CN104616908B - Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material - Google Patents
Composite material of nickel hydroxide/graphene or graphite and preparation method for composite material Download PDFInfo
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- CN104616908B CN104616908B CN201510045280.2A CN201510045280A CN104616908B CN 104616908 B CN104616908 B CN 104616908B CN 201510045280 A CN201510045280 A CN 201510045280A CN 104616908 B CN104616908 B CN 104616908B
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Abstract
The invention discloses a composite material of nickel hydroxide/graphene or graphite which is structurally Ni(OH)2/graphite or layered Ni(OH)2/graphene composite material alternated with Ni(OH)2 and graphene, wherein the weight content of the nickel hydroxide is 10-90%. The invention further discloses a method for preparing the composite material. The composite material is simple in process, low in cost, environment-friendly and easy for batch production.
Description
Technical field
The present invention relates to the composite of a kind of nickel hydroxide/Graphene or graphite.
The invention further relates to the method for preparing above-mentioned composite.
Background technology
Ultracapacitor has that power density is high, the discharge and recharge time is short, advantages of environment protection, is widely used in storage
Solar energy, wind energy and miniaturized electronics.As the whole world is to environmental requirement more and more higher and the increasingly scarcity of fossil energy, surpass
Level capacitor is considered as the electrical source of power of automobile of future generation.But can not evade, it is big that ultracapacitor is also faced with present two
Challenge：One is that energy density is low, is not enough to support the long distance running of automobile；Two is that price is relatively expensive.This is mainly
Because existing electrode material for super capacitor major part adopts activated carbon, the mode of its storage electric charge is mainly Electrostatic Absorption.
Activated carbon specific surface area is big but poorly conductive, and pore ratio is high；Graphene has big specific surface area and excellent
Electric conductivity, it is considered to be preferably electrode material for super capacitor, but graphene film exists easily to return and builds up graphite and valency
The shortcomings of lattice are expensive.The problems such as conducting polymer composite has easily swelling and stability difference.For pseudo-capacitance oxide or hydrogen-oxygen
Compound electrode material, anodizing ruthenium is good pseudo-capacitance electrode material, but ruthenium is expensive；Cobalt hydroxide has high ratio
Surface area and ion deinsertion speed, but cobalt is poisonous and price is also higher；Manganese oxide has relatively cheap price, low toxicity, environment
The advantages of safety and high theoretical specific capacitance, but the shortcomings of there is low soluble, specific surface area, conductive son and diversion sub- poor performance；
Iron oxides low price, environmental friendliness, but electron conduction is poor and self discharge is serious；Vanadic anhydride poorly conductive, dioxy
The specific capacitance for changing stannum is much lower compared with other oxides；Nickel oxide or nickel hydroxide theory specific capacitance are up to 3750F g-1,
Low price and nontoxic, but resistance is big and cycle performance is poor.In a word, metal-oxide or hydroxide have theoretical specific capacitance high
The advantages of, but while and there are problems that poorly conductive and particle easily.Therefore, current electrode material for super capacitor grinds
Send out and be concentrated mainly on the metal-oxide for synthesizing pattern and structure-controllable/material with carbon element nano-complex aspect, especially hydroxide
Nickel/graphene complex.
With Graphene as carrier, using its big specific surface area and excellent electric conductivity, grow thereon particle diameter it is little and
Nano-sized nickel hydroxide particle with specific morphology, prepares Ni (OH)2/ graphene nanocomposite material, to super capacitor electrode
Capacitive can improvement and be of great importance in the application of practical field.Ni (OH) is prepared at present2/ graphene nanocomposite material
Main method has：The sedimentation method, solid phase method, water (solvent) full-boiled process and electrochemical method etc..The sedimentation method are relatively easy, easy to operate,
But Ni (OH)2Particle size differs, particle size distribution range big, need to be aged certain hour to obtain the preferable nanoparticle of degree of crystallinity
Son.In order to control Ni (OH)2Nanoparticle Size, generally requires to add carbamide, hydrazine or surfactant, controls OH-Ion is released
Put speed or suppress Ni (OH)2The nuclei growth speed of particle, this undoubtedly causes the response time elongated and operation difficulty becomes big.Gu
Phase method uses less, Sun[1]After nickel salt and graphite oxide or Graphene are fully ground, Ni is made in filter process2+Water
Solution is converted into Ni (OH)2, Ni2+Hydrolysis rate must be far longer than the rate of dissolution of nickel salt and could obtain Ni (OH)2, the method
There is reaction wayward, equally there is also the shortcoming as the sedimentation method, i.e. Ni (OH)2Size is uneven.
Hydro-thermal method or solvent-thermal method are that one kind can preferably control Ni (OH)2The preparation method of pattern.Once had been reported that：
1) hexagon monocrystalline Ni (OH) is grown on the graphene oxide sheet of reduction by hydro-thermal reaction2Nanometer sheet,
Electric current density is 2.8A g-1, acquisition specific capacitance is 1335F g-1。
2) using solvent thermal reaction method, graphite oxide and Ni salt are reacted into 24h at 200 DEG C in benzyl alcohol medium and is obtained
Ni(OH)2, the alternate stratiform α-Ni of Graphene (OH)2/ graphene composite material, when the composite is for super flexible all solid state
When in thin film ultracapacitor, its specific capacitance is 660.8F cm-3, and without substantially decline after discharge and recharge 2000 times.
The above-mentioned second way can be greatly enhanced the heap density of composite, and reduce graphene film returns folded trend, most
The energy density of ultracapacitor is improved eventually.But the problems such as method is disadvantageous in that being difficult to batch prepares and be time-consuming.
Electrochemical deposition method low cost, preparation process is simple, the thickness (quality) and the structure of material of electrode active material
It is controllable and be widely used.Electrochemical deposition method can be divided into anodic deposition method and cathodic deposition by polarity of electrode.Sun
Pole sedimentation is that hydrolysis occur near electrode using salt of weak acid to generate OH-, while Ni2+Oxidation generates Ni3+, last OH-
With Ni3+Reaction generates NiOOH, but general less using this depositional mode.The most frequently used mode or cathodic deposition, by outer
Power up signal can be divided into constant potential or galvanostatic deposition, dynamic potential deposition (cyclic voltammetric), pulse current deposition, electrophoretic deposition
Etc. mode.Dynamic current potential sedimentation is usually used to the current potential for determining potentiostatic electrodeposition method, has been reported that using cyclic voltammetric legal system
For Co (OH)2-Ni(OH)2Binary metal hydroxide, when cobalt/nickle atom compares 66:34, when sweep speed is 50mV/s, its ratio
Electric capacity is 1102F g-1.The electrolyte that electrophoretic deposition is used is dispersion system of colloid, from unlike constant potential electro-deposition it
Externally-applied potential it is generally higher.Have been reported that and Ni/EMCMBs (expanded mesoporous carbon micro-spheres) complex is obtained with electrophoretic deposition,
5A g-1When the complex specific capacitance be 491F g-1.So, mode the most frequently used at present is potentiostatic electrodeposition, constant current sinks
Product and pulse current deposition.
Have been reported that with potentiostatic electrodeposition method with Ni (NO3)2For nickel precursor, the direct electro-deposition Ni of 0.5mg in nickel foam
(OH)2, 4A g-1When specific capacitance be 3152F g-1But, its specific capacitance loss 48% after 300 circulations.Have been reported that with enhancing etc.
Gas ions chemical vapour deposition technique is prepared for the Graphene in nickel foam arranged vertically, is then existed using galvanostatic deposition mode
Electro-deposition on graphene film obtains Ni (OH)2Nanoparticle, so as to obtain Ni (OH)2It is evenly distributed on the compound of graphenic surface
Thing, the Ni (OH)2/ graphene complex active material utilization is high, 2.3A g-1When specific capacitance be 2215F g-1, 23.1A g-1
When specific capacitance be 1305F g-1, and specific capacitance remains to holding 77% after under this condition constant current charge-discharge circulates 2000 times, but make
Standby process is more complicated and unit area active substance quality is only 0.43mg.Have been reported that and be prepared for CNT/ with pulse current sedimentation
NiOx(OH)y, highest specific capacitance reaches 1451F g after heat treatment-1, they also with the CNT/NiO prepared by galvanostatic deposition methodx
(OH)yPerformance compare, find NiO prepared by pulse current sedimentationx(OH)yParticle size is less, chemical property
Also it is higher, but can be seen that the reversible charge-discharge performance of the material is poor from its cyclic voltammetry curve.
The significant challenge that at present ultracapacitor faces is that energy density is low and price is partially expensive.Therefore energy density is synthesized
High composite, while it is one of present research emphasis to reduce its cost.
The content of the invention
It is an object of the invention to provide the composite of a kind of stratiform high-performance nickel hydroxide/Graphene or graphite.
It is yet another object of the invention to provide the method for preparing above-mentioned composite.
For achieving the above object, the composite of nickel hydroxide/Graphene that the present invention is provided, its structure is Ni (OH)2、
Alternate stratiform Ni of Graphene (OH)2/ Graphene, wherein weight of nickel hydroxide content are 10~90%；Obtained by following methods
Arrive：
1) by expanded graphite and the mass ratio 8~9 of binding agent:2~1, expanded graphite and binding agent are added in ethanol
Sonic oscillation prepares expanded graphite suspension；
2) the expanded graphite suspension for preparing step 1 is coated in electrode basement surface；
3) product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
4) product drying for preparing step 3 is simultaneously hot-forming；
5) by the product immersion alkali liquor of step 4, electrochemical activation is carried out using cyclic voltammetry and obtains Ni (OH)2, stone
Alternate stratiform Ni (OH) of black alkene2/ Graphene.
The composite of nickel hydroxide/graphite that the present invention is provided, its structure is Ni (OH)2/ graphite, wherein nickel hydroxide
Weight content is 10~90%；Obtained by following methods：
1) by graphite and the mass ratio 8~9 of binding agent:2~1, graphite and binding agent are added to into sonic oscillation in ethanol
Prepare graphite suspension；
2) graphite suspension prepared by step 1 is coated in into electrode basement surface；
3) product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
4) product drying for preparing step 3 is simultaneously hot-forming；
5) by the product immersion alkali liquor of step 4, electrochemical activation is carried out using cyclic voltammetry and obtains nickel hydroxide/stone
Ink.
In described composite, addition has white carbon black or CNT.
In described composite, binding agent is politef or Nafion solution；Electrode basement is nickel foam or copper
Paper tinsel；Soluble nickel salt is one or more of Nickel dichloride., nickel sulfate, nickel acetate, nickel nitrate；Alkali liquor for KOH, NaOH one kind or
Two kinds.
The method of the composite for preparing above-mentioned nickel hydroxide/Graphene of present invention offer：
1) by expanded graphite and the mass ratio 8~9 of binding agent:2~1, expanded graphite and binding agent are added in ethanol
Sonic oscillation prepares expanded graphite suspension；
2) the expanded graphite suspension for preparing step 1 is coated in electrode basement surface；
3) product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
4) product drying for preparing step 3 is simultaneously hot-forming；
5) by the product immersion alkali liquor of step 4, electrochemical activation is carried out using cyclic voltammetry and obtains Ni (OH)2, stone
Alternate stratiform Ni (OH) of black alkene2/ Graphene.
The method of the composite for preparing above-mentioned nickel hydroxide/graphite of present invention offer：
1) by graphite and the mass ratio 8~9 of binding agent:2~1, graphite and binding agent are added to into sonic oscillation in ethanol
Prepare graphite suspension；
2) graphite suspension prepared by step 1 is coated in into electrode basement surface；
3) product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
4) product drying for preparing step 3 is simultaneously hot-forming；
5) by the product immersion alkali liquor of step 4, electrochemical activation is carried out using cyclic voltammetry and obtains nickel hydroxide/stone
Ink.
In described method, binding agent is politef or polyvinylidene fluoride emulsion or Nafion solution in step 1.
In described method, adding in step 1 has white carbon black or CNT.
In described method, the electrode basement in step 2 is nickel foam or Copper Foil.
In described method, the soluble nickel salt in step 3 be Nickel dichloride., nickel sulfate, nickel acetate, one kind of nickel nitrate or
It is several.
In described method, the alkali liquor in step 5 is one or two of KOH, NaOH.
The Ni (OH) of the present invention2The composite of/Graphene or graphite, its layer structure can make the volume of ultracapacitor
Energy density is significantly improved, while from low-cost expanded graphite or graphite, it is to avoid using expensive graphite
Alkene, can make its cost decline to a great extent, so as to effectively overcome the significant challenge of ultracapacitor.The method has operation extremely
Simply, the features such as time-consuming short, nontoxic, environmental friendliness, with low cost and easy amplification are produced is one the high property of Commercial Prospect
Can Ni (OH)2The complex of/Graphene or graphite prepares approach.
Description of the drawings
Fig. 1 is the complex micromodel figure that stratiform of the present invention replaces nickel hydroxide/Graphene.
Fig. 2 is the scanning electron microscope (SEM) photograph that stratiform of the present invention replaces nickel hydroxide/Graphene.
Fig. 3 is the cyclic voltammetry curve figure of made electrode in embodiment 1, is displayed in 68wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene；Wherein active substance quality is 2.8mg, and electrolyte is 6M KOH solutions.
Fig. 4 is the cyclic voltammetry curve figure of made electrode in embodiment 2, is displayed in 76wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene, wherein active substance quality are 2.1mg, and electrolyte is 6M KOH solutions.
Fig. 5 is the cyclic voltammetry curve figure of made electrode in embodiment 3, is displayed in 82wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene, wherein active substance quality are 2.7mg, and electrolyte is 6M KOH solutions.
Fig. 6 is the cyclic voltammetry curve figure of made electrode in embodiment 4, is displayed in 80wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene, wherein active substance quality are 2.6mg, and electrolyte is 6M KOH solutions.
Fig. 7 is the constant-current discharge curve chart of made electrode in embodiment 4, is displayed in 80wt%Ni (OH) 2/ under different electric currents
The discharge curve of Graphene, wherein active substance quality are 2.6mg, and electrolyte is 6M KOH solutions.
Fig. 8 is the cyclic voltammetry curve figure of made electrode in embodiment 5, is displayed in 67wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene, wherein active substance quality are 1.8mg, and electrolyte is 6M KOH solutions.
Fig. 9 is the cyclic voltammetry curve figure of made electrode in embodiment 6, is displayed in 55wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/Graphene, wherein active substance quality are 4.2mg, and electrolyte is 6M KOH solutions.
Figure 10 is the cyclic voltammetry curve figure of made electrode in embodiment 7, is displayed in 73wt%Ni under different scanning rates
(OH)2The cyclic voltammetry curve of/graphite, wherein active substance quality are 3.0mg, and electrolyte is 6M KOH solutions.
Specific embodiment
Nickel hydroxide/the graphene composite material of the present invention is made up of nickel hydroxide, Graphene, weight of nickel hydroxide content
For 10~90%.It is heavy in graphite layers or graphite surface by controlling electrochemical deposition parameter from expanded graphite or graphite
Product goes out size tunable W metal nanoparticle, and dry, tabletting obtains final product the alternate Ni/ stones of metal nano Ni particles, Graphene stratiform
Black alkene complex, or the complex of Ni/ graphite.Ni (OH) is obtained final product by cyclic voltammetry in-situ activation in KOH solution2, stone
Alternate stratiform Ni (OH) of black alkene2/ Graphene, or Ni (OH)2The composite of/graphite.Simultaneously can be preparing expanded graphite
Or graphite serosity when add conductive agent such as white carbon black or CNT to further enhance the electric conductivity of the complex, and then raising
Its cycle life and high rate performance.
Specifically, stratiform of the invention replaces microstructure models figure such as Fig. 1 of nickel hydroxide/graphene composite material
It is shown, scanning electron microscope (SEM) photograph such as Fig. 2；Can be prepared by the following method：
The first step：With dehydrated alcohol as solvent, control 8~9 by the mass ratio of expanded graphite and binding agent:2~1, will
Expanded graphite and binding agent are added to sonic oscillation in ethanol and for a period of time, obtain homodisperse expanded graphite suspension；
Second step：Using dropwise method, after the expanded graphite uniform suspension prepared in the first step is coated in into process
Electrode basement (nickel foam or Copper Foil) surface, and be dried.After drying, expanded graphite quality is 0.5~4mg；
3rd step：Compound concentration is 5~20mg mL-1Soluble nickel saline solution；
4th step：As working electrode, compressing electrode basement is to electrode and ginseng to the electrode prepared with second step
Than electrode, in nickel chloride solution, electro-deposition is started under constant current potential, sedimentation potential is controlled between -0.7~-3V；Deposition
The quality of metallic nickel flow through the electricity of working electrode to realize by control, make the alternate nano metal nickel particles of stratiform/
Graphene；
5th step：Electrode in 4th step is dried in a vacuum or in atmosphere, and 0.1~10MPa, 80
It is hot-forming at~130 DEG C；
6th step：The aqueous solution of certain density water soluble alkali is prepared as electrochemical activation electrolyte, concentration exists
0.5mol L-1~6mol L-1Between；
7th step：In the electrode immersion alkali liquor that 5th step is obtained, electrochemical activation acquisition is carried out using cyclic voltammetry
Nickel hydroxide/Graphene.
The composite of nickel hydroxide/graphite of the present invention can be prepared by the following method：
The first step：With dehydrated alcohol as solvent, control 8~9 by the mass ratio of graphite and binding agent:2~1, by graphite
Sonic oscillation in ethanol is added to binding agent for a period of time, obtain homodisperse graphite suspension；
Second step：Using dropwise method, the graphite suspension prepared in the first step is coated uniformly on into the electrode after processing
Substrate (nickel foam or Copper Foil) surface, and be dried.After drying, graphite quality is 0.5~4mg；
3rd step：Compound concentration is 5~20mg mL-1Soluble nickel saline solution；
4th step：As working electrode, compressing electrode basement is to electrode and ginseng to the electrode prepared with second step
Than electrode, in nickel chloride solution, electro-deposition is started under constant current potential, sedimentation potential is controlled between -0.7~-3V；Deposition
The quality of metallic nickel flow through the electricity of working electrode to realize by control, make nano metal nickel particles/graphite；
5th step：Electrode in 4th step is dried in a vacuum or in atmosphere, and 0.1~10MPa, 80
It is hot-forming at~130 DEG C；
6th step：The aqueous solution of certain density water soluble alkali is prepared as electrochemical activation electrolyte, concentration exists
0.5mol L-1~6mol L-1Between；
7th step：In the electrode immersion alkali liquor that 5th step is obtained, electrochemical activation acquisition is carried out using cyclic voltammetry
Nickel hydroxide/graphite.
In said method：
Binding agent can be politef, Kynoar, Nafion solution in step one；
Soluble nickel salt can be Nickel dichloride., nickel sulfate, nickel acetate etc. in step 2；
Solubility alkali liquor can be KOH, NaOH in step 3.
The present invention is further illustrated with reference to specific embodiment.Those skilled in the art should be apparent that the embodiment is only
Only help understand the present invention, be not construed as the concrete restriction to the present invention.
Embodiment 1：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and Nafion with dehydrated alcohol as solvent:1, expanded graphite and Nafion are added
Enter in ethanol sonic oscillation for a period of time, obtain homodisperse expanded graphite suspension；
Second step, making expanded graphite/foam nickel electrode
Using dropwise method, 10 × 10 bubbles expanded graphite uniform suspension prepared in the first step being coated in after processing
Foam nickel surface, and be dried.After drying, expanded graphite quality is about 1mg；
3rd step, compound concentration are 10mg mL-1Nickel chloride solution；
4th step, the alternate nano metal nickel particles/Graphene/foam nickel electrode of making stratiform
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel chloride solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -3V；Flow through the electricity of working electrode
Measure as 2.08C；
It is 5th step, by the pole drying in the 4th step and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 1284F g-1, 10mV s-1When remain to reach 1068F
g-1, specific capacitance conservation rate is 83%, and its cyclic voltammetry curve is referring to Fig. 3.
Embodiment 2：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and politef with dehydrated alcohol as solvent:1, by expanded graphite and poly- four
Fluorothene is added to sonic oscillation in ethanol and for a period of time, obtains homodisperse expanded graphite suspension；
Second step, making expanded graphite/copper foil electrode
Using dropwise method, the expanded graphite uniform suspension prepared in the first step is coated in into 10 × 10 bronze medals after processing
Paper tinsel surface, and be dried.After drying, expanded graphite quality is about 1mg；
3rd step, compound concentration are 20mg mL-1Nickel sulfate solution；
4th step, the alternate nano metal nickel/Graphene/copper foil electrode of making stratiform
As working electrode, 20 × 20 compressing copper foils are to electrode and reference electricity to the electrode prepared with second step
Pole, in nickel sulfate solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -3V；Flow through the electricity of working electrode
For 1.04C；
5th step, the electrode in the 4th step is placed under vacuum condition it is dried, it is and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1NaOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 1086F g-1, 10mV s-1When remain to reach 909F
g-1, specific capacitance conservation rate is 84%, and its cyclic voltammetry curve is referring to Fig. 4.
Embodiment 3：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and Nafion with dehydrated alcohol as solvent:1, expanded graphite and Nafion are added
Enter in ethanol sonic oscillation for a period of time, obtain homodisperse expanded graphite suspension；
Second step, making expanded graphite/foam nickel electrode
Using dropwise method, 10 × 10 bubbles expanded graphite uniform suspension prepared in the first step being coated in after processing
Foam nickel surface, and be dried.After drying, expanded graphite quality is about 1mg；
3rd step, compound concentration are 20mg mL-1Nickel nitrate solution；
4th step, the alternate nano metal nickel particles/Graphene/foam nickel electrode of making stratiform
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel nitrate solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -2V；Flow through the electricity of working electrode
Measure as 1.04C；
5th step, the electrode in the 4th step is placed under vacuum condition it is dried, it is and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 1216F g-1, 10mV s-1When remain to reach 959F
g-1, specific capacitance conservation rate is 79%, and its cyclic voltammetry curve is referring to Fig. 5.
Embodiment 4：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and Nafion with dehydrated alcohol as solvent:1, expanded graphite and Nafion are added
Enter in ethanol sonic oscillation for a period of time, obtain homodisperse expanded graphite suspension；
Second step, making expanded graphite/foam nickel electrode
Using dropwise method, 10 × 10 bubbles expanded graphite uniform suspension prepared in the first step being coated in after processing
Foam nickel surface, and be dried.After drying, expanded graphite quality is about 1mg；
3rd step, compound concentration are 20mg mL-1Nickel acetate solution；
4th step, the alternate nano metal nickel particles/Graphene/foam nickel electrode of making stratiform
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel acetate solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -1V；Flow through the electricity of working electrode
Measure as 1.04C；
5th step, the electrode in the 4th step is placed under vacuum condition it is dried, it is and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide particle/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 1488F g-1, 10mV s-1When remain to reach 1206F
g-1, specific capacitance conservation rate is 81%, and its cyclic voltammetry curve is referring to Fig. 6；In 1A g-1When specific capacitance be 1943Fg-1,10A g-1
When specific capacitance be 1355F g-1, specific capacitance conservation rate is 70%, and its constant-current discharge curve participates in Fig. 7.
Embodiment 5：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and Nafion with dehydrated alcohol as solvent:1, expanded graphite and Nafion are added
Enter in ethanol sonic oscillation for a period of time, obtain homodisperse expanded graphite suspension；
Second step, making expanded graphite/foam nickel electrode
Using dropwise method, 10 × 10 bubbles expanded graphite uniform suspension prepared in the first step being coated in after processing
Foam nickel surface, and be dried.After drying, expanded graphite quality is about 1mg；
3rd step, compound concentration are 10mg mL-1Nickel chloride solution；
4th step, the alternate nano metal nickel particles/Graphene/foam nickel electrode of making stratiform
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel chloride solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -3V；Flow through the electricity of working electrode
Measure as 1.04C；
5th step, the electrode in the 4th step is placed under vacuum condition it is dried, it is and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 946F g-1, 10mV s-1When remain to reach 847F
g-1, specific capacitance conservation rate is 90%, and its cyclic voltammetry curve is referring to Fig. 8.
Embodiment 6：Prepare nickel hydroxide/graphene composite material
The first step, preparation expanded graphite suspension
It is 9 by the mass ratio of expanded graphite and Nafion with dehydrated alcohol as solvent:1, expanded graphite and Nafion are added
Enter in ethanol sonic oscillation for a period of time, obtain homodisperse expanded graphite suspension；
Second step, making expanded graphite/foam nickel electrode
Using dropwise method, 10 × 10 bubbles expanded graphite uniform suspension prepared in the first step being coated in after processing
Foam nickel surface, and be dried in air dry oven, temperature control makes nanometer nickel particles straight between room temperature and 250 DEG C
Connect and be oxidized to nickel oxide.After drying, expanded graphite quality is about 2mg；
3rd step, compound concentration are 20mg mL-1Nickel chloride solution；
4th step, the alternate nano metal nickel particles/Graphene/foam nickel electrode of making stratiform
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel chloride solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -1V；Flow through the electricity of working electrode
Measure as 4.16C；
5th step, the electrode in the 4th step is placed in air drying, and it is hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, the alternate nano-sized nickel hydroxide/Graphene/foam nickel electrode of preparation stratiform
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and obtains layer
Alternate nano-sized nickel hydroxide/Graphene/the foam nickel electrode of shape.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 853F g-1, 10mV s-1When remain to reach 594F
g-1, specific capacitance conservation rate is 70%, and its cyclic voltammetry curve is referring to Fig. 9.
Embodiment 7：Prepare nickel hydroxide/graphite composite material
The first step, preparation graphite suspension
It is 9 by the mass ratio of graphite and Nafion with dehydrated alcohol as solvent:1, graphite and Nafion are added to into ethanol
Middle sonic oscillation for a period of time, obtains homodisperse graphite suspension；
Second step, making graphite/foam nickel electrode
Using dropwise method, the graphite suspension prepared in the first step is coated uniformly on into 10 × 10 nickel foam after processing
Surface, and be dried.After drying, graphite quality is about 1mg；
3rd step, compound concentration are 10mg mL-1Nickel chloride solution；
4th step, making nano metal nickel particles/graphite/foam nickel electrode
As working electrode, 20 × 20 compressing foam nickel sheet are to electrode and reference to the electrode prepared with second step
Electrode, in nickel chloride solution, starts electro-deposition under constant current potential, sedimentation potential is controlled in -3V；Flow through the electricity of working electrode
Measure as 2.08C；
5th step, the electrode in the 4th step is placed under vacuum condition it is dried, it is and hot-forming at 10MPa, 130 DEG C；
6th step, preparation electrochemical activation electrolyte
Prepare 6mol L-1KOH aqueous solutions；
7th step, prepare nano-sized nickel hydroxide/graphite/foam nickel electrode
The electrode immersion 6mol L that 5th step is obtained-1In KOH, electrochemical activation is carried out using cyclic voltammetry and is received
Rice nickel hydroxide/graphite/foam nickel electrode.
In the electrode cycle volt-ampere test, 2mV s-1When specific capacitance be 1103F g-1, 10mV s-1When remain to reach 818F
g-1, specific capacitance conservation rate is 74%, and its cyclic voltammetry curve is referring to Figure 10.
Claims (16)
1. a kind of composite of nickel hydroxide/Graphene, its structure is Ni (OH)2, alternate stratiform Ni of Graphene (OH)2/ stone
Black alkene, wherein weight of nickel hydroxide content are 10~90%；Obtained by following methods：
Step 1, by expanded graphite and the mass ratio 8~9: 2~1 of binding agent, expanded graphite and binding agent is added in ethanol
Sonic oscillation prepares expanded graphite suspension；
Step 2, expanded graphite suspension prepared by step 1 is coated in electrode basement surface, and control mass area ratio is 0.5
~4mg cm-2；
Step 3, product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
Step 4, product drying prepared by step 3 is simultaneously hot-forming；
Step 5, by the product immersion alkali liquor of step 4, carries out electrochemical activation and obtains Ni (OH) using cyclic voltammetry2, graphite
Alternate stratiform Ni of alkene (OH)2/ Graphene.
2. composite according to claim 1, wherein, adding in the expanded graphite suspension that step 1 is prepared has white carbon black
Or CNT.
3. composite according to claim 1, wherein, the binding agent in step 1 is politef or polyvinylidene fluoride
Alkene emulsion or Nafion solution；Electrode basement in step 2 is nickel foam or Copper Foil；Soluble nickel salt in step 3 is chlorination
One or more of nickel, nickel sulfate, nickel acetate, nickel nitrate；Alkali liquor in step 5 is one or two of KOH, NaOH.
4. a kind of composite of nickel hydroxide/graphite, its structure is Ni (OH)2/ graphite, wherein weight of nickel hydroxide content is
10~90%；Obtained by following methods：
Step 1, by graphite and the mass ratio 8~9: 2~1 of binding agent, by graphite and binding agent sonic oscillation in ethanol is added to
Prepare graphite suspension；
Step 2, by graphite suspension prepared by step 1 electrode basement surface is coated in, control mass area ratio 0.5~
4mg cm-2；
Step 3, product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
Step 4, product drying prepared by step 3 is simultaneously hot-forming；
Step 5, by the product immersion alkali liquor of step 4, carries out electrochemical activation and obtains nickel hydroxide/stone using cyclic voltammetry
The composite of ink.
5. composite according to claim 4, wherein, adding in the graphite suspension that step 1 is prepared has white carbon black or carbon
Nanotube.
6. composite according to claim 4, wherein, the binding agent in step 1 is politef or polyvinylidene fluoride
Alkene emulsion or Nafion solution；Electrode basement in step 2 is nickel foam or Copper Foil；Soluble nickel salt in step 3 is chlorination
One or more of nickel, nickel sulfate, nickel acetate, nickel nitrate；Alkali liquor in step 5 is one or two of KOH, NaOH.
7. the method for preparing nickel hydroxide/Graphene described in claim 1：
Step 1, by expanded graphite and the mass ratio 8~9: 2~1 of binding agent, expanded graphite and binding agent is added in ethanol
Sonic oscillation prepares expanded graphite suspension；
Step 2, expanded graphite suspension prepared by step 1 is coated in electrode basement surface；
Step 3, product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
Step 4, product drying prepared by step 3 is simultaneously hot-forming；
Step 5, by the product immersion alkali liquor of step 4, carries out electrochemical activation and obtains Ni (OH) using cyclic voltammetry2, graphite
Alternate stratiform Ni of alkene (OH)2/ Graphene.
8. method according to claim 7, wherein, adding in the expanded graphite suspension that step 1 is prepared has white carbon black or carbon
Nanotube.
9. method according to claim 7, wherein, the electrode basement in step 2 is nickel foam or Copper Foil.
10. method according to claim 7, wherein, the soluble nickel salt in step 3 is Nickel dichloride., nickel sulfate, acetic acid
One or more of nickel, nickel nitrate.
11. methods according to claim 7, wherein, the alkali liquor in step 5 is one or two of KOH, NaOH.
12. methods for preparing the composite of nickel hydroxide/graphite described in claim 4：
Step 1, by graphite and the mass ratio 8~9: 2~1 of binding agent, by graphite and binding agent sonic oscillation in ethanol is added to
Prepare graphite suspension；
Step 2, by graphite suspension prepared by step 1 electrode basement surface is coated in；
Step 3, product prepared by step 2 is placed in the solution of soluble nickel salt and starts electro-deposition；
Step 4, product drying prepared by step 3 is simultaneously hot-forming；
Step 5, by the product immersion alkali liquor of step 4, carries out electrochemical activation and obtains nickel hydroxide/stone using cyclic voltammetry
Ink.
13. methods according to claim 12, wherein, adding in the graphite suspension that step 1 is prepared has white carbon black or carbon to receive
Mitron.
14. methods according to claim 12, wherein, the electrode basement in step 2 is nickel foam or Copper Foil.
15. methods according to claim 12, wherein, the soluble nickel salt in step 3 is Nickel dichloride., nickel sulfate, acetic acid
One or more of nickel, nickel nitrate.
16. methods according to claim 12, wherein, the alkali liquor in step 5 is one or two of KOH, NaOH.
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| CN106024424A (en) * | 2016-07-01 | 2016-10-12 | 东华大学 | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof |
| CN106784644B (en) * | 2016-11-09 | 2019-04-26 | 陕西科技大学 | A kind of assembling cube Ni (OH)2The preparation method of/GO composite material |
| US10982069B2 (en) | 2017-04-17 | 2021-04-20 | Baker Hughes, A Ge Company, Llc | Acid resistant carbon composites, methods of manufacture, and articles formed thereof |
| CN106975489B (en) * | 2017-04-26 | 2019-12-31 | 浙江大学 | Preparation method of nickel oxide in-situ coated graphene nanocomposite |
| CN108609599A (en) * | 2018-05-30 | 2018-10-02 | 北京化工大学常州先进材料研究院 | The preparation method of nickel hydroxide nano piece self assembly nickel phosphates cobalt club shaped structure composite material |
| CN108987123B (en) * | 2018-06-07 | 2020-08-04 | 武汉科技大学 | Ternary composite super-capacitor electrode material and preparation method thereof |
| CN110970224A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Nickel hydroxide/graphite composite material |
| CN110970225A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Preparation method of nickel hydroxide/graphite composite material |
| CN109830381B (en) * | 2019-04-04 | 2021-01-19 | 兰州理工大学 | MXene/MoS for supercapacitor electrodes2Method for preparing composite material |
| CN111101149B (en) * | 2020-02-18 | 2021-10-01 | 南昌航空大学 | Electro-catalytic hydrogen evolution porous Ni2Mg alloy electrode and preparation method thereof |
| CN112647092B (en) * | 2020-12-18 | 2022-02-15 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN113120978B (en) * | 2021-04-19 | 2022-07-01 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
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