CN107275611B - A kind of spherical zinc oxide material of nanometer and preparation method of polypyrrole cladding - Google Patents
A kind of spherical zinc oxide material of nanometer and preparation method of polypyrrole cladding Download PDFInfo
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Abstract
The spherical zinc oxide material of nanometer and preparation method for the polypyrrole cladding with core-shell structure that the present invention relates to a kind of.For the spherical zinc oxide of nanometer of polypyrrole cladding using the spherical zinc oxide of nanometer as core, 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, forms polypyrrole clad in zinc oxide particle surfaces.The nano zine oxide of core-shell structure polypyrrole cladding prepared by the present invention has biggish 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 the nano zinc oxide materials and preparation method of a kind of polypyrrole cladding, are applied to nickel zinc alkali secondary
The invertibity and coulombic efficiency that electrode can be effectively improved in battery cathode, improve the cycle life of electrode, particularly belong to alkalinity two
Secondary nickel zinc battery cathode material technical field.
Background technique
As most popular negative electrode material in aqueous solution one-shot battery system, zinc electrode have the advantages that it is very much, than
Such as high-energy density, high open circuit voltage, no pollution to the environment, and rich reserves are low in cost.So applying zinc electrode in alkali
Property secondary cell in trial be constantly subjected to people concern.But when as secondary battery cathode material, since its electric discharge produces
Object is soluble in electrolyte, causes during the 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 that additive, which is added, in active material, such as in electrode material
Calcium is added in material, bismuth, tin, indium, metal oxides or the hydroxide such as silver and titanium can enough inhibit zinc electrode dendrite to a certain degree
And the generation of deformation.Organic additive is mainly used for electrolyte, for improving the uniformity of zinc deposition.However, inorganic addition
Contact of the agent with active material is not enough, and main function is to improve hydrogen-evolution overpotential, unobvious to the dissolution of discharging product
Effect, and organic additive increases electrode polarization, is efficiency for charge-discharge reduction, and is easy to decompose 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 wide range of applications with high conductivity, high stability, such as supercapacitor, erosion shield and chemical sensor etc.,
Its many outstanding performance causes the attention of scientific research personnel.Since zinc oxide is a kind of outstanding semiconductor material, polypyrrole
Compound with zinc oxide brings a series of interesting photoelectric properties, and researcher is to zinc oxide-polypyrrole compound at present
Preparation has carried out wide research, and preparation method includes chemical method and electrochemical process.Zhang Chengxiang etc. is closed by electrochemical method
At polypyrrole/zinc oxide nanometer composite material, polypyrrole is in typical cauliflower-shaped structure, and white ZnO particulate inclusion exists
In PPy, it is filled in the intergranular gap PPy.Rastogi etc. is prepared for PPy by electrochemical method and coats rodlike oxidation
Zinc shows preferable capacitive property.Li et al. is prepared for PPy in oxidation zincode substrate in the method for gas-phase polymerization, 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 in the spherical zinc oxide surface of nanometer by chemical oxidization method, not only
Preparation method is simplified, the influence of voltage and 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 be realized 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.
Summary 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 inhibits the generation of zinc dendrite in zinc electrode charge and discharge process, extend cycle life.
A kind of spherical zinc oxide material of nanometer of present invention polypyrrole cladding and the preparation method is as follows:
(1) the spherical zinc oxide material of nanometer of polypyrrole cladding
The spherical zinc oxide material of nanometer of polypyrrole cladding is using the spherical zinc oxide of the nanometer of partial size 40-150nm as core, surface
Uniformly cladding is with a thickness of the polypyrrole shell of 5-25nm, and wherein the mass percent of polypyrrole is 5%-20%.
(2) the spherical zinc oxide preparation method of nanometer of polypyrrole cladding
Step 1: the molar ratio of control precipitating reagent and zinc salt is 1 ~ 2: 4, by the deionized water or ethylene glycol solution of precipitating reagent
It is uniformly mixed with zinc salt, thereafter the hydro-thermal reaction 5-10h at 150 ~ 200 DEG C；Product is filtered after being cooled to room temperature, and respectively
With water, ethanol washing 3 times, it is then dried to obtain the spherical zinc oxide of nanometer again.
Step 2: surfactant and the spherical zinc oxide of nanometer are added the spherical zinc oxide of above-mentioned nanometer by 1: 4 molar ratio
Enter into the aqueous solution of surfactant, 5 ~ 30min of ultrasonic disperse, forms the zinc oxide colloidal sol of stable dispersion.
Step 3: the molar ratio of control pyrrole monomer and nano zine oxide is 1 ~ 3: 20, and pyrrole monomer is dissolved in deionized water
In, it is then added in zinc oxide colloidal sol, 10 ~ 30min of ultrasonic disperse；Oxidant and pyrrole monomer press 1 ~ 2: 2 molar ratio, hold
Oxidant progress pyrroles's polymerization reaction is added under continuous stirring condition to use respectively after being stirred to react 5 ~ 10h at a temperature of 0-8 DEG C
Deionized water, methanol wash 5 times repeatedly, and obtained grey black product through 3 ~ 6h dry at a temperature of 50 ~ 80 DEG C, obtains polypyrrole again
The spherical zinc oxide of the nanometer of cladding.
The zinc salt is one of zinc acetate, zinc citrate, zinc lactate.
The precipitating reagent is one of urea, hexa or sodium hydroxide.
The surfactant is one of dodecyl sodium sulfate, sodium laurate or polyethylene glycol or its mixing
Object.
The 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 cathode, application is the result shows that the spherical zinc oxide of nanometer of polypyrrole cladding can alleviate the shape of dendrite significantly
At, 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 the described polypyrrole cladding nanometer of 65-85 parts by weight, 5-10 parts by weight conductive agent,
The zinc compound of 5-20 parts by weight carries out mechanical mixture and obtains negative electrode material mixture；
(b) dispersing agent of 0.02-5 parts by weight is dissolved in the deionized water of 25-35 parts by weight；
(c) step (b) acquired solution is added in the negative electrode material mixture of step (a), then under vigorous stirring
Binder solution is added, the negative electrode material weight ratio that binder solution and step (a) obtain is 1-5:100, is uniformly flowed
Dynamic property zinc load slurry；
(d) the zinc load slurry of step (c) is uniformly coated on zinc electrode collector two sides, dries, cuts after rolling
For zinc load finished product pole piece.
Step (a) conductive agent is the mixed of electrically conductive graphite and conductive carbon black, acetylene black, indium powder, aluminium powder, glass putty or copper powder
Close object；The zinc compound is zinc powder and zinc oxide, zinc-indium, zinc-indium-bismuth, zinc-tin or the mixing of zinc-Sn-In alloy powder
The mixture of one or both of object；Dispersing agent described in step (b) includes neopelex, dodecyl sulphur
Suan Na ﹑ cetyl trimethylammonium bromide, sodium hypophosphite, hexamethylenetetramine, Ju Yi bis- Chun ﹑ tetrabutyl phosphonium bromide An ﹑ thiocarbamide,
One or more of teabrom, Triton X-100；Binder described in step (c) be polytetrafluoroethylene (PTFE),
The one or more of sodium carboxymethylcellulose, polyvinyl alcohol, fluoropolymer, polyethylene, rubber and waterglass.
Beneficial effects of the present invention
The spherical zinc oxide of nanometer of polypyrrole cladding of the present invention can effectively inhibit compared to conventional oxidation zinc electrode material
The reunion of Zinc oxide particles and in charge and discharge process zinc dendrite formation, be remarkably improved electrode invertibity, coulomb effect
The cycle life of rate and electrode.
The present invention coats polypyrrole in the spherical zinc oxide surface of nanometer by chemical oxidization method, and preparation method is easy, abandons
The influence of voltage and current and electrode type to final product in electrochemical method, while not needing preparation harsh in vapor phase method
Condition can be realized and carry out effective modification of polypyrrole on nano granular of zinc oxide surface, and application is the result shows that polypyrrole coats
The spherical zinc oxide of nanometer have significant electrochemical reversibility and charge-discharge performance.
Detailed description of the invention
Fig. 1 is the TEM figure of the spherical zinc oxide of nanometer of polypyrrole of the present invention cladding；Fig. 2 is polypyrrole of the present invention cladding
The cyclic voltammetry curve figure of the spherical zinc oxide of nanometer；Fig. 3 is the charge and discharge of the spherical zinc oxide of nanometer of polypyrrole of the present invention cladding
Curve graph；Fig. 4 is the cycle life figure of conventional oxidation zinc；Fig. 5 is following for the spherical zinc oxide of nanometer of polypyrrole of the present invention cladding
Ring life diagram；SEM after Fig. 6 is conventional oxidation Zinc form schemes；Fig. 7 is the spherical zinc oxide of nanometer of polypyrrole of the present invention cladding
SEM figure after being circulated throughout.
Specific embodiment
In order to more specifically describe the present invention, with reference to the accompanying drawing and specific embodiment is to technical solution of the present invention
It carries out detailed.It is intended to further illustrate the present invention, is not intended to limit the present invention.
Embodiment 1
It takes 200mg zinc acetate to be dissolved in 50ml deionized water, 70mg hexa is separately taken to be dissolved in 50ml deionized water
In, above two solution is mixed, stirs 5 minutes, is subsequently transferred in 200ml hydrothermal reaction kettle, keeps hydrothermal temperature
160 DEG C, natural cooling after reacting 8 hours is taken out and is filtered, repeatedly rear obtained by drying to nanosphere with deionized water and ethanol washing
Shape Zinc oxide particles.It takes 37mg dodecyl sodium sulfate to be dissolved in 50ml deionized water, 100mg nano zine oxide is separately taken to be added
It states in solution, ultrasonic agitation makes the Nano sol of zinc oxide formation stable dispersion for 10 minutes, by above-mentioned colloidal sol as 5 DEG C of incubators
In, it is lasting to stir, 20mg pyrrole monomer is added, stirring dissolves it sufficiently in 30 minutes, 68mg ammonium persulfate is separately taken to be dissolved in 10ml
In deionized water, ammonium persulfate solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, after addition
Continue to be stirred to react 8 hours, is filtered, washed repeatedly with deionized water and methanol after reaction, the powder that will have been washed
It is placed in the baking oven of vacuum or inert gas environment, dries 3 hours in 60 DEG C to get the spherical oxidation of nanometer coated to polypyrrole
Zinc material, TEM figure are shown in Fig. 1.The spherical zinc oxide of 0.85g polypyrrole cladding nanometer and 0.05g zinc powder ﹑ 0.05g are led into electric stone ink ﹑
0.02g sodium carboxymethylcellulose and 0.03g polytetrafluoroethylene (PTFE) are added to after stirring in the beaker of 25ml, are added appropriate
Deionized water be modulated into the negative electrode slurry of uniform mobility, the slurry is coated to copper mesh two sides with scraper, after rolling simultaneously
It is dry, through the zinc load pole piece for being tailored into the mm of 20 mm × 20.Anode uses dimensions for the sintrered nickel of the mm of 50 mm × 50
Anode pole piece.It uses microporous polypropylene membrane and polypropylene non-woven cloth diaphragm to wrap up layer 2-3 respectively positive and negative anodes pole piece, is made into opening electricity
Pond, wherein electrolyte is 5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Embodiment 2
It takes 200mg zinc acetate to be dissolved in 80ml ethylene glycol, 15mg sodium hydroxide is separately taken to be dissolved in 20ml deionized water, it will be upper
Two kinds of solution mixing are stated, stirs 30 minutes, then mixed solution is transferred in 200ml hydrothermal reaction kettle, keep hydro-thermal reaction
150 DEG C of temperature, natural cooling after reaction 10 hours is taken out and is filtered, with deionized water and ethanol washing repeatedly after obtained by drying arrive
The spherical Zinc oxide particles of nanometer.It takes 55mg polyethylene glycol (PEG400) to be dissolved in 50ml deionized water, separately takes 100mg nano oxidized
Zinc is added in above-mentioned solution, and ultrasonic agitation makes the Nano sol of zinc oxide formation stable dispersion for 30 minutes, by above-mentioned colloidal sol as 0
It is lasting to stir in DEG C incubator, 15mg pyrrole monomer is added, stirring dissolves it sufficiently in 30 minutes, separately takes 10ml dioxygen water-soluble
In 10ml deionized water, hydrogen peroxide solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, has been added
Continue to be stirred to react 10 hours after finishing, filtering and washing repeatedly is carried out with deionized water and methanol after reaction, by what is washed
Powder is placed in the baking oven of vacuum or inert gas environment, dries 5 hours in 60 DEG C to get spherical to the nanometer of polypyrrole cladding
Zinc oxide material.By carbon coating zinc-aluminum hydrotalcite and the 0.1g zinc of 0.75g-Sn-In alloy Fen ﹑ 0.1g Yi Que Hei ﹑ 0.01g carboxylic first
Base sodium cellulosate and 0.04g polytetrafluoroethylene (PTFE) are added to after stirring in the beaker of 25ml, and suitable deionization is added
Water is modulated into the negative electrode slurry of uniform mobility, and the slurry is coated to copper mesh two sides with scraper, after rolling and dry, through cutting out
The zinc load pole piece of the mm of 20 mm × 20 is made.Anode uses dimensions for the sintrered nickel anode pole piece of the mm of 50 mm × 50.
It uses microporous polypropylene membrane and polypropylene non-woven cloth diaphragm to wrap up layer 2-3 respectively positive and negative anodes pole piece, is made into open cell, wherein electricity
Solution liquid is 5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Embodiment 3
It takes 200mg zinc acetate to be dissolved in 50ml deionized water, separately takes 25mg urea in 50ml deionized water, by above-mentioned two
Kind solution mixing, stirs 10 minutes, is subsequently transferred in 200ml hydrothermal reaction kettle, kept for 180 degrees Celsius of hydrothermal temperature,
Natural cooling after reacting 6 hours is taken out and is filtered, repeatedly rear obtained by drying to the spherical oxidation of nanometer with deionized water and ethanol washing
Zinc particle.It takes 30mg sodium laurate to be dissolved in 50ml deionized water, 100mg nano zine oxide is separately taken to be added in above-mentioned solution, surpass
Sound stirs the Nano sol for making zinc oxide form stable dispersion for 20 minutes, by above-mentioned colloidal sol as in 5 degrees Celsius of incubators, shading
15mg pyrrole monomer is added in lasting stirring, and stirring dissolves it sufficiently in 30 minutes, separately take 55mg ammonium persulfate be dissolved in 10ml go from
In sub- water, ammonium persulfate solution is added dropwise in the nano-zinc oxide sol containing pyrrole monomer, is continued after addition
It is stirred to react 10 hours, carries out filtering and washing repeatedly with deionized water and methanol after reaction, the powder washed is placed in
It is 3 hours dry in 80 degrees Celsius in the baking oven of vacuum or inert gas environment.Obtain the spherical oxidation of nanometer of polypyrrole cladding
Zinc material.It is fine that the spherical zinc oxide of 0.85g polypyrrole cladding nanometer and 0.05g zinc powder ﹑ 0.05g are led into electric stone ink ﹑ 0.02g carboxymethyl
It ties up plain sodium and 0.03g polytetrafluoroethylene (PTFE) is added to after stirring in the small beaker of 25ml, suitable deionized water is added
It is modulated into the negative electrode slurry of uniform mobility, the slurry is coated to copper mesh two sides with scraper, it is after rolling and dry, through tailoring
At the zinc load pole piece of the mm of 20 mm × 20.Anode uses dimensions for the sintrered nickel anode pole piece of the mm of 50 mm × 50.It will
Positive and negative anodes pole piece uses microporous polypropylene membrane and polypropylene non-woven cloth diaphragm to wrap up layer 2-3 respectively, open cell is made into, wherein being electrolysed
Liquid is 5.5M KOH, 1M NaOH, 0.5 M LiOH and the mixed liquor for being oxidized zincification.
Battery performance test
The battery that above-described embodiment is assembled does following activation processing, and: 0.1C charges 10 h, shelves 20min, after with
0.2C is discharged to 1.4 V, then shelves 20 min；Such charge and discharge 5 times, complete activation.Selection Hg/HgO is reference electrode, composition three
Electrode system carries out cyclic voltammetry.After being completed, then with the charging of 1C electric current under room temperature (25 ± 2 DEG C), 1C is put
Electricity, the cycle life of circulation measurement Ni-MH secondary battery.Test cell terminates test after recycling 200 times.Test result difference
It is shown in attached drawing 2,3,4,5,6 and 7.Analysis chart 2,3,4,5,6 and 7, it can be deduced that polypyrrole cladding prepared by the present invention is received
The spherical zinc oxide of rice, the presence of polypyrrole layer reduces zinc oxide and the probability of side reaction occurs for electrolyte, has good fill
Invertibity of discharging and charge and discharge platform, conventional oxidation zinc its capacity after 100 circulations has decreased to 220mAh/ as can be seen from Figure 4
G, and the polypyrrole cladding spherical zinc oxide of nanometer is also able to maintain the capacity of about 400 mAh/g after 200 circulations, after circulation
SEM figure shows that conventional oxidation zinc forms columnar dendrite, and polypyrrole coats the spherical zinc oxide of nanometer, and there is no apparent dendrite shapes
At illustrating that it alleviates the formation of dendrite significantly, significantly improve the cycle life of Ni-MH secondary battery.
Claims (4)
1. a kind of preparation method of the polypyrrole cladding spherical zinc oxide material of nanometer, it is characterised in that: the material preparation method
It is as follows:
(1) the spherical zinc oxide material of nanometer of polypyrrole cladding
For the spherical zinc oxide material of nanometer of polypyrrole cladding using the spherical zinc oxide of the nanometer of partial size 40-150nm as core, surface is uniform
The polypyrrole shell with a thickness of 5-25nm is coated, wherein the mass percent of polypyrrole is 5%-20%；
(2) the spherical zinc oxide preparation method of nanometer of polypyrrole cladding
Step 1: the molar ratio of control precipitating reagent and zinc salt is 1~2: 4, by the deionized water of precipitating reagent or ethylene glycol solution and zinc
Salt is uniformly mixed, thereafter the hydro-thermal reaction 5-10h at 150~200 DEG C；Product is filtered after being cooled to room temperature, and is used respectively
Then water, ethanol washing 3 times are dried to obtain the spherical zinc oxide of nanometer again；
Step 2: the spherical zinc oxide of above-mentioned nanometer is added to by surfactant and the spherical zinc oxide of nanometer by 1: 4 molar ratio
In the aqueous solution of surfactant, 5~30min of ultrasonic disperse forms the zinc oxide colloidal sol of stable dispersion；
Step 3: the molar ratio of control pyrrole monomer and nano zine oxide is 1~3: 20, and pyrrole monomer is dissolved in deionized water,
It is then added in zinc oxide colloidal sol, 10~30min of ultrasonic disperse；Oxidant and pyrrole monomer press 1~2: 2 molar ratio, hold
Oxidant progress pyrroles's polymerization reaction is added under continuous stirring condition to use respectively after being stirred to react 5~10h at a temperature of 0-8 DEG C
Deionized water, methanol wash 5 times repeatedly, and obtained grey black product through 3~6h dry at a temperature of 50~80 DEG C, obtains poly- pyrrole again
Cough up the spherical zinc oxide of nanometer of cladding.
2. a kind of preparation method of polypyrrole cladding spherical zinc oxide material of nanometer according to claim 1, feature exist
In: the precipitating reagent is one of urea, hexa or sodium hydroxide.
3. a kind of preparation method of polypyrrole cladding spherical zinc oxide material of nanometer according to claim 1, feature exist
In: the surfactant is or mixtures thereof one of dodecyl sodium sulfate, sodium laurate or polyethylene glycol.
4. a kind of preparation method of polypyrrole cladding spherical zinc oxide material of nanometer according to claim 1, feature exist
In: the oxidant is ammonium persulfate or hydrogen peroxide.
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