CN103972485B - A kind of porous metals combination electrode material and preparation method thereof - Google Patents
A kind of porous metals combination electrode material and preparation method thereof Download PDFInfo
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- CN103972485B CN103972485B CN201410232302.1A CN201410232302A CN103972485B CN 103972485 B CN103972485 B CN 103972485B CN 201410232302 A CN201410232302 A CN 201410232302A CN 103972485 B CN103972485 B CN 103972485B
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
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Abstract
The invention provides a kind of porous metals combination electrode material, be covered with the complex being made up of CNT and nickel fiber in three-dimensional netted porous metal material surface.The preparation method of above-mentioned material, processes obtain porous metals combination electrode material using making surface treatment surface cold spraying complex high temperature reduction as the porous metal material of substrate, and described cold spraying complex is CNT and nickel fiber.The porous metals combination electrode material of the present invention has higher specific surface area, is conducive to promoting the loading of electrode active material, can be effectively improved battery capacity, shortens the charging interval of battery.
Description
Technical field
The present invention relates to a kind of porous metals combination electrode material and preparation method thereof.
Background technology
Along with being on the rise of global energy crisis and earth environment deterioration problem, people increasingly pay attention to the use of new forms of energy, and wherein chemical energy storage is one of current most widely used general, the most ripe technology.Current new chemical energy storage components and parts are mainly all types of electrochmical power sources and physics electrical storage device part etc..The positive electrode material making electrochmical power source mainly uses foam porous metal material as carrier, but porous metal material is confined to the development of technology, cannot effectively meet the inherent character such as high-specific surface area, high conduction resistance, therefore seriously limit the development of electrochmical power source.
Summary of the invention
It is desirable to provide a kind of, there is high specific surface area, the porous composite electrode material that can improve battery capacity, raising battery charge efficiency and preparation method thereof.
The present invention is realized by below scheme:
A kind of porous metals combination electrode material, is being covered with the complex being made up of CNT and nickel fiber in three-dimensional netted porous metal material surface, and wherein CNT is (0.5 ~ 1) with the mass ratio of nickel fiber: (0.05 ~ 0.1).
Experiment finds, the thickness of CNT and nickel fiber composite layer is 5 ~ 10 μm, and the caliber of CNT is 50 ~ 100nm, and length is 1 ~ 10 μm；The diameter of nickel fiber is 1 ~ 10 μm, and during length 100 ~ 500 μm, material property is more excellent.
The preparation method of above-mentioned porous metals combination electrode material, sequentially includes the following steps:
(1) surface treatment: process 1 ~ 5h using being placed in as the porous metal material of substrate to have in reducing atmosphere and reduction furnace that temperature is 700 ~ 1000 DEG C.Porous metal material as substrate can adopt percent opening to be 80 ~ 98%, and thickness is 0.5 ~ 1.0mm, and average pore size is the existing porous metal materials such as nickel foam, the foam copper of 100 ~ 500 μm.
(2) surface cold spraying complex: be in mass ratio (0.5 ~ 1): (0.05 ~ 0.1) is by CNT and nickel fiber mixing, then adopting cold spray process to be sprayed into by mixed-powder on the porous metal material surface of substrate and form one layer of complex, keeping surface cold spraying composite layer thickness is 5 ~ 10 μm.In complex, the caliber of CNT is 50 ~ 100nm, and length is 1 ~ 10 μm；In complex, the diameter of nickel fiber is 1 ~ 10 μm, length 100 ~ 500 μm.
(3) high temperature reduction processes: is placed in by the material through step (2) and has in reducing atmosphere and reduction furnace that temperature is 300 ~ 500 DEG C and process 3 ~ 5h, obtain porous metals combination electrode material.
Compared with prior art, advantages of the present invention is embodied in:
1. the porous metals combination electrode material of the present invention, the complex having carried one layer of CNT with nickel fiber is covered on porous metal material surface, its specific surface area is higher by more than 45% than conventional electrode materials, electric conductivity is better, material of the present invention is used to prepare the electrochmical power source such as ultracapacitor or Ni-MH power cell, can completing charging process within a short period of time, improve charge efficiency, capacitance can promote more than 20% simultaneously.
2. the present invention adopts cold spray process to make the firm binding force of compound porous metal material, matrix material and composite coating material, and technique is simpler.
Detailed description of the invention
Embodiment 1
The foam nickel material that to adopt percent opening be 80%, thickness is 0.5mm, average pore size is 100 μm is base material, is prepared according to the following steps:
(1) surface treatment: foam nickel material is placed in and has in hydrogen atmosphere and reduction furnace that temperature is 700 DEG C and process 5h, the oxide-film on the nickel material surface that defoams.
(2) surface cold spraying complex: first by caliber to be 50nm, length be CNT and the diameter of 1 μm be 1 μm, length be that the nickel fiber of 100 μm mixes for 0.5:0.05 in mass ratio, then adopting cold spray process to be sprayed into by mixed-powder on foam nickel material surface and form one layer of complex, cold spraying composite layer thickness in surface is 5 μm.
(3) high temperature reduction processes: is placed in by the material through step (2) and has in hydrogen reducing atmosphere and reduction furnace that temperature is 300 DEG C and process 5h, obtain nickel porous combination electrode material.
Embodiment 2
The nickel porous combination electrode material that embodiment 1 method prepares, by detecting, CNT and the composite thickness of nickel fiber composition that nickel porous combination electrode material surface is covered with are 5 μm；CNT caliber is 50nm, length is 1 μm, and the diameter of nickel fiber is 1 μm, length is 100 μm.
Nickel porous combination electrode material embodiment 1 method prepared carries out comparison and detection with conventional foam nickel material, and its testing result is in shown in Table one.Testing result contrast from table one is found out, its specific surface area of nickel porous combination electrode material of the present invention is higher by 87.5% than conventional nickel foam.
The performance comparison testing result of table one different materials
By same process, the nickel porous combination electrode material of the present invention being made Ni-H 2 power SC3000 battery with conventional foam nickel material, uses 5C discharge and recharge to be circulated life span comparison's detection, its testing result is in shown in Table two.Testing result contrast from table one is found out, uses its 5C charge and discharge circulation life number of times of battery that the nickel porous combination electrode material of the present invention is made higher by 66.7% than the battery using usual foam nickel material to make.
The battery performance comparison and detection result that table two different materials is made
Embodiment 3
The foam nickel material that to adopt percent opening be 90%, thickness is 0.8mm, average pore size is 300 μm is base material, is prepared according to the following steps:
(1) surface treatment: foam nickel material is placed in and has in hydrogen reducing atmosphere and reduction furnace that temperature is 800 DEG C and process 3h, the oxide-film on the nickel material surface that defoams.
(2) surface cold spraying complex: first by caliber to be 80nm, length be CNT and the diameter of 5 μm be 5 μm, length be that the nickel fiber of 70 μm mixes for 0.8:0.08 in mass ratio, then adopting cold spray process to be sprayed into by composite powder on foam nickel material surface and form one layer of complex, cold spraying composite layer thickness in surface is 8 μm.
(3) high temperature reduction processes: is placed in by the material through step (2) in the reducing atmosphere comprising ammonolysis craft gas and reduction furnace that temperature is 400 DEG C and processes 4h, obtains nickel porous combination electrode material.
Preparing nickel porous combination electrode material as stated above, its surface is covered with after testing CNT and the composite thickness of nickel fiber composition are 8 μm；CNT caliber is 80nm, length is 5 μm；Nickel fibre diameter is 5 μm, length is 70 μm.
Embodiment 4
The foam nickel material that to adopt percent opening be 98%, thickness is 1.0mm, average pore size is 500 μm is base material, is prepared according to the following steps:
(1) surface treatment: foam nickel material is placed in the reducing atmosphere including decomposed ammonia and reduction furnace that temperature is 1000 DEG C and processes 2h, the oxide-film on the nickel material surface that defoams.
(2) surface cold spraying complex: first by caliber to be 100nm, length be CNT and the diameter of 10 μm be 10 μm, length be that the nickel fiber of 100 μm mixes for 1.0:0.1 in mass ratio, then adopting cold spray process to be sprayed into by composite powder on foam nickel material surface and form one layer of complex, cold spraying composite layer thickness in surface is 10 μm.
(3) high temperature reduction processes: is placed in by the material through step (2) and has in hydrogen reducing atmosphere and reduction furnace that temperature is 500 DEG C and process 3h, obtain nickel porous combination electrode material.
Preparing nickel porous combination electrode material as stated above, its surface is covered with after testing CNT and the composite thickness of nickel fiber composition are 10 μm；CNT caliber is 100nm, length is 10 μm；Nickel fibre diameter is 10 μm, length is 100 μm.
Claims (7)
1. a porous metals combination electrode material, it is characterised in that: be covered with the complex being made up of CNT and nickel fiber in three-dimensional netted porous metal material surface, wherein CNT is 0.5～1:0.05～0.1 with the mass ratio of nickel fiber.
2. a kind of porous metals combination electrode material as claimed in claim 1, it is characterised in that: the composite thickness of described CNT and nickel fiber composition is 5～10 μm.
3. a kind of porous metals combination electrode material as claimed in claim 1 or 2, it is characterised in that: it is 50～100nm that the caliber of CNT in load complex is covered on described surface, and length is 1～10 μm；The diameter of nickel fiber is 1～10 μm, and length is 100～500 μm.
4. the method for the porous metals combination electrode material that a kind is prepared as described in one of claims 1 to 3, it is characterized in that: comprise the following steps, porous metal material surface treatment surface cold spraying complex high temperature reduction processes, and the complex of surface cold spraying is the complex of CNT and nickel fiber and the mass ratio of CNT and nickel fiber is 0.5～1:0.05～0.1.
5. a kind of method preparing porous metals combination electrode material as claimed in claim 4, it is characterised in that: the thickness controlling described surface cold spraying composite layer is 5～10 μm.
6. a kind of method preparing porous metals combination electrode material as claimed in claim 5, it is characterised in that: in described surface cold spraying complex, the caliber of CNT is 50～100nm, and length is 1～10 μm；The nickel fibre diameter of described complex is 1～10 μm, and length is 100～500 μm.
7. a kind of method preparing porous metals combination electrode material as described in as arbitrary in claim 4～6, it is characterised in that: described surface treatment step is process 1～5h in having reducing atmosphere and reduction furnace that temperature is 700～1000 DEG C；Described reduction treatment step is process 3～5h in having reducing atmosphere and reduction furnace that temperature is 300～500 DEG C.
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| CN114229966B (en) * | 2021-12-17 | 2023-10-13 | 东北电力大学 | Nickel/hydroxylation multiwall carbon nanotube/titanium composite electrode and preparation method and application thereof |
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