CN107275611A - The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding - Google Patents
The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding Download PDFInfo
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of spherical zinc oxide material of nanometer of polypyrrole cladding with core shell structure and preparation method.The spherical zinc oxide of nanometer of polypyrrole cladding is using the spherical zinc oxide of nanometer as core, and polypyrrole is that shell is coated on zinc oxide particle surfaces.Its process is that precipitating reagent such as hexa etc. is added into zinc source, and the spherical Zinc oxide particles of nanometer are made by hydro-thermal reaction；Nano zine oxide is added in the solution containing surfactant, zinc oxide colloidal sol is formed, pyrrole monomer is added and oxidant carries out in-situ oxidizing-polymerizing, in zinc oxide particle surfaces formation polypyrrole clad.The nano zine oxide of core shell structure polypyrrole cladding prepared by the present invention has larger specific surface area, improving its activity simultaneously, the reunion of nano granular of zinc oxide can be prevented very well, the presence of polypyrrole clad effectively alleviates the formation of Zinc oxide particles dendrite in charge and discharge process, significantly improves electrode cycle life.
Description
Technical field
The present invention relates to a kind of nano zinc oxide material of polypyrrole cladding and preparation method, applied to nickel zinc alkali secondary
The invertibity and coulombic efficiency of electrode can be effectively improved in GND, the cycle life of electrode is improved, alkalescence two is particularly belonged to
Secondary nickel zinc battery cathode material technical field.
Background technology
As most popular negative material in aqueous solution one-shot battery system, zinc electrode have the advantages that it is a lot, than
Such as high-energy-density, high open circuit voltage is environmentally safe, and rich reserves, with low cost.So zinc electrode is applied in alkali
Property secondary cell in trial be constantly subjected to people concern.But when as secondary battery cathode material, due to its electric discharge production
Thing is soluble in electrolyte, causes in charging process, and lysed active material can be deposited to unevenly in zinc electrode again, promotees
Make the growth of dendrite and the deformation of electrode, guiding discharge capacity is decayed rapidly, and cycle life is low.
In order to improve the cycle life of zinc electrode, it is common method to add additive in active material, such as in electrode material
Add calcium in material, bismuth, tin, indium, metal oxide or the hydroxide such as silver and titanium can enough suppress zinc electrode dendrite to a certain degree
And the generation of deformation.Organic additive is mainly used in electrolyte, the uniformity for improving zinc deposition.However, inorganic addition
Contact of the agent with active material is not abundant enough, and main function is to improve hydrogen-evolution overpotential, and the dissolving to discharging product is not obvious
Effect, and organic additive increases electrode polarization, is efficiency for charge-discharge reduction, and easily decomposed in charge and discharge process.
Polypyrrole (PPy) is used as a kind of most common conducting polymer, the macrocyclic structure with pi-conjugated electronics, after doping
It has high conductivity, and high stability has wide range of applications, such as ultracapacitor, erosion shield and chemical sensor etc.,
Its many outstanding performance causes the attention of scientific research personnel.Because zinc oxide is a kind of outstanding semi-conducting material, polypyrrole
Compound with zinc oxide brings a series of interesting photoelectric properties, and current researcher is to zinc oxide-polypyrrole compound
Preparation has carried out wide research, and preparation method includes chemical method and electrochemical process.Zhang Chengxiang etc. is closed by electrochemical method
Into polypyrrole/zinc oxide nanometer composite material, polypyrrole is in typical cauliflower-shaped structure, and white ZnO particulate inclusions exist
In PPy, it is filled in the intergranular gaps of PPy.Rastogi etc. is prepared for PPy by electrochemical method and coats bar-shaped oxidation
Zinc, shows preferable capacitive property.Li etc. is prepared for PPy in the method for gas-phase polymerization in oxidation zincode substrate, is used as gas
The material of body sensor.From the above analysis, the preparation research of zinc oxide polypyrrole compound is concentrated mainly on electrochemistry side
Synthesis of the method on bulk substrate.The present invention coats polypyrrole by chemical oxidization method in the spherical zinc oxide surface of nanometer, not only
Preparation method is simplified, the influence of voltage x current and electrode type to final product in electrochemical method has been abandoned, has been not required to simultaneously
Preparation condition harsh in vapor phase method is wanted, can realize and carry out the modification of polypyrrole on nano granular of zinc oxide surface, using knot
Fruit shows that the spherical zinc oxide of nanometer of polypyrrole cladding has good electrochemical reversibility and charge-discharge performance.
The content of the invention
For the deficiency of existing zinc oxide surface method of modifying, the present invention provides a kind of spherical oxygen of nanometer of polypyrrole cladding
Change Zinc material and preparation method thereof, effectively inhibit the generation of zinc dendrite in zinc electrode charge and discharge process, extend cycle life.
The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding of the present invention are as follows：
(1) the spherical zinc oxide material of nanometer of polypyrrole cladding
Nanometer spherical zinc oxide material using the particle diameter 40-150nm of polypyrrole the cladding spherical zinc oxide of nanometer is cores, and surface is uniform
The polypyrrole shell that thickness is 5-25nm is coated, the wherein mass percent of polypyrrole is 5%-20%.
(2) the spherical zinc oxide preparation method of nanometer of polypyrrole cladding
Step 1：The mol ratio for controlling precipitating reagent and zinc salt is 1 ~ 2: 4, by the deionized water or ethylene glycol solution and zinc of precipitating reagent
Salt is well mixed, thereafter the hydro-thermal reaction 5-10h at 150 ~ 200 DEG C；Product is cooled to after room temperature and filtered, and uses respectively
Water, ethanol are washed 3 times, then again through being dried to obtain the spherical zinc oxide of nanometer.
Step 2：Surfactant presses 1: 4 mol ratio with the spherical zinc oxide of nanometer, and the spherical zinc oxide of above-mentioned nanometer is added
Enter into the aqueous solution of surfactant, 5 ~ 30min of ultrasonic disperse, form the zinc oxide colloidal sol of stable dispersion.
Step 3：The mol ratio for controlling pyrrole monomer and nano zine oxide is 1 ~ 3: 20, and pyrrole monomer is dissolved in into deionized water
In, then it is added in zinc oxide colloidal sol, 10 ~ 30min of ultrasonic disperse；Oxidant presses 1 ~ 2: 2 mol ratio with pyrrole monomer, holds
Oxidant is added under continuous stirring condition and carries out pyrroles's polymerisation, after 5 ~ 10h of stirring reaction at a temperature of 0-8 DEG C, is used respectively
Deionized water, methanol cyclic washing 5 times, obtained grey black product through drying 3 ~ 6h at a temperature of 50 ~ 80 DEG C, obtain polypyrrole again
The spherical zinc oxide of nanometer of cladding.
Described zinc salt is one kind in zinc acetate, zinc citrate, zinc lactate.
Described precipitating reagent is one kind in urea, hexa or sodium hydroxide.
Described surfactant is one kind in dodecyl sodium sulfate, sodium laurate or polyethylene glycol or its mixing
Thing.
Described oxidant is ammonium persulfate or hydrogen peroxide.
The spherical zinc oxide material of nanometer that the polypyrrole of above-mentioned preparation is coated is applied to alkali as zinc negative active substance
Property Ni-MH secondary battery negative pole, using result show polypyrrole cladding the spherical zinc oxide of nanometer can alleviate the shape of dendrite significantly
Into, and the cycle life of Ni-MH secondary battery can be significantly improved.
Concrete application method is as follows：
（a）By the spherical zinc oxide of polypyrrole cladding nanometer, the conductive agent of 5-10 parts by weight, the 5-20 described in 65-85 parts by weight
The zinc compound of parts by weight carries out mechanical mixture and obtains negative material mixture；
（b）In the deionized water that the dispersant of 0.02-5 parts by weight is dissolved in 25-35 parts by weight；
（c）By step（b）Resulting solution is added to step（a）Negative material mixture in, then add under vigorous stirring
Binder solution, binder solution and step（a）Obtained negative material weight ratio is 1-5:100, obtain uniform mobility
Zinc load slurry；
（d）By step（c）Zinc load slurry be uniformly coated on zinc electrode collector two sides, after rolling dry, be cut into
Zinc load finished product pole piece.
Step（a）The conductive agent is the mixed of electrically conductive graphite and conductive carbon black, acetylene black, indium powder, aluminium powder, glass putty or copper powder
Compound；Described zinc compound is the mixing of zinc powder and zinc oxide, zinc-indium, zinc-indium-bismuth, zinc-tin or zinc-Sn-In alloy powder
The mixture of one or both of thing；Step（b）Described in dispersant include neopelex, dodecyl sulphur
Suan Na ﹑ cetyl trimethylammonium bromides, sodium hypophosphite, hexamethylenetetramine, Ju Yi bis- Chun ﹑ tetrabutyl phosphonium bromide An ﹑ thiocarbamides,
One or more in teabrom, Triton X-100；Step（c）Described in binding agent be polytetrafluoroethylene (PTFE),
Sodium carboxymethylcellulose, polyvinyl alcohol, fluoropolymer, polyethylene, the one or more of rubber and waterglass.
Beneficial effects of the present invention
The spherical zinc oxide of nanometer of polypyrrole cladding of the present invention can effectively suppress oxidation compared to conventional oxidation zinc electrode material
The reunion of zinc particle and in charge and discharge process zinc dendrite formation, be remarkably improved the invertibity of electrode, coulombic efficiency and
The cycle life of electrode.
The present invention coats polypyrrole by chemical oxidization method in the spherical zinc oxide surface of nanometer, and preparation method is easy, abandons
The influence of voltage x current and electrode type to final product in electrochemical method, without the need for preparation harsh in vapor phase method
Condition, can realize and carry out effective modification of polypyrrole on nano granular of zinc oxide surface, show that polypyrrole is coated using result
The spherical zinc oxide of nanometer there is significant electrochemical reversibility and charge-discharge performance.
Brief description of the drawings
Fig. 1 is the TEM figures for the spherical zinc oxide of nanometer that polypyrrole of the present invention is coated；Fig. 2 is what polypyrrole of the present invention was coated
The cyclic voltammetry curve figure of the spherical zinc oxide of nanometer；Fig. 3 is the discharge and recharge for the spherical zinc oxide of nanometer that polypyrrole of the present invention is coated
Curve map；Fig. 4 is the cycle life figure of conventional oxidation zinc；Fig. 5 is following for the spherical zinc oxide of nanometer that polypyrrole of the present invention is coated
Ring life diagram；SEM after Fig. 6 is conventional oxidation Zinc form schemes；Fig. 7 is the spherical zinc oxide of nanometer that polypyrrole of the present invention is coated
SEM figures after being circulated throughout.
Embodiment
In order to more specifically describe the present invention, below in conjunction with the accompanying drawings and embodiment is to technical scheme
Carry out detailed.The present invention is intended to further illustrate, is not intended to limit the present invention.
Embodiment 1
Take 200mg zinc acetates to be dissolved in 50ml deionized waters, separately take 70mg hexas to be dissolved in 50ml deionized waters, will
Above two solution is mixed, and is stirred 5 minutes, is subsequently transferred in 200ml hydrothermal reaction kettles, keeps 160 DEG C of hydrothermal temperature,
Natural cooling after reacting 8 hours, takes out suction filtration, and rear drying is washed repeatedly with deionized water and ethanol to the spherical oxidation of nanometer
Zinc particle.Take 37mg dodecyl sodium sulfates to be dissolved in 50ml deionized waters, separately take 100mg nano zine oxides to add above-mentioned solution
In, ultrasonic agitation makes the Nano sol of zinc oxide formation stable dispersion for 10 minutes, by above-mentioned colloidal sol as in 5 DEG C of incubators, holds
Continuous stirring, adds 20mg pyrrole monomers, and stirring makes it fully dissolve in 30 minutes, separately takes 68mg ammonium persulfates to be dissolved in 10ml deionizations
In water, ammonium persulfate solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, addition continues to stir after finishing
Reaction 8 hours is mixed, reaction carries out repeatedly suction filtration, washing with deionized water and methanol, the powder washed is placed in very after terminating
In the baking oven of empty or inert gas environment, dried 3 hours in 60 DEG C, that is, obtain the spherical zinc oxide material of nanometer of polypyrrole cladding
Material, its TEM figure is shown in Fig. 1.0.85g polypyrroles are coated into the spherical zinc oxide of nanometer and 0.05g zinc powder ﹑ 0.05g lead electric stone ink ﹑
0.02g sodium carboxymethylcelluloses and 0.03g polytetrafluoroethylene (PTFE) are added to stirred in 25ml beaker after, add appropriate
Deionized water be modulated into the cathode size of uniform mobility, the slurry is coated to copper mesh two sides with scraper, after rolling simultaneously
Dry, through the zinc load pole piece for being tailored into the mm of 20 mm × 20.Positive pole uses dimensions for the mm of 50 mm × 50 sintrered nickel
Anode pole piece.By both positive and negative polarity pole piece respectively with microporous polypropylene membrane and polypropylene non-woven cloth diaphragm parcel layer 2-3, opening electricity is made
Pond, wherein electrolyte are 5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Embodiment 2
Take 200mg zinc acetates to be dissolved in 80ml ethylene glycol, separately take 15mg sodium hydroxides to be dissolved in 20ml deionized waters, by above-mentioned two
Solution mixing is planted, stirs 30 minutes, then mixed solution is transferred in 200ml hydrothermal reaction kettles, hydrothermal temperature is kept
150 DEG C, natural cooling after reacting 10 hours takes out suction filtration, and rear drying is washed repeatedly with deionized water and ethanol to nanometer
Spherical Zinc oxide particles.Take 55mg polyethylene glycol (PEG400) to be dissolved in 50ml deionized waters, separately take 100mg nano zine oxides to add
Enter in above-mentioned solution, ultrasonic agitation makes the Nano sol of zinc oxide formation stable dispersion for 30 minutes, by above-mentioned colloidal sol as 0 DEG C of guarantor
In incubator, lasting stirring adds 15mg pyrrole monomers, and stirring makes it fully dissolve in 30 minutes, separately takes 10ml hydrogen peroxide to be dissolved in
In 10ml deionized waters, hydrogen peroxide solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, addition is finished
Continue stirring reaction afterwards 10 hours, reaction carries out filtering and washing repeatedly after terminating with deionized water and methanol, by the powder washed
End is placed in the baking oven of vacuum or inert gas environment, is dried 5 hours in 60 DEG C, that is, obtains the spherical oxygen of nanometer of polypyrrole cladding
Change Zinc material.By 0.75g carbon coating zinc-aluminum hydrotalcite and 0.1g zinc-Sn-In alloy Fen ﹑ 0.1g Yi Que Hei ﹑ 0.01g carboxymethyls
Sodium cellulosate and 0.04g polytetrafluoroethylene (PTFE) are added to stirred in 25ml beaker after, add appropriate deionized water
The cathode size of uniform mobility is modulated into, the slurry is coated to copper mesh two sides with scraper, it is after rolling and dry, through tailoring
Into the mm of 20 mm × 20 zinc load pole piece.Positive pole uses dimensions for the mm of 50 mm × 50 sintrered nickel anode pole piece.Will
Both positive and negative polarity pole piece with microporous polypropylene membrane and polypropylene non-woven cloth diaphragm parcel layer 2-3, makes open cell, wherein being electrolysed respectively
Liquid is 5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Embodiment 3
Take 200mg zinc acetates to be dissolved in 50ml deionized waters, separately take 25mg urea in 50ml deionized waters, above two is molten
Liquid is mixed, and is stirred 10 minutes, is subsequently transferred in 200ml hydrothermal reaction kettles, keeps 180 degrees Celsius of hydrothermal temperature, reaction 6
Natural cooling after hour, takes out suction filtration, and rear drying is washed repeatedly with deionized water and ethanol to the spherical zinc oxide of nanometer
Grain.Take 30mg sodium laurates to be dissolved in 50ml deionized waters, separately take 100mg nano zine oxides to add in above-mentioned solution, ultrasound is stirred
Mixing makes the Nano sol of zinc oxide formation stable dispersion for 20 minutes, and by above-mentioned colloidal sol as in 5 degrees Celsius of incubators, shading is lasting
Stirring, adds 15mg pyrrole monomers, and stirring makes it fully dissolve in 30 minutes, separately takes 55mg ammonium persulfates to be dissolved in 10ml deionized waters
In, ammonium persulfate solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, addition continues to stir after finishing
Reaction 10 hours, reaction carries out filtering and washing repeatedly after terminating with deionized water and methanol, and the powder washed is placed in into vacuum
Or in the baking oven of inert gas environment, dried 3 hours in 80 degrees Celsius.Obtain the spherical zinc oxide material of nanometer of polypyrrole cladding
Material.0.85g polypyrroles are coated into the spherical zinc oxide of nanometer and 0.05g zinc powder ﹑ 0.05g lead electric stone ink ﹑ 0.02g carboxymethyl celluloses
Sodium and 0.03g polytetrafluoroethylene (PTFE) are added to stirred in 25ml small beaker after, add appropriate deionized water modulation
Into the cathode size of uniform mobility, the slurry is coated to copper mesh two sides with scraper, it is after rolling and dry, through being tailored into 20
The mm of mm × 20 zinc load pole piece.Positive pole uses dimensions for the mm of 50 mm × 50 sintrered nickel anode pole piece.By both positive and negative polarity
Pole piece with microporous polypropylene membrane and polypropylene non-woven cloth diaphragm parcel layer 2-3, makes open cell, wherein electrolyte is respectively
5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Battery performance test
Above-described embodiment is assembled to obtained battery and does following activation process：0.1C charge 10 h, shelve 20min, after with 0.2C
1.4 V are discharged to, then shelve 20 min；So charge and discharge 5 times, completes activation.It is reference electrode from Hg/HgO, constitutes three electrodes
System, carries out cyclic voltammetry.After being completed, then in room temperature（25±2℃）Under with 1C electric currents charge, 1C electric discharge, follow
Ring measures the cycle life of Ni-MH secondary battery.Test cell terminates test after circulating 200 times.Test result is shown in
Accompanying drawing 2,3,4,5,6 and 7.Analysis chart 2,3,4,5,6 and 7, it can be deduced that the polypyrrole cladding nanometer prepared by the present invention is spherical
Zinc oxide, the presence of polypyrrole layer reduces zinc oxide and the probability of side reaction occurs with electrolyte, can with good discharge and recharge
Inverse property and charge and discharge platform, its capacity have decreased to 220mAh/g after conventional oxidation zinc is circulated at 100 times as can be seen from Figure 4, and gather
Pyrroles, which is coated after the spherical zinc oxide of nanometer is circulated at 200 times, can also keep about 400 mAh/g capacity, and the SEM figures after circulation are aobvious
Show that conventional oxidation zinc forms columnar dendrite, the polypyrrole cladding spherical zinc oxide of nanometer does not have obvious dendrite and formed, explanation
It alleviates the formation of dendrite significantly, significantly improves the cycle life of Ni-MH secondary battery.
Claims (5)
1. the spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding, it is characterised in that：Described material and system
Preparation Method is as follows：
(1) the spherical zinc oxide material of nanometer of polypyrrole cladding
Nanometer spherical zinc oxide material using the particle diameter 40-150nm of polypyrrole the cladding spherical zinc oxide of nanometer is cores, and surface is uniform
The polypyrrole shell that thickness is 5-25nm is coated, the wherein mass percent of polypyrrole is 5%-20%；
(2) the spherical zinc oxide preparation method of nanometer of polypyrrole cladding
Step 1：The mol ratio for controlling precipitating reagent and zinc salt is 1 ~ 2: 4, by the deionized water or ethylene glycol solution and zinc of precipitating reagent
Salt is well mixed, thereafter the hydro-thermal reaction 5-10h at 150 ~ 200 DEG C；Product is cooled to after room temperature and filtered, and uses respectively
Water, ethanol are washed 3 times, then again through being dried to obtain the spherical zinc oxide of nanometer；
Step 2：Surfactant presses 1: 4 mol ratio with the spherical zinc oxide of nanometer, and the spherical zinc oxide of above-mentioned nanometer is added to
In the aqueous solution of surfactant, 5 ~ 30min of ultrasonic disperse forms the zinc oxide colloidal sol of stable dispersion；
Step 3：The mol ratio for controlling pyrrole monomer and nano zine oxide is 1 ~ 3: 20, and pyrrole monomer is dissolved in deionized water,
Then it is added in zinc oxide colloidal sol, 10 ~ 30min of ultrasonic disperse；Oxidant presses 1 ~ 2: 2 mol ratio with pyrrole monomer, continues
Oxidant is added under stirring condition and carries out pyrroles's polymerisation, after 5 ~ 10h of stirring reaction at a temperature of 0-8 DEG C, is spent respectively
Ionized water, methanol cyclic washing 5 times, obtained grey black product through drying 3 ~ 6h at a temperature of 50 ~ 80 DEG C, obtain polypyrrole bag again
The spherical zinc oxide of nanometer covered.
2. the spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding according to claim 1, its feature
It is：Described zinc salt is one kind in zinc acetate, zinc citrate, zinc lactate.
3. the spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding according to claim 1, its feature
It is：Described precipitating reagent is one kind in urea, hexa or sodium hydroxide.
4. the spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding according to claim 1, its feature
It is：Described surfactant is one kind or its mixture in dodecyl sodium sulfate, sodium laurate or polyethylene glycol.
5. the spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding according to claim 1, its feature
It is：Described oxidant is ammonium persulfate or hydrogen peroxide.
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