CN101098003B - Alkaline battery cathode additive agent - Google Patents
Alkaline battery cathode additive agent Download PDFInfo
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- CN101098003B CN101098003B CN 200610028114 CN200610028114A CN101098003B CN 101098003 B CN101098003 B CN 101098003B CN 200610028114 CN200610028114 CN 200610028114 CN 200610028114 A CN200610028114 A CN 200610028114A CN 101098003 B CN101098003 B CN 101098003B
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- rare earth
- earth oxide
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- 239000000654 additive Substances 0.000 title claims abstract description 26
- 230000000996 additive effect Effects 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 title claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims description 25
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical group [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000006258 conductive agent Substances 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 23
- 229910000420 cerium oxide Inorganic materials 0.000 description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- Y02E60/12—
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an additive of battery cathode, which contains rare-earth oxide. The invention also provides a battery cathode which contains the additive and a relative battery with the cathode. The inventive additive will not change the internal structure of battery, with low cost and better anti-leakage safety, which can improve the electric property of battery significantly.
Description
Technical field
The present invention relates to a kind of additive that is used for battery, specifically relate to a kind of cathode additive agent that is used for a dry cell of mercury-free alkali Zn-Mn.
Background technology
Along with the development of consuming device, also more and more higher to the requirement of battery performance; The battery of good combination property, the battery of superior performance such as little as the internal resistance of cell, that shelf characteric good, gassing rate is little is more and more paid close attention to by enterprise.Both at home and abroad each battery production enterprise improves battery performance by all means, the normal at present methods such as raising that raw-material preferred, inside battery space is arranged that adopt.These methods can be to a certain degree the raising battery performance, yet owing to be subjected to the restriction of raw material technology and the finiteness of battery self-capacity, make and improve battery performance by this method and be subjected to restriction to a certain degree.
Rare earth oxide can change the surface state of active material, improves the activity of active material, is widely used in the industrial production.The rare earth metal resource of China is very abundant, and production scale and technical merit all are in prostatitis, the world.
In battery industry, rare earth oxide is used more in hydrogen storage cell and fuel cell.The research report is arranged in recent years, in positive pole, negative pole or the electrolyte of battery, add additive, can reduce the internal resistance of cell, increase the formation that ionic conduction ability or prevention have the accessory substance of negative effect.But the adding of some additive, battery cost increases on the one hand, can make the company of battery put the performance reduction or increase the battery gassing rate on the other hand, and the anti-leakage security performance of battery is reduced.
In sum, this area lacks that a kind of cost is low, the company of battery puts that performance is good, the anti-leakage security performance of battery does not well change battery structure simultaneously but can effectively improve the additive of alkaline battery performance; Therefore, this area presses for that a kind of low cost of exploitation, anti-leakage security performance are good, battery connects that to put performance good and can obviously improve the additive of battery electrical property.
Summary of the invention
The object of the present invention is to provide that a kind of low cost, anti-leakage security performance are good, battery connects that to put performance good and can obviously improve the cathode additive agent of battery electrical property.
Another object of the present invention is to provide that a kind of low cost, anti-leakage security performance are good, battery connects that to put performance good and can obviously improve the negative pole of battery electrical property.
Another object of the present invention is to provide a kind of low cost, prevent that the leakage security performance is good, battery is even put the good battery of performance.
A further object of the invention is to provide a kind of rare earth oxide particles composition.
The present invention has a purpose to be to provide a kind of purposes of rare earth oxide particles again.
One aspect of the present invention provides a kind of alkaline battery cathode additive agent, and described cathode additive agent is a rare earth oxide particles,
Described rare earth oxide is selected from praseodymium oxide, cerium oxide or its combination;
Described particle grain size is 0.01-100 μ m.
In preferred implementation of the present invention, described negative pole contains 0.1-5.0wt% additive of the present invention, in the negative pole total weight.
The present invention has an aspect that a kind of alkaline battery is provided again, and described battery comprises:
One positive pole, described positive pole contain the positive active material of effective dose and the conductive agent of effective dose,
One electrolyte, described electrolyte is alkaline solution,
Described battery also comprises: negative pole of the present invention.
In a preferred embodiment of the present invention,
Described positive pole contains the positive active material of 90～98 weight portions, the conductive agent of 2～10 weight portions,
And the total weight of described positive active material and conductive agent accounts for the 95-100wt% of anodal total weight.
In preferred implementation of the present invention, described battery also comprises and is selected from following component:
Positive active material in the described positive pole is a manganese dioxide, and described conductive agent is a graphite.
In preferred implementation of the present invention, the internal resistance 90-120m Ω of described battery.Preferably, the internal resistance of described battery is 96-98m Ω.
In preferred implementation of the present invention, 1.8 Ω pulses of described battery are at 650-690 time.Preferably, after 7 days, 1.8 Ω pulses to the value of 0.9V is 509-523 time to battery of the present invention 70 ℃ of storages.
In preferred implementation of the present invention, the gassing rate 0.10-0.20mL of described battery.Preferably, the gassing rate 0.11-0.16mL of battery of the present invention.
A further aspect of the invention provides a kind of rare earth oxide particles composition that is used as the cathode additive agent of alkaline battery, contains the rare earth oxide particles of effective dose and auxiliary agent, carrier or its combination of surplus; And
The particle diameter of described rare earth oxide particles is 0.01-100 μ m, and described rare earth oxide is selected from praseodymium oxide, cerium oxide or its combination.
The present invention has an aspect that a kind of purposes of rare earth oxide particles is provided again, the particle diameter of wherein said rare earth oxide particles is 0.01-100 μ m, and described rare earth oxide is selected from praseodymium oxide, cerium oxide or its combination, and described rare earth oxide particles is as the cathode additive agent of alkaline battery.
Description of drawings
Fig. 1 is cerium oxide addition and battery gassing rate graph of a relation.
The addition of cerium oxide is meant the weight content of cerium oxide, in the total weight of negative pole.
Embodiment
The inventor is through extensive and deep research, the negative pole of finding the alcaliotropism battery adds rare earth oxide and has the beyond thought effect that improves electrical property, especially performance, 1.8 Ω pulses or 1 Ω continuous discharge performance is put in the company of the internal resistance reduction of battery, battery and has the beyond thought effect that significantly improves.Finished the present invention on this basis.
Additive of the present invention, negative pole, battery are described as follows.
Rare earth oxide
Rare earth oxide in the battery cathode additive of the present invention comprises praseodymium oxide, cerium oxide or other rare earth oxides, preferred praseodymium oxide or cerium oxide.
Being applicable to that rare earth oxide of the present invention can be an one matter, also can be mixture (for example mixture of the mixture of praseodymium oxide and cerium oxide, praseodymium oxide and cerium oxide and other rare earth oxides).
The content of rare earth oxide generally accounts for battery cathode total weight 0.1-5.0wt%, preferred 0.1-1.2wt%. for example, account for the praseodymium oxide of the 0.1-0.4wt% of battery cathode total weight, more preferably account for 0.15-0.25wt%. or account for the cerium oxide of the 0.6-1.2wt% of battery cathode total weight, more preferably account for 0.75-0.85wt%. and prescribe a time limit when content is lower than down, the effect that reduces internal resistance or gassing rate is not too obvious; When content is higher than above-mentioned going up in limited time, can not further effectively reduce internal resistance or gassing rate and can increase cost.
Add praseodymium oxide and/or cerium oxide in alkaline battery cathode, can change the surface state of negative pole zinc powder, make the contact between zinc powder more tight, the electric conductivity of electrode improves, and the internal resistance of cell reduces.For example, for praseodymium oxide, addition was at 0.2% o'clock, and the internal resistance of battery reduces 12.7% than originally.
The particle diameter of rare earth oxide particles of the present invention is 0.01-100 μ m.
In a preference of the present invention, the rare earth oxide that adds (for example use the method preparation of this area routine or buy and obtain) process mechanical ball milling or chemical surface treatment before adding, thereby improve the electro-chemical activity of rare earth oxide, improve battery high current load discharge performance.
In a preference of the present invention, described rare earth oxide joins in the negative pole by the mechanical agitation mixed method.
Negative pole
Main Ingredients and Appearance in the negative pole is a negative electrode active material.Negative electrode active material is made through conventional preparation method by active component.Main active component can be selected from zinc, hydrogen or metal hydride.Other element such as iron, lead or cadmium also can be considered to use under some special-purpose.
For example, the active component of negative pole comprises 60-80 weight portion zinc powder, 18.5-39.5 weight portion electrolyte, 0.5-1.5 weight portion gel.
When negative pole is zinc, normally zinc powder is mixed with gelling agent.Preferably, use polypropylene acid type macromolecular material in the negative electrode active material, thereby can reduce battery gassing rate, the reduction internal resistance of cell, raising battery discharge current potential as gel.Gelling agent is including, but not limited to as polymethylacrylic acid potassium or polymethylacrylic acid, carboxy methyl cellulose, starch, and their derivative.
Can contain metal corrosion inhibitor in the negative pole, for example very a spot of lead, cadmium, indium, gallium, bismuth, or even mercury can be contained in the prescription of negative pole, and organic corrosion inhibitor, to reduce the hydrogen that is produced in battery.Randomly, also Zinc oxide powder can be contained in the negative electrode prescription.
Alternatively, can comprise the corrosion inhibiter of 0.002-0.050 weight portion in the active component, preferably contain the corrosion inhibiter of 0.002-0.010 weight portion.
Preferably described corrosion inhibiter is a corrosion inhibitor as mercury substitute, for example indium oxide, silica, sodium metasilicate etc.
Composition
The invention provides a kind of rare earth oxide particles composition that is used as the cathode additive agent of alkaline battery, contain the rare earth oxide particles of effective dose and auxiliary agent, carrier or the combination of surplus.
" effective dose " is meant, the addition that the performance of described battery makes moderate progress.For example, performance, 1.8 Ω pulses or 1 Ω continuous discharge performance being put in the company of the internal resistance reduction of battery, battery makes moderate progress.For example, composition weight accounts for battery cathode total weight 0.1-5.0wt%, and wherein composition middle rare earth oxide particle amount is the 10-90wt% of composition weight.
Described auxiliary agent is meant: the additive of other this area for example is used to improve the performance of negative pole, or is used for the compound of Catalytic Oxygen and hydrogen or is convenient to the manufacturing processing of electrode.
For example, described auxiliary agent is a metal corrosion inhibitor, for example very a spot of lead, and cadmium, indium, gallium, bismuth, or even mercury can be contained in the prescription of negative pole, and organic corrosion inhibitor, to reduce the hydrogen that is produced in battery.Randomly, also can be Zinc oxide powder.
Alternatively, can comprise the corrosion inhibiter that accounts for negative pole total weight 0.002-0.050wt% in the composition, preferably contain the corrosion inhibiter of 0.002-0.010wt%.
Preferably described corrosion inhibiter is a corrosion inhibitor as mercury substitute, for example indium oxide, silica, sodium metasilicate etc.
The negative pole preparation method
Negative electrode active component (for example zinc powder, gel, corrosion inhibiter) done mix the back and add electrolyte and carry out wet mixing and close, promptly make negative electrode active material through vacuum defoamation again.
Negative electrode active material prepares negative pole according to conventional method.For example, negative pole by negative pole at the bottom of, the sub-fastener assembling of negative electrode active material and current collection obtains.
Anodal
The positive pole that is applicable to battery of the present invention is not particularly limited, and can be the conventional known positive pole of positive pole, especially technical staff that uses in this area, for example, contains the positive pole of manganese dioxide and graphite powder.
In a preference, prepare positive pole of the present invention as follows:
(a) manganese dioxide and all are selected component is mixed to form uniform dry mixture;
(b) in uniform dry mixture, add a certain amount of alkaline electrolyte that is used for positive electrode composition, and mix this mixture continuously;
(c) if necessary, mixture is sieved; And under any circumstance all to form wet even mixed mixture;
(d) this mixed mixture of compacting;
(e) with the mixed mixture pelleting of compacting;
(f) compound particles is sieved;
(g) the in blocks or jar shape with the compound particles compacting;
(h) sheet or jar are put into the positive pole of suitable battery case as the battery that will make.
Based on the character of battery, insert in the jar anodal mouldable back in blocks, and then compacting.In addition, also can directly positive pole be squeezed into jar, or roll-in or be cast as is used to turn to spiral battery or even is used for the plate electrode of button or Coin-shaped battery.
The electrolyte of battery
The electrolyte that is applicable to battery of the present invention is not particularly limited, and can be the conventional known electrolyte of electrolyte, especially technical staff that uses in this area.
Usually, the key component of electrolyte aqueous solution (being electrolyte) should adapt to positive pole of the present invention and the negative pole group is right, especially can be selected from alkali metal hydroxide, as KOH, NaOH and LiOH or their mixed liquor, can contain a certain proportion of ZnO in the alkali metal hydroxide, or certain acid is as H
2SO
4, H
3BO
3, or H
3PO
4, or its mixture, also can be ZnCl
2, NH
4Cl, the salting liquid of NaCl or KCl, or its mixture.
A kind of particularly preferred alkaline electrolyte contains 40 ± 5% KOH.
Battery
The battery structure, shape and the specification that are applicable to battery of the present invention are not particularly limited, and can be conventional battery structure, shape and the specification of using in this area, and conventional method are prepared.
Usually, the technical staff can select corresponding positive pole, negative pole and electrolyte as required for use, is assembled into alkaline battery of the present invention.Be provided with separator between positive pole and the negative pole, preferably, described separator is a diaphragm paper.Electrolyte is included in both positive and negative polarity and permeates in diaphragm paper.
Below in conjunction with specific embodiment, further illustrating the present invention. should understand, these embodiment only are used for the present invention is described and are not used in and limit the scope of the invention. the experimental technique of the unreceipted actual conditions of the following example, usually according to normal condition, or the condition of advising according to manufacturer. ratio and percentage are based on the total weight of electrode, unless stated otherwise.
Embodiment 1
The additive praseodymium oxide is added in the raw material of preparation negative pole, make negative pole A, manufacture experimently into battery then.
Measure the electrical property of this electrode with DM2000 battery intelligent automatic checkout system, measure the internal resistance of cell and gassing rate respectively, the result is as shown in table 1:
Table 1 adds the influence of the praseodymium oxide of different content to the internal resistance of cell and gassing rate
Measure the electrical property of this electrode with DM2000 battery intelligent automatic checkout system, measure 70 ℃ of performances of placing down after 7 days of battery, the result is as shown in table 2:
Table 2 adds the influence of the praseodymium oxide of different content to electrical property
Table 3 adds the praseodymium oxide of different content to battery high pressure section Effect on Performance
The above results shows that the adding of praseodymium oxide can improve the electrical property of battery, the shelf characteric of battery especially, when the addition of praseodymium oxide 0.2% the time, it is best that the performance of battery reaches; 70 ℃ of storages of battery are after 7 days, and 10 Ω connect to put to 0.9V raising 3.8%, 1.8 Ω pulse to 0.9V raising 11.0%, 1 Ω even to be put to 0.75V raising 9.0%.
The adding of praseodymium oxide can improve the battery high pressure section discharge platform in when discharge, and when adding 0.2% praseodymium oxide, battery was stored 7 days for 70 ℃, and 10 Ω connect to put and improve 3.2%, 1.8 Ω pulse to 1.1V and improve 10.0%, 1 Ω to 1.1V and connect to put to 1.0V and improve 12.5%.
Embodiment 2
The additive cerium oxide is added in the raw material of preparation negative pole, the described negative pole B that obtains manufactures experimently into battery.
Measure the internal resistance of cell and gassing rate respectively, result such as table 4 and shown in Figure 1:
Table 4 adds the influence of cerium oxide to the internal resistance of cell and gassing rate
The above results shows, adds cerium oxide in alkaline battery cathode, can improve the hydrogen overpotential of zinc surface, reduces the gassing rate of battery, can improve the leak resistance of battery.
The variation of the gassing rate when in addition, cerium oxide content further increases is as shown in Figure 1. and wherein, as the addition of cerium oxide 0.8% the time (corresponding data such as Fig. 1), the gassing rate of battery reduces 38.9% than originally, reach minimum value.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (5)
1. the negative pole of an alkaline battery is characterized in that, described negative pole contains the 0.1-5.0wt% cathode additive agent, in the negative pole total weight;
Described cathode additive agent is a rare earth oxide particles, and described rare earth oxide is selected from praseodymium oxide; Described particle grain size is 0.01-100 μ m.
2. alkaline battery, described battery comprises:
One positive pole, described positive pole contain the positive active material of effective dose and the conductive agent of effective dose,
One electrolyte, described electrolyte is alkaline solution,
It is characterized in that described battery also comprises:
One negative pole as claimed in claim 1.
3. alkaline battery as claimed in claim 2 is characterized in that,
Described positive pole contains the positive active material of 90～98 weight portions, the conductive agent of 2～10 weight portions,
And the total weight of described positive active material and conductive agent accounts for the 95-100wt% of anodal total weight.
4. alkaline battery as claimed in claim 3 is characterized in that, described battery also comprises and is selected from following component:
Positive active material in the described positive pole is a manganese dioxide, and described conductive agent is a graphite.
5. the purposes of a rare earth oxide particles, the particle diameter of wherein said rare earth oxide particles is 0.01-100 μ m, and described rare earth oxide is selected from praseodymium oxide, it is characterized in that described rare earth oxide particles is as the cathode additive agent of alkaline battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610028114 CN101098003B (en) | 2006-06-26 | 2006-06-26 | Alkaline battery cathode additive agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610028114 CN101098003B (en) | 2006-06-26 | 2006-06-26 | Alkaline battery cathode additive agent |
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|---|---|
| CN101098003A CN101098003A (en) | 2008-01-02 |
| CN101098003B true CN101098003B (en) | 2010-05-12 |
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| CN 200610028114 Expired - Fee Related CN101098003B (en) | 2006-06-26 | 2006-06-26 | Alkaline battery cathode additive agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102751478B (en) * | 2012-07-03 | 2014-11-26 | 北京中航长力能源科技有限公司 | Zinc gel for zinc-air battery and preparation method thereof |
| CN103779572B (en) * | 2012-10-26 | 2016-02-24 | 华为技术有限公司 | A kind of lithium ion battery negative additive and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery |
| CN103794766B (en) * | 2012-11-02 | 2016-01-20 | 华为技术有限公司 | Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
| 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 |
| CN109817981B (en) * | 2018-12-25 | 2022-04-08 | 宁波富邦电池有限公司 | Alkaline battery cathode synthesis gel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1445810A2 (en) * | 2002-12-13 | 2004-08-11 | Celaya, Emparanza Y Galdos S.A. (Cegasa) | Electrochemical Element or Cell and Cathode thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1445810A2 (en) * | 2002-12-13 | 2004-08-11 | Celaya, Emparanza Y Galdos S.A. (Cegasa) | Electrochemical Element or Cell and Cathode thereof |
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Assignee: NINGBO SONLUK ENERGY TECHNOLOGY CO.,LTD. Assignor: ZHONGYIN (NINGBO) BATTERY Co.,Ltd. Contract record no.: 2010990000383 Denomination of invention: Additive for cathode of alkaline battery Granted publication date: 20100512 License type: Exclusive License Open date: 20080102 Record date: 20100617 |
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