CN106532058A - Zinc negative electrode material of zinc air cell and preparation method for zinc negative electrode material - Google Patents
Zinc negative electrode material of zinc air cell and preparation method for zinc negative electrode material Download PDFInfo
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- CN106532058A CN106532058A CN201611191755.XA CN201611191755A CN106532058A CN 106532058 A CN106532058 A CN 106532058A CN 201611191755 A CN201611191755 A CN 201611191755A CN 106532058 A CN106532058 A CN 106532058A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a zinc negative electrode material of a zinc air cell and a preparation method for the zinc negative electrode material. The negative electrode material comprises metal zinc powder, zinc oxide powder, a binder, and a dual-functional additive with a one-dimensional tubular structure and formed by dual-layer metal oxide; the preparation method comprises the steps of adding the metal zinc powder, the zinc oxide powder, a conductive agent and the dual-functional additive into a binder-containing solution, performing ultrasonic dispersion processing, and heating and evaporating a solvent while stirring to obtain the zinc negative electrode material. The zinc negative electrode material is added with the dual-functional additive which can lower electrode internal resistance as well as supply a diffusion channel for an electrolyte, so that the discharging capacity and the rate capability of the cell can be improved; and meanwhile, a titanium dioxide inner layer has super-hydrophilic property and insulativity, so that the water delivery property of the electrolyte diffusion channel is forcefully enlarged, channel blocking is prevented, and the cycling life and the capacity stability of the cell are effectively prolonged and improved.
Description
Technical field
The present invention relates to a kind of zinc load material and preparation method thereof, more particularly to a kind of to be used for the secondary electricity of alkaline zinc-air
The zinc load material in pond, belongs to air cell field.
Background technology
Alkaline zinc-air secondary cell has high capacity, open-circuit voltage height, the cost of raw material low, environmentally friendly, safe
Advantage, be a kind of secondary cell of green high-capacity environment-protecting.However, zinc air secondary battery is easily densified by zinc load, put
In passivation and charging process in electric process, deformation, the impact of dendritic growth, cause discharge capacity of the cell low, in discharge process
Capacity attenuation is fast, and capacity is unstable, so that its application is limited by very large.
Oxidation product of the zinc oxide as zinc-air battery negative electrode active material, its poorly conductive, internal resistance in charging process
Consume big, cause efficiency for charge-discharge low, in discharge process, easily cause metallic zinc passivation, capacity is difficult to be given full play to.In order to
Solve the problems, such as that zinc oxide poorly conductive brings, people will be acetylene black, Nanometer Copper, bismuth metal or bismuth oxide etc. various with height
The additive of electric conductivity is uniformly mixed with active material and bonding agent, and coating is fabricated to zinc load on a current collector, so as to reach
Reduce electrode internal resistance, improve battery charging and discharging voltage platform, improve efficiency for charge-discharge, discharge capacity and the high rate performance of battery
Effect.
But, common conductive additive, either still one-dimensional or other patterns of zero dimension, cannot all solve zinc
Zinc powder electrode densification problem caused by the redistribution of active material in negative pole, with being repeated for battery charging and discharging, electricity
Pole porosity and reaction specific surface area reduce rapidly, participate in the H of electrochemical reaction2O and OH-Therefore the diffusion admittance of ion is received
To obstruction, the raising for ultimately resulting in the discharge capacity and high rate performance of battery can not be maintained, and the cycle life of battery is low.
The content of the invention
Redistributing under the conditions of repeated charge for existing zinc air secondary battery negative electrode active material zinc causes
Zinc powder electrode densification, participate in electrochemical reaction H2O and OH-The diffusion admittance of ion is blocked, discharge capacity and multiplying power
Performance continuous decrease, the problem that battery cycle life shortens, first purpose of the present invention be provide a kind of good conductivity,
Porosity and storage liquid rate are high, can persistently improve the discharge capacity and high rate performance of zinc-air battery, extend zinc-air battery circulation
The zinc load material in life-span.
Second object of the present invention be a kind of simple to operate, low cost is provided prepare the zinc load material
Method.
In order to realize above-mentioned technical purpose, the invention provides a kind of zinc-air battery zinc load material, comprising metallic zinc
Powder (Zn), oxide powder and zinc (ZnO) and bonding agent, also comprising addictive with dual functions；The addictive with dual functions is with by double-deck gold
The one-dimensional tubular structure that category oxide is constituted, its inner layer metal oxide are titanium dioxide (TiO2), outer layer metal oxide is
Bismuth oxide (Bi2O3), indium oxide (In2O3), tin ash (SnO2), lead oxide (PbO), brown lead oxide (PbO2), three oxidation two
Chromium (Cd2O3) at least one.
Technical scheme, it is critical only that and a kind of special difunctional add is with the addition of in conventional zinc load material
Plus agent, which has the one-dimensional tubular structure being made up of two layer metal oxide, while having electronic conduction ability and electrolyte defeated
Send ability.Addictive with dual functions outer layer metal oxide after activation is reduced to the metal simple-substance of high electronic conduction ability,
Inner space has storage electrolyte simultaneously, provides the effect of diffusion admittance for electrolyte.Addictive with dual functions have be different from
The hollow structure of common metal oxides, not only remains the distribution of common metal oxides uniform current, reduces in electrode ohmic
The advantage of resistance, and due to inner hollow, tube wall porous, improve the porosity of zinc electrode；Meanwhile, internal layer titanium dioxide layer exists
Stable metal micron tubular construction is played during activation, is increased the Water conductance of electrolyte diffusion admittance, is prevented zinc oxide
Internal deposition, so that its porosity is not affected by electrode densification and is gradually reduced, ultimately improves zinc-air battery
Discharge capacity and high rate performance, significantly improve the cycle life and capacity stability of battery.
Addictive with dual functions of the present invention is prepared as follows and obtains：With fiber as template, lead in fibrous template successively
Cross chemical method deposition of titanium oxide layer and metal oxide layer.Concrete grammar is as follows：By vinal acetone ethanol
Mixed liquor (v/v 1:1) oil removing 3h, subsequently with the potassium hydroxide solution ultrasonic oscillation roughening 2h of 1mol/L.After roughening
Fiber soaks the alkali lye that 10min removes remained on surface with watery hydrochloric acid, and deionized water is cleaned 2 times, is dried in air dry oven.
The fiber that 1g was processed is dispersed in (absolute ethyl alcohol in the solution of the 200mL containing 0.9mL concentrated ammonia liquors as template:Water, v/v
=4:1), ultrasonic 30min.Solution after dispersion is slowly added dropwise 2mL butyl titanates, and 45 DEG C of magnetic agitations reactions 6～
24h, after product filtration, deionized water and ethanol are respectively washed 3 times, obtain the polyvinyl alcohol of different-thickness coated by titanium dioxide
Fiber, dry for standby.Dried product is added in the certain density metal salt solutions of 250mL, ultrasonic disperse 30min
Afterwards, mechanical agitation add NaOH to be adjusted to certain pH value, after 30min, obtain accordingly aoxidizing containing different-thickness metal
The addictive with dual functions presoma of nitride layer or hydroxide layer.Presoma is taken out, deionized water cleans drying.Presoma is put
It is heat-treated in temperature programmed control stove in atmosphere, 1～10 DEG C/min of heating rate, 500～900 DEG C of thermostat temperature, constant temperature
2～6h of time, removes fibrous template, naturally cools to room temperature, obtain corresponding addictive with dual functions.
The outer layer metal source that the present invention is adopted during addictive with dual functions is prepared is respectively five nitric hydrate bismuth (Bi
(NO3)3·5H2O), nitric hydrate indium (In (NO3)3·4.5H2O), two hydrated stannous chloride (SnCl2·2H2O), plumbi nitras (Pb
(NO3)2), six hydrated chromium trichloride (CrCl3·6H2O), the amount of material is 4mmol～25mmol, the pH value of deposition is respectively 2,
3.3、0.9、4.1、4。
The bismuth salt and tin-salt solution in deposited metal source of the present invention also contains nitric acid (HNO respectively3) and hydrochloric acid (HCl), concentration
For 0.137mol/L.
The present invention is prepared in the metal salt solution of brown lead oxide addictive with dual functions while being also added with 10g sodium hypochlorite
(NaClO) as oxidant.
Preferred scheme, the internal diameter of the addictive with dual functions is 0.01～0.3 μm, 0.02～0.5 μm of wall thickness, draw ratio
1:20～1:300.
More preferably scheme, the titanium dioxide internal layer thickness of the addictive with dual functions is 2～20nm.
More preferably scheme, the zinc load material include following mass percent component：Metal zinc 5%～10%,
Oxide powder and zinc 75%～80%, addictive with dual functions 2%～7%, bonding agent 3%～8%.
Preferred scheme, the bonding agent include polytetrafluoroethylene (PTFE) (PTFE), polyacrylic acid (PAA), polyvinyl alcohol
(PVA) at least one in.
Preferred scheme, the zinc load material include≤5% conductive agent.Most preferably conductive agent includes conductive charcoal
At least one in black, acetylene black, Super-P.
Present invention also offers a kind of preparation method for preparing described zinc-air battery zinc load material, the method be
Under stirring condition, metal zinc, oxide powder and zinc, conductive agent and addictive with dual functions are added in the solution containing bonding agent, are surpassed
Sound decentralized processing, then under the conditions of being stirred, heating evaporation solvent obtains zinc load material.
Preferred scheme, ultrasonic disperse process time are 30～60min.
Preferred scheme, boiling point of the heating-up temperature less than solvent in heating evaporation dissolving agent process.
The concrete preparation method of the zinc load material of the present invention：Bonding agent is added in solvent (solvent adding amount is more than
More than 1.4 times of zinc load material gross mass), 10～30min is stirred, the solution containing bonding agent is obtained；By metal zinc, oxidation
Zinc powder, conductive agent, addictive with dual functions, are separately added in the above-mentioned solution containing bonding agent while stirring, subsequently ultrasound point
Dissipate and process 30～60min；Solution heated at constant temperature stirring after ultrasonic disperse is processed, mixing speed are more than 500 revs/min, make
Solvent evaporation obtains the zinc load material with certain viscosity.
The solvent that the present invention is adopted is at least one in water, absolute ethyl alcohol, acetone and dimethylformamide.Evaporation process
Boiling point of the temperature of middle heating less than solvent, evaporation time are determined by the viscosity of negative material.
Among addictive with dual functions to be added to technical scheme zinc load material, after activation, hollow is double
The outer layer metal oxide of functional additive is changed into the metal level of porous, while electrode internal resistance is reduced, can be significant
The porosity of electrode is improved, while titanium dioxide internal layer has high-hydrophilic and insulating properties, electrolyte diffusion is effectively increased
The storage liquid rate of passage and Water conductance, prevent the blocking of passage.And pass through the present invention zinc load material preparation method, can have
Effect avoid negative material prepare and electrode activation during addictive with dual functions it is destructurized.
Compared with prior art, technical scheme brings following beneficial effect：
(1) addictive with dual functions is added with zinc load material of the invention, addictive with dual functions has one-dimensional hollow pipe
Shape structure, which raises the porosity of zinc load.As higher porosity improves the storage liquid rate of electrode, so as to reduce electricity
Solution diffusion length of the liquid from bulk solution to active material surface so that the depth of discharge of electrode is further improved, and changes
It has been apt to the discharge capacity of electrode.
(2) in zinc load material of the invention, addictive with dual functions, after activation, is changed into inner hollow, tube wall porous
Structure, while inwall also deposits the titanium dioxide of one layer of Superhydrophilic, can significantly improve the expansion of electrode interior electrolyte
Scattered ability.The transfusion ability of superelevation and the larger liquid rate porosity that stores are conducive to reducing inhibition of the solid phase to electrolyte, carry
The uniformity coefficient of high pass electric current distribution, the final multiplying power discharging ability for causing electrode are further improved.
(3) addictive with dual functions inwall of the invention equably deposits one layer of stable semi-conducting material of electrochemical properties
Titanium dioxide, solves common metal oxides pipe in electroreduction due to structural instability that phase transition is caused, it is easy to collapse
Collapse and electrode is densified the shortcoming for causing electrolyte diffusion admittance to block.Due to addictive with dual functions activation when structure
Protected, metallic zinc is avoided when charge and discharge cycles in its internal electrochemical deposition, zinc load is in multiple discharge and recharge
After circulation, addictive with dual functions remains in that complete design feature and stable pick up, so as to avoid the cause of zinc load
Densification, improves the cycle life of battery.
In a word, the addictive with dual functions for adding in zinc load material of the invention is while have electronic conduction ability and electrolysis
Liquid conveying capacity.Addictive with dual functions after activated is reduced to the metal simple-substance of high electronic conduction ability, while internal empty
Between have storage electrolyte, provide the effect of diffusion admittance for electrolyte.The addictive with dual functions of the present invention has different from general
The hollow structure of logical metal oxide, which not only remains the distribution of common metal oxides uniform current, reduces in electrode ohmic
Resistance advantage, and due to inner hollow, tube wall porous, the porosity of electrode is beneficially improved, meanwhile, internal layer titanium dioxide layer
Stable metal micron tubular construction is played during activation, is increased the Water conductance of electrolyte diffusion admittance, is prevented zinc oxide
Inside deposition so that its porosity is not densified by electrode and being affected and being gradually reduced, ultimately improve putting for battery
Capacitance and high rate performance, significantly improve the cycle life and capacity stability of battery.
Description of the drawings
【Fig. 1】Structural representation after bismuth oxide addictive with dual functions activation of the present invention.
Specific embodiment
Specific examples below is intended to further illustrate present invention, rather than limits the protection of the claims in the present invention
Scope.
Embodiment 1
Addictive with dual functions：Internal diameter 50nm, titanium dioxide layer thickness 8nm, bismuth oxide layer thickness 100nm, 45 μm of length.
Percentage by weight：Metal zinc 5%, oxide powder and zinc 80%, addictive with dual functions 7%, conductive black 5%, poly- four
PVF 3%.
The preparation of zinc load material：Prepare 10mL absolute ethyl alcohols, add 60% suspension of 4d polytetrafluoroethylene (PTFE), magnetic agitation
20min.A certain amount of metal zinc, oxide powder and zinc, addictive with dual functions, conductive black are weighed by above proportioning, is sequentially added
To in the ethanol solution containing polytetrafluoroethylene (PTFE), stirring 30min is continued thereafter with.Scattered solution is continued into stirring, stirring speed
600 revs/min of degree, concurrently sets 60 DEG C of dispersant evaporating temperature, obtains cathode size after 10 minutes.
This slurry is uniformly coated on the brass screen of 2cm × 2cm, and in aeration cabinet, 80 DEG C are dried 5h, most
It is thick for 0.3mm in 20MPa lower sheetings afterwards.
Relative to common bismuth oxide additive with the zinc load prepared by identical preparation method, this material institute after activation
Obtained zinc load has the advantages that discharge capacity height, good rate capability, has extended cycle life.Aoxidized with the saturation of 6mol/LKOH
Zinc solution is electrolyte, commercial nickel hydroxide (Ni (OH)2) electrode be positive pole, be assembled into simulated battery, with filling for 0.2C/0.5C
The charge and discharge cycles test of 1C/1C is carried out after 4 circle of discharge-rate activation.The discharge capacity first of ordinary electrode is 503mAh g-1,
And the discharge capacity first of zinc load prepared by the present invention is 578mAh g-1；After 100 circle of circulation, the discharge capacity of ordinary electrode
For 243mAh g-1, and the discharge capacity of zinc load of the present invention is 497mAh g-1；Control cell front 100 circle in charging
In buckle line and discharge voltage profile, the low 0.174V compared with common batteries is pressed in the charging of battery of the present invention, in electric discharge, presses high
0.032V.To common zinc load and zinc load of the present invention respectively in the multiplying power of 1C/1C, 2C/2C, 5C/5C, 10C/10C and 1C/1C
Continuously do high rate performance test 50 to enclose under the conditions of discharge and recharge, as a result show that the discharge capacity of zinc load of the present invention compares common zinc oxide
Negative pole will be higher by 70mAh g under different multiplying-1、62mAh g-1、37mAh g-1、19mAh g-1、68mAh g-1.Result above
Utilization rate and its high rate performance invention significantly improves zinc negative active substance are illustrated, following for zinc load is effectively extended
Ring performance.
Embodiment 2
Addictive with dual functions A：Internal diameter 50nm, titanium dioxide layer thickness 12nm, chrome green thickness degree 200nm, length
23μm；
Addictive with dual functions B：Internal diameter 50nm, titanium dioxide layer thickness 10nm, brown lead oxide thickness degree 180nm, 23 μ of length
m。
Percentage by weight：Metal zinc 10%, oxide powder and zinc 76%, addictive with dual functions A 2%, addictive with dual functions B
2%th, conductive black 5%, polyvinyl alcohol 5%.
The preparation of zinc load material：Prepare 15mL acetone, add 0.0588g polyvinyl alcohol, magnetic agitation 30min.By with
Upper proportioning weighs certain metal zinc, oxide powder and zinc, addictive with dual functions A and B, conductive black, is added sequentially to containing poly-
In the acetone soln of vinyl alcohol, stirring 30min is continued thereafter with.Scattered solution is continued into stirring, 2000 revs/min of mixing speed
Clock, concurrently sets 50 DEG C of dispersant evaporating temperature, obtains cathode size after 8 minutes.
This slurry is uniformly coated on the brass screen of 2cm × 2cm, in aeration cabinet, 80 DEG C are dried 5h, and
20MPa lower sheetings are that 0.3mm is thick.
It is relative to common chrome green and brown lead oxide additive with the zinc load prepared by identical preparation method, living
Zinc load obtained by this material after change has the advantages that discharge capacity height, good rate capability, has extended cycle life.With 6mol/L
The saturation burnett's solution of KOH be electrolyte, commercial nickel hydroxide (Ni (OH)2) electrode be positive pole, be assembled into simulated battery, use
The charge and discharge cycles test of 1C/1C is carried out after 4 circle of charge-discharge magnification activation of 0.2C/0.5C.The electric discharge first of ordinary electrode is held
Measure as 496mAh g-1, and the discharge capacity first of zinc load prepared by the present invention is 564mAh g-1；After 100 circle of circulation, commonly
The discharge capacity of electrode is 257mAh g-1, and the discharge capacity of zinc load of the present invention is 507mAh g-1；Control cell front
Buckle line and discharge voltage profile in charging in 100 circles, in the charging of battery of the present invention, press low compared with common batteries
0.114V, presses high 0.05V in electric discharge.To common zinc load and zinc load of the present invention respectively in 1C/1C, 2C/2C, 5C/5C, 10C/
Continuously do high rate performance test 50 to enclose under the conditions of the rate charge-discharge of 10C and 1C/1C, as a result show the electric discharge of zinc load of the present invention
Capacity Ratio common zinc oxide negative pole will be higher by 64mAhg under different multiplying-1、55mAh g-1、39mAh g-1、13mAh g-1、
66mAh g-1.Utilization rate and its high rate performance invention significantly improves zinc negative active substance are these results suggest that, effectively
The cycle performance for extending zinc load.
Embodiment 3
Addictive with dual functions：Internal diameter 100nm, titanium dioxide layer thickness 4nm, bismuth oxide layer thickness 300nm, 14 μm of length.
Percentage by weight：Metal zinc 10%, oxide powder and zinc 78%, addictive with dual functions 2%, acetylene black 5%, polytetrafluoro
Ethene 5%.
The preparation of zinc load material：Prepare 13mL deionized waters, add 60% suspension of 3d polytetrafluoroethylene (PTFE), magnetic agitation
30min.Certain metal zinc, oxide powder and zinc, addictive with dual functions, acetylene black are weighed by above proportioning, is added sequentially to contain
In having the dispersion liquid of polytetrafluoroethylene (PTFE), stirring 30min is continued thereafter with.Scattered solution is continued into stirring, mixing speed 2000
Rev/min, 75 DEG C of dispersant evaporating temperature is concurrently set, after 21 minutes, cathode size is obtained.
This slurry is uniformly coated on the brass screen of 2cm × 2cm, in aeration cabinet, 80 DEG C are dried 5h, and
20MPa lower sheetings are that 0.3mm is thick.
Relative to common indium oxide additive with the zinc load prepared by identical preparation method, this material institute after activation
Obtained zinc load has the advantages that discharge capacity height, good rate capability, has extended cycle life.Aoxidized with the saturation of 6mol/LKOH
Zinc solution is electrolyte, commercial nickel hydroxide (Ni (OH)2) electrode be positive pole, be assembled into simulated battery, with filling for 0.2C/0.5C
The charge and discharge cycles test of 1C/1C is carried out after 4 circle of discharge-rate activation.The discharge capacity first of ordinary electrode is 489mAh g-1,
And the discharge capacity first of zinc load prepared by the present invention is 534mAh g-1；After 100 circle of circulation, the discharge capacity of ordinary electrode
For 157mAh g-1, and the discharge capacity of zinc load of the present invention is 398mAh g-1；Control cell front 100 circle in charging
In buckle line and discharge voltage profile, the low 0.103V compared with common batteries is pressed in the charging of battery of the present invention, in electric discharge, presses high
0.037V.To common zinc load and zinc load of the present invention respectively in the multiplying power of 1C/1C, 2C/2C, 5C/5C, 10C/10C and 1C/1C
Continuously do high rate performance test 50 to enclose under the conditions of discharge and recharge, as a result show that the discharge capacity of zinc load of the present invention compares common zinc oxide
Negative pole will be higher by 50mAh g under different multiplying-1、43mAh g-1、29mAh g-1、11mAh g-1、49mAh g-1.Result above
Utilization rate and its high rate performance invention significantly improves zinc negative active substance are illustrated, following for zinc load is effectively extended
Ring performance.
Embodiment 4
Addictive with dual functions A：Internal diameter 20nm, titanium dioxide layer thickness 11nm, tin dioxide layer thickness 40nm, 22 μ of length
m；
Addictive with dual functions B：Internal diameter 20nm, titanium dioxide layer thickness 14nm, brown lead oxide thickness degree 50nm, 22 μ of length
m。
Percentage by weight：Metal zinc 10%, oxide powder and zinc 75%, addictive with dual functions A5%, brown lead oxide are difunctional
Additive B 2%, polyacrylic acid 7%.
The preparation of zinc load material：Prepare 10mL dimethylformamides, add 0.1176g polyacrylic acid, magnetic agitation
30min.Certain metal zinc, oxide powder and zinc, addictive with dual functions A and B are weighed by above proportioning, is added sequentially to containing poly-
In acrylic acid dimethyl formamide solution, stirring 30min is continued thereafter with.Scattered solution is continued into stirring, mixing speed
1500 revs/min, 70 DEG C of dispersant evaporating temperature is concurrently set, after 18 minutes, cathode size is obtained.
This slurry is uniformly coated on the brass screen of 2cm × 2cm, in aeration cabinet, 80 DEG C are dried 10h, and
It is that 0.3mm is thick in 20MPa lower sheetings.
Relative to common tin ash and brown lead oxide additive with the zinc load prepared by identical preparation method, activate
Zinc load obtained by this material afterwards has the advantages that discharge capacity height, good rate capability, has extended cycle life.With 6mol/L
The saturation burnett's solution of KOH be electrolyte, commercial nickel hydroxide (Ni (OH)2) electrode be positive pole, be assembled into simulated battery, use
The charge and discharge cycles test of 1C/1C is carried out after 4 circle of charge-discharge magnification activation of 0.2C/0.5C.The electric discharge first of ordinary electrode is held
Measure as 513mAh g-1, and the discharge capacity first of zinc load prepared by the present invention is 552mAh g-1；After 100 circle of circulation, commonly
The discharge capacity of electrode is 174mAh g-1, and the discharge capacity of zinc load of the present invention is 523mAh g-1；Control cell front
Buckle line and discharge voltage profile in charging in 100 circles, in the charging of battery of the present invention, press low compared with ordinary electrode
0.191V, presses high 0.099V in electric discharge.To common zinc load and zinc load of the present invention respectively 1C/1C, 2C/2C, 5C/5C,
Continuously do high rate performance test 50 to enclose under the conditions of the rate charge-discharge of 10C/10C and 1C/1C, as a result show zinc load of the present invention
Discharge capacity will be higher by 67mAhg under different multiplying than common zinc oxide negative pole-1、56mAh g-1、29mAh g-1、6mAh g-1、
64mAh g-1.Utilization rate and its high rate performance invention significantly improves zinc negative active substance are these results suggest that, effectively
The cycle performance for extending zinc load.
Embodiment 5
Addictive with dual functions A：Internal diameter 250nm, titanium dioxide layer thickness 10nm, bismuth oxide layer thickness 300nm, 17 μ of length
m；
Addictive with dual functions B：Internal diameter 250nm, titanium dioxide layer thickness 11nm, tin dioxide layer thickness 250nm, length 17
μm。
Percentage by weight：Metal zinc 10%, oxide powder and zinc 78%, addictive with dual functions A3%, addictive with dual functions
B2%, super-p2%, polyvinyl alcohol 5%.
The preparation of zinc load material：Prepare 10ml dimethylformamides, add 0.0558 polyvinyl alcohol, magnetic agitation
30min.Certain metal zinc, oxide powder and zinc, addictive with dual functions A and B, super-p are weighed by above proportioning, is sequentially added
To in the dimethyl formamide solution containing polyvinyl alcohol, stirring 15min is continued thereafter with.Scattered solution is continued into stirring,
1000 revs/min of mixing speed, concurrently sets 70 DEG C of dispersant evaporating temperature, obtains cathode size after 30 minutes.
This slurry is uniformly coated on the brass screen of 2cm × 2cm, in aeration cabinet, 80 DEG C are dried 10h, and
It is that 0.3mm is thick in 20MPa lower sheetings.
Relative to common indium oxide and tin dioxide additive with the zinc load prepared by identical preparation method, after activation
This material obtained by zinc load there is discharge capacity height, good rate capability, have extended cycle life.With 6mol/L KOH
Saturation burnett's solution be electrolyte, commercial nickel hydroxide (Ni (OH)2) electrode be positive pole, be assembled into simulated battery, use
The charge and discharge cycles test of 1C/1C is carried out after 4 circle of charge-discharge magnification activation of 0.2C/0.5C.The electric discharge first of ordinary electrode is held
Measure as 509mAh g-1, and the discharge capacity first of zinc load prepared by the present invention is 543mAh g-1；After 100 circle of circulation, commonly
The discharge capacity of electrode is 57mAhg-1, and the discharge capacity of zinc load of the present invention is 517mAh g-1；Control cell front
Buckle line and discharge voltage profile in charging in 100 circles, in the charging of battery of the present invention, press low compared with ordinary electrode
0.204V, presses high 0.124V in electric discharge.To common zinc load and zinc load of the present invention respectively 1C/1C, 2C/2C, 5C/5C,
Continuously do high rate performance test 50 to enclose under the conditions of the rate charge-discharge of 10C/10C and 1C/1C, as a result show zinc load of the present invention
Discharge capacity will be higher by 46mAh g under different multiplying than common zinc oxide negative pole-1、35mAh g-1、46mAh g-1、53mAh
g-1、76mAh g-1.Utilization rate and its high rate performance invention significantly improves zinc negative active substance are these results suggest that,
The cycle performance of zinc load is extended effectively.
Presently preferred embodiments of the present invention is the foregoing is only, is not used to limit the scope of the claims in the present invention, other fortune
With the equivalence changes of the spirit of the present invention, all should all belong to protection scope of the present invention.
Claims (10)
1. a kind of zinc-air battery zinc load material, comprising metal zinc, oxide powder and zinc and bonding agent, it is characterised in that：Comprising
Addictive with dual functions；, with the one-dimensional tubular structure being made up of two layer metal oxide, its internal layer is golden for the addictive with dual functions
Category oxide be titanium dioxide, outer layer metal oxide be bismuth oxide, indium oxide, tin ash, lead oxide, brown lead oxide, three
Aoxidize at least one in two chromium.
2. zinc-air battery zinc load material according to claim 1, it is characterised in that：The addictive with dual functions it is interior
Footpath is 0.01～0.3 μm, 0.02～0.5 μm of wall thickness, draw ratio 1:20～1:300.
3. zinc-air battery zinc load material according to claim 1 and 2, it is characterised in that：The addictive with dual functions
Titanium dioxide internal layer thickness be 2～20nm.
4. the zinc-air battery zinc load material according to any one of claims 1 to 3, it is characterised in that：The zinc load
Material includes following mass percent component：
Metal zinc 5%～10%,
Oxide powder and zinc 75%～80%,
Addictive with dual functions 2%～7%,
Bonding agent 3%～8%.
5. zinc-air battery zinc load material according to claim 4, it is characterised in that：The bonding agent includes polytetrafluoro
At least one in ethene, polyacrylic acid, polyvinyl alcohol.
6. zinc-air battery zinc load material according to claim 4；It is characterized in that：The zinc load material comprising≤
5% conductive agent.
7. zinc-air battery zinc load material according to claim 6, it is characterised in that：The conductive agent includes conductive charcoal
At least one in black, acetylene black, Super-P.
8. the preparation method of the zinc-air battery zinc load material according to any one of claim 1～7, it is characterised in that：
Under agitation, metal zinc, oxide powder and zinc, conductive agent and addictive with dual functions are added in the solution containing bonding agent,
Ultrasonic disperse process, then under the conditions of being stirred, heating evaporation solvent obtains zinc load material.
9. the preparation method for preparing zinc-air battery zinc load material according to claim 8, it is characterised in that：Ultrasound point
Scattered process time is 30～60min.
10. the preparation method for preparing zinc-air battery zinc load material according to claim 8, it is characterised in that：Heating
Boiling point of the heating-up temperature less than solvent during evaporation solvent.
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