CN1744355A - Negative material of a kind of alkaline secondary zinc electrode and preparation method thereof - Google Patents
Negative material of a kind of alkaline secondary zinc electrode and preparation method thereof Download PDFInfo
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- CN1744355A CN1744355A CNA2005100609415A CN200510060941A CN1744355A CN 1744355 A CN1744355 A CN 1744355A CN A2005100609415 A CNA2005100609415 A CN A2005100609415A CN 200510060941 A CN200510060941 A CN 200510060941A CN 1744355 A CN1744355 A CN 1744355A
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Abstract
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, kernel evenly is enclosed with nano granular of zinc oxide outward, and the main chemical composition of this Zinc oxide-base conductive oxide is ZnO and Co
2O
3This Zinc oxide-base conductive oxide can also contain Bi
2O
3, Co
2O
3, Nb
2O
5, Y
2O
3, La
2O
3Deng conductive oxide.Adopt homogeneous precipitation method to prepare negative material of the present invention.Beneficial effect of the present invention shows: 1. the Zinc oxide-base conductive oxide adds the nucleus of crystal when can be used as the zinc electrode charging in the zinc electrode to, improve the active material utilization and the discharge capacity of zinc electrode, reduce and stop the generation of zinc dendrite, improve electrode cycle life.2. can reduce the internal resistance of electrode, the comprehensive electrochemical of improving secondary zinc electrode is had good effect.
Description
(1) technical field
The present invention relates to negative material of a kind of alkaline secondary zinc electrode and preparation method thereof.
(2) background technology
Nickel-zinc battery is the high energy secondary cell of development in recent years a kind of novelty of getting up, adopt zinc as negative pole, nickel hydroxide is as positive pole, has higher (the theoretical 326Wh/kg of being of specific energy, the actual 115Wh/kg that is not less than), but heavy-current discharge (specific power surpass 200W/kg), operating voltage height (average 1.65V), outstanding advantages such as steady, with low cost, the non-environmental-pollution of discharging, be the novel environment-friendly type electrokinetic cell of a class, have and use widely and development prospect.The alkaline secondary zinc electrode of other types also has broad application prospects.
Because the electro-chemical activity of zinc in alkaline solution is big, the macroscopic property instability, and charging product zincate solubility height in strong base solution, therefore distortion, dendritic growth, the phenomenon such as corrosion and passivation certainly appear in electrode easily in charge and discharge process, cause easily the phenomenons such as electrode failure and battery short circuit, thereby cause the inefficacy of battery, so the industrialization of nickel-zinc battery realizes not yet fully.
The active oxidation zinc powder is generally adopted in the at present preparation of secondary zinc electrode (being the negative pole of alkaline secondary zinc electrode), its granularity is generally more than micron order, particle distribution range is big, " dendrite ", " distortion ", " self discharge " and problems such as " electrode passivations " in order to solve the zinc negative pole needs to add Ca (OH) in electrode production process simultaneously
2, Ba (OH)
2Or Sr (OH)
2, In (OH)
3With metal oxide PbO, Bi
2O
3, CdO, Ga
2O
3And Ti
2O
3Deng additive, because the light specific gravity of zinc oxide is not easy to disperse, additive is not easy to disperse lack of homogeneity in active material.Therefore, after making electrode, the poorly conductive of electrode, the charging acceptance is low, simultaneously because also there is poorly conductive in the present additive that adopts, modified effect to zinc electrode is not lasting, cause zinc electrode commonly used at present to exist active material utilization low, the charging acceptance is poor, the capacity instability, problems such as especially cycle life is short are serious hindrances of the industrialization of alkaline secondary zinc electrode.
(3) summary of the invention
The secondary zinc electrode active material utilization of making for the negative material that overcomes prior art neutral and alkali secondary zinc electrode is low, poorly conductive, the charging acceptance is low, capacity is unstable, cycle life is short deficiency, the invention provides a kind of alkaline secondary zinc electrode negative material, stablized, had extended cycle life by secondary zinc electrode active material utilization height, good conductivity, charging acceptance height, capacity that this negative material is made, the present invention also provides the preparation method of described negative material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of negative material of alkaline secondary zinc electrode, the negative material of described alkaline secondary zinc electrode are take the Zinc oxide-base conductive oxide as kernel, and described kernel evenly is enclosed with nano granular of zinc oxide outward; Its main chemical composition of described Zinc oxide-base conductive oxide is: the ZnO of 90～98 weight portions; The Co of 2～5 weight portions
2O
3Here refer to ZnO, Co
2O
3Be the main chemical composition of Zinc oxide-base conductive oxide, the meaning is that described additive can be ZnO, Co
2O
3, also can be with ZnO, Co
2O
3The conductive oxide component that adds again a small amount of other for Main Ingredients and Appearance.
Further, described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 90～98 weight portions; The Co of 2～5 weight portions
2O
30.5 the Bi of～10 weight portions
2O
3
Further, described its chemical composition of Zinc oxide-base conductive oxide is the ZnO of 90～98 weight portions; The Co of 2～5 weight portions
2O
30.5 the Bi of～10 weight portions
2O
30.05 the Nb of～0.1 weight portion
2O.
Further, described its chemical composition of Zinc oxide-base conductive oxide is the ZnO of 90～98 weight portions; The Co of 2～5 weight portions
2O
30.5 the Bi of～10 weight portions
2O
30.05 the Nb of～0.1 weight portion
2O; 0.02 the Re of～0.1 weight portion
2O
3, wherein Re is La (lanthanum) or Y (yttrium).
Further, its granularity of the negative material of described alkaline secondary zinc electrode is 100～300nm.
Further, in the negative material of described alkaline secondary zinc electrode, the mass percent of the negative material of the shared alkaline secondary zinc electrode of described Zinc oxide-base conductive oxide is 5～10%.
The preparation method of the negative material of above-mentioned alkaline secondary zinc electrode, the employing zinc nitrate is a raw material, ammoniacal liquor, urea is precipitation reagent, be dissolved in zinc nitrate and urea in the distilled water respectively, fully the dissolving after with the two mixing, in solution, add described Zinc oxide-base conductive oxide then, ultrasonic stirring is heated to 90～100 ℃, be incubated 2～3 hours, cooled and filtered, washing, drying, obtaining with the Zinc oxide-base conductive oxide is kernel, kernel evenly is enclosed with the particle of zinc nitrate outward, calcining made zinc nitrate be converted into nano zine oxide in 1～2 hour under 400～500 ℃ then, obtained the negative material of alkaline secondary zinc electrode.
The preparation method of the negative material of described alkaline secondary zinc electrode, described washing is preferably with the washing of distilled water and ethanol, and described drying is preferably 100～120 ℃ of dryings 1～3 hour; Described Zinc oxide-base conductive oxide is 1: 28～59 with the preferred mass ratio of described zinc nitrate.
The beneficial effect of negative material of alkaline secondary zinc electrode of the present invention and preparation method thereof mainly shows: 1. the Zinc oxide-base conductive oxide does not dissolve in alkaline electrolyte, has very low room temperature resistivity (2.5～4.5 * 10
-2Ω m), have good conductivity at room temperature, therefore add in the zinc electrode, the nucleus of crystal when can be used as the zinc electrode charging, the active material utilization and the discharge capacity of raising zinc electrode reduce and stop the generation of zinc dendrite, improve the cycle life of electrode.2. because doping zinc-oxide base conductive oxide has good electric conductivity, also can reduce the internal resistance of electrode, stop dissolving and the separating out of hydrogen of zinc in electrolyte, the comprehensive electrochemical of improving secondary zinc electrode is had good effect.
(4) embodiment
Below in conjunction with the drawings and specific embodiments the present invention is further described.
Embodiment one
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 92 weight portions, the Bi of 5.5 weight portions
2O
3, the Co of 2.5 weight portions
2O
3, the Nb of 0.075 weight portion
2O
5, the Y of 0.025 weight portion
2O
3
The employing zinc nitrate is raw material, and ammoniacal liquor, urea are precipitating reagent, is dissolved in respectively zinc nitrate and urea in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 92 weight portions, the Bi of 5.5 weight portions
2O
3, the Co of 2.4 weight portions
2O
3, the Nb of 0.075 weight portion
2O
5, the Y of 0.025 weight portion
2O
3, its room temperature resistivity is about 3.76 * 10
-2Ω m, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate are 1: 28.Ultrasonic agitation is heated to 95 ℃, is incubated 3 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 120 ℃ of dryings 2 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 500 ℃ then made zinc nitrate be converted into nano zine oxide in 2 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 10%.
Consist of: the ZnO of 92 weight portions, the Bi of 5.5 weight portions
2O
3, the Co of 2.4 weight portions
2O
3, the Nb of 0.075 weight portion
2O
5, the Y of 0.025 weight portion
2O
3The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Co
2O
3Powder, Bi
2O
3Powder and Nb
2O
5Powder is put into ball grinder then by the stoichiometric proportion mix, and adds distilled water and poly amic acid dispersant in ball grinder, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ of calcinings 2 hours, sieve after the cooling intermediate raw material;
Butyl titanate is dissolved in the mixed liquor of glacial acetic acid, glycerol and ethanol, adds and obtain uniform butyl titanate solution after thermal agitation obtains;
Press stoichiometric proportion with Y (NO
3)
36H
2O is dissolved in the deionized water, and adds glycerine and ethanol, slowly is added in the described butyl titanate solution after heating stirs, and obtains the doped solution of Y (yttrium) element;
In the doped solution of Y element, add described intermediate raw material, after mixing, heating, drying, then in Muffle furnace be warmed up to 1500 ℃ of 100 ℃/h, be incubated 5 hours, in ball mill, pulverize again after the cooling, sieve the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m), form simulated battery with nickel electrode, make reference electrode with Hg/HgO, electrolyte is 8.0mol/LKOH solution.The simulated battery Experimental cell that assembles adopts 20mA/cm after placing 6h
2Constant current charge-discharge, environment temperature is 25 ± 2 ℃, zinc electrode-1.46～-1.10V (vs.Hg/HgO) between iterative cycles measure doping zinc-oxide base conductive oxide additive of the present invention to the impact of zinc electrode comprehensive electrochemical.
The chemical property of nano oxidized zinc electrode sees Table 1:
Table 1
Embodiment two
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 95 weight portions; The Co of 5 weight portions
2O
3
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 95 weight portions, the Co of 5 weight portions
2O
3, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 59.Ultrasonic agitation is heated to 120 ℃, is incubated 2 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 120 ℃ of dryings 1 hour, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 400 ℃ then made zinc nitrate be converted into nano zine oxide in 2 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 5%.
Consist of the ZnO of 95 weight portions, the Co of 5 weight portions
2O
3The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Co
2O
3Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 2:
Table 2
Embodiment three
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 98 weight portions; The Co of 2 weight portions
2O
3
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 98 weight portions, the Co of 2 weight portions
2O
3, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 40.Ultrasonic agitation is heated to 90 ℃, is incubated 3 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 100 ℃ of dryings 3 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 500 ℃ then made zinc nitrate be converted into nano zine oxide in 1 hour, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 7%.
Consist of the ZnO of 98 weight portions, the Co of 2 weight portions
2O
3The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Co
2O
3Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 3:
Table 3
Embodiment four
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 96 weight portions; 0.5 the Bi of weight portion
2O
33.5 the Co of weight portion
2O
3
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 96 weight portions, the Bi of 0.5 weight portion
2O
3, 3.5 weight portions Co
2O
3, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28.Ultrasonic agitation is heated to 90 ℃, is incubated 3 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 100 ℃ of dryings 3 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 500 ℃ then made zinc nitrate be converted into nano zine oxide in 1 hour, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 410%.
Consist of the ZnO of 96 weight portions, the Bi of 0.5 weight portion
2O
3, 3.5 weight portions Co
2O
3The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Co
2O
3Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 4:
Table 4
Embodiment five
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 91 weight portions; The Bi of 5 weight portions
2O
3The Co of 4 weight portions
2O
3
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 91 weight portions, the Bi of 5 weight portions
2O
3, 4 weight portions Co
2O
3, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28.Ultrasonic agitation is heated to 95 ℃, is incubated 2.5 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 110 ℃ of dryings 2 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 450 ℃ then made zinc nitrate be converted into nano zine oxide in 1.5 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 10%.
Consist of the ZnO of 91 weight portions, the Bi of 5 weight portions
2O
3, 4 weight portions Co
2O
3The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Bi
2O
3Powder, Co
2O
3Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 5:
Table 5
Embodiment six
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 93 weight portions; 2.4 the Bi of weight portion
2O
34.5 the Co of weight portion
2O
30.1 the Nb of weight portion
2O
5
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 93 weight portions, the Bi of 2.4 weight portions
2O
3, 4.5 weight portions Co
2O
3, 0.1 weight portion Nb
2O
5, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28.Ultrasonic agitation is heated to 95 ℃, is incubated 2.5 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 110 ℃ of dryings 2 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 450 ℃ then made zinc nitrate be converted into nano zine oxide in 1.5 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 10%.
Consist of the ZnO of 93 weight portions, the Bi of 2.4 weight portions
2O
3, 4.5 weight portions Co
2O
3, 0.1 weight portion Nb
2O
5The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Bi
2O
3Powder, Co
2O
3Powder, Nb
2O
5Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 6:
Table 6
Embodiment seven
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the ZnO of 90 weight portions; 6.5 the Bi of weight portion
2O
33.425 the Co of weight portion
2O
30.075 the Nb of weight portion
2O
5
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 9O weight portion, the Bi of 6.5 weight portions
2O
3, 3.425 weight portions Co
2O
3, 0.075 weight portion Nb
2O
5, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28.Ultrasonic agitation is heated to 100 ℃, is incubated 3 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 110 ℃ of dryings 2 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 500 ℃ then made zinc nitrate be converted into nano zine oxide in 2 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 10%.
Consist of the ZnO of 90 weight portions, the Bi of 6.5 weight portions
2O
3, 3.425 weight portions Co
2O
3, 0.075 weight portion Nb
2O
5The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Bi
2O
3Powder, Co
2O
3Powder, Nb
2O
5Powder is by the stoichiometric proportion mix, put into then ball grinder, and in ball grinder, add distilled water and poly amic acid dispersant, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ the calcining 2 hours, sieve after the cooling the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 7:
Table 7
Embodiment eight
A kind of negative material of alkaline secondary zinc electrode, take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, and described its chemical composition of Zinc oxide-base conductive oxide is: the Bi of the ZnO of 92 weight portions, 5.5 weight portions
2O
3, 2.5 weight portions Co
2O
3, 0.075 weight portion Nb
2O
5, 0.025 weight portion La
2O
3
The employing zinc nitrate is raw material, ammoniacal liquor, urea are precipitating reagent, zinc nitrate and urea are dissolved in respectively in the distilled water, fully the dissolving after with the two mixing, add then described Zinc oxide-base conductive oxide in solution, it consists of the ZnO of 92 weight portions, the Bi of 5.5 weight portions
2O
3, 2.5 weight portions Co
2O
3, 0.075 weight portion Nb
2O
5, 0.025 weight portion La
2O
3, the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28.Ultrasonic agitation is heated to 95 ℃, is incubated 3 hours.Cooled and filtered, with distilled water and ethanol washing precipitate, then 120 ℃ of dryings 2 hours, obtain with the Zinc oxide-base conductive oxide be kernel, kernel evenly be enclosed with outward the zinc nitrate particle particle, calcining down at 500 ℃ then made zinc nitrate be converted into nano zine oxide in 2 hours, obtain the negative material of alkaline secondary zinc electrode, its particle size distribution is at 100～300nm, nano granular of zinc oxide is wrapped in the surface of Zinc oxide-base conductive oxide equably, the Zinc oxide-base conductive oxide account for secondary zinc electrode the negative material quality 10%.
Consist of (ZnO)
0.920(Bi
2O
3)
0.055(Co
2O
3)
0.025(Nb
2O
5)
0.00075(La
2O
3)
0.00025The preparation method of Zinc oxide-base conductive oxide be: with ZnO powder, Co
2O
3Powder, Bi
2O
3Powder and Nb
2O
5Powder is put into ball grinder then by the stoichiometric proportion mix, and adds distilled water and poly amic acid dispersant in ball grinder, powder wet-milling 60 hours in ball grinder, after the oven dry again 1000 ℃ of calcinings 2 hours, sieve after the cooling intermediate raw material;
Butyl titanate is dissolved in the mixed liquor of glacial acetic acid, glycerol and ethanol, adds and obtain uniform butyl titanate solution after thermal agitation obtains;
Press stoichiometric proportion with La (NO
3)
3Be dissolved in the deionized water, and add glycerine and ethanol, slowly be added in the described butyl titanate solution after heating stirs, obtain the doped solution of La (lanthanum) element;
In the doped solution of La element, add described intermediate raw material, after mixing, heating, drying, then in Muffle furnace be warmed up to 1500 ℃ of 100 ℃/h, be incubated 5 hours, in ball mill, pulverize again after the cooling, sieve the Zinc oxide-base conductive oxide.
With mix about 5% electrically conductive graphite of the negative material of the aforementioned alkaline secondary zinc electrode that obtains, ball milling mixed 1 hour in ball mill then, add an amount of 60%PTFE and 3%CMC after taking out as binding agent, add simultaneously a small amount of distilled water and be mixed with the oxidation calamine cream, then with the full-filling of oxidation calamine cream in the copper of the bubble of zinc-plated or bismuth end, scrape off floating powder on surface after the vacuum drying, be rolled into pole plate at twin rollers then, the electrode carrying capacity is 0.15g/cm
2, thickness 0.20mm, the about 90～100mAh/cm of electrode theory capacity
2Nickel electrode adopts conventional slurry legal system standby.One deck polypropylene non-woven fabric is wrapped up on the zinc electrode surface for preparing earlier, and thickness is 0.18mm, and then parcel one deck Celgard2300 barrier film (thickness 2.5 μ m, effective aperture 0.02 μ m) and nickel electrode composition simulated battery, the results are shown in Table 8:
Table 8
Claims (10)
1. the negative material of an alkaline secondary zinc electrode, it is characterized in that: the negative material of described alkaline secondary zinc electrode is a kernel with the Zinc oxide-base conductive oxide, described kernel evenly is enclosed with nano granular of zinc oxide outward;
Its main chemical composition of described Zinc oxide-base conductive oxide is:
The ZnO of 90～98 weight portions;
The Co of 2～5 weight portions
2O
3
2. the negative material of alkaline secondary zinc electrode as claimed in claim 1, it is characterized in that: described its chemical composition of Zinc oxide-base conductive oxide is:
The ZnO of 90～98 weight portions;
The Co of 2～5 weight portions
2O
3
0.5 the Bi of～10 weight portions
2O
3
3. the negative material of alkaline secondary zinc electrode as claimed in claim 1, it is characterized in that: described its chemical composition of Zinc oxide-base conductive oxide is:
The ZnO of 90～98 weight portions;
The Co of 2～5 weight portions
2O
3
0.5 the Bi of～10 weight portions
2O
3
0.05 the Nb of～0.1 weight portion
2O
5
4. the negative material of alkaline secondary zinc electrode as claimed in claim 1, it is characterized in that: described its chemical composition of Zinc oxide-base conductive oxide is:
The ZnO of 90～98 weight portions;
The Co of 2～5 weight portions
2O
3
0.5 the Bi of～10 weight portions
2O
3
0.05 the Nb of～0.1 weight portion
2O
5
0.02 the Re of～0.1 weight portion
2O
3, wherein Re is La or Y.
5. as the negative material of the described alkaline secondary zinc electrode of one of claim 1～4, it is characterized in that: its granularity of the negative material of described alkaline secondary zinc electrode is 100～300nm.
6. the negative material of alkaline secondary zinc electrode as claimed in claim 5, it is characterized in that: in the negative material of described alkaline secondary zinc electrode, the mass percent of the negative material of the shared alkaline secondary zinc electrode of described Zinc oxide-base conductive oxide is 5～10%.
7. as the preparation method of the negative material of alkaline secondary zinc electrode as described in one of claim 1～4, the employing zinc nitrate is a raw material, ammoniacal liquor, urea is precipitation reagent, be dissolved in zinc nitrate and urea in the distilled water respectively, fully the dissolving after with the two mixing, in solution, add described Zinc oxide-base conductive oxide then, ultrasonic stirring is heated to 90～100 ℃, be incubated 2～3 hours, cooled and filtered, washing, drying, obtaining with the Zinc oxide-base conductive oxide is kernel, kernel evenly is enclosed with the particle of zinc nitrate outward, calcining made zinc nitrate be converted into nano zine oxide in 1～2 hour under 400～500 ℃ then, obtained the negative material of alkaline secondary zinc electrode.
8. the preparation method of the negative material of alkaline secondary zinc electrode as claimed in claim 7 is characterized in that: described washing is with distilled water and ethanol washing, and described drying is 100～120 ℃ of dryings 1～3 hour.
9. the preparation method of the negative material of alkaline secondary zinc electrode as claimed in claim 7, it is characterized in that: the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28～59.
10. the preparation method of the negative material of alkaline secondary zinc electrode as claimed in claim 8, it is characterized in that: the mass ratio of described Zinc oxide-base conductive oxide and described zinc nitrate is 1: 28～59.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022472A (en) * | 2012-12-17 | 2013-04-03 | 湖南丰日电源电气股份有限公司 | Large-power zinc-nickel mixed battery cathode slurry and preparation method thereof |
| CN107039645A (en) * | 2017-04-11 | 2017-08-11 | 宁波富邦电池有限公司 | Primary alkaline battery negative electrode material and preparation method thereof |
| CN115172647A (en) * | 2022-09-02 | 2022-10-11 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000030695A (en) * | 1998-07-10 | 2000-01-28 | Toshiba Battery Co Ltd | Manufacture of gelatinous zinc negative electrode for zinc alkaline battery |
| US6203943B1 (en) * | 1998-11-13 | 2001-03-20 | Eveready Battery Company, Inc. | Electrochemical cell having electrode additives |
| CA2325637A1 (en) * | 2000-11-10 | 2002-05-10 | Jeffrey Phillips | Formulation of zinc negative electrode for rechargeable cells having an alkaline electrolyte |
| US6808847B2 (en) * | 2001-09-17 | 2004-10-26 | The Gillette Company | Alkaline cell with improved cathode including copper hydroxide and a sulfur additive |
| CN1462083A (en) * | 2002-05-30 | 2003-12-17 | 江苏海四达集团有限公司 | Preparation method of alkaline secondary zinc battery negative electrode active substance |
| CN1235303C (en) * | 2003-01-30 | 2006-01-04 | 江苏海四达集团有限公司 | Preparation method of alkaline secondary zinc battery negative electrode active material |
| CN1283022C (en) * | 2003-03-10 | 2006-11-01 | 华南理工大学 | Zinc-nickel secondary cell and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022472A (en) * | 2012-12-17 | 2013-04-03 | 湖南丰日电源电气股份有限公司 | Large-power zinc-nickel mixed battery cathode slurry and preparation method thereof |
| CN103022472B (en) * | 2012-12-17 | 2015-03-11 | 湖南丰日电源电气股份有限公司 | Large-power zinc-nickel mixed battery cathode slurry and preparation method thereof |
| CN107039645A (en) * | 2017-04-11 | 2017-08-11 | 宁波富邦电池有限公司 | Primary alkaline battery negative electrode material and preparation method thereof |
| CN107039645B (en) * | 2017-04-11 | 2020-01-31 | 宁波富邦电池有限公司 | Primary alkaline battery negative electrode material and preparation method thereof |
| CN115172647A (en) * | 2022-09-02 | 2022-10-11 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
| CN115172647B (en) * | 2022-09-02 | 2022-12-13 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
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