CN108288695A - A kind of zinc-based secondary battery cathode material and preparation method thereof - Google Patents
A kind of zinc-based secondary battery cathode material and preparation method thereof Download PDFInfo
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- CN108288695A CN108288695A CN201810025014.7A CN201810025014A CN108288695A CN 108288695 A CN108288695 A CN 108288695A CN 201810025014 A CN201810025014 A CN 201810025014A CN 108288695 A CN108288695 A CN 108288695A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The present invention relates to a kind of zinc-based secondary battery cathode material and preparation method thereof, the present invention, which adds modifying agent, makes zinc oxide surface be evenly distributed with positive charge, and resin cation is uniformly coated on zinc oxide surface by Electrostatic Absorption, and thickness is 5nm~50nm.The zinc oxide that resin cation coats is put into mixed salt solution and is stirred, metal ion is equably adsorbed in resin cation clad, and reducing agent, which is added, makes metal ion be reduced into 3nm~7nm metal simple-substances.Zn (OH) can be effectively inhibited by being coated on the resin cation of zinc oxide surface4 2‑It is spread into electrolyte, prevents or slow down the growth that zinc load is deformed in charge and discharge cycles with dendrite, be adsorbed on nanoscale metal particles in resin cation layer, overpotential of hydrogen evolution and coulombic efficiency can be improved, reduce gas-evolving electrodes and dendritic growth.The cycle performance that zinc load can be improved through the invention, is conducive to the marketization of zinc-base secondary battery.
Description
Technical field
The present invention relates to the preparation fields of alkaline secondary cell negative electrode material, negative more particularly to a kind of zinc-base secondary battery
Pole material and preparation method thereof.
Technical background
With the improvement of people's environmental awareness, develop it is environmentally protective, have extended cycle life, safe and reliable novel secondary it is dynamic
Power battery becomes the hot spot that various countries fall over each other research.Zinc-base secondary battery have operating voltage high, energy density and power density it is high,
There is no the advantages of memory effect.Compared to lithium ion battery, zinc-base secondary battery belongs to water system battery, in the mistake for producing and using
It not can cause environmental pollution in journey, and zinc resource rich reserves, cost is relatively low, so that zinc-base secondary battery is had wide
Market application prospect.
But it is that zinc load is deposited during charge and discharge cycles to hinder the bottleneck of zinc-base secondary battery marketization application at present
Serious deformation, zinc dendrite growth, the gas-evolving electrodes the problems such as, lead to that battery capacity decaying is very fast and cycle life is shorter.Zinc
It is that zinc oxide is soluble in alkaline electrolyte formation Zn (OH) that cathode, which deforms with the basic reason of dendritic growth,4 2-, repeatedly
In charging process, Zn (OH) in electrolyte4 2-Nonuniform deposition can cause the deformation of electrode and the growth of dendrite.Inhibit at present
The method that zinc oxide dissolving enters in electrolyte can be divided mainly into two kinds：(1) some additives are added into electrode or electrolyte；
(2) one layer of organic matter or inorganic matter are coated in zinc oxide particle surfaces.It is wherein that a kind of can effectively inhibit using the method for cladding
The approach of zinc oxide dissolving, but used covering material is to reduce the contact area of zinc oxide and electrolyte at present,
It cannot prevent Zn (OH)4 2-The problem of being spread to electrolyte, still remaining zinc electrode deformation and dendritic growth, and adopted at present
Covering material can not effectively inhibit the generation of hydrogen, and as charge and discharge carry out, the cycle performance decaying of battery is very fast.Cause
This, which needs to find a kind of covering material, can effectively inhibit Zn (OH)4 2-It is spread to electrolyte, while can effectively inhibit liberation of hydrogen rotten again
Erosion.
Invention content
It all cannot effectively inhibit Zn (OH) for current covering material4 2-To electrolyte diffusion and gas-evolving electrodes.The present invention
It proposes a kind of method for the resin cation coating zinc oxide having metal adsorption, prepares a kind of new zinc-based secondary battery cathode
Material.The resin cation of zinc oxide surface is coated on to Zn (OH)4 2-There is stronger electrostatic repulsion, can effectively prevent putting
The Zn (OH) generated in electric process4 2-Diffusion into electrolyte reduces the meltage of zinc oxide in the electrolytic solution, to effectively
The deformation and dendritic growth problem that ground inhibition zinc load generates in charge and discharge process.It is adsorbed on receiving in resin cation simultaneously
Rice metallic can improve overpotential of hydrogen evolution and coulombic efficiency, reduce gas-evolving electrodes.
A kind of zinc-based secondary battery cathode material of the present invention includes following component by weight percentage：
Zinc oxide 85%~95%, the particle diameter distribution of the zinc oxide is between 50nm~950nm；
Resin cation 2%~12%；In the resin cation, perfluorinated sulfonic resin account for resin cation 75~
95%, remaining resin cation accounts for 5~25%；Resin cation is uniformly coated on zinc oxide surface, thickness 5nm~
Between 50nm,
Metal 1%~3%, the metal includes non-rare earth metal and rare earth metal, wherein non-rare earth metal and rare earth gold
The mass ratio of category is in (1~5):Between 1；The metal is uniformly distributed in resin cation, and the grain size of single metal is 3nm
~7nm.In the present invention, the thickness of resin cation is greater than the grain size of single metal.
A kind of zinc-based secondary battery cathode material of the present invention, the zinc oxide are made of the zinc oxide of different-grain diameter；It is described
Mass percent between different-grain diameter zinc oxide is respectively：
Grain size is the zinc oxide 60~70% of 50nm~199.99nm；
Grain size is the zinc oxide 20~30% of 200nm~499.99nm；
Grain size is the zinc oxide 1~10% of 500nm~950nm.
A kind of zinc-based secondary battery cathode material of the present invention, the zinc oxide are modified zinc oxide, the modified zinc oxide；
The modified zinc oxide is with the zinc oxide after the solution immersion treatment containing modifying agent.The solution containing modifying agent includes ammonia
Water, ammonium acetate solution, ammonium nitrate solution, ammonium sulfate, sal volatile, one kind in cetyl ammonium bromide solution or more
Kind.
A kind of zinc-based secondary battery cathode material of the present invention, remaining described resin cation be fluorochemical urethane resin,
At least one of fluoroacrylic resin, polystyrene-divinylbenzene sulfonate resin.
A kind of zinc-based secondary battery cathode material of the present invention, the non-rare earth metal include tin, bismuth, indium, silver, gallium, cadmium,
At least one of lead, thallium, the rare earth metal include at least one of lanthanum, cerium, praseodymium, neodymium.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, includes the following steps：
Step 1
Zinc oxide powder is weighed in proportion, is added in dispersant and is uniformly mixing to obtain zinc oxide fluid dispersion；Then toward oxidation
Modifying agent is added in zinc dispersion liquid, stir and adjusts the pH value of system to 8~11；It filters, obtains modified after continuing stirring
Zinc oxide powder is denoted as solid A；
Step 2
Solid A is added in the solution of cation resin, keep mixeding liquid temperature be -10 DEG C~90 DEG C and ultrasound 60~
400min is separated by filtration and washs, and obtains the Zinc oxide powder of resin cation cladding, is denoted as solid B；
Step 3
Solid B is added in the solution of mixed metal salt, solution ph is adjusted to 2~6, after stirring, reducing agent is added,
Metal ion in resin cation is reduced into metal simple-substance, the cation by being filtered, washed to obtain metal adsorption is set
Fat coating zinc oxide is denoted as solid C；The mixed metal salt by containing non-rare earth metal element salt and containing thulium
Salt forms；
Step 4
Solid C is dried in vacuo, is kept the temperature at a temperature of 100~220 DEG C, the zinc-based secondary battery cathode is obtained
Material.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, the dispersant used in step 1 be water,
It is one or more in methanol, ethyl alcohol, acetone, ethylene glycol, polyethylene glycol 200, the liquid-solid ratio of dispersant and zinc oxide be (2~
10):1。
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, the modifying agent used in step 1 includes ammonia
Water, ammonium acetate solution, ammonium nitrate solution, ammonium sulfate, sal volatile, one kind in cetyl ammonium bromide solution or more
Kind, the mass percentage concentration of the modifying agent is 2%~8%.Preferably, the modifying agent choosing used in step 1 of the present invention
At least one of ammonium hydroxide, ammonium acetate solution, ammonium sulfate are selected, the mass percentage concentration of the modifying agent is 3%~6%.This
The mass ratio of zinc oxide and modifying agent is (10~50) in invention:1.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, the resin cation used in step 2 include
One in perfluorinated sulfonic resin, fluorochemical urethane resin, fluoroacrylic resin, polystyrene-divinylbenzene sulfonate resin
Kind, the mass fraction of the anions in solution resin of the cation resin is 5%~25%, the cation resin
Solvent is the mixed liquor that water and organic solvent form in solution, wherein the volume ratio of organic solvent and water is (1~5):1；It is described
Organic solvent includes at least one of methanol, ethyl alcohol, propyl alcohol, acetone, ether, ethylene glycol, the cation resin it is molten
The liquid-solid ratio of liquid and modified zinc oxide is (1~10):1.After resin cation coating zinc oxide used in the present invention, it can be formed
The film in appropriate aperture and porosity；When in the solution for placing it in mixed metal salt, it is convenient for rare earth element and non-rare earth metal
The immersion of element；After immersion, rare earth element and non-rare earth metal element uniform adsorption are in resin cation film；This goes back for the later stage
The metallic particles that original is evenly distributed and grain size is 3-7nm, provides necessary condition.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention in step 1, weighs oxide powder and zinc in proportion
End, is added to and stirs the aaerosol solution that 10~20min forms zinc oxide in dispersant, and ultrasonic 30min~120min obtains zinc oxide
Dispersion liquid；Modifying agent is added dropwise to the dispersion liquid and stirs 5~10min, be added buffer solution adjust the pH value of solution 8~
Between 11, continue 100~300min of stirring, modified Zinc oxide powder is obtained by filtration, is denoted as solid A；Used buffering
Liquid is ammonium hydroxide-ammonium chloride buffer, sodium dihydrogen phosphate-potassium dihydrogen phosphate, borax-borate buffer, borax-sodium hydroxide, boron
One kind in sand-sodium carbonate buffer, sodium carbonate-bicarbonate buffer solution.Preferably, in step 1 of the present invention, buffering is molten
Liquid selects one kind in ammonium hydroxide-ammonium chloride buffer, sodium carbonate-bicarbonate buffer solution, borax-sodium carbonate buffer.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, in step 2, by solid A be added to fellatio from
In the solution of subtree fat, it is 40 DEG C~90 DEG C and 60~400min of ultrasound to keep mixeding liquid temperature, is separated by filtration and washs for several times,
The Zinc oxide powder of resin cation cladding is obtained, solid B is denoted as.In the present invention by controlling concentration, the dosage of resin, leaching
The temperature of stain, time control cladding thickness of the resin cation on Zinc oxide powder.
Preferably, in step 2 of the present invention, the preferred perfluorinated sulfonic resin of resin cation and fluorochemical urethane resin contain
The mass percentage concentration of the solution of resin cation is 10%~20%.
Preferably, in step 2 of the present invention, solvent is water and organic solvent group in the solution of the cation resin
At mixed liquor, wherein the volume ratio of organic solvent and water be (2~3.8):1.
Preferably, in step 2 of the present invention, the solution of the cation resin and the liquid of modified zinc oxide are solid
Than for (3~8):1.
Solid B in step 3, is added to mixing gold by a kind of preparation method of zinc-based secondary battery cathode material of the present invention
In the solution for belonging to salt, for the pH value of the solution of the mixed metal salt adjusted with No. 1 buffer solution to 2~6, it is 25 to keep solution temperature
DEG C~50 DEG C under conditions of stir 5h~12h, be added dropwise reducing agent by the metal ion being adsorbed in resin cation restore
At metal simple-substance, the resin cation coating zinc oxide of metal adsorption is obtained by being filtered, washed, is denoted as solid C；Described 1
It is slow that number buffer solution is selected from disodium hydrogen phosphate-citrate buffer solution, phthalic acid-hydrochloride buffer, citric acid-sodium citrate
One kind in fliud flushing, acetic acid-sodium acetate buffer solution, glycine-HCI buffer solution.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, in step 3, mixed metal salt is water solubility
Salt；In the mixed metal salt, anion is selected from least one of chlorion, nitrate anion, sulfate radical, acetate；Containing non-dilute
The salt of earth metal element is selected from least one of pink salt, bismuth salt, indium salts, silver salt, gallium salt, cadmium salt, lead salt, thallium salt；It is described to contain
The salt of thulium is selected from least one of lanthanum salt, cerium salt, praseodymium salt, neodymium salt；In the solution of the mixed metal salt；Gold
Belong to a concentration of 0.1mol/L~1.0mol/L of element；In the solution of the mixed metal salt, non-rare earth metal element and rare earth
The molar ratio of element is (1~5):1.Preferably, in step 3 of the present invention, in mixed salt solution, metallic element it is dense
Degree is preferably 0.2mol/L~0.7mol/L.Preferably, the salt containing non-rare earth metal element is selected from pink salt, bismuth salt, indium salts, cadmium
At least one of salt.Preferably, the salt containing thulium is selected from least one of lanthanum salt, cerium salt.Preferably,
Non-rare earth metal element and the molar ratio of rare earth element are (2~4):1.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention, in step 3, the reducing agent includes formyl
At least one of amine, sodium borohydride, potassium borohydride, lithium aluminium hydride reduction, ascorbic acid, sodium nitrite, hydrazine hydrate.
A kind of preparation method of zinc-based secondary battery cathode material of the present invention in step 4, when vacuum drying, controls in stove
Air pressure is 10Pa~100Pa, and soaking time is 120min~400min.Preferably, in step 4, when vacuum drying, in stove
Air pressure is 30Pa~70Pa, and soaking time is 150min~300min.
The present invention has the advantage that：
1. a kind of preparation method of zinc-based secondary battery cathode material of the present invention is changed by modifying agent and is aoxidized
The surface that resin cation is uniformly coated on zinc oxide may be implemented in the distribution of zinc surface positive charge, changes and cation is added
The concentration of resin can obtain the clad of different-thickness (thickness is between 5nm~50nm).
2. a kind of preparation method of zinc-based secondary battery cathode material of the present invention, metal ion pass sequentially through ion
It exchanges and reduction is equably adsorbed on resin cation clad, compared with traditional method, the Metal Distribution of zinc oxide surface
More uniformly, the modification effect of metal is improved.
3. a kind of preparation method of zinc-based secondary battery cathode material of the present invention, keeps the temperature, energy under an inert atmosphere
The tightness degree combined between resin cation and zinc oxide is improved, keeps resin cation not easily to fall off in charge and discharge process.
4. a kind of zinc-based secondary battery cathode material of the present invention can not only inhibit Zn (OH)4 2-It spreads to electrolyte, can also reduce
Gas-evolving electrodes.Zn (OH) can effectively be hindered by being coated on the resin cation on the surfaces ZnO4 2-It is spread into electrolyte, reduces oxidation
The dissolving of zinc in the electrolytic solution improves zinc-nickel secondary batteries to effectively inhibit the deformation of zinc load and the growth of dendrite
Cyclical stability.The metal being adsorbed in resin cation simultaneously can reduce the internal resistance of battery, and overpotential of hydrogen evolution improves 20
~60mV is maintained at 70% or more by the charge and discharge cycles coulombic efficiency of 300 circles.
5. a kind of zinc-based secondary battery cathode material of the present invention can reduce electrode using the zinc oxide of different-grain diameter
Internal gap, realizes the densification of electrode, higher than the volume and capacity ratio of common zinc oxide by 10~20%.
Specific embodiment of the present invention is as follows：
Embodiment 1
(1) Zinc oxide powder for weighing 5g in proportion is added in the deionized water of 50ml, and stirring 10min forms zinc oxide
The aaerosol solution at zinc oxide, then ultrasound 40min formed zinc oxide fluid dispersion.5ml mass is added dropwise to the dispersion liquid
Score is 3% ammonium hydroxide and stirs 5min, and it is 8.5 that sodium carbonate-bicarbonate buffer solution, which is added, and adjusts the pH value of solution, continues to stir
Then modified Zinc oxide powder is obtained by filtration in 120min.
(2) modified Zinc oxide powder is added to the fluorine-containing of perfluorinated sulfonic resin that 30ml contains 7wt% and 1wt%
In the mixed solution of acrylic resin, it is 50 DEG C and ultrasound 100min to keep mixeding liquid temperature, is then isolated by filtration, obtains
Resin cation coating zinc oxide powder.
(3) SnCl of a concentration of 0.4mol/L of 50ml is measured2With the LaCl of a concentration of 0.1mol/L3Methanol mixed solution is put
Enter in beaker, the Zinc oxide powder of resin cation cladding be then added, disodium hydrogen phosphate-citrate buffer solution is added dropwise,
The pH value for adjusting solution is 4, and holding solution temperature stirs 6h under conditions of being 30 DEG C, is eventually adding ascorbic acid solution and stirs
0.5h obtains the zinc oxide of the resin cation cladding of Sn and La absorption by being filtered, washed.
(4) and then by obtained product it is put into vacuum drying chamber, controlled at 120 DEG C, keeps the temperature 200min, remove residual
The organic solvent stayed obtains a kind of zinc-based secondary battery cathode material, after testing the resin cation of zinc oxide surface
The thickness of layer is about 5nm~7nm, mass fraction 4.1%, and metallic tin and lanthanum are evenly distributed in the clad of resin cation
In, mass fraction 1.4%.
(5) material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/
The aqueous solution of LKOH carries out loop test as electrolyte, is recycled by the charge and discharge cycles of 100,200,300 circles, measures electrolysis
Zn (OH) in liquid4 2-Concentration be respectively 0.1mmol/L, 0.2mmol/L, 0.5mmol/L, the overpotential of hydrogen evolution of zinc load improves
20mV.It is maintained at 71% by the charge and discharge cycles coulombic efficiency of 300 circles, the capacity of battery is maintained at theoretical capacity
73%.
Embodiment 2
(1) Zinc oxide powder for weighing 5g in proportion is added in the methanol of 60ml, and stirring 15min forms the outstanding of zinc oxide
Solution is floated, then ultrasound 60min forms zinc oxide fluid dispersion.It is 5% ammonium chloride that 3ml mass fractions, which are added dropwise, to the dispersion liquid
Solution ＆ stir 5min, it is 9.4 that ammonium hydroxide-ammonium chloride buffer, which is added, and adjusts the pH value of solution, continues to stir 150min, then mistake
Filter obtains modified Zinc oxide powder.
(2) modified Zinc oxide powder is added to perfluorinated sulfonic resin that 35ml contains 10wt% and 1.5wt%
In the mixed solution of fluorochemical urethane resin, it is 60 DEG C and ultrasound 150min to keep mixeding liquid temperature, is then isolated by filtration,
Obtain resin cation coating zinc oxide powder.
(3) a concentration of 0.3mol/LBi (NO of 40ml are measured3)3With 0.1mol/LCe (NO3)3The mixed solution of ethylene glycol is put
Enter in beaker, the Zinc oxide powder of resin cation cladding is then added, citric acid-sodium citrate buffer solution is added dropwise, adjusts
The pH value for saving solution is 3.5, and holding solution temperature stirs 8h under conditions of being 35 DEG C, is eventually adding sodium borohydride solution and stirs
0.5h.By being filtered, washed to obtain the zinc oxide of the resin cation cladding of Bi and Ce absorption.
(4) and then by obtained product it is put into vacuum drying chamber, controlled at 150 DEG C, keeps the temperature 250min, remove residual
The organic solvent stayed obtains a kind of zinc-based secondary battery cathode material, after testing the resin cation of zinc oxide surface
The thickness of layer is about 10nm~12nm, mass fraction 5.8%, and bismuth metal and cerium are evenly distributed in the cladding of resin cation
In layer, mass fraction 2.4%.
(5) material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/L
KOH aqueous solutions as electrolyte carry out loop test, by 100,200,300 circle charge and discharge cycles recycle, measure electrolysis
Zn (OH) in liquid4 2-Concentration is respectively 0.08mmol/L, 0.18mmol/L, 0.45mmol/L, and the overpotential of hydrogen evolution of zinc load carries
High 30mV.Charge and discharge cycles coulombic efficiency by 300 circles is 72%, and the capacity of battery is maintained at theoretical capacity
74.5%.
Embodiment 3
(1) Zinc oxide powder for weighing 5g is added in the ethyl alcohol of 70ml, and the suspension that stirring 20min forms zinc oxide is molten
Liquid, then ultrasound 90min formation zinc oxide fluid dispersion, 6ml mass fractions are added dropwise as 5% sal volatile to the dispersion liquid
And be stirred continuously, it is 10 that borax-sodium carbonate buffer, which is added, and adjusts the pH value of solution, continues to stir 200min, then filter
To modified Zinc oxide powder.
(2) modified Zinc oxide powder is added to the perfluorinated sulfonic resin and 2wt% polyphenyl that 30ml contains 15wt%
In ethylene-divinylbenzene sulfonic acid mixed resin solution, it is 80 DEG C and liquid ultrasound 100min to keep mixeding liquid temperature, is then passed through
It is separated by filtration, obtains resin cation coating zinc oxide powder.
(3) a concentration of 0.6mol/LIn (NO of 50ml are measured3)3With a concentration of 0.2mol/L Pr (NO3)3Aqueous solution is put into burning
In cup, the Zinc oxide powder of resin cation cladding is then added, acetic acid-sodium acetate buffer solution is added dropwise, adjusts solution
PH value is 6.5, and holding solution temperature stirs 10h under conditions of being 45 DEG C, is eventually adding formamide solution and stirs 0.5h, passes through
It is filtered, washed to obtain the resin cation of In and Pr absorption
The zinc oxide of cladding.
(4) and then obtained product is put into vacuum drying chamber, controlled at 180 DEG C, is kept the temperature 300min, is removed residual
Organic solvent, obtain a kind of zinc-based secondary battery cathode material, after testing the resin cation layer of zinc oxide surface
Thickness be about 15nm~17nm, mass fraction 8.3%, metal is evenly distributed in the clad of resin cation, matter
It is 2.6% to measure score.
(5) material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/L
KOH aqueous solutions as electrolyte carry out loop test, by 100,200,300 circle charge and discharge cycles recycle, measure electrolysis
Zn (OH) in liquid4 2-Concentration is respectively 0.06mmol/L, 0.15mmol/L, 0.35mmol/L, and the overpotential of hydrogen evolution of zinc load carries
High 40mV.It is maintained at 72.5% by the charge and discharge cycles coulombic efficiency of 300 circles, the capacity of battery is maintained at theoretical capacity
75.5%.
Comparative example 1
It tests as a comparison, the surface modifying agents for being added without zinc oxide is compared with embodiment 1.
(1) after testing, if being added without modifying agent, resin cation cannot be uniformly coated on the surface of zinc oxide,
Thickness is about in 0~30nm, mass fraction 3.5%, and metallic tin and lanthanum are evenly distributed in the clad of resin cation, matter
It is 1.1% to measure score.
(2) material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/L
KOH aqueous solutions as electrolyte carry out loop test, by 100,200,300 circle charge and discharge cycles, measure electrolyte in
Zn(OH)4 2-Concentration is respectively 0.36mmol/L, 0.92mmol/L, 2.1mmol/L, and coulombic efficiency is maintained at 61%, passes through
The capacity of the charge and discharge cycles battery of 300 circles is maintained at the 63% of theoretical capacity.
If not using modifying agent, resin cation cannot be uniformly coated on zinc oxide surface, have part Zn
(OH)4 2-It is diffused into electrolyte, reduces resin cation and prevent Zn (OH)4 2The effect spread into electrolyte causes to be electrolysed
Zn (OH) in liquid4 2-It increases, the cycle performance of battery reduces.
Comparative example 2
It tests, is not kept the temperature under an inert atmosphere with the comparison of embodiment 2 as a comparison.
The material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/L's
KOH aqueous solutions carry out loop test as electrolyte, are recycled by the charge and discharge cycles of 100,200,300 circles, measure electrolyte
Middle Zn (OH)4 2-Concentration is respectively 2.5mmol/L, 5.2mmol/L, 10.6mmol/L.Coulombic efficiency is 50%, by 300 circles
The capacity of charge and discharge cycles battery be maintained at the 52% of theoretical capacity.
If the zinc oxide of obtained resin cation cladding is tied without heat preservation between resin cation layer and zinc oxide
The tightness degree of conjunction can reduce, and cause resin cation layer easy to fall off, the Zn (OH) that discharge process generates4 2It can expand into electrolyte
It dissipates, leads to the Zn (OH) in electrolyte4 2It drastically increases, battery capacity decaying is very fast.
Comparative example 3
It tests, is compared without adsorption of metal ions with embodiment 3 as a comparison.
(1) after testing, without adsorption of metal ions, the thickness of the resin cation layer of zinc oxide surface does not change,
About 15nm~17nm, mass fraction 8.5%.
(2) material is made 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with 6mol/L
KOH aqueous solutions as electrolyte carry out loop test, by 100,200,300 circle charge and discharge cycles recycle, measure electrolysis
Zn (OH) in liquid4 2-Concentration is respectively 0.07mmol/L, 0.17mmol/L, 0.38mmol/L.Coulombic efficiency is maintained at
65.5%, it is maintained at the 63.5% of theoretical capacity by the capacity of the charge and discharge cycles battery of 300 circles.
If without adsorption of metal ions, apparent influence not will produce on the cycle performance of battery, but can cause tight
The gas-evolving electrodes of weight, cause coulombic efficiency relatively low.
Examples of series 4
As to experiment, the function and effect of more different resin cation concentration.
(1) the modified Zinc oxide powders of 5g are added separately to the perfluor that 30ml contains 1wt%, 15wt%, 35wt%
In sulfonate resin and 1.5wt% fluoroacrylic resin mixed solutions, it is 50 DEG C and difference 100min to keep mixeding liquid temperature, so
After be isolated by filtration, obtain the Zinc oxide powder of different resin cation covering amounts, be denoted as S respectively1、S2、S3。
(2) SnCl of three parts of a concentration of 0.4mol/L of 50ml is measured2With the LaCl of a concentration of 0.1mol/L3Methanol mixing is molten
Liquid is put into beaker, is separately added into S1、S2、S3, disodium hydrogen phosphate-citrate buffer solution is added dropwise, the pH value for adjusting solution is
4, holding solution temperature stirs 8h under conditions of being 30 DEG C, is eventually adding ascorbic acid solution and stirs 0.5h, by filtering, washing
It washs to obtain the resin cation coating zinc oxide of Sn and La absorption.Then obtained product is put into filled with N2The baking oven of protection
In, controlled at 120 DEG C, 200min is kept the temperature, remaining organic solvent is removed, obtains the different resin cation covering amounts
Zinc oxide, after testing the resin cation layer of zinc oxide surface have different thickness：S11~2nm of thickness, resin cation
Mass fraction is 0.5%, and the mass fraction of metal is 0.4%；S2About thickness 13nm~15nm, the mass fraction of resin cation are
7.5%, the mass fraction of metal is 2.5%；S3The mass fraction of about thickness 55nm~65nm, resin cation are 17.5%, gold
The mass fraction of category is 4.7%.
(3) by S1、S2、S3It is respectively prepared 1 × 1cm sizes, the zincode piece of thick 0.3mm, using NiOOH as to electrode, with
The KOH of 6mol/L carries out loop test as electrolyte, recycles by the charge and discharge cycles of 100,200,300 circles, measures respectively
Zn (OH) in electrolyte4 2-The capacity of concentration, coulombic efficiency, battery.The result of measurement such as the following table 1.
Indices of the different resin cation coating zinc oxides of table 1 as negative material
It can be obtained from table and coat oxidation using the perfluorinated sulfonic resin and 1.5wt% fluoroacrylic resins of 15wt%
When zinc, obtained resin cation layer is about 13nm~15nm, has preferable cyclical stability；Use 1% perfluorinated sulfonic acid
When resin, resin cation clad is too thin, to inhibiting Zn (OH)4 2-Diffusion effect unobvious, have part Zn (OH)4 2-Meeting
It enters in electrolyte, makes Zn in electrolyte (OH)4 2-The cycle performance of higher concentration, battery will be low；Use 35% perfluor
When sulfonate resin, resin cation clad is too thick, although to inhibiting Zn (OH)4 2-The effect spread to electrolyte is preferable, still
Also it will increase OH-Resistance is reacted with zinc oxide, electrode can be passivated, and capacity attenuation is very fast.
Claims (10)
1. a kind of zinc-based secondary battery cathode material, it is characterised in that；Include following component by weight percentage：
Zinc oxide 85%~95%, the particle diameter distribution of the zinc oxide is between 50nm~950nm；
Resin cation 2%~12%；In the resin cation, perfluorinated sulfonic resin accounts for the 75~95% of resin cation,
Remaining resin cation accounts for 5~25%；Resin cation is uniformly coated on zinc oxide surface, thickness 5nm~50nm it
Between,
Metal 1%~3%, the metal include non-rare earth metal and rare earth metal, wherein non-rare earth metal and rare earth metal
Mass ratio is in (1~5):Between 1；The metal is uniformly distributed in resin cation, and the grain size of single metal be 3nm~
7nm。
2. a kind of zinc-based secondary battery cathode material according to claim 1, it is characterised in that：The zinc oxide is by difference
The zinc oxide of grain size is constituted；Mass percent between the different-grain diameter zinc oxide is respectively：
Grain size is the zinc oxide 60~70% of 50nm~199.99nm；
Grain size is the zinc oxide 20~30% of 200nm~499.99nm；
Grain size is the zinc oxide 1~10% of 500nm~950nm；
The zinc oxide is modified zinc oxide, the modified zinc oxide；The modified zinc oxide is soaked with the solution containing modifying agent
Bubble treated zinc oxide；The solution containing modifying agent include ammonium hydroxide, ammonium acetate solution, ammonium nitrate solution, ammonium sulfate,
It is one or more in sal volatile, cetyl ammonium bromide solution.
3. a kind of zinc-based secondary battery cathode material according to claim 1, it is characterised in that：Remaining resin cation
For at least one of fluorochemical urethane resin, fluoroacrylic resin, polystyrene-divinylbenzene sulfonate resin.
4. a kind of zinc-based secondary battery cathode material according to claim 1, it is characterised in that：Non- rare earth metal includes
At least one of tin, bismuth, indium, silver, gallium, cadmium, lead, thallium, rare earth metal include at least one of lanthanum, cerium, praseodymium, neodymium.
5. a kind of method preparing the zinc-based secondary battery cathode material as described in claim 1-4 any one, it is characterised in that
Include the following steps：
Step 1
Zinc oxide powder is weighed in proportion, is added in dispersant and is uniformly mixing to obtain zinc oxide fluid dispersion；Then toward zinc oxide point
Modifying agent is added in dispersion liquid, stir and adjusts the pH value of system to 8~11；It is filtered after continuing stirring, obtains modified oxidation
Zinc powder is denoted as solid A；
Step 2
Solid A is added in the solution of cation resin, keep mixeding liquid temperature be -10 DEG C~90 DEG C and ultrasound 60~
400min is separated by filtration and washs, and obtains the Zinc oxide powder of resin cation cladding, is denoted as solid B；
Step 3
Solid B is added in the solution of mixed metal salt, solution ph is adjusted to 2~6, after stirring, reducing agent is added, will inhale
The metal ion being attached in resin cation is reduced into metal simple-substance, and the cation of metal adsorption is obtained by being filtered, washed
Resin coating zinc oxide is denoted as solid C；The mixed metal salt by containing non-rare earth metal element salt and contain thulium
Salt composition；
Step 4
Solid C is dried in vacuo, is kept the temperature at a temperature of 100~220 DEG C, the zinc-based secondary battery cathode material is obtained
Material.
6. a kind of preparation method of zinc-based secondary battery cathode material according to claim 5, it is characterised in that：Step 1
Used in dispersant be water, it is methanol, ethyl alcohol, acetone, ethylene glycol, one or more in polyethylene glycol 200, dispersant with
The liquid-solid ratio of zinc oxide is (2~10):1；
Modifying agent used in step 1 includes that ammonium hydroxide, ammonium acetate solution, ammonium nitrate solution, ammonium sulfate, ammonium carbonate are molten
One or more in liquid, cetyl ammonium bromide solution, the mass percentage concentration of the modifying agent is 2%~8%.
7. a kind of preparation method of zinc-based secondary battery cathode material according to claim 5, it is characterised in that：Step 2
The middle resin cation used includes perfluorinated sulfonic resin, fluorochemical urethane resin, fluoroacrylic resin, polystyrene-two
One kind in vinylbenzenesulfonic acid resin, the mass fraction of the anions in solution resin of the cation resin is 5%~
25%, solvent is the mixed liquor that water and organic solvent form in the solution of the cation resin, wherein organic solvent and water
Volume ratio be (1~5):1；The organic solvent includes at least one in methanol, ethyl alcohol, propyl alcohol, acetone, ether, ethylene glycol
Kind, the liquid-solid ratio of the solution of the cation resin and modified zinc oxide is (1~10):1.
8. a kind of zinc-based secondary battery cathode material according to claim 5 and preparation method thereof, it is characterised in that：
In step 1, Zinc oxide powder is weighed in proportion, and the suspension for being added to 10~20min of stirring formation zinc oxide in dispersant is molten
Liquid, ultrasonic 30min~120min obtain zinc oxide fluid dispersion；To the dispersion liquid be added dropwise modifying agent and stir 5~
10min is added the pH value of buffer solution adjusting solution between 8~11, continues 100~300min of stirring, be obtained by filtration modified
Zinc oxide powder, be denoted as solid A；The buffer solution is ammonium hydroxide-ammonium chloride buffer, sodium dihydrogen phosphate-potassium dihydrogen phosphate, boron
One kind in sand-borate buffer, borax-sodium hydroxide, borax-sodium carbonate buffer, sodium carbonate-bicarbonate buffer solution；
In step 2, solid A is added in the solution of cation resin, mixeding liquid temperature is kept to be 40 DEG C~90 DEG C and surpass
60~400min of sound is separated by filtration and washs the Zinc oxide powder for obtaining resin cation cladding for several times, is denoted as solid B；
In step 3, solid B is added in the solution of mixed metal salt, the mixed metal salt adjusted with No. 1 buffer solution
For the pH value of solution to 2~6, holding solution temperature stirs 5h~12h under conditions of being 25 DEG C~50 DEG C, and reducing agent is added dropwise will
The metal ion being adsorbed in resin cation is reduced into metal simple-substance, by be filtered, washed to obtain the sun of metal adsorption from
Subtree fat coating zinc oxide, is denoted as solid C；No. 1 buffer solution is selected from disodium hydrogen phosphate-citrate buffer solution, adjacent benzene two
In formic acid-hydrochloride buffer, citric acid-sodium citrate buffer solution, acetic acid-sodium acetate buffer solution, glycine-HCI buffer solution
It is a kind of.
9. a kind of zinc-based secondary battery cathode material according to claim 5 and preparation method thereof, it is characterised in that：
In step 3, mixed metal salt is water soluble salt；In the mixed metal salt, anion is selected from chlorion, nitrate anion, sulphur
At least one of acid group, acetate；
The salt containing non-rare earth metal element in pink salt, bismuth salt, indium salts, silver salt, gallium salt, cadmium salt, lead salt, thallium salt extremely
Few one kind；
The salt containing thulium is selected from least one of lanthanum salt, cerium salt, praseodymium salt, neodymium salt；
In the solution of the mixed metal salt；A concentration of 0.1mol/L~1.0mol/L of metal ion；The mixed metal salt
Solution in, the molar ratio of non-rare earth metal element and rare earth element is (1~5):1；
In step 3, the reducing agent includes formamide, sodium borohydride, potassium borohydride, lithium aluminium hydride reduction, ascorbic acid, nitrous acid
At least one of sodium, hydrazine hydrate.
10. a kind of zinc-based secondary battery cathode material according to claim 3 and preparation method thereof, it is characterised in that：Step
In rapid four, when vacuum drying, it is 10Pa~100Pa to control air pressure in stove, and soaking time is 120min~400min.
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