CN101533908A - Alkaline zinc-based secondary battery cathode material and preparation method thereof - Google Patents
Alkaline zinc-based secondary battery cathode material and preparation method thereof Download PDFInfo
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- CN101533908A CN101533908A CN200910097279A CN200910097279A CN101533908A CN 101533908 A CN101533908 A CN 101533908A CN 200910097279 A CN200910097279 A CN 200910097279A CN 200910097279 A CN200910097279 A CN 200910097279A CN 101533908 A CN101533908 A CN 101533908A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
An alkaline zinc-based secondary battery cathode material disclosed by the invention is a nano-bismuth composite surface-modified ZnO zinc-based battery material of Bi2O3 and BiO, and comprises, based on mass percent, 60-80% of Zn, 0.1-15% of Bi and O as the balance. The preparation method thereof comprises the following steps of: taking ZnO and Bi(NO3)35H2O based on a mass ratio of 100:1-100:30, dissolving the Bi(NO3)35H2O in HNO3, and after the Bi(NO3)35H2O is completely dissolved, diluting with distilled water so that the concentration of Bi(NO3)3 stands at 0.1-10g/L, adding the ZnO and filtering and drying after sufficient agitation, and then calcining for at least 30min over 300 DEG C in the air. The alkaline zinc-based secondary battery made of the material has outstandingly improved service life, stable circulatory performance and high average utilization rate of the ZnO as well as can be used for driving electric tools, vehicles, model toys, small household appliances, communication equipment and illumination, etc.
Description
Technical field
The present invention relates to alkaline zinc-based secondary battery cathode material and preparation method thereof.
Background technology
Alkaline zinc-based secondary battery is to be negative material with zinc oxide (ZnO), nickel hydroxide (Ni (OH)
2), manganese oxide (MnO
2), silver oxide (AgO) or air be the green rechargeable battery of positive electrode.The subject matter of this class battery is the cycle life instability, is difficult to satisfy the practicability requirement.Zinc electrode deforms in the cycle charge discharge electric process, dendritic growth, and passivation is the unsettled main cause of cycle life.Well-known zinc oxide is amphiprotic substance, at strong base solution bigger solubility is arranged, metallic zinc also can react to dissolve and enter alkali lye with highly basic simultaneously, and alkaline zinc-based secondary battery mostly with highly basic as electrolyte, so the zinc-base battery electrolyte contains a large amount of zinc salts, can not deposit to the stripping position during these zinc salts chargings, cause electrode deformation, make the zinc electrode passivation, reduce electro-chemical activity, the ZnO utilance is descended.Because zinc is the close-packed hexagonal crystal structure, the easy skeleton that forms of zinc deposition causes internal short-circuit during charging.Can know that from above-mentioned analysis the basic reason of zinc-base secondary battery dendrite and problem on deformation also is ZnO and the Zn dissolving in alkaline electrolyte.Present technical solution mainly concentrates on and adds the organic or inorganic additive in electrode and the electrolyte, improves barrier film, improve charging system etc., but these methods can not fundamentally solve the problems of dissolution of ZnO and Zn, and is therefore limited to the raising of battery performance.
Summary of the invention
The objective of the invention is the stock utilization as alkaline zinc-based secondary battery cathode material for raising ZnO, the cycle life of discharge capacity stability and battery, and a kind of alkaline zinc-based secondary battery cathode material and preparation method thereof is proposed.
Alkaline zinc-based secondary battery cathode material of the present invention is Bi
2O
3Modify ZnO zinc-base battery material with the nanometer bismuth composite surface of BiO, contain mass percent and be 60-80% Zn, 0.1-15% Bi, all the other are O.
The preparation method of alkaline zinc-based secondary battery cathode material of the present invention, its step is as follows:
Get ZnO and Bi (NO
3)
35H
2O, ZnO and Bi (NO
3)
35H
2The mass ratio of O is 100:1～100:30, earlier with Bi (NO
3)
35H
2O is dissolved in the HNO of mass concentration 30-67%
3In, HNO
3Consumption be at least Bi (NO
3)
3 5H
22 times of O quality to dissolving fully, are used distilled water diluting, make Bi (NO
3)
3Concentration at 0.1～10g/L, add ZnO then, fully stir the back and filter, 30min is at least calcined in oven dry more than 300 ℃ in air.
Adopt negative material of the present invention to prepare alkaline zinc-based secondary battery cathode: in finishing ZnO alkaline zinc-based secondary battery cathode material, to add a spot of CMC and PTFE binding agent, be coated on the collector nickel foam after stirring with water, drying, compacting, shearing are made.
Battery cathode and anodal Ni (OH) with preparation
2, barrier film forms the battery of cylindrical or square structure.Electrolyte is for containing 1.5M K
2BO
3, the saturated 4.5M KOH of the ZnO mixed aqueous solution of 0.8M KF and 0.05M LiOH.After in 25 ± 2 ℃ of environment, discharging and recharging 3 circulations of activation with 0.1C, discharge and recharge with 0.2C again, the charge-discharge performance of zinc-nickel secondary batteries and the variation of cyclical stability are measured in circulation repeatedly.
Bi (NO among the present invention
3)
3Hydrolysis generates Bi (OH)
2NO
3, be the nano particle of particle diameter about the 20-50 nanometer.These particle depositions carry out finishing to ZnO on ZnO, Bi (OH)
2NO
3Instability is nanometer Bi through calcining and decomposing in the air more than 300 ℃
2O
3Compound with bismuths such as BiO.The compound of bismuth is the alkaline metal oxide of current potential calibration, promptly all is reduced to metal Bi in battery operated preceding 1 to 2 circulation, and exists with metal Bi form all the time in battery operated voltage range.Bi is high overpotential of hydrogen evolution metal, can suppress the liberation of hydrogen and the self discharge effect of zinc-nickel secondary batteries.These finishing things have reduced the contact area of ZnO and alkaline electrolyte simultaneously, thereby slowed down the dissolving of ZnO, active material ZnO is remained on the Zn electrode, kept the activity of electrode material, reduced the distortion of Zn electrode, improve the ZnO utilance, improved the cyclical stability of alkaline zinc-based secondary battery.Because reduced the ZnO quantity that enters in the electrolyte, make to deposit the corresponding minimizing of Zn number of coming out that this makes the number of Zn dendrite also reduce, and has therefore suppressed the zinc dendrite growth, has prolonged the life-span that recycles of battery.Cathode material preparation method of the present invention is easy, this material can be used for zinc-manganese, zinc-silver, other alkaline zinc-based secondary batteries such as zinc air can be widely used in driving fields such as electric tool, the vehicles, model toy, small household appliance, communication apparatus and illumination.
Description of drawings
Fig. 1 is the cycle charge-discharge performance curve of alkaline zinc-based secondary battery cathode material.
Embodiment
Embodiment 1:
Get 7.7g ZnO and 1.5g Bi (NO
3)
35H
2O is with Bi (NO
3)
35H
2O is dissolved in the dense 55%HNO of 7.2g quality
3, be stirred to fully dissolving after, use distilled water diluting, make Bi (NO
3)
3Concentration at 8g/L, add ZnO, fully stir the back and filter, 80 ℃ of oven dry, 350 ℃ of calcining 30min obtain Bi in air
2O
3Modify ZnO zinc-base battery material with the nanometer bismuth composite surface of BiO, the Bi weight percent content is 9.4%, and the Zn weight percent content is 65%, and all the other are O.
Embodiment 2:
Get 6.8g ZnO and 1g Bi (NO
3)
35H
2O is with Bi (NO
3)
35H
2O is dissolved in 4.8g mass concentration 55%HNO
3, be stirred to fully dissolving after, use distilled water diluting, make Bi (NO
3)
3Concentration at 4g/L, add ZnO, fully stir the back and filter, 80 ℃ of oven dry, 350 ℃ of calcining 30min obtain Bi in air
2O
3Modify ZnO zinc-base battery material with the nanometer bismuth composite surface of BiO, the Bi weight percent content is 7.6%, and the Zn weight percent content is 71%, and all the other are O.
Embodiment 3:
Get 5.9g ZnO and 0.5g Bi (NO
3)
35H
2O is with Bi (NO
3)
35H
2O is dissolved in 2.4g mass concentration 55%HNO
3, be stirred to fully dissolving after, use distilled water diluting, make Bi (NO
3)
3Concentration at 2g/L, add ZnO, fully stir the back and filter, 80 ℃ of oven dry, 350 ℃ of calcining 30min obtain Bi in air
2O
3Modify ZnO zinc-base battery material with the nanometer bismuth composite surface of BiO, the Bi weight percent content is 3.6%, and the Zn weight percent content is 78%, and all the other are O, and nanometer bismuth compound is with Bi
2O
3With BiO be main.
Make the negative pole of alkaline zinc-based secondary battery, modify a spot of CMC of adding and PTFE binding agent in the ZnO negative material in nanometer bismuth composite surface, be coated on the collector nickel foam after stirring with water, drying, compacting, shear forming are of a size of: 20 * 20 * 0.4mm
3Just very on nickel foam, scrape the Ni (OH) of slurry compression moulding
2Electrode.Positive electrode capacity is 3 times of utilances that make battery capacity can reflect negative material of capacity of negative plates, is of a size of: 45 * 30 * 0.6mm
3Adopt GP-1 barrier film parcel negative pole, be fitted into battery case, inject and contain 1.5M K with positive pole
2BO
3, the saturated 4.5M KOH of the ZnO mixed electrolytic solution of 0.8M KF and 0.05M LiOH is made square zinc-nickel cell.Cell activation is handled the back, and (with 0.1CA charging 13h, shelve 10min, 0.1CA is discharged to 1.2V; Activate 3 times), with 0.2CA current charges and discharge, the charge-discharge performance of alkali zinc nickel secondary cell is measured in circulation under 25 ± 2 ℃ of ambient temperatures.
The cycle charge-discharge performance curve of alkaline zinc-based secondary battery cathode material as shown in Figure 1, wherein curve 1 is the cycle charge-discharge performance curve of embodiment 1; Curve 2 is the cycle charge-discharge performance curve of embodiment 2; Curve 3 is the cycle charge-discharge performance curve of embodiment 3; Curve 4 is the cycle charge-discharge performance curve of unmodified ZnO.
As seen from Figure 1, the discharge capacity of finishing ZnO does not obviously reduce after 30 circulations, has only 240mAh/g, has only 58% of the cyclic discharge capacity first time, is 39% of its theoretical capacity.Surface finish nano bismuth compound has improved the cyclical stability of zinc-nickel cell.Under major part circulation cycle, the discharge capacity that nanometer bismuth composite surface of the present invention is modified the ZnO negative material is higher than unmodified ZnO negative material.Along with the increase of Bi content, the discharge capacity and the cyclical stability of finishing ZnO negative material are significantly increased.The finishing ZnO discharge capacity that contains 9.5wt.%Bi is the most stable in 50 circulations, and it is the slowest to decay.Contain 7.6 and the finishing ZnO discharge capacity of 3.6wt.%Bi after 25 circulations apparently higher than the discharge capacity of unmodified zinc oxide, and have certain stability.
The zinc-nickel secondary batteries that adopts embodiment 1-3 prepared finishing ZnO to prepare as active material, the average discharge capacity of ZnO and its average utilization in 50 charge and discharge cycles processes (average discharge capacity/theoretical discharge capacity) see Table 1.By table 1 as seen, ZnO compares with unmodified, nanometer bismuth composite surface is modified and has been significantly improved average discharge capacity of ZnO and ZnO average utilization, and wherein the relative unmodified ZnO of the average discharge capacity of 9.5wt.%Bi finishing ZnO has improved 41%, and performance is best.
Finishing has also reduced threshold voltage in the charging of zinc-nickel secondary batteries.For example in the 15th charge and discharge cycles, is 1.91V with unmodified ZnO as threshold voltage in the charging of the zinc-nickel secondary batteries of active material preparation, and be 1.68V with embodiment 1 as threshold voltage in the charging of the zinc-nickel secondary batteries of active material preparation, embodiment 2 is 1.75V, and embodiment 3 is 1.88V.In the charging threshold voltage reduce help improving charge efficiency, reduce the generation of gas in the charging process, improve the fail safe of battery.
Table 1
Claims (2)
1. an alkaline zinc-based secondary battery cathode material is characterized in that it is Bi
2O
3Modify ZnO zinc-base battery material with the nanometer bismuth composite surface of BiO, contain mass percent and be 60-80% Zn, 0.1-15% Bi, all the other are O.
2. the preparation method of alkaline zinc-based secondary battery cathode material according to claim 1, its step is as follows: get ZnO and Bi (NO
3)
35H
2O, ZnO and Bi (NO
3)
35H
2The mass ratio of O is 100:1～100:30, earlier with Bi (NO
3)
35H
2O is dissolved in the HNO of mass concentration 30-67%
3In, HNO
3Consumption be at least Bi (NO
3)
35H
22 times of O quality to dissolving fully, are used distilled water diluting, make Bi (NO
3)
3Concentration at 0.1～10g/L, add ZnO then, fully stir the back and filter, 30min is at least calcined in oven dry more than 300 ℃ in air.
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| CN101533908B CN101533908B (en) | 2011-07-20 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437382A (en) * | 2011-12-19 | 2012-05-02 | 梅岭化工厂 | Electrolyte of silver-zinc storage battery with long wet charged life and preparation method thereof |
| 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 |
| CN103259024A (en) * | 2013-05-16 | 2013-08-21 | 中国科学院长春应用化学研究所 | Composite negative plate of cerium and zinc redox flow cell and preparation method of plate |
| CN106848315A (en) * | 2017-03-09 | 2017-06-13 | 河南师范大学 | Zinc-nickel battery anode material and preparation method thereof and the battery using the negative material |
| CN109036866A (en) * | 2018-08-09 | 2018-12-18 | 盐城工学院 | A kind of flexible fabric base electrode material and preparation method thereof |
| CN110492092A (en) * | 2019-07-24 | 2019-11-22 | 宁波双鹿新能源科技有限公司 | Rare earth alloy doped zinc-manganese battery and preparation method thereof |
| CN113241432A (en) * | 2021-05-12 | 2021-08-10 | 江苏理工学院 | ZnO/Bi 2 O 3 Preparation method of composite material and application of composite material in nickel-zinc battery |
| CN114551873A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Bismuth trioxide modified indium-doped zinc oxide material and preparation and application thereof |
Families Citing this family (1)
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| CN103030171B (en) * | 2012-12-17 | 2014-05-28 | 湖南丰日电源电气股份有限公司 | Method for preparing modified zinc oxide |
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| CN100373669C (en) * | 2006-06-02 | 2008-03-05 | 浙江大学 | Alkaline zinc-based secondary battery negative electrode material and its preparing method |
-
2009
- 2009-04-02 CN CN2009100972799A patent/CN101533908B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437382A (en) * | 2011-12-19 | 2012-05-02 | 梅岭化工厂 | Electrolyte of silver-zinc storage battery with long wet charged life and preparation method thereof |
| 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 |
| CN103259024A (en) * | 2013-05-16 | 2013-08-21 | 中国科学院长春应用化学研究所 | Composite negative plate of cerium and zinc redox flow cell and preparation method of plate |
| CN103259024B (en) * | 2013-05-16 | 2015-11-18 | 中国科学院长春应用化学研究所 | Cerium zinc redox flow batteries composite negative plate and preparation method thereof |
| CN106848315A (en) * | 2017-03-09 | 2017-06-13 | 河南师范大学 | Zinc-nickel battery anode material and preparation method thereof and the battery using the negative material |
| CN106848315B (en) * | 2017-03-09 | 2020-03-10 | 河南师范大学 | Zinc-nickel battery cathode material, preparation method thereof and battery using cathode material |
| CN109036866A (en) * | 2018-08-09 | 2018-12-18 | 盐城工学院 | A kind of flexible fabric base electrode material and preparation method thereof |
| CN110492092A (en) * | 2019-07-24 | 2019-11-22 | 宁波双鹿新能源科技有限公司 | Rare earth alloy doped zinc-manganese battery and preparation method thereof |
| CN110492092B (en) * | 2019-07-24 | 2021-08-10 | 宁波双鹿新能源科技有限公司 | Zinc-manganese battery and preparation method thereof |
| CN114551873A (en) * | 2020-11-26 | 2022-05-27 | 中国科学院大连化学物理研究所 | Bismuth trioxide modified indium-doped zinc oxide material and preparation and application thereof |
| CN113241432A (en) * | 2021-05-12 | 2021-08-10 | 江苏理工学院 | ZnO/Bi 2 O 3 Preparation method of composite material and application of composite material in nickel-zinc battery |
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|---|---|
| CN101533908B (en) | 2011-07-20 |
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