CN1264238C - Valve controlled lead acid cell with composite oxides additive contained in positive electrode - Google Patents
Valve controlled lead acid cell with composite oxides additive contained in positive electrode Download PDFInfo
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- CN1264238C CN1264238C CNB2004100254324A CN200410025432A CN1264238C CN 1264238 C CN1264238 C CN 1264238C CN B2004100254324 A CNB2004100254324 A CN B2004100254324A CN 200410025432 A CN200410025432 A CN 200410025432A CN 1264238 C CN1264238 C CN 1264238C
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- metal oxide
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention belongs to the technical field of electrochemistry, which particularly relates to a valve-controlled lead-acid accumulator with a composite oxide additive contained in a positive pole. The composite additive is composed of a rare earth oxide and a V group metallic element oxide containing a certain of stoichiometric ratio. The rare earth oxide as any kind of lanthanide rare earth oxide has the proportion by weight of 3 to 9% in a composite oxide. The V group metallic element oxide takes the proportion by weight of 97 to 91% in the composite oxide. The composite oxide additive is added in lead power according to the proportion by weight of 0.03 to 1.0 % of the lead powder to prepare positive lead plaster and further prepare the valve-controlled lead-acid accumulator. Due to the composite oxides added in the positive pole of the accumulator, the discharge capacity of the accumulator is enlarged, the service life of the accumulator is prolonged, and the present invention has important practical value in developing the dynamic power sources of electric bicycles and the application of lead accumulators in other fields.
Description
Technical field
The invention belongs to the electrochemical energy technical field, be specifically related to the valve-regulated lead-acid battery that a kind of positive pole contains the composite oxides additive.
Background technology
In recent years, be the exhaustion day by day of alleviating natural energy resources and the serious environmental problems that urban transportation causes, a kind of short distance of non-pollution discharge, portable electric bicycle be each big or middle city, the whole nation, even vast rural area, cities and towns fast development, and increases fast with the speed that is multiplied year by year.Undoubtedly, be substituted with the fuel vehicle that severe contamination discharges gradually, not only great practical significance arranged, and be the difficult problem that present city inhabitant generally is concerned about and is needed to be resolved hurrily preventing the pollution of the environment and saving natural energy resources with " zero discharge " electric motor car.
In the past few years, the experience of the electric bicycle marketization shows, desires to obtain popularizing of electric motor car maximum magnitude, and people are the most deeply concerned remains its power section---chemical power source.Although the chemical power source that some are novel, include developmental research in succession in as Ni-H cell, lithium ion battery and fuel cell, but from the recent period, in multiple alternative chemical power source, the valve-controlled sealed lead-acid battery still with the P/C of the best than and mature technique advantage and become the supporting first-selected power supply of present electric motor car.
Yet it is lower that lead acid accumulator also exists specific energy at present, the weakness that cycle life is too short, and this has greatly limited electric bicycle applying on market.A large amount of studies show that; Be limited by positive pole the useful life of lead acid accumulator.This except since the density of lead and compound thereof big, also exist low this critical defect of active material utilization.The latter generally belongs to following factors:
(1) product PbSO
4Bad conductivity, hindered inner active material and continued to participate in electrode reaction;
(2) the inner preferential PbSO that forms of electrode surface
4Because of its molal volume increases the duct of having stopped up between the active material, hindered the conduction of ion in the hole;
(3) disintegration of active material gel-network configuration makes active material soften prematurely, come off, thus premature loss battery initial capacity and shortened useful life of battery.
Be performance that improves lead acid battery positive electrode and the useful life that prolongs battery, for a long time, people extremely pay attention to studying the influence of anode additive to positive electrode active material utilization.For example, add conductive carbon cellulosic material such as carbon fiber, anisotropy graphite and acetylene carbon black for improving cathode performance, but all do not reach the Expected Results of extending battery life.This mainly is because positive active material PbO
2Strong oxidizing property and battery at the residing high anode current potential of charged state, make the oxidation and losing efficacy gradually in the cyclic process of battery of these carbon element additives, so still be difficult to find the stable material of anti-this kind high anode current potential oxidation so far, this makes by seeking conduction carbon element additive and comes the various trials of extending battery life to produce little effect.For this reason, be badly in need of starting to develop another kind of new anode diachylon additive, to improve product PbSO from seeking non-carbon materials aspect
4Bad conductivity, prevent the obstruction in electrode duct and suppress softening too early, coming off of active material, thereby improve the discharge performance of lead-acid battery effectively and prolong useful life of battery.
Summary of the invention
The objective of the invention is to propose a kind of anode diachylon and contain the long valve-regulated lead-acid battery that charges and discharge cycle life of having of composite oxides additive.
The valve-regulated lead-acid battery that the present invention proposes, its positive pole contains the composite oxides additive, this additive is made up of rare-earth oxide and V family metal oxide by certain stoichiometric proportion, by mass percentage, rare earth oxide accounts for 3～9% of additive total amount, and the V family metal oxide accounts for 91～97%; Content of additive is the 0.03-1.0% of anodal plumbous quality.Other structure of storage battery and composition and original valve-control storage battery are identical.
In the above-mentioned storage battery, rare-earth oxide is a certain among the lanthanide rare metal oxide (for example Gd, oxide), and the V family metal oxide is a kind of among the oxide of metallic element in the V main group, for example antimony (the oxide of Sb) (Bi) .The purity of composite oxides additive middle rare earth oxide preferably is not less than 99.9%, and the purity of V family metal oxide preferably is not less than 99.5%.
Among the present invention, anodal composite oxides additive adopts chemical codeposition method or mechanical milling method preparation.With the rare-earth metal chloride of certain stoichiometric proportion and V family metal chloride is dissolved in the water or absolute ethyl alcohol in, promptly generate the composite oxides sediment with excessive aqueous slkali reaction, fully washing is subsequently filtered, drying, and obtains desired composite oxides through special dehydration and refinement.
Another straightforward procedure of the anodal composite oxides preparation that the present invention proposes is that rare earth and the V family metal oxide with aforementioned mass percent mixes with the lead powder of 10～20 times of weight ratios, abundant mechanical lapping and mix thoroughly and obtain in ball mill.
The content of anodal composite oxides additive in anode diachylon that the present invention proposes is generally the quality 0.03～1.0% of lead powder.The additive of aforementioned proportion is added lead powder, is (1.35～1.40) g.cm with density again
-3Rare H
2SO
4Evenly mixing and fully mix and stir and make apparent density with the deionized water that contains a small amount of high polymer short fiber is (4.15～4.40) g.cm
-3Lead plaster, be coated with subsequently and fill in anode plate grid, through solidify, drying, promptly obtain positive plate after changing into for the lead-acid battery use.All the other manufacture crafts of storage battery are identical with original storage battery.
The composite oxides additive that the present invention proposes plays following useful effect to positive pole:
1. significantly improve (II) compound of Pb in the lead plaster and electrode reaction product P bSO
4Electronic conductance.It is theoretical to mix according to Hauffe, the rare earth ion RE (III) (RE be in the lanthanide series rare-earth elements a certain) of high price can be doped in Pb (II) compound at a low price, thereby significantly improve charge carrier (electronics) concentration of lower valency Pb (II) compound, improved the conductivity of electrode reaction product thus, and the improvement of this conductivity can be as carbon materials because of the lasting charging oxidation deactivation of battery.
2.V the element oxide M of family
2O
3(M be in the V group element a kind of) under the curing temperature and humidity of rational Match, can effectively strengthen the adhesion between positive plate and the active material.Thus, alleviated " no antimony effect " that the Pb-Ca alloy grid is produced, improved the dark circulation ability and the useful life that has prolonged battery of battery.
3.V family's element oxide change into charging process in, can be present in the positive active material with water-fast M (III) form, and can be with PbO
2Reduction and reduce, strengthened PbO effectively
2Intergranular gel-network configuration has kept PbO
2Particle is led at the electricity in gel district, has prevented anodal premature capacity loss.
Among the present invention, anodal composite oxides additive has the effect of obvious raising battery initial discharge capacity.The 12V-10Ah battery of electric bicycle that makes with this anodal compound additive is brought up to 144min its discharge time when identical 2h leads (5A) constant-current discharge, not additivated relatively (about 130min) improves about 11%.
Among the present invention, but the cycle charge discharge life-span of anodal composite oxides additive significant prolongation battery.By the Shanghai quality inspection the life tests report carried out according to national standard (JB/T 10262-2001) obtain, it charges and discharge circulation greater than 650 times, near the twice of national standard (350 times).
Among the present invention, anodal composite oxides additive can obviously improve the deep discharge cycle performance of battery.Adopt the electric motor car industry standard that the 12V-10Ah battery of electric bicycle is led (5A) constant-current discharge with 2h and carry out the deep discharge circulation to 10.5V (100%DOD), its average cycle life reaches 364 times, and the conventional batteries (about 200-250 time) that does not more add this additive prolongs dark cycle charge discharge number of times and reaches more than 100 times.
Among the present invention, anodal composite oxides additive can improve the big electric current fast charging and discharging ability of battery.With the 20A 42min that discharges, 10A charging 18min strengthens the fast charging and discharging test to the 12V-10Ah electric bicycle, and battery reaches average 460 times and charges and discharge circulation, and conventional batteries (about 180～250 times) is significantly increased relatively.
Among the present invention, anodal composite oxides additive can not increase the ease gas dehydration of battery when rationally controlling addition.Is example with the 12V-10Ah battery of electric bicycle in the dehydration that charges and discharge in the circulation for 316 times, and the battery single cycle dehydration that contains this additive is about 0.28g/ time, and conventional batteries is 0.31g/ time, slightly reduces than conventional batteries.But, might increase the ease gas dehydration of battery if addition is improper.
Among the present invention, anodal composite oxides additive not only can effectively improve the initial capacity of battery, but and the useful life of significant prolongation battery under various recurrent states, this is to improving the quality of electric bicycle electrokinetic cell, and the development of accelerating China's electric motor car industry has the important application prospect.
Embodiment
The co-electrodeposition method preparation of embodiment 1. anodal composite oxides additives:
With rare-earth metal chloride (RECl
3.6H
2O) (RE is Gd in the lanthanide series rare-earth elements) and the metal chloride MCl of V family
3(M is the metallic element Sb of V family) presses corresponding to the percentage by weight in its oxide (is RECl
3.6H
2O: MCl
3=5: 95) be dissolved in the absolute ethyl alcohol, slowly join in the excessive sodium hydrate solution of high-speed stirred and promptly obtain co-precipitation hydroxide.With sedimentation and filtration, washing is to there not being Cl
-Afterwards, carry out drying, and through the dehydration of specific step and thinning processing and obtain desired co-precipitation composite oxides.Product is crossed 300 mesh sieves after grinding.Again with 10 times lead powder mixed grinding, after evenly disperseing and mixing, after 300 mesh sieves and be stored in the drying equipment, promptly obtain thus with cream in the anodal composite oxides additive that uses.Attention in the metering process of preparation lead plaster, should count add 10 times lead powder weight.
Embodiment 2. is in embodiment 1, and RE adopts Gd, and M adopts Bi, and the mass ratio of two kinds of oxides is 9: 91, and with the mixed grinding of 20 times lead powder, all the other steps make the composite oxides additive with embodiment 1 again.
The preparation of embodiment 3. storage batterys
Take by weighing 100 kilograms of lead powder, add weight and be the example 1 of 0.1 kilogram or 0.5 kilogram or 1.0 kilograms or example 2 prepared composite oxides additives (noting the lead powder weight in the additive is counted in 100 kilograms the lead powder).Additive and lead powder are stirred in paste mixing machine, add 7.5～9.5 kilograms deionized water containing small amount of short and mix and stir and be " moisture lead plaster ", slowly adding density subsequently is 1.35g.cm
-3Dilute sulfuric acid (8.0～9.5) kg, be expanded to while stirring and form apparent density and be (4.15～4.40) g.cm
-3Even lead plaster.
Above-mentioned lead plaster evenly is coated with fills in anode plate grid, after roll extrusion → solidify → change into → wash → drying, obtain positive plate.
With this positive plate with certain just/negative ratio is assembled into the 12V-10Ah valve-regulated lead-acid battery.After tested, under identical discharging current, can improve the initial capacity about 11% of battery, under identical initial capacity, the dark cycle life that can prolong battery is more than 100 times.
Claims (3)
1, a kind of valve-regulated lead-acid battery, it is characterized in that positive pole contains the composite oxides additive, this additive is made up of rare-earth oxide and V family metal oxide, by mass percentage, rare-earth oxide accounts for 5～9%, and the V family metal oxide accounts for 95～91%. Content of additive is 0.1～1.0% of an anodal plumbous quality; Described rare-earth oxide is a certain in the lanthanide rare metal oxide, and the V family metal oxide is a kind of among the oxide of the metallic element in the V main group in the periodic table of elements.
2, valve-regulated lead-acid battery according to claim 1 is characterized in that the purity of said additive middle rare earth metal oxide is not less than 99.9%; The purity of V family metal oxide is not less than 99.5%.
3, the preparation method of the described valve-regulated lead-acid battery of a kind of claim 1 is characterized in that the additive of lead powder quality 0.1～1.0% ratio is joined in the lead powder, is 1.35-1.40g/cm with density again
3Rare H
2SO
4With the deionized water that contains the small amount of polymer short fiber, make lead plaster through stirring, and be coated with and fill in anode plate grid, through solidify, drying makes the positive plate for the lead acid accumulator use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100254324A CN1264238C (en) | 2004-06-24 | 2004-06-24 | Valve controlled lead acid cell with composite oxides additive contained in positive electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100254324A CN1264238C (en) | 2004-06-24 | 2004-06-24 | Valve controlled lead acid cell with composite oxides additive contained in positive electrode |
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| Publication Number | Publication Date |
|---|---|
| CN1595690A CN1595690A (en) | 2005-03-16 |
| CN1264238C true CN1264238C (en) | 2006-07-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569806A (en) * | 2011-10-27 | 2012-07-11 | 深圳格林兰德环保科技有限公司 | Frequency-controlled lead acid storage battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101841030B (en) * | 2010-05-27 | 2012-07-11 | 江苏华富控股集团有限公司 | Method for preparing positive plate of lead storage battery |
| CN101964421A (en) * | 2010-09-16 | 2011-02-02 | 南京双登科技发展研究院有限公司 | Super lead storage battery anode active substance for electric automobile |
| CN105428664B (en) * | 2015-11-10 | 2017-12-08 | 辽宁石油化工大学 | A kind of preparation method of the electrode of SOFC |
| CN114069060A (en) * | 2021-10-28 | 2022-02-18 | 天能电池集团股份有限公司 | Negative lead paste of valve-regulated lead storage battery, preparation method of negative lead paste and valve-regulated lead storage battery |
-
2004
- 2004-06-24 CN CNB2004100254324A patent/CN1264238C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569806A (en) * | 2011-10-27 | 2012-07-11 | 深圳格林兰德环保科技有限公司 | Frequency-controlled lead acid storage battery |
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|---|---|
| CN1595690A (en) | 2005-03-16 |
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| C10 | Entry into substantive examination | ||
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| C14 | Grant of patent or utility model | ||
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Assignee: B. B. Battery Co., Ltd. Assignor: Fudan University Contract record no.: 2011440000267 Denomination of invention: Valve controlled lead acid cell with composite oxides additive contained in positive electrode Granted publication date: 20060712 License type: Exclusive License Open date: 20050316 Record date: 20110331 |
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Effective date of registration: 20180604 Address after: 235100 1 Ying Chun Road, Suixi Economic Development Zone, Huaibei, Anhui Patentee after: Anhui Lishi Power Technology Co., Ltd. Address before: 200433 No. 220, Handan Road, Shanghai Patentee before: Fudan University |