CN1588684A - Additive for reducing nickel-hydrogen cell internal pressure - Google Patents

Additive for reducing nickel-hydrogen cell internal pressure Download PDF

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Publication number
CN1588684A
CN1588684A CNA2004100802634A CN200410080263A CN1588684A CN 1588684 A CN1588684 A CN 1588684A CN A2004100802634 A CNA2004100802634 A CN A2004100802634A CN 200410080263 A CN200410080263 A CN 200410080263A CN 1588684 A CN1588684 A CN 1588684A
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battery
chlorophyll
additive
multiplying power
final
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CN1305162C (en
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吴锋
王芳
陈实
张存中
王国庆
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The internal voltage raising speed in battery charging process and final internal voltage value are marked increased by adding a certain ratio of green category macromolecule additive with high catalytic activity and special biological activity in secondary nickel-hydrogen battery, thus to effectively improve safe performance of the battery, increase charging efficiency of the battery and extend charge-discharge life of the battery. THe final internal votlage value can be reduced 20-80 percent according to differences of added ratio of active substance and adding mode.

Description

A kind of additive that reduces internal pressure of NiH battery
Technical field
The present invention is a kind of additive that reduces internal pressure of NiH battery, relates to the battery production technology, belongs to the environmental protection field.
Background technology
Ni-MH battery has the energy density height as the typical case of the green battery of novel high-performance representative, no cadmium pollution, and characteristics such as electric current fast charging and discharging have obtained application widely in the small portable electronic device greatly.Along with research work deeply and the continuous development of technology, also along with the becoming increasingly conspicuous of energy problem and environmental protection problem, this class battery also progressively is applied on electric tool, motor vehicle and hybrid vehicle, forms new development.In order to satisfy the requirement of Ni-MH power cell, the fail safe and the stability that improve combination property, the especially battery of battery are the task of top priority.Because the interior pressure of Ni-MH battery is the factor that has a strong impact on battery security, reduce inner pressure of battery rising speed and final in the pressure value, improve the fail safe of battery and stability with one of key issue of the combination property that improves battery.
The objective of the invention is fail safe and stability problem at the required raising of Ni-MH power cell, one class additive and addition manner is provided, reduced the high-speed and final interior pressure value of the interior voltage rise in the battery charging process by a relatively large margin, improved the charge efficiency of battery, improved the overall performance of battery, thereby made the performance of battery be more suitable for the requirement of electrokinetic cell.
Summary of the invention
Content of the present invention is achieved in that
In Ni-MH battery, add the additive that certain proportion (below 5%) has high catalytic activity, it is characterized in that in battery cathode active substance, battery electrode sheet surface, battery electrolyte and the surface of battery diaphragm is added and to be had the big molecular additives of green bio class of high catalytic activity, make sealed cell, battery size is unrestricted.The additive types that present technique adopts has: the chlorophyll with characteristic of semiconductor; The chlorophyll slaine; With the long key of the polyisoprene of polyenoid key is the carotenoid of branch subcenter.The chlorophyll slaine is characterised in that in these additives: chlorophyllous central metallic ions magnesium is replaced with other metal, metal is in the space in the middle of the tetrapyrrole ring, combining with it through covalent bond and coordinate bond forms the chlorophyll slaine, as sodium copper chlorophyllin, and sodium-iron-chlorophyllin etc.; Carotenoid is characterised in that: dividing subcenter all is the long key of polyisoprene of ethylene linkage, based on this, and the various derivatives that modes such as the adding by terminal oxidation, oxygen or the rotation of key and isomerization produce.(as:
Figure A20041008026300031
Deng).Add after the additive, the interior pressure of Ni-MH battery can descend 20%~80% usually, because the reaction more complicated that relates in the cell reaction process, the high catalytic activity of additive and special biologically active generally all show by the reduction of inner pressure of battery.These additives can directly adopt the chemically pure reagent of selling on the market.
Concrete addition manner is as follows:
The present invention is when the nickel-hydrogen battery negative pole active material adds additive, employing is mixed additive in the battery cathode active substance less than 5% ratio with mass percent when making battery pole piece, add 1.5~2% concentration again and be 60% ptfe emulsion, by size mixing, prepared such as smear, vacuumize, compressing tablet becomes negative pole piece of battery, again with commercialization positive plate and membrane coil coiled battery.During the charging of its 0.4 multiplying power of the battery that this method is made final total in pressure value final can reduce nearly 60%, 1 multiplying power charging the time pressure value can reduce nearly 80%.
The present invention is when additive is added on nickel-hydrogen battery electrode sheet surface, and employing evenly applies on commercial battery pole piece surface and uses the consoluet additive of absolute ethyl alcohol in advance, is wound into battery together with barrier film then.During the charging of its 0.4 multiplying power of the battery that this method is made final in pressure value final can reduce nearly 50%, 1 multiplying power charging the time pressure value can reduce nearly 70%.
The present invention adds in Ni-MH battery electrolyte in the additive, adopts before the battery liquid-filling of winding, and additive is sneaked in the electrolyte less than 5% ratio with mass percent, seals then and makes battery.During the charging of its 0.4 multiplying power of the battery that this method is made final in pressure value final can reduce nearly 30%, 1 multiplying power charging the time pressure value can reduce nearly 40%.
The present invention is when additive is added on the surface of battery diaphragm, and it is prior with the consoluet additive of absolute ethyl alcohol to adopt membrane surface evenly to apply, and is wound into battery together with the commercialization battery positive/negative plate then.During the charging of its 0.4 multiplying power of the battery that this method is made final in pressure value final can reduce nearly 30%, 1 multiplying power charging the time pressure value can reduce nearly 40%.
The present invention adds above-mentioned additive in battery, technology is comparatively simple, need not change existing equipment.According to adding active material ratio and addition manner difference, final in the pressure value can reduce by 20~80%, make battery have better stability and fail safe, thereby give secondary cell better charge-discharge performance.
The invention has the advantages that:
1, by adds the big molecular additives of green bio class be lower than 5% high catalytic activity at inside battery, can reduce battery charge significantly and the process of overcharging in battery interior voltage rise high-amplitude and final in the pressure value, thereby significantly improve the fail safe and the stability of battery.Technology is simple, and is easy to operate.
2, this green bio class macromolecular substances is all environmentally friendly, is a kind of new additive agent of safe green.
3, by add the big molecular additives of green bio class of a spot of high catalytic activity according to certain ratio that is not higher than 5%, according to adding active material ratio and addition manner difference, the pressure value can reduce by 20~80% in final, make battery have better stability and fail safe, thereby give Ni-MH power cell better charge-discharge performance.
Description of drawings
Fig. 1 is battery 0.5 multiplying power of having added the battery of additive with method provided by the invention and the not added additive inner pressure of battery rising situation comparison diagram in 300 later 0.4 multiplying power charging processes that circulates.Charging system is: 0.4 multiplying power charges to 150% of rated capacity.In Fig. 1, the A line represents to have added with method provided by the invention the inner pressure of battery rising curve of additive, and the B line represents not add the high curve of interior voltage rise of the reference cell of additive.As can be seen from Figure, with method provided by the invention added the interior voltage rise of battery when 0.4 multiplying power is overcharged of additive high-speed and final in the pressure value all be starkly lower than the reference cell that does not add any additives.
Fig. 2 carries out the comparison diagram of inner pressure of battery and cell voltage in the 1 multiplying power pulse current charge process for the battery that added the battery of additive and do not added additive with method provided by the invention for 2000 times later in floating charge.In Fig. 2, A VoltageLine and A The interior pressureVoltage curve when line represents to have added 1 multiplying power charging after the battery float of additive with method provided by the invention and in the line of buckling, B VoltageLine and B The interior pressureThe reference cell that line represents not add additive after floating charge the cell voltage curve the during charging of 1 multiplying power and in the line of buckling.As can be seen from Figure, the charging voltage platform that has added the battery of additive with method provided by the invention is starkly lower than the reference cell that does not add any additives; And the high-speed and final interior pressure value of interior voltage rise of having added the battery of additive with method provided by the invention all is starkly lower than the reference cell that does not add any additives.
Fig. 3 charges to 150% of rated capacity for the battery that has added the battery of additive and do not added additive with method provided by the invention successively carries out 0.4 multiplying power, 0.4 multiplying power discharging to 1 volt and 1 multiplying power charge to inner pressure of battery rising situation comparison diagram in 150%, 0.4 multiplying power discharging to the 1 volt process of rated capacity.In Fig. 3, the A line represents to have added with method provided by the invention the inner pressure of battery rising curve of additive, and the B line represents not add the high curve of interior voltage rise of the reference cell of additive.As can be seen from Figure, the interior voltage rise of the battery that has added additive with method provided by the invention when 0.4 multiplying power and 1 multiplying power are overcharged high-speed and final in the pressure value all be starkly lower than the reference cell that does not add any additives.
Fig. 4 for the battery that added the battery of additive and do not added additive with addition manner provided by the invention in the floating charge process battery charging and discharging platform with the change curve of floating charge number of times.In Fig. 4, the A line represents to have added with method provided by the invention the battery float characteristic curve of additive, and the B line represents not add the floating charge characteristic curve of the reference cell of additive.As can be seen from Figure, the charging voltage platform that has added battery battery in the floating charge process of additive with method provided by the invention raises slowly, and the charging voltage platform of reference cell is obvious with floating charge process rising speed.
Embodiment
Embodiment 1:
No. 5 battery cathode active substance (AB 5The type alloy, A and B are mishmetal) middle 4.8% sodium-iron-chlorophyllin that adds, add ptfe emulsion etc. again, by size mixing, prepared such as smear, vacuumize, compressing tablet becomes No. 5 battery cathode sheets (42mm * 110mm * 0.38mm), with commercialization positive plate (42mm * 80mm * 0.68mm) and No. 5 batteries of membrane coil coiled, voltage rise was high-speed in battery 0.4 multiplying power was charged reduces by 50%, and final interior pressure value has reduced by 52%; Voltage rise was high-speed in 1 multiplying power was charged reduces by 77%, and final interior pressure value has reduced by 78%, and the charging voltage platform reduces by 16%.
Embodiment 2:
No. 5 battery cathode active substance (AB 5The type alloy, A and B are mishmetal) in add 1.5% sodium copper chlorophyllin, other step is with embodiment 1, voltage rise is high-speed in the battery 0.4 multiplying power charging of making reduces by 43%, final in the pressure value reduced by 45%; Voltage rise was high-speed in 1 multiplying power was charged reduces by 56%, and final interior pressure value has reduced by 60%.
Embodiment 3:
No. 5 battery cathode active substance (AB 5The type alloy, A and B are mishmetal) in add 1.5% chlorophyll (chlorophyll magnesium sodium salt), other step is with embodiment 1, voltage rise is high-speed in the battery 0.4 multiplying power charging of making reduces by 30%, final in the pressure value reduced by 34%; Voltage rise was high-speed in 1 multiplying power was charged reduces by 32%, and final interior pressure value has reduced by 32%.
Embodiment 4:
No. 5 battery cathode active substance (AB 5The type alloy, A and B are mishmetal) in add 3% carotenoid, other step is with embodiment 1, voltage rise is high-speed in the battery 0.4 multiplying power charging of making reduces by 32%, final in the pressure value reduced by 37%; Voltage rise was high-speed in 1 multiplying power was charged reduces by 32%, and final interior pressure value has reduced by 33%.
Embodiment 5:
With commercialization positive plate (42mm * 80mm * 0.68mm), negative plate (the surface-coated one deck sodium copper chlorophyllin (3mg) of 42mm * 110mm * 0.38mm), be wound into battery No. 5, inner pressure of battery rising speed reduces by 60% when carrying out 1 multiplying power pulse current charge again behind the battery float 2000 times, final in the pressure value reduce by 65%.
Embodiment 6:
With commercialization positive plate (42mm * 80mm * 0.68mm), negative plate (the surface-coated one deck sodium-iron-chlorophyllin (1.5mg) of 42mm * 110mm * 0.38mm), be wound into battery No. 5, inner pressure of battery rising speed reduces by 68% when carrying out 1 multiplying power pulse current charge again behind the battery float 2000 times, final in the pressure value reduce by 70%.
Embodiment 7:
With commercialization positive plate (42mm * 80mm * 0.68mm), (the surface-coated one deck chlorophyll (chlorophyll magnesium sodium salt) of 42mm * 110mm * 0.38mm) (1.5mg) for negative plate, be wound into battery No. 5, inner pressure of battery rising speed reduces by 42% when carrying out 1 multiplying power pulse current charge again behind the battery float 2000 times, final in the pressure value reduce by 48%.
Embodiment 8:
With commercialization positive plate (42mm * 80mm * 0.68mm), negative plate (the surface-coated one deck carotenoid (1.5mg) of 42mm * 110mm * 0.38mm), be wound into battery No. 5, inner pressure of battery rising speed reduces by 34% when carrying out 1 multiplying power pulse current charge again behind the battery float 2000 times, final in the pressure value reduce by 35%.
Embodiment 9:
Add 2% carotenoid in the electrolyte, inject No. 5 battery, anode is Ni (OH) 2(42mm * 80mm * 0.68mm), battery cathode is AB 5(42mm * 110mm * 0.38mm), the circulation of battery 1 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 1 multiplying power forces to overcharge to rated capacity and is reduced by 26% after 160 weeks, final in the pressure value reduce by 31%.
Embodiment 10:
Add 2% chlorophyll (chlorophyll magnesium sodium salt) in the electrolyte, inject No. 5 battery, other is with embodiment 9, and the circulation of battery 1 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 1 multiplying power forces to overcharge to rated capacity and reduced by 21% after 160 weeks, final in the pressure value reduce by 24%.
Embodiment 11:
Add 2% sodium copper chlorophyllin in the electrolyte, injects No. 5 battery, other is with embodiment 9, and the circulation of battery 1 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 1 multiplying power forces to overcharge to rated capacity and reduced by 29% after 160 weeks, final in pressure value reduction by 32%.
Embodiment 12:
Add 2% sodium-iron-chlorophyllin in the electrolyte, injects No. 5 battery, other is with embodiment 9, and the circulation of battery 1 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 1 multiplying power forces to overcharge to rated capacity and reduced by 36% after 160 weeks, final in pressure value reduction by 39%.
Embodiment 13:
Membrane surface applies 2.5% sodium-iron-chlorophyllin, is wound into battery with the commercialization battery positive/negative plate, and anode is Ni (OH) 2(42mm * 80mm * 0.68mm), battery cathode is AB 5(42mm * 110mm * 0.38mm), the circulation of battery 0.5 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 0.4 multiplying power forces to overcharge to rated capacity and is reduced by 22% after 160 weeks, final in the pressure value reduce by 24%.
Embodiment 14:
Membrane surface applies 2.5% sodium copper chlorophyllin, and other step is with embodiment 13, and the circulation of battery 0.5 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 0.4 multiplying power forces to overcharge to rated capacity and reduced by 21% after 160 weeks, final in the pressure value reduce by 22%.
Embodiment 15:
Membrane surface applies 2.5% chlorophyll (chlorophyll magnesium sodium salt), other step is with embodiment 13, battery 0.5 multiplying power circulation is carried out the 150% o'clock inner pressure of battery rising speed that 0.4 multiplying power forces to overcharge to rated capacity and is reduced by 25% after 160 weeks, final in the pressure value reduce by 27%.
Embodiment 16:
Membrane surface applies 2.5% carotenoid, and other step is with embodiment 13, and the circulation of battery 0.5 multiplying power is carried out the 150% o'clock inner pressure of battery rising speed that 0.4 multiplying power forces to overcharge to rated capacity and reduced by 20% after 160 weeks, final in the pressure value reduce by 22%.

Claims (6)

1, a kind of new additive agent that reduces internal pressure of NiH battery is characterized in that: have high catalytic activity and the big molecular additives of special bioactive green bio class.
2, have according to a kind of addition manner that reduces the new additive agent of internal pressure of NiH battery described in the claim 1: make an addition in the electrode material, be added on the electrode plates surface, make an addition in the electrolyte, make an addition on the barrier film.
3, according to a kind of new additive agent that reduces internal pressure of NiH battery described in the claim 1, it is characterized in that: chlorophyll with semiconductor property; Chlorophyll slaine and carotenoid series.
4, be chlorophyll magnesium sodium salt according to the chlorophyll with semiconductor property described in the claim 3, the metal ion in the space in the middle of the tetrapyrrole ring is a magnesium ion.
5, according to the chlorophyll slaine described in the claim 3, it is characterized in that: chlorophyllous central metallic ions magnesium is replaced with other metal, metal combines with it through covalent bond and coordinate bond in the space in the middle of the tetrapyrrole ring, forms the chlorophyll slaine.As sodium copper chlorophyllin, sodium-iron-chlorophyllin etc.
6. according to the carotenoid described in the claim 3, it is characterized in that: dividing subcenter all is the long key of polyisoprene of ethylene linkage, based on this, and the various derivatives that modes such as the adding by terminal oxidation, oxygen or the rotation of key and isomerization produce.
CNB2004100802634A 2004-09-29 2004-09-29 Additive for reducing nickel-hydrogen cell internal pressure Expired - Fee Related CN1305162C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI426647B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Method for manufaturing a battery
TWI426640B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Isolation membrane, method for manufacturing thereof and organic battery
TWI426645B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Method for manufaturing a battery
TWI449249B (en) * 2010-12-13 2014-08-11 Innot Bioenergy Holding Co Battery
TWI478424B (en) * 2010-12-13 2015-03-21 Innot Bioenergy Holding Co Method for manufaturing organic negative electrode
TWI560929B (en) * 2010-12-13 2016-12-01 Innot Bioenergy Holding Co Battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO119270B1 (en) * 1997-11-25 2004-06-30 Institutul De Tehnologie Izotopică Şi Moleculară Composition for producing hydride electrodes of alkaline electric accumulators and process for producing the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI426647B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Method for manufaturing a battery
TWI426640B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Isolation membrane, method for manufacturing thereof and organic battery
TWI426645B (en) * 2010-12-13 2014-02-11 Innot Bioenergy Holding Co Method for manufaturing a battery
TWI449249B (en) * 2010-12-13 2014-08-11 Innot Bioenergy Holding Co Battery
TWI478424B (en) * 2010-12-13 2015-03-21 Innot Bioenergy Holding Co Method for manufaturing organic negative electrode
TWI560929B (en) * 2010-12-13 2016-12-01 Innot Bioenergy Holding Co Battery

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