oxide electrode material To foam nickel base direction (curve in corresponding diagram 3 from down to up), different depth Ni2p3/2Peak intensity substantially gradually rise, And Co2p3/2Peak intensity substantially gradually reduce.This explanation Ni (OH)2Content by electrode surface to nickel foam conductive substrates not Disconnected increase, Co (OH)2Content then constantly reduce.
From the point of view of layer structure, although the present invention has carried out 5 depositions using the solution of 5 parts of concentration-gradients, but Fig. 3 is aobvious It is showing as a result, when between 60nm~480nm different depth carry out XPS analysis when, three-dimensional gradient metal hydroxides/oxidation Ni2p in thing electrode material3/2And Co2p3/2More than 5 layers of the variable gradient of peak intensity, this also demonstrates Fig. 1 spatial intersecting shape Looks, illustrate there is transition between the different sedimentaries of three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided Layer, when the transition zone is front and rear use various concentrations liquid deposition, the nanometer sheet newly formed by original nanometer sheet interstital growth, And it is staggered to form the transitional region layer of mesh nanometer pattern.
In order to further illustrate beneficial effects of the present invention, the invention provides three-dimensional gradient metal prepared by embodiment 1 The effect example of hydroxide/oxide electrode material：
Effect example 1
Three-dimensional gradient metal hydroxides/oxide electrode material prepared by embodiment 1 directly as working electrode, with Mercury oxidation mercury and platinum plate electrode are assembled into the electrochemistry that three-electrode system carries out ultracapacitor for reference electrode and to electrode It can test, wherein electrolyte is 6M KOH solutions.
The super of the assembling of effect example 1 is tested using electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) The cyclic voltammetry curve of level capacitor, is tested under different scanning rates, and electric current is with the changing rule of current potential, and Fig. 4 is super electricity Cyclic voltammetry curve figure under container electrode material different scanning speed；Abscissa be current density (current density, A/g), ordinate is current potential (potential, V).
In Fig. 4, arrow across 5 curves correspondence go back virgin curve, arrow not across 5 curves correspondence oxidation curve, Wherein, arrow across 5 curves be from top to bottom corresponding in turn to 2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s scanning Speed, arrow not across 5 curves be from bottom to top corresponding in turn to and answer 2mV/s, 5mV/s, 10mV/s, 20mV/s, 50mV/s Sweep speed.
From fig. 4, it can be seen that every CV curve all has a pair of redox peaks, this is due to Co (OH)2With Ni (OH)2 Caused by generation redox reaction, the faraday's reaction that its electrode surface occurs is shown below：
The electric capacity of tested electrode material for super capacitor is mostly derived from the fake capacitance that above-mentioned redox reaction is produced.Anode Peak is attributed to Co (OH)2With Ni (OH)2CoOOH and NiOOH process are oxidized to, negative electrode peak then corresponds to its inverse process.CV curves Shape shows that the discharge and recharge invertibity for being tested electrode material for super capacitor is preferable.Electrode material for super capacitor is swept in difference The shape for retouching the cyclic voltammetry curve under speed has no significant changes with the change of sweep speed, and this illustrates the knot of the electrode material Structure is conducive to mass transfer faster and electric charge transfer in electrochemical reaction, reduces polarization phenomena.
The super of the assembling of effect example 1 is tested using electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) The constant current charge-discharge curve of level capacitor, specific capacity of the test electrode material under different current densities, Fig. 5 is ultracapacitor Constant current charge-discharge curve map under the different current densities of electrode material, abscissa is specific capacity (specific Capacitance, F/g), ordinate is current potential (V).
In Fig. 5, by arrow direction, the current density that curve is corresponding in turn to is 100A/g, 50A/g, 20A/g, 10A/ g、5A/g、2A/g、1A/g。
As shown in Figure 5, when discharge current density be respectively 1,2,5,10,20,50,100A/g when, corresponding single electrode ratio Capacitance is respectively 1759,1712,1646,1619,1480,1260,1100F/g.As can be seen here, the three-dimensional ladder that the present invention is provided The ultracapacitor of degree metal hydroxides/oxide electrode material assembling still has very high on larger discharge current density Specific capacitance.Illustrate that three-dimensional gradient metal hydroxides/oxide electrode material that the present invention is provided has higher big electricity Flow rate capability performance.Fig. 4 and Fig. 5 illustrate three-dimensional gradient metal hydroxides/oxide electrode material prepared by the present invention With good discharge and recharge invertibity and high specific capacity and good high rate performance.
Effect example 2
1) by 0.04g Ketjen blacks and 2mL absolute ethyl alcohols, mechanical mixture is uniform in mortar, delays during continuous grinding It is slow to add the polytetrafluoroethylsolution solution for adding that 0.2g mass fractions are 5% under continuous grinding, continue to be ground to ethanol and wave completely Hair, obtains the mixing material of rubber pureed, uniformly rolls and is pressed into after thickness is about 0.5mm, 10mm × 10mm pole piece is cut into, with thing The nickel foam first handled well is rolled on roll squeezer together, 80 DEG C of vacuum drying 12h.
2) pole piece for preparing step (1) is as negative pole, three-dimensional gradient metal hydroxides/oxygen prepared by embodiment 1 Compound electrode material is assembled into the electrochemical property test that two electrode systems carry out Asymmetric Supercapacitor as positive pole, its Middle electrolyte is 6M KOH solutions.
The super of the assembling of effect example 1 is tested using electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) The cyclic voltammetry curve of level capacitor, is tested under different scanning rates, and electric current is with the changing rule of current potential, and Fig. 6 is asymmetric Cyclic voltammetry curve figure under the different scanning speed of ultracapacitor；Abscissa be current density (current density, A/g), ordinate is current potential (potential, V).
In Fig. 6, arrow across 5 curves correspondence oxidation curve, arrow not across 5 curves correspondence go back virgin curve, Wherein, arrow across 5 curves be from bottom to top corresponding in turn to sweeping for 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s Retouch speed, arrow not across 5 curves be from top to bottom corresponding in turn to 5mV/s, 10mV/s, 20mV/s, 50mV/s, 100mV/s Sweep speed.
The super of the assembling of effect example 1 is tested using electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) The constant current charge-discharge curve of level capacitor, specific capacity of the test electrode material under different current densities, Fig. 7 is asymmetric super Constant current charge-discharge curve map under the different current densities of capacitor, abscissa be energy density (energy density, Wh/kg), ordinate is power density (power density, W/kg).
The super of the assembling of effect example 1 is tested using electrochemical workstation (CHI660E, Shanghai Chen Hua Instrument Ltd.) The cycle life of level capacitor, specific capacity change of the test electrode material after charge and discharge cycles are tested, test condition：Electric current Density is 5A/g, and potential window is 0~1.5V；Fig. 8 is the cycle life figure of Asymmetric Supercapacitor, and abscissa is specific volume Measure (specific capacitance, F/g), ordinate is period；The abscissa of small figure is current potential (V), ordinate in Fig. 8 For the time (s).
Fig. 6~Fig. 8 illustrates using prepared by the three-dimensional gradient metal hydroxides/oxide electrode material of the invention provided Asymmetric Supercapacitor there is high-energy-density, excellent high rate performance and stable cycle life.
Embodiment 2
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Ni2+:Co2+Molar concentration rate be respectively 4:1,3:1,2:1,1:1 ratio, 4 parts of metal ions of configuration are total Concentration is 0.02mol/L sulfate liquor；Foam copper is cut into a diameter of 1.8cm circular pole piece, and passes through 3mol/L Hydrochloric acid solution ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；With Treated foam copper, respectively as reference electrode and to electrode, assembles three electrodes as working electrode, saturation calomel and platinized platinum System, the constant current 0.001A on CHI660E electrochemical workstations, successively in Ni2+:Co2+Mol ratio is 4:1,3:1,2:1, 1:In 1 nitrate solution, electro-deposition 2 minutes respectively；The foam nickel electrode obtained after deposition is used into deionized water and nothing respectively Water-ethanol is washed three times successively, and is dried 12 hours in 110 DEG C of baking oven；Calcine 2 hours, obtain under 300 DEG C of nitrogen atmospheres Three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydroxides/oxide electrode material bag Include three-dimensional conductive substrate (foam copper) and be deposited on the nickel cobalt oxide layer on foam copper surface, the material of the nickel cobalt oxide layer Matter is nickel cobalt oxide, and the molecular formula of the nickel cobalt oxide is NixCoyO4, x span is 0<x<4, y span For 0<y<8/3,2x+3y=8；The content of cobalt element is continuously increased upwards along substrate in the nickel cobalt oxide layer, nickel element Content is constantly reduced.
In order to absolutely prove beneficial effects of the present invention, the present embodiment additionally provides gained three-dimensional gradient metal hydroxide Application of the thing/oxide electrode material in battery is prepared：Three-dimensional gradient metal hydroxides/oxide electrode material will be prepared Directly as working electrode, done using metal lithium sheet to electrode, polypropylene porous film does barrier film, 1.0mol/L LiPF6EC： DMC=1:The mixed solution of 1 (volume ratio) does electrolyte, and 2016 type button cells are assembled into anhydrous and oxygen-free control box.
Embodiment 3
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Ni2+:Co2+Mol ratio be respectively 4:1,3:1,2:1,1:1 ratio, configures 4 parts of metal ion total concentrations It is 0.02mol/L chloride brine；Foam copper is cut into a diameter of 1.8cm circular pole piece, and passes through 3mol/L salt Acid solution ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；To locate The foam copper managed, respectively as reference electrode and to electrode, assembles three electrode bodies as working electrode, saturation calomel and platinized platinum System, the constant current 0.001A on CHI660E electrochemical workstations, successively in Ni2+:Co2+Mol ratio is 4:1,3:1,2:1,1: In 1 nitrate solution, electro-deposition 2 minutes respectively；The foam nickel electrode obtained after deposition is used to deionized water respectively and anhydrous Ethanol is washed three times successively, and is dried 12 hours in 110 DEG C of baking oven；Calcined 2 hours under 300 DEG C of nitrogen atmospheres, obtain three Graded metal hydroxide/oxide electrode material is tieed up, the three-dimensional gradient metal hydroxides/oxide electrode material includes Three-dimensional conductive substrate (foam copper) and the nickel cobalt hydroxide layer for being deposited on foam copper surface, the nickel cobalt hydroxide layer Material is nickel cobalt hydroxide, and the molecular formula of the nickel cobalt hydroxide is NixCoyO4, x span is 0<x<4, y take It is 0 to be worth scope<y<8/3,2x+3y=8；The content of cobalt element constantly increases upwards along foam copper substrate in the nickel cobalt oxide layer Plus, the content of nickel element is constantly reduced.
In order to absolutely prove beneficial effects of the present invention, the present embodiment additionally provides gained three-dimensional gradient metal hydroxide Application of the thing/oxide electrode material in battery is prepared：Three-dimensional gradient metal hydroxides/oxide electrode material will be prepared Directly as working electrode, done using metal lithium sheet to electrode, glass fibre membrane does barrier film, double (the fluoroform sulphurs of 1.0mol/L Acid imide) lithium/tetraethyleneglycol dimethyl ether mixed solution does electrolyte, is assembled into that 2032 types are porous to be buckled in anhydrous and oxygen-free control box Formula battery.
Embodiment 4
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Mn2+:Co2+Molar concentration rate be respectively 3:1、2:1、1:1、1:2、1:3 ratio, is respectively configured metal Total ion concentration is 0.02mol/L nitrate solution；Foam copper is cut into a diameter of 1.8cm circular pole piece, and passed through 3mol/L hydrochloric acid solutions ultrasound 10 minutes, removes the oxidation film on its surface, then wash 3 successively with deionized water and absolute ethyl alcohol It is secondary；Using treated foam copper as working electrode, saturation calomel and platinized platinum as reference electrode and to electrode, assembling three Electrode system, the constant current 0.001A on CHI660E electrochemical workstations, successively in Mn2+:Co2+Mol ratio is 3:1、2:1、 1:1、1:2、1:In 3 nitrate solution, electro-deposition 2 minutes respectively；By the foam nickel electrode obtained after deposition spend respectively from Sub- water and absolute ethyl alcohol are washed three times successively, and are dried 12 hours in 110 DEG C of baking oven；Forged under 400-600 DEG C of air atmosphere Burn 2 hours, obtain three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydroxides/oxidation Thing electrode material includes three-dimensional conductive substrate (foam copper) and is deposited on the nickel cobalt hydroxide layer on foam copper surface, the nickel The material of cobalt hydroxide layer is nickel cobalt hydroxide, and the molecular formula of the nickel cobalt hydroxide is MnxCoyO4, x value model Enclose for 0<x<4, y span is 0<y<8/3,2x+3y=8；The content of cobalt element is along foam in the manganese cobalt oxidation nitride layer Copper-based bottom is continuously increased upwards, and the content of manganese element is constantly reduced.
In order to absolutely prove beneficial effects of the present invention, the present embodiment additionally provides gained three-dimensional gradient metal hydroxide Application of the thing/oxide electrode material in battery is prepared：Three-dimensional gradient metal hydroxides/oxide electrode material will be prepared Directly as working electrode, done using metal lithium sheet to electrode, polypropylene porous film does barrier film, 1.0mol/L LiPF6EC： DMC=1:The mixed solution of 1 (volume ratio) does electrolyte, and 2016 type button cells are assembled into anhydrous and oxygen-free control box.
Embodiment 5
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Mn2+:Co2+Molar concentration rate be respectively 3:1、2:1、1:1、1:2、1:3 ratio, is respectively configured 5 parts of gold Category total ion concentration is 0.02mol/L nitrate solution；Nickel foam is cut into a diameter of 1.8cm circular pole piece, and passed through 3mol/L hydrochloric acid solutions ultrasound 10 minutes are crossed, the oxidation film on its surface are removed, then washed successively with deionized water and absolute ethyl alcohol Wash 3 times；Using treated nickel foam as working electrode, saturation calomel and platinized platinum as reference electrode and to electrode, group Fill three-electrode system, the constant current 0.001A on CHI660E electrochemical workstations, successively in Mn2+:Co2+Mol ratio is 3:1、 2:1、1:1、1:2、1:In 3 nitrate solution, electro-deposition 2 minutes respectively；The foam nickel electrode obtained after deposition is used respectively Deionized water and absolute ethyl alcohol are washed three times successively, and are dried 12 hours in 110 DEG C of baking oven；In 400-600 DEG C of air atmosphere Lower calcining 2 hours, obtains three-dimensional gradient metal hydroxides/oxide electrode material, and the three-dimensional gradient metal hydroxides/ Oxide electrode material includes three-dimensional conductive substrate (foam copper) and is deposited on the nickel cobalt hydroxide layer on foam copper surface, institute The material for stating magnesium cobalt hydroxide layer is magnesium cobalt hydroxide, and the molecular formula of the magnesium cobalt hydroxide is MnxCoyO4, x's takes It is 0 to be worth scope<x<4, y span is 0<y<8/3,2x+3y=8；The content edge of cobalt element in the manganese cobalt oxidation nitride layer Foam copper substrate is continuously increased upwards, and the content of manganese element is constantly reduced.
In order to absolutely prove beneficial effects of the present invention, the present embodiment additionally provides gained three-dimensional gradient metal hydroxide Application of the thing/oxide electrode material in battery is prepared：Three-dimensional gradient metal hydroxides/oxide electrode material will be prepared Directly as working electrode, done using metal lithium sheet to electrode, glass fibre membrane does barrier film, double (the fluoroform sulphurs of 1.0mol/L Acid imide) lithium/tetraethyleneglycol dimethyl ether mixed solution does electrolyte, is assembled into that 2032 types are porous to be buckled in anhydrous and oxygen-free control box Formula battery.
Embodiment 6
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
1) according to Fe2+:Co2+Molar concentration rate is respectively 1:0,2:1,1:1,1:2,0:1 ratio, 5 parts of configurations are golden respectively Category total ion concentration is 5mol/L nitrate solution；Nickel foam is cut into 1 × 1cm2Size, and it is molten by 3mol/L hydrochloric acid Liquid ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；With treated Nickel foam as working electrode, saturation calomel and platinized platinum respectively as reference electrode and to electrode, assemble three-electrode system, Constant current 0.1A on CHI660E electrochemical workstations, successively in Fe2+:Co2+Mol ratio is 1:0,2:1,1:1,1:2,0:1 In nitrate solution, electro-deposition 60 seconds respectively；The foam nickel electrode obtained after deposition is used into deionized water and absolute ethyl alcohol respectively Wash three times, and dried 12 hours in 110 DEG C of baking oven successively, obtain three-dimensional gradient metal hydroxides/oxide electrode material Material, the three-dimensional gradient metal hydroxides/oxide electrode material includes three-dimensional conductive substrate (nickel foam) and is deposited on The iron cobalt hydroxide layer of foam nickel surface, the material of the iron cobalt hydroxide layer is iron cobalt hydroxide, the iron cobalt hydrogen The molecular formula of oxide is FexCoy(OH)2, x span is 0<x<1, y span is 0<y<1, x+y=1；It is described The content of cobalt element is continuously increased upwards along base in iron cobalt hydroxide layer, and the content of ferro element is constantly reduced.
2) further by three-dimensional gradient metal hydroxides/oxide electrode material obtained by step (1) in 600 DEG C of nitrogen Calcined 3 hours under atmosphere, obtain three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydrogen-oxygen Compound/oxide electrode material includes three-dimensional conductive substrate (foam copper) and is deposited on the iron cobalt/cobalt oxide on foam copper surface Layer, the material of the iron cobalt oxidation nitride layer is iron cobalt/cobalt oxide, and the molecular formula of the iron cobalt/cobalt oxide is FexCoyO4, x value Scope is 0<x<4, y span is 0<y<8/3,2x+3y=8；The content of cobalt element is along substrate in the iron cobalt/cobalt oxide It is continuously increased upwards, the content of ferro element is constantly reduced.
Embodiment 7
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Cu2+:Co2+Molar concentration rate is respectively 4:1,3:1,2:1,1:1 ratio, is respectively configured 4 parts of metal ions Total concentration is 0.5mol/L nitrate solution；Foam copper is cut into a diameter of 1.8cm circular pole piece, and passes through 3mol/L Hydrochloric acid solution ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；With Treated foam copper, respectively as reference electrode and to electrode, assembles three electrodes as working electrode, saturation calomel and platinized platinum System, the constant current 0.001A on CHI660E electrochemical workstations, successively in Cu2+:Co2+Mol ratio is 4:1,3:1,2:1, 1:In 1 nitrate solution, electro-deposition 300 seconds respectively；The foam nickel electrode obtained after deposition is used into deionized water and nothing respectively Water-ethanol is washed three times successively, and is dried 12 hours in 110 DEG C of baking oven；Calcine 1 hour, obtain under 300 DEG C of nitrogen atmospheres Three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydroxides/oxide electrode material bag Include three-dimensional conductive substrate (foam copper) and be deposited on the copper cobalt oxidation nitride layer on foam copper surface, the material of the copper cobalt oxidation nitride layer Matter is copper cobalt/cobalt oxide, and the molecular formula of the copper cobalt/cobalt oxide is CuxCoyO4, x span is 0<x<4, y value model Enclose for 0<y<8/3,2x+3y=8；The content of cobalt element is continuously increased upwards along substrate in the copper cobalt oxidation nitride layer, copper Content constantly reduce.
Embodiment 8
A kind of preparation method of three-dimensional gradient metal hydroxides/oxide electrode material is present embodiments provided, including Following steps：
According to Ni2+:Fe2+Molar concentration rate is respectively 4:1,3:1,2:1,1:1 ratio, is respectively configured 4 parts of metal ions Total concentration is 0.02mol/L nitrate solution；Foam copper is cut into a diameter of 1.8cm circular pole piece, and passes through 3mol/ L hydrochloric acid solutions ultrasound 10 minutes, removes the oxidation film on its surface, then washed successively 3 times with deionized water and absolute ethyl alcohol；With Treated foam copper, respectively as reference electrode and to electrode, assembles three electrodes as working electrode, saturation calomel and platinized platinum System, the constant current 0.001A on CHI660E electrochemical workstations, successively in Ni2+:Fe2+Mol ratio is 4:1,3:1,2:1, 1:In 1 nitrate solution, electro-deposition 600 seconds respectively；The foam nickel electrode obtained after deposition is used into deionized water and nothing respectively Water-ethanol is washed three times successively, and is dried 12 hours in 110 DEG C of baking oven；Calcine 2 hours, obtain under 300 DEG C of nitrogen atmospheres Three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydroxides/oxide electrode material bag Include three-dimensional conductive substrate (foam copper) and be deposited on the nickel iron hydroxide layer on foam copper surface, the nickel iron hydroxide layer Material be nickel iron hydroxide, the molecular formula of the nickel iron hydroxide is NixFeyO4, x span is 0<x<4, y Span is 0<y<8/3,2x+3y=8；The content of ferro element is continuous upwards along foam copper substrate in the iron-doped nickel oxide layer Increase, the content of nickel element is constantly reduced.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (14)

1. a kind of three-dimensional gradient metal hydroxides/oxide electrode material, the three-dimensional gradient metal hydroxides/oxide Electrode material includes conductive substrates and metal compound layer, and the metal compound layer is located at or be formed at the conductive substrates Surface；The material that the metal compound layer is used is the hydroxide or oxide of metal, the hydroxide of the metal Or oxide is three-dimensional, the network structure of nanometer dendritic morphology framework, the nanometer dendritic morphology includes nano wire, received Rice bar, nano-pillar, nanometer blocks, nanometer taper, hollow nanometer tubular or nanometer sheet, the metal are transition metal, the transition Metal is Me and M, wherein, the one kind of the Me and M in Mn, Fe, Co, Ni, Cu and Zn, and Me is different with M； The metal compound layer is to each tenor in conductive substrates direction：Transition metal M e concentration gradients reduction, M content ladder Degree rise；Three-dimensional gradient metal hydroxides/the oxide electrode material is made by way of electro-deposition, the electro-deposition Mode use galvanostatic method or potentiostatic method, using the solution of many parts of water-soluble metal salts in concentration-graded for be electrolysed Liquid, successively in conductive substrates electro-deposition for a period of time, obtains three-dimensional gradient metal hydroxides/oxide electrode material.
2. three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 1, it is characterised in that the gold The molecular formula of the hydroxide of category is MexMy(OH)2, wherein, x span is 0<x<1, y span is 0<y<1, x+ Y=1；Me and M are selected from Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind.
3. three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 1, it is characterised in that the metal Oxide molecular formula be MexMyO4, wherein, M is doped metal ion, and x span is 0<x<4, y span For 0<y<8/3,2x+3y=8；Me and M are selected from Mn2+、Fe3+、Co3+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In one kind.
4. a kind of preparation method of three-dimensional gradient metal hydroxides 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 various concentrations is configured, at least 2 parts water solubilitys in concentration-graded are obtained Metal salt solution；Wherein, the metal is transition metal, in described each part water-soluble metal salting liquid, per metal ion species Molar concentration be raised and lowered portionwise；
(2) take reference electrode and to electrode, three-electrode system is assembled by working electrode of conductive substrates；
(3) galvanostatic method or potentiostatic method are used, the water-soluble metal salting liquid of concentration-graded made from step (1) is taken, presses According to the molar concentration order from high to low or from low to high of a certain metal, the three-electrode system is placed in step portionwise (1) electro-deposition is carried out in the water-soluble metal salting liquid of concentration-graded made from, three-dimensional gradient is obtained after washing, drying Metal hydroxides electrode material, wherein, the three-dimensional gradient metal hydroxides electrode material includes conductive substrates and metal Compound layer, the metal compound layer is located at or is formed at the surface of the conductive substrates；The metal compound layer is adopted Material is metal hydroxides, and the metal hydroxides is three-dimensional, the netted knot of nanometer dendritic morphology framework Structure, the nanometer dendritic morphology includes nano wire, nano strip, nano-pillar, nanometer blocks, nanometer taper, hollow nanometer tubular or received Rice piece, the metallic element in the metal hydroxides is transition metal, and the transition metal is Me and M, wherein, the Me and The one kind of M in Mn, Fe, Co, Ni, Cu and Zn, and Me is different with M；The metal compound layer is to conductive base Each tenor in bottom direction is：Transition metal M e concentration gradients reduction, M concentration gradients rise.
5. the preparation method of three-dimensional gradient metal hydroxides electrode material as claimed in claim 4, it is characterised in that described In step (1), in each part water-soluble metal salting liquid, the metal ion includes Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In At least one.
6. the preparation method of three-dimensional gradient metal hydroxides electrode material as claimed in claim 4, it is characterised in that described In step (1), the metal ion total concentration in every part of water-soluble metal salting liquid is 0.01~5mol/L.
7. the preparation method of three-dimensional gradient metal hydroxides electrode material as claimed in claim 4, it is characterised in that described In step (2), the conductive substrates are selected from nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet and led One kind in electric glass.
8. the preparation method of three-dimensional gradient metal hydroxides electrode material as claimed in claim 4, it is characterised in that described In step (3), the condition of the electro-deposition is：It is each portionwise to deposit 60~600 seconds with 0.5~100mA electric current.
9. a kind of preparation method of three-dimensional gradient metal 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 various concentrations is configured, at least 2 parts water solubilitys in concentration-graded are obtained Metal salt solution；Wherein, the metal is transition metal, in described each part water-soluble metal salting liquid, per metal ion species Molar concentration be raised and lowered portionwise；
(2) take reference electrode and to electrode, three-electrode system is assembled by working electrode of conductive substrates；
(3) galvanostatic method or potentiostatic method are used, the water-soluble metal salting liquid of concentration-graded made from step (1) is taken, presses According to the molar concentration order from high to low or from low to high of a certain metal, the three-electrode system is placed in step portionwise (1) carry out electro-deposition in the water-soluble metal salting liquid of concentration-graded made from, washing, dry after obtain conductive substrates/ Transition metal hydroxide presoma, the conductive substrates/transition metal hydroxide presoma includes conductive substrates and deposition Transition metal hydroxide on conductive substrates surface；
(4) under inert gas shielding, by conductive substrates/transition metal hydroxide presoma made from step (3) 300~ Calcining 1~6 hour is carried out at a temperature of 600 DEG C, three-dimensional gradient metal oxide electrode material is obtained；Wherein, the three-dimensional gradient Metal oxide electrode material includes conductive substrates and metal compound layer, and the metal compound layer is located at or be formed at described The surface of conductive substrates；The material that the metal compound layer is used is metal oxide, and the metal oxide is nanometer Three-dimensional, the network structure of dendritic morphology framework, the nanometer dendritic morphology include nano wire, nano strip, nano-pillar, received Metallic element in rice block, nanometer taper, hollow nanometer tubular or nanometer sheet, the metal oxide is transition metal, described Transition metal is Me and M, wherein, the one kind of the Me and M in Mn, Fe, Co, Ni, Cu and Zn, and Me and M It is different；The metal compound layer is to each tenor in conductive substrates direction：Transition metal M e concentration gradients reduction, M's Concentration gradients are raised.
10. the preparation method of three-dimensional gradient metal oxide electrode material as claimed in claim 9, it is characterised in that described In step (1), in each part water-soluble metal salting liquid, the metal ion includes Mn2+、Fe2+、Co2+、Ni2+、Cu2+And Zn2+In At least one.
11. the preparation method of three-dimensional gradient metal oxide electrode material as claimed in claim 9, it is characterised in that described In step (1), the metal ion total concentration in every part of water-soluble metal salting liquid is 0.01~5mol/L.
12. the preparation method of three-dimensional gradient metal oxide electrode material as claimed in claim 9, it is characterised in that described In step (2), the conductive substrates are selected from nickel foam, foam copper, carbon fiber paper, carbon cloth, stainless steel substrates, titanium sheet, nickel sheet and led One kind in electric glass.
13. the preparation method of three-dimensional gradient metal oxide electrode material as claimed in claim 9, it is characterised in that described In step (3), the condition of the electro-deposition is：It is each portionwise to deposit 60~600 seconds with 0.5~100mA electric current.
14. a kind of three-dimensional gradient metal hydroxides/oxide electrode material as claimed in claim 1 is preparing electrode material With the application in battery.
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