CN105070515A - Foamed nickel composite material, and preparation method and application thereof - Google Patents

Foamed nickel composite material, and preparation method and application thereof Download PDF

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Publication number
CN105070515A
CN105070515A CN201510512798.2A CN201510512798A CN105070515A CN 105070515 A CN105070515 A CN 105070515A CN 201510512798 A CN201510512798 A CN 201510512798A CN 105070515 A CN105070515 A CN 105070515A
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nickel
nickel foam
graphene
foam composite
graphene oxide
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CN201510512798.2A
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Chinese (zh)
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周静红
张梓澜
杨实润
隋志军
钱刚
周兴贵
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华东理工大学
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Abstract

The invention relates to a preparation method of a foamed nickel composite material. The method comprises the following steps that oxidized graphene and a surfactant are added to a water and methanol mixed solution, and ultrasonic processing is carried out to obtain a oxidized graphene solution; nickel nitrate and cobalt chloride are added into the oxidized graphene solution and stirred and mixed to form a uniform suspension; and the uniform suspension is poured into a hydro-thermal reactor kettle, foamed nickel is immersed into the suspension, solvothermal reaction is carried out at 100-200 DEG C, the oxidized graphene is changed to graphene by reduction while nickel and cobalt hydroxide is generated at the surface of the foamed nickel in situ, and thus, the foamed nickel composite material whose surface is covered with a graphene and nickel-cobalt hydrotalcite like layer is obtained. The invention also relates to the obtained foamed nickel composite material and application thereof. The preparation method is simple, easy to control and low in cost, and the obtained foamed nickel composite material which serves as electrode material of a super capacitor has higher specific capacitance and high cycle stability.

Description

A kind of prepare nickel foam composite material method and thus obtained nickel foam composite material and application thereof

Technical field

The present invention relates to a kind of electrochemical material, more specifically, relate to a kind of prepare nickel foam composite material method and thus obtained nickel foam composite material and application thereof.

Background technology

The demand of world today's energy mainly relies on chemical fuel, but chemical fuel is day by day in short supply.People are in the urgent need to novel energy that is efficient, clean, reusable edible.So novel renewable energy research is a focus.But regenerative resource, if the utilization of the regenerative resource such as wind energy, solar energy is by season, the having a strong impact on of meteorology and regional condition, therefore development of new energy storage device is effective one of key issue utilizing regenerative resource.Scientists has successively developed dissimilar electrochemical energy storing device, as lithium ion battery, fuel cell, ultracapacitor etc.

Ultracapacitor is novel energy storage device, has significant advantage: energy density is high, and the discharge and recharge time is short, has extended cycle life.For a capacitor, its core is electrode, and electrode material is the key of the chemical property of determining electrode.Different according to the principle of ultracapacitor storage power, electrode material probably can be divided three classes: material with carbon element (as active carbon, Graphene etc.), metal hydroxides or oxide (as ruthenium-oxide, nickel hydroxide, cobalt hydroxide, nickel oxide, manganese dioxide etc.) and conducting polymer (as polyacetylene, polythiophene etc.).

Graphene, as the special novel material with carbon element of structure, has the advantages such as high-specific surface area, high conductivity, high-mechanical property, can shorten the bang path of ion and electronics.But because strong π-π effect makes it be very easy to reunite between graphene sheet layer, thus reduce specific area and ion diffusion rates, so when Graphene does separately electrode material, ratio capacitance is lower.On the other hand, nickel cobalt houghite is a kind of layered double hydroxide, due to its higher theoretical capacity and cheap cost (compared with noble ruthenium), be very promising electrode material, but its cyclical stability is poor.In ultracapacitor field, exist between Graphene and metal hydroxides composite material and act synergistically, caused and paid close attention to widely.The such as graphenenanosheet/Ni of the preparation such as Gao 2+/ Al 3+lDH ratio capacitance when 1A/g is 781.5F/g (GaoZ, etal.ChemistryofMaterials, 2011,23 (15): 3509-3516.), GO/NiCo-carbonatehydroxide ratio capacitance when 1A/g of the preparation such as Yang is 1398F/g (YangJ, etal.AdvancedFunctionalMaterials, 2015,25 (14): 2109-2116).But the ratio capacitance of the material that said method obtains is still well below theoretical value, cannot reach the requirement of practical application.

Summary of the invention

The present invention aim to provide a kind of prepare nickel foam composite material method and thus obtained nickel foam composite material and application thereof, thus obtain the nickel foam composite material of electrochemical performance.

The invention provides a kind of method preparing nickel foam composite material, comprise the following steps: S1, graphene oxide and surfactant are joined in the mixed solution of water and methyl alcohol and carry out ultrasonicly obtaining graphene oxide aaerosol solution; S2, adds nickel nitrate and cobalt chloride, is uniformly mixed in described graphene oxide aaerosol solution, forms unit for uniform suspension; S3, described unit for uniform suspension is poured in water heating kettle, then nickel foam is immersed in suspension, solvent thermal reaction is carried out at 100-200 DEG C, while graphene oxide is reduced to Graphene, in-situ preparation nickel cobalt hydroxide in the surface of nickel foam, thus obtains the nickel foam composite material of surface coverage Graphene and nickel cobalt houghite layer.Wherein, step S1 above and step S2 is only the mixing of raw material, only formed the nickel foam composite material of surface coverage Graphene and nickel cobalt houghite layer in step s3 by alcohol thermal response one kettle way (one-potconversion), preparation method's simple and effective.

In described step S1, described surfactant is conducive to the formation of the multi-stage artery structure of final nickel foam composite material.Described surfactant is preferably softex kw (CTAB), poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer (P123), neopelex (SDS), kayexalate (PSS), more preferably CTAB and SDS.Wherein, the mass ratio of surfactant and graphene oxide is preferably 3-100, is more preferably 30-50.The mass ratio of methyl alcohol and water is preferably 50-1, is more preferably 25-3.The mass ratio of methyl alcohol and graphene oxide is preferably 500-3000, is more preferably 800-2000.Wherein, if methyl alcohol and graphene oxide mass ratio too little, graphene oxide can not be dispersed in solvent well; If mass ratio is too large, then the quality of unit volume internal oxidition Graphene very little, is unfavorable for compound and the interaction of graphene sheet layer and nickel cobalt hydroxide, the poor-performing of the nickel foam composite material finally obtained.

In described step S2, the mol ratio of described nickel nitrate and cobalt chloride is preferably 0.5-3.0, is more preferably 0.8-2.3.The mass ratio of graphene oxide and nickel nitrate is preferably 0.005-1.300, is more preferably 0.01-0.8.Wherein, the mol ratio of nickel nitrate and cobalt chloride can guarantee the double-metal hydroxide of the hydrotalcite-like compound forming stratiform better.If the mass ratio of graphene oxide and nickel nitrate is too large, then the ratio capacitance of nickel foam composite material can be lower, and if mass ratio is too little, then the cyclical stability of nickel foam composite material is bad.

Nickel foam in described step S3 passes through following pre-treatment before use: get nickel foam and use the ultrasonic process of acetone, hydrochloric acid, deionized water and absolute ethyl alcohol respectively.The concentration of described hydrochloric acid is preferably 0.01-7.00M, is more preferably 3.00-6M.The ultrasonic time of acetone, hydrochloric acid, deionized water, absolute ethyl alcohol is respectively 5-60min, is more preferably 15-30min.Wherein, above-mentioned pre-treatment is organic substance in order to clear up nickel foam surface and oxide, if nickel foam is enough clean, also can not carry out above-mentioned pre-treatment.

In described step S3, the temperature of described solvent thermal reaction is preferably 120-180 DEG C.Reaction time is preferably 9-39h, is more preferably 12-30h.This step also comprises has the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out the step of carrying out washing and drying growth.Wherein, the thermal creep stress of solvent thermal reaction can ensure that methyl alcohol and nitrate ion react and produce hydroxide ion, thus with nickel and cobalt ions generation precipitation reaction, generate the nickel cobalt hydroxide of hydrotalcite-like compound, ensure that graphene oxide is reduced to Graphene simultaneously.

The present invention also provides a kind of nickel foam composite material obtained by said method, and this nickel foam composite material is the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.

Described nickel foam composite material has multi-stage artery structure, there is aperture simultaneously and is less than the micropore of 2nm, aperture between the macropore of the mesoporous of 2-50nm and aperture more than 50nm.

The present invention also provides a kind of application of above-mentioned nickel foam composite material, it is characterized in that, this nickel foam composite material uses as electrode material on the capacitor.By experiment, applicant finds, this nickel foam composite material has excellent chemical property.

Nickel foam composite material provided by the invention, because initial feed graphene oxide has larger specific area and surface is rich in oxygen-containing functional group, be conducive to the nucleation of nickel ion, cobalt ions, and the electric conductivity of Graphene own is relatively good, the resistance of electrode reaction can be reduced, thus improve chemical property.Nickel cobalt houghite is that nickel foam composite material provides excellent fake capacitance.Nickel foam as collector (collecting the part of electric current) directly contacts with electrode material activity material (growing the Graphene in nickel foam and nickel cobalt hydroxide stratiform houghite), reduces electrode resistance.The multilevel hierarchy of the nickel foam composite material formed, is conducive to the transmission of electronics, thus is conducive to promoting chemical property.In addition, do not need in the preparation process of electrode extra to add conductive agent and adhesive, environmental protection.In a word, the method route of preparation nickel foam composite material of the present invention is simple, be easy to control, cost is low, be conducive to large-scale production, and the nickel foam composite material provided have larger ratio capacitance and excellent cyclical stability as electrode material for super capacitor.

Accompanying drawing explanation

Fig. 1 a is the scanning electron microscopy of independent nickel foam;

Fig. 1 b is the scanning electron microscopy of the nickel foam composite material that embodiment 1 obtains;

Fig. 2 a is the transmission electron microscope picture of the nickel foam composite material that embodiment 1 obtains;

Fig. 2 b is the partial enlarged drawing of Fig. 2 a;

Fig. 3 is the single electrode ratio capacitance comparison diagram of obtained by embodiment 1, reference examples 1, reference examples 2, reference examples 3, reference examples 4 respectively nickel foam composite material, Graphene, nickel cobalt houghite, separately nickel hydroxide, separately cobalt hydroxide;

Fig. 4 is the unipolar cycle performance figure of the obtained nickel foam composite material of embodiment 1 as electrode material.

Embodiment

In this article, hydrotalcite refers to the magnalium basic carbonate root salt with layer structure, and common molecular formula is Mg 6al 2cO 3(OH) 164 (H 2o).

Houghite refers to structure and follows the compound like hydrotalcite with layer structure.

Layered double hydroxide (layereddoublehydroxides, LDHs) is the general designation of hydrotalcite and hydrotalcite-like materials, its chemical composition can be expressed as [M II 1-xm III x(OH) 2] x+(A n-) x/nmH 2o, wherein M II is Mg 2+, Ni 2+, Co 2+, Zn 2+, Cu 2+deng divalent metal; M III is Al 3+, Cr 3+, Fe 3+, Sc 3+deng trivalent metal cation; A n-for anion, as CO 3 2-, NO 3-, Cl -, OH -, SO 4 2-, PO 4 3-, C 6h 4(COO) 2 2-etc. inorganic and organic ion and complex ion.

Nickel cobalt hydroxide stratiform houghite is the mixture be made up of two kinds of metal hydroxidess, also containing intercalating ions such as certain hydroxyl/bromide ions in its composition.

Below in conjunction with accompanying drawing, provide preferred embodiment of the present invention, and be described in detail.

The preparation of embodiment 1 nickel foam composite material

(1) 0.01g graphene oxide GO and 10g surfactant sodium dodecyl base benzene sulfonic acid sodium salt are dissolved in the mixed solution of 150g methyl alcohol and 3g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) 0.81mol nickel nitrate and 0.27mol cobalt chloride are dissolved in above-mentioned graphene oxide suspension, stir 20min, obtain unit for uniform suspension.

(3) nickel foam of 1cm × 1cm is used respectively acetone, 0.01M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 5min respectively.

(4) unit for uniform suspension described in (2) is poured in water heating kettle, then nickel foam is immersed in suspension, at 100 DEG C, react 12h.Have the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out growth after reaction terminates, washing, drying, obtain the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

The nickel foam scanning electron microscope (SEM) photograph used in the present embodiment is as Fig. 1 a, the scanning electron microscope (SEM) photograph of the nickel foam composite material of gained as shown in Figure 1 b, nickel foam composite material is thick by tens nanometer and nanometer sheet that is micron order size is that petal has been assembled into flower-like structure, diameter is that the flower-shaped nickel foam compound material ball of several microns is evenly distributed on the nickel foam skeleton of porous, therefore, this nickel foam composite material has multi-stage artery structure.Multi-stage artery structure herein refers to that there is aperture is less than the micropore of 2nm, aperture between the macropore of the mesoporous of 2-50nm and aperture more than 50nm simultaneously.As shown in Figure 2 a and 2 b, nickel cobalt houghite is evenly dispersed in the surface of Graphene to the transmission electron microscope picture of the nickel foam composite material of gained, and can be clear that the interface between nickel cobalt houghite, and this illustrates that combination is between the two more firm.

The preparation of embodiment 2 nickel foam composite material

(1) 0.05g graphene oxide and 0.15g ten sodium hisbenzene sulfonate are dissolved in the mixed solution of 75g methyl alcohol and 3g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) 0.63mol nickel nitrate and 0.27mol cobalt chloride are dissolved in above-mentioned graphene oxide suspension, stir 20min, obtain unit for uniform suspension.

(3) nickel foam of 1cm × 1cm is used respectively acetone, 6M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 30min respectively.

(4) unit for uniform suspension described in (2) is poured in water heating kettle, then nickel foam is immersed in suspension, at 200 DEG C, react 43h.Have the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out growth after reaction terminates, washing, drying, obtain the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

The preparation of embodiment 3 nickel foam composite material

(1) 0.05g graphene oxide and 1.5g neopelex are dissolved in the mixed solution of 60g methyl alcohol and 20g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) 0.39375mol nickel nitrate and 0.7875mol cobalt chloride are dissolved in above-mentioned graphene oxide suspension, stir 20min, obtain unit for uniform suspension.

(3) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 30min respectively.

(4) unit for uniform suspension described in (2) is poured in water heating kettle, then nickel foam is immersed in suspension, at 180 DEG C, react 30h.Have the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out growth after reaction terminates, washing, drying, obtain the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

The preparation of embodiment 4 nickel foam composite material

(1) 0.05g graphene oxide and 1.5gP123 are dissolved in the mixed solution of 60g methyl alcohol and 20g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) 0.63mol nickel nitrate and 0.7875mol cobalt chloride are dissolved in above-mentioned graphene oxide suspension, stir 20min, obtain unit for uniform suspension.

(3) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 15min respectively.

(4) unit for uniform suspension described in (2) is poured in water heating kettle, then nickel foam is immersed in suspension, at 100 DEG C, react 9h.Have the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out growth after reaction terminates, washing, drying, obtain the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

The preparation of embodiment 5 nickel foam composite material

(1) 0.05gGO and 1.5gP123 is dissolved in the mixed solution of 60g methyl alcohol and 20g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) 0.63mol nickel nitrate and 0.42mol cobalt chloride are dissolved in above-mentioned graphene oxide suspension, stir 20min, obtain unit for uniform suspension.

(3) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 30min respectively.

(4) unit for uniform suspension described in (2) is poured in water heating kettle, then nickel foam is immersed in suspension, at 120 DEG C, react 24h.Have the nickel foam of Graphene and nickel cobalt hydroxide stratiform houghite to take out growth after reaction terminates, washing, drying, obtain the nickel foam composite material that growth in situ has Graphene and nickel cobalt houghite layer.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

Reference examples 1, Graphene/nickel foam

(1) 0.03gGO and 1gCTAB is dissolved in the mixed solution of 24g methyl alcohol and 6g water, the uniform graphene oxide suspension of ultrasonic formation.

(2) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 15min respectively.

(3) nickel foam of the suspension of (1) gained and (2) gained is poured in 100ml water heating kettle 150 DEG C of reaction 12h.After reactant absolute ethyl alcohol and water washing, vacuumize, obtains Graphene/nickel foam.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

Reference examples 2, nickel cobalt houghite/nickel foam

(1) 0.63mol nickel nitrate and 0.42mol cobalt chloride are dissolved in the mixed solution of 24g methyl alcohol and 6g water, stir 20min, obtain homogeneous solution.

(2) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 15min respectively.

(3) nickel foam of the solution of (1) gained and (2) gained is poured in 100ml water heating kettle 150 DEG C of reaction 12h.After reactant absolute ethyl alcohol and water washing, vacuumize, obtains nickel cobalt houghite/nickel foam.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

Reference examples 3, nickel hydroxide/nickel foam

(1) 0.63mol nickel nitrate is dissolved in the mixed solution of 24g methyl alcohol and 6g water, stirs 20min.

(2) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 15min respectively.

(3) nickel foam of the solution of (1) gained and (2) gained is poured in 100ml water heating kettle 150 DEG C of reaction 12h.After reactant absolute ethyl alcohol and water washing, vacuumize, obtains nickel hydroxide/nickel foam.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

Reference examples 4, cobalt hydroxide/nickel foam

(1) 0.42mol cobalt chloride is dissolved in the mixed solution of 24g methyl alcohol and 6g water, stirs 20min.

(2) nickel foam of 1cm × 1cm is used respectively acetone, 3M hydrochloric acid, deionized water and absolute ethyl alcohol ultrasonic 15min respectively.

(3) nickel foam of the solution of (1) gained and (2) gained is poured in 100ml water heating kettle 150 DEG C of reaction 12h.After reactant absolute ethyl alcohol and water washing, vacuumize, obtains cobalt hydroxide/nickel foam.This nickel foam composite material directly can be used as work electrode, carries out electro-chemical test.

Application examples

Product prepared by embodiment 1-5 and reference examples 1-4 is directly used as work electrode.Capacity measurement adopts three-electrode system, and active material is work electrode, Pt electrode as to electrode, Hg-Hg 2cl 2electrode, as reference electrode, carries out constant current charge-discharge test in 6MKOH solution, after calculating to electrode ratio capacitance, the results are shown in Table 1.

Table 1

The nickel foam composite material of growth in situ Graphene of the present invention and nickel cobalt houghite layer has higher ratio capacitance and good cyclical stability as shown in Table 1, and the combination of Graphene and nickel cobalt houghite and this three of nickel foam has given full play to respective advantage.

Fig. 3 gives the ratio capacitance comparison diagram of embodiment 1 nickel foam composite material, Graphene/nickel foam, nickel cobalt houghite/nickel foam, nickel hydroxide/nickel foam, cobalt hydroxide/nickel foam.Therefrom can find out, the ratio capacitance of nickel foam composite material of the present invention, apparently higher than other several control sample, illustrates that their compound can improve the performance of material.

Fig. 4 is the unipolar cycle performance figure of nickel foam composite material according to the present invention as electrode material, it can thus be appreciated that nickel foam composite material provided by the present invention has excellent cyclical stability.

In sum, growth in situ of the present invention has the nickel foam composite material of Graphene and nickel cobalt houghite layer to have multi-stage artery structure and excellent chemical property.And last handling process is simple, can large-scale application in follow-up commercial Application and industrial amplification process.

Above-described, be only preferred embodiment of the present invention, and be not used to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Namely every claims according to the present patent application and description are done simple, equivalence change and modify, and all fall into the claims of patent of the present invention.The not detailed description of the present invention be routine techniques content.

Claims (10)

1. prepare a method for nickel foam composite material, comprise the following steps:
S1, joins graphene oxide and surfactant in the mixed solution of water and methyl alcohol and carries out ultrasonicly obtaining graphene oxide aaerosol solution;
S2, adds nickel nitrate and cobalt chloride, is uniformly mixed in described graphene oxide aaerosol solution, forms unit for uniform suspension;
S3, described unit for uniform suspension is poured in water heating kettle, then nickel foam is immersed in suspension, solvent thermal reaction is carried out at 100-200 DEG C, while graphene oxide is reduced to Graphene, in-situ preparation nickel cobalt hydroxide in the surface of nickel foam, thus obtains the nickel foam composite material of surface coverage Graphene and nickel cobalt houghite layer.
2. method according to claim 1, it is characterized in that, in described step S1, described surfactant is selected from: softex kw, poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer, neopelex, kayexalate.
3. method according to claim 2, is characterized in that, in described step S1, the mass ratio of described surfactant and graphene oxide is 3-100; The mass ratio of methyl alcohol and water is 50-1; The mass ratio of methyl alcohol and graphene oxide is 500-3000.
4. method according to claim 1, is characterized in that, in described step S2, the mol ratio of described nickel nitrate and cobalt chloride is 0.5-3.0; The mass ratio of graphene oxide and nickel nitrate is 0.005-1.300.
5. method according to claim 1, is characterized in that, the nickel foam in described step S3 passes through following pre-treatment before use: get nickel foam and use the ultrasonic process of acetone, hydrochloric acid, deionized water and absolute ethyl alcohol respectively.
6. method according to claim 5, is characterized in that, the concentration of described hydrochloric acid is 0.01-7.00M; The ultrasonic time of acetone, hydrochloric acid, deionized water, absolute ethyl alcohol is respectively 5-60min.
7. method according to claim 1, is characterized in that, in described step S3, the temperature of described solvent thermal reaction is 120-180 DEG C, and the reaction time is 9-39h.
8. the nickel foam composite material that the method any one of claim 1-7 described in claim obtains, is characterized in that, this nickel foam composite material is the nickel foam composite material that growth has Graphene and nickel cobalt houghite layer.
9. nickel foam composite material according to claim 8, is characterized in that, described nickel foam composite material has multi-stage artery structure, there is aperture simultaneously and is less than the micropore of 2nm, aperture between the macropore of the mesoporous of 2-50nm and aperture more than 50nm.
10. an application for nickel foam composite material according to claim 8 or claim 9, it is characterized in that, this nickel foam composite material uses as electrode material on the capacitor.
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CN105632781A (en) * 2016-03-03 2016-06-01 哈尔滨工程大学 Preparation method of super capacitor electrode material containing cadmium sulfide
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CN105895383A (en) * 2016-04-11 2016-08-24 中国工程物理研究院材料研究所 Supercapacitor-used alloy/amorphous nickel cobalt hydroxide composite electrode and preparation method thereof
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CN106865627A (en) * 2017-02-28 2017-06-20 四川理工学院 Ultra-thin Ni Co layer structure hydroxide and its preparation method and application
CN106865627B (en) * 2017-02-28 2018-12-07 四川理工学院 Ultra-thin Ni-Co layer structure hydroxide and its preparation method and application
CN106876150A (en) * 2017-03-10 2017-06-20 上海应用技术大学 A kind of porous C oAl bimetallic oxides two dimension hierarchical structure electrode material and preparation method thereof
CN106876695A (en) * 2017-03-10 2017-06-20 上海应用技术大学 A kind of spherical Co (OH)2Combination electrode material and preparation method thereof
CN106876695B (en) * 2017-03-10 2019-12-03 上海应用技术大学 A kind of spherical Co (OH)2Combination electrode material and preparation method thereof
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