CN110379647A - A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material - Google Patents
A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material Download PDFInfo
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
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- H—ELECTRICITY
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- 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
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Abstract
A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material.This method is using Ni-Zr-Ti alloy as presoma, by impregnating and being heat-treated in HF solution, three-electrode system is reused in one layer of ultra-thin cobalt hydroxide nanometer sheet of above-mentioned strip face electro-deposition, nanoporous nickel nickel is obtained and loads ultra-thin cobalt hydroxide nanometer sheet flexible electrode material.The present invention has the advantages that simple, safe, inexpensive, the electrode of super capacitor material adhesive-free and collector of preparation, with large specific surface area and preferable chemical property, overcomes and currently prepare the defects of nanoporous nickel, cobalt electrode material technology process are complicated, consuming time is long, with high costs.
Description
Technical field:
The invention belongs to electrode material for super capacitor preparation field, relate generally on nanoporous nickel nickel surface
Load the preparation of ultra-thin cobalt hydroxide nanometer sheet electrode material.
Background technique:
Global warming and the exhaustion of fossil fuel have become the environmental problem that the 21 century mankind have to face.With people
Improvement of living standard, mobile phone, removable computer, new-energy automobile have become a part indispensable in daily life.
The normal use of these products be unable to do without energy storage device, but current energy storage device specific capacitance is small, charge/discharge speed is slow, energy
The disadvantages of metric density is small seriously affects the routine use experience of these products.Compared with traditional capacitor, supercapacitor
Because the good characteristic that its is safe and environment-friendly, charge/discharge speed is fast, power density and energy density are high receives numerous researchers'
Concern.
A key factor for influencing supercapacitor chemical property is exactly electrode material.Electrode material for super capacitor
It is broadly divided into three classes, respectively metal oxide, conducting polymer and various absorbent charcoal materials.It is living compared with other materials
The high-specific surface area of property Carbon Materials is the big characteristic of one, but excessively high specific surface area also means that the increase of micropore, and micro-
Increasing for hole hinders the electronics conduction of Carbon Materials itself.Therefore, although the specific surface area of Carbon Materials is high, its utilization rate is not
It is high.Compared with carbon material, the cost of conducting polymer materials is cheaper, and can reduce the equivalent resistance of electrode.But by
In lacking effective N doping, the cell voltage of conducting polymer can not be high as the voltage of carbon-based battery, and long-term
Polymer can cause its cyclical stability poor because volume expansion and contraction are degraded in cyclic process.Ni and Co conduct
It its oxide of transition metal and hydroxide rich reserves, cheap and theoretical specific capacitance with higher and preferably follows
Ring stability is considered as the novel energy-storing electrode material for most having application prospect.
However, the nano nickel and cobalt electrode material that prepare at present are also far from meeting routine use requirement.On the one hand, powder
The oxide or hydroxide of shape Ni and Co are easy to happen the transmission reunited and hindered between ion, and need mixed with bonding agent
Load its capacitance characteristic of competence exertion on a current collector is closed, and the introducing of bonding agent and collector will necessarily cause in electron-transport
The increase of resistance causes the utilization rate of active material to reduce;On the other hand, the flexibility of electrode and its electricity under differently curved angle
The stability of chemical property is also to influence a key factor of its application.Therefore, it develops a kind of with greater activity substance benefit
With rate, can self-supporting flexible wearable electrode material be researcher instantly priority research areas.
First technology, a kind of publication number CN109686581A " cobalt hydroxide/rGO/ nickel hydroxide sandwich-like flexible electrode
Material and preparation method thereof ", in the patent, using the carbon cloth of ultrasonic treatment as substrate, hydro-thermal process 3 after dry 12~48h
~9h deposits one layer of nickel hydroxide on carbon cloth, and the method that electro-deposition is reused after dry deposits one layer of rGO on its surface, so
To be deposited with the carbon cloth of rGO/ nickel hydroxide, as substrate, 6~15h of hydro-thermal process deposits one layer of cobalt hydroxide again afterwards, obtains hydrogen-oxygen
Change cobalt/rGO/ nickel hydroxide sandwich-like flexible electrode material.The preparation process flow is complicated, total period is long and efficiency is extremely low,
Equipment and experimental situation are required strictly, to be not easy to realize the controllable preparation of electrode material and large scale preparation.
First technology, publication number CN106710889A " a kind of multilevel structure cobalt hydroxide electrode material and its preparation side
Cobalt nitrate, aluminum nitrate, urea and deionized water in the patent, are mixed hydro-thermal reaction 12~for 24 hours by method ", after reaction from
The heart, washing and 24~48h of freeze-drying can obtain cobalt aluminium hydroxide, and the cobalt aluminium hydroxide of preparation is dissolved in deionized water
In and be added sodium hydroxide or potassium hydroxide solution etching aluminium hydroxide can obtain multistage cobalt hydroxide electrode material.It is first
First, it is difficult to control using the extent of reaction of alkaline solution etching aluminium hydroxide.Secondly, the active material of this method preparation needs to bear
It is loaded in its capacitance characteristic of the online competence exertion of Pt, the introducing of the collectors such as one side Pt net will necessarily cause electron-transport internal resistance
Increase, reduces the utilization rate of active material;On the other hand, which easily snaps off and chemical property under wide-angle bending
It is easy to be affected.
Summary of the invention:
It is an object of the present invention to provide a kind of nanoporous nickel nickel load for deficiency present in current techniques
The preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material.This method using Ni-Zr-Ti alloy as presoma, by
It impregnates and is heat-treated in HF solution, reuse three-electrode system in one layer of ultra-thin cobalt hydroxide nanometer of above-mentioned strip face electro-deposition
Piece obtains nanoporous nickel nickel and loads ultra-thin cobalt hydroxide nanometer sheet flexible electrode material.The present invention has simple, peace
Entirely, inexpensive advantage, the electrode of super capacitor material adhesive-free and collector of preparation, with large specific surface area and preferably
Chemical property overcomes and currently prepares that nanoporous nickel, cobalt electrode material technology process are complicated, consuming time is long, at high cost
The defects of high.
The technical solution of the present invention is as follows:
A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material, should
Method the following steps are included:
The first step prepares nanoporous nickel nickel template
Using alloying technology is taken off naturally, using the alloy amorphous band of Ni-Zr-Ti as presoma, by it in 0.03~0.08M
Nanoporous nickel is made in 2~6h of immersion corrosion in HF solution;Strip face is rinsed after etching, and is then placed in tube furnace,
It is heat-treated 2~4h at 250~450 DEG C, oxygen is during which continually fed into the rate of 200~400mL/min, nanoporous is made
Nickel nickel template;
Second step, the preparation of cobalt hydroxide nanometer sheet
Under three-electrode system, working electrode is the nanoporous nickel nickel template prepared in the first step, is to electrode
Metal platinized platinum, reference electrode are Ag/AgCl electrode;The nanoporous nickel nickel template prepared in the first step is set to be placed in cobalt source
In solution, one layer of electro-deposition ultra-thin cobalt hydroxide nanometer sheet, i.e. nanoporous nickel nickel load ultra-thin cobalt hydroxide nanometer sheet
Flexible electrode material;
Wherein, sedimentation potential is -1.5~-1.0V, and sedimentation time is 10~60min;The cobalt source solution is to contain six
The mixed solution of nitric hydrate cobalt and urea, molar ratio are cabaltous nitrate hexahydrate: urea=5:1~10:1;In cobalt source solution, six
The molar concentration of nitric hydrate cobalt is 3~8mM.
The Ni-Zr-Ti alloy is preferably Ni40Zr20Ti40。
The amorphous ribbon is preferably dimensioned to be 1cm × 1mm × 20 μm~5cm × 3mm × 30 μm.
Above-mentioned nanoporous nickel nickel loads to be set used in the preparation of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material
Standby and raw material pass through known approach and obtain, and preparation method is simple, is easily mastered.
Compared with prior art, substantive distinguishing features outstanding of the invention are as follows:
(1) nanoporous nickel nickel template prepared by the present invention is ribbon, directly in nanoporous nickel nickel
Electro-deposition can not only remove nickel foam from template or self-supporting, but also the presence of nickel oxide underlayer are realized in the introducing of active carbon cloth
Additional specific capacitance is imparted for the electrode material.
(2) nanoporous nickel nickel template prepared by the present invention has high porosity, and hydroxide both may be implemented
Cobalt nanometer sheet and matrix are combined closely, and cobalt hydroxide nanometer sheet can effectively be avoided to reunite in deposition.
Compared with prior art, the present invention has following income effect:
(1) do not have also at present and prepare electrode in its surface electro-deposition cobalt hydroxide using nanoporous nickel nickel as template
The relevant report of material.With Ni40Zr20Ti40Amorphous ribbon is presoma, and middle layer remains as amorphous state, Ke Yiwei after de- alloy
Electrode material provides fabulous flexibility.
(2) with Conventional nano is porous, nanometer sheet metal phase ratio, the present invention deposited on nanoporous nickel nickel surface
One layer of super-thin sheet-shaped cobalt hydroxide, there are certain gaps between piece and piece, so that contacting between hole and piece there are also certain, no
The specific surface area for being only conducive to improve electrode material, also helps the transmission of electrolyte intermediate ion, largely improves
The utilization rate of active material.Compared with the chemical property of nanoporous nickel nickel electrode, electro-deposition cobalt hydroxide is ultra-thin to be received
The electrode of rice piece has shown high specific capacitance, this is because not only including the ratio of bottom nickel nickel in total specific capacitance
Capacitor, there are also the specific capacitances of surface layer cobalt hydroxide.It can reach by the regulation source Co concentration and sedimentation time, best specific capacitance
1243.6F/cm3。
(3) electrode material prepared by the present invention not only has fabulous flexibility, also has fabulous electrochemical stability,
Electrode material its chemical property under different bending angle does not fluctuate widely, in flexible wearable electrode material
Field has shown preferable application prospect.
Detailed description of the invention:
Fig. 1: the scanning electron microscope that nanoporous nickel nickel loads ultra-thin cobalt hydroxide nanometer plate electrode in embodiment 1 is shone
Piece.
Fig. 2: nanoporous nickel nickel loads the element power spectrum point of ultra-thin cobalt hydroxide nanometer plate electrode in embodiment 1
Analysis figure.
Fig. 3: nanoporous nickel nickel loads the charging and discharging curve of ultra-thin cobalt hydroxide nanometer plate electrode in embodiment 1
Figure.
Fig. 4: nanoporous nickel nickel/cobalt hydroxide ultrathin nanometer plate electrode constant current charge-discharge curve in embodiment 2
Figure.
Fig. 5: nanoporous nickel nickel/cobalt hydroxide ultrathin nanometer plate electrode charging and discharging curve figure in embodiment 3.
Specific embodiment
Embodiment 1:
The present invention provides a kind of active nano porous nickel/nickel oxide loaded ultra-thin cobalt hydroxide nanometer sheet flexible electrode materials
The preparation method of material, mainly includes the next steps:
S1: selection alloying component is Ni40Zr20Ti40, the amorphous ribbon having a size of 2cm × 1.5mm × 20 μm is as forerunner
Body uses 0.03M HF solution as corrosive liquid, presoma is submerged into corrosive liquid and corrodes 6h, uses deionization after etching
Water rinses the HF solution of strip face remnants, then places it in tube furnace and is heat-treated 2h at 250 DEG C, during which with 200mL/
The rate of min is continually fed into oxygen, and nanoporous nickel nickel template can be made;
S2: using deionized water and alcohol rinse 3~4 times after S1 institute pallet is cooled to room temperature, then using three electricity
Under polar body system, it is dipped in in the mixed solution of the cabaltous nitrate hexahydrate of molar concentration rate 10:1 and urea, wherein six water
The molar concentration for closing cobalt nitrate is 8mM, and one layer of cobalt hydroxide is deposited in nanoporous nickel nickel template.
Wherein, depositing system used is three-electrode system, and using S1 institute's pallet as working electrode, metal platinized platinum is to electricity
Pole, Ag/AgCl electrode are reference electrode, and sedimentation potential is -1.0V, time 10min.
In order to which the electrochemistry to made electrode material can be carried out test, using electrochemical workstation under three-electrode system
Test its constant current charge-discharge curve.The electrode material prepared in S2 is working electrode, and metal platinized platinum is to electrode, Ag/AgCl
Electrode is reference electrode, and electrolyte is 1mol/L KOH solution, and constant current charge-discharge current density is 1A/cm3, voltage window is
0.45V。
Fig. 1 is the scanning electricity that nanoporous nickel nickel loads ultra-thin cobalt hydroxide nanometer plate electrode in the implementation case
Mirror figure, here it is apparent that the uniform sheet cobalt hydroxide that nanoporous nickel nickel surface grows up to uses NanoMeasure
Survey Software measures cobalt hydroxide nanometer sheet thickness and only has 9.63nm, and is uniformly distributed in bottom nickel nickel template, is
The attachment of active material provides bigger specific surface area;Moreover, certain spacing is also maintained between piece and piece, not
Transmission of the electrode process intermediate ion in bottom hole is influenced, so that existing in the specific capacitance of the combination electrode of preparation
The specific capacitance of nickel nickel, and have the specific capacitance of surface layer cobalt hydroxide.
Fig. 2 is the power spectrum point that nanoporous nickel nickel loads ultra-thin cobalt hydroxide nanometer plate electrode in the implementation case
Analysis is schemed, and the peak of metallic nickel and cobalt occurs in figure, shows exist while cobalt and nickel, further true in conjunction with X-ray diffraction detection
Determine nickel nickel/cobalt hydroxide to exist simultaneously.
Fig. 3 is the nanoporous nickel nickel/cobalt hydroxide nanometer sheet constant current charge-discharge song prepared in the implementation case
Line chart is apparent that apparent charging and discharging platform from the curve, opposite with oxidation reaction and reduction reaction respectively
It answers, shows its fake capacitance characteristic.It is calculated at 1A/cm3Specific capacitance is up to 1243.6F/cm under current density3。
Embodiment 2:
S1: selection alloying component is Ni40Zr20Ti40, the amorphous ribbon having a size of 1cm × 1mm × 20 μm as presoma,
Use 0.05M HF solution as corrosive liquid, corrode 4h, the HF for rinsing strip face remnants with deionized water after etching is molten
Then liquid places it in and is heat-treated 3h in tube furnace at 350 DEG C, be during which continually fed into oxygen just with the rate of 300mL/min
Nanoporous nickel nickel template can be made;
S2: deionized water and alcohol rinse 3~4 times are used after S1 institute pallet is cooled to room temperature, are then dipped in
In the solution mixed to cabaltous nitrate hexahydrate and urea with molar concentration rate 8:1, wherein the molar concentration of cabaltous nitrate hexahydrate is
6mM deposits one layer of cobalt hydroxide in nanoporous nickel nickel template.
Wherein, depositing system used is three-electrode system, and using S1 institute's pallet as working electrode, metal platinized platinum is to electricity
Pole, Ag/AgCl electrode are reference electrode, and sedimentation potential is -1.2V, time 30min.
In order to which the electrochemistry to made electrode material can be carried out test, using electrochemical workstation under three-electrode system
Test its constant current charge-discharge curve.The electrode material prepared in S2 is working electrode, and metal platinized platinum is to electrode, Ag/AgCl
Electrode is reference electrode, and electrolyte is 1mol/L KOH solution, and constant current charge-discharge current density is 1A/cm3, voltage window is
0.45V。
Fig. 4 is electrode material constant current charge-discharge curve graph obtained in the implementation case, here it is apparent that almost equal
Charging time and discharge time, show electrode material have fabulous coulombic efficiency.By calculating, in 1A/cm3Electric discharge
Specific capacitance under current density is 1042.3F/g.
Embodiment 3:
S1: selection alloying component is Ni40Zr20Ti40, the amorphous ribbon having a size of 5cm × 3mm × 30 μm as presoma,
Use 0.08M HF solution as corrosive liquid, corrode 2h, the HF for rinsing strip face remnants with deionized water after etching is molten
Liquid, then places it in and is heat-treated 2h in tube furnace at 200 DEG C, be during which continually fed into oxygen can be made nanoporous nickel/
Nickel oxide template;
S2: deionized water and alcohol rinse 3~4 times are used after S1 institute pallet is cooled to room temperature, are then dipped in
In the solution mixed to cabaltous nitrate hexahydrate and urea with concentration ratio 5:1, wherein the molar concentration of cabaltous nitrate hexahydrate is that 3mM exists
One layer of cobalt hydroxide is deposited in nanoporous nickel nickel template.
Wherein, depositing system used is three-electrode system, and using S1 institute's pallet as working electrode, metal platinized platinum is to electricity
Pole, Ag/AgCl electrode are reference electrode, and sedimentation potential is -1.5V, time 60min.
In order to which the electrochemistry to made electrode material can be carried out test, using electrochemical workstation under three-electrode system
Test its constant current charge-discharge curve.The electrode material prepared in S2 is working electrode, and metal platinized platinum is to electrode, Ag/AgCl
Electrode is reference electrode, and electrolyte is 1mol/L KOH solution, and constant current charge-discharge current density is 1A/cm3, voltage window is
0.45V。
Fig. 5 is the charge-discharge performance figure of the electrode material prepared in the implementation case, be can clearly be seen that from the curve
Charge and discharge platform corresponding with fake capacitance characteristic and almost equal charge and discharge time, show the electrode have it is good can
Inverse property.It is further calculated in 1A/cm3Discharge current density under specific capacitance be 972.5F/cm3。
Comparative example 1:
Band after de- alloy is heat-treated 1h at 150 DEG C and oxygen is passed through with the rate of 80mL/min, other steps
It is same as Example 1.Energy spectrum analysis and X-ray diffraction detection are carried out to the electrode material of preparation, wherein the ratio of oxygen atom and cobalt
Example has only detected the crystal peak of cobalt hydroxide and nickel close to 2:1, and in X-ray diffraction spectrogram, illustrates that surface layer has only formed hydrogen
Cobalt oxide, there is no the amount of nickel oxide or nickel oxide is fewer.
Comparative example 2:
Selection cabaltous nitrate hexahydrate solution is electric depositing solution, other steps are same as Example 1, the hydrogen-oxygen prepared
Changing cobalt microscopic appearance is in hexagon, and with a thickness of 3 μm, specific capacitance only has 621.5F/cm3。
Comparative example 3:
Selection sedimentation potential is -0.8V, other steps are identical with case study on implementation 1, and it is microcosmic to observe its after the completion of deposition
Pattern, discovery surface have no apparent nanometer sheet and generate.Survey its chemical property, discovery and nanoporous nickel nickel electrode
It is not much different, further determined and do not deposit one layer of cobalt hydroxide nanometer sheet on nanoporous nickel nickel surface.
Comparative example 4:
Nano-pore nickel nickel surface deposition cobalt hydroxide time extend to 2h, other steps with case study on implementation 1
In it is identical.Band is obviously bent after the completion of deposition, illustrates that internal stress is changed.When testing its flexibility, to item
It has just been crushed with the external force for applying minimum, cannot achieve self-support.
The above comparative example is the case under the failure of an experiment, and arbitrarily change preparation process, which will lead to experimental result, to reach
To expection.Through multiple regulation experiment parameter, stringent control process procedure determines that preparation nanometer is more after the practice work with perseverance
Stringent control heat treatment temperature and time are needed when the nickel nickel template of hole, and need to be continually fed into oxygen.Electro-deposition prepares hydrogen
Cobalt source and urea concentration ratio are controlled when cobalt oxide ultrathin nanometer piece between 10:1~5:1, wherein cabaltous nitrate hexahydrate is dense
Degree is 3~8mM;Sedimentation potential is -1.5~-1.0V, and the time is 1min~60min.When all parameters are within above range
Shi Caineng prepares the nanoporous nickel nickel with high electrochemical performance and loads ultra-thin cobalt hydroxide nanometer sheet flexible electrode
Material.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material, special
Sign be method includes the following steps:
The first step prepares nanoporous nickel nickel template
It is using the alloy amorphous band of Ni-Zr-Ti as presoma, it is molten in 0.03~0.08M HF using alloying technology is taken off naturally
Nanoporous nickel is made in 2~6h of immersion corrosion in liquid;Strip face is rinsed after etching, and is then placed in tube furnace,
It is heat-treated 2~4h at 250~450 DEG C, oxygen is during which continually fed into the rate of 200~400mL/min, nanoporous is made
Nickel nickel template;
Second step, the preparation of cobalt hydroxide nanometer sheet
Under three-electrode system, working electrode is the nanoporous nickel nickel template prepared in the first step, is metal to electrode
Platinized platinum, reference electrode are Ag/AgCl electrode;The nanoporous nickel nickel template prepared in the first step is set to be placed in cobalt source solution
In, it is flexible that one layer of electro-deposition ultra-thin cobalt hydroxide nanometer sheet, i.e. nanoporous nickel nickel load ultra-thin cobalt hydroxide nanometer sheet
Electrode material;
Wherein, sedimentation potential is -1.5~-1.0V, and sedimentation time is 10~60min;The cobalt source solution is containing six hydrations
The mixed solution of cobalt nitrate and urea, molar ratio are cabaltous nitrate hexahydrate: urea=5:1~10:1;In cobalt source solution, six hydrations
The molar concentration of cobalt nitrate is 3~8mM.
2. nanoporous nickel nickel as described in claim 1 loads ultra-thin cobalt hydroxide nanometer sheet flexible electrode material
Preparation method, it is characterized in that the Ni-Zr-Ti alloy is preferably Ni40Zr20Ti40。
3. nanoporous nickel nickel as described in claim 1 loads ultra-thin cobalt hydroxide nanometer sheet flexible electrode material
Preparation method, it is characterized in that the amorphous ribbon is preferably dimensioned to be 1cm × 1mm × 20 μm~5cm × 3mm × 30 μm.
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Cited By (2)
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CN114639805A (en) * | 2022-02-17 | 2022-06-17 | 广东邦普循环科技有限公司 | Preparation method and application of porous-structure nickel phosphide @ carbon negative electrode material |
CN115440510A (en) * | 2022-09-13 | 2022-12-06 | 三峡大学 | Method for improving capacity of cobalt-based hydroxide containing embedded anions |
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