1、AbstractA lead battery or accumulator in which each electrode is wrapped in a web of say, fiber glass, the electrolyte consists of a mixture of sulphuric acid and phosphoric acid, and the electrolyte is made thixotropic by addition of a jell-forming material, such as silicon dioxide with a particle
2、size of 0.01 to 0.02 microns. The web provides pockets which hold the electrolyte, and between adjacent electrodes there are disposed perforated, undulant spacers. The electrode grids are preferably made of a lead-calcium base. Preferably the electrodes are charged while dry, then wrapped in the fib
3、er web, then assembled into the battery housing; then the electrolyte is introduced into the housing; and the housing is ventilated. 硫酸电解质添加磷酸与粒径 0.01-0.02mm 的触变性SiO2 凝胶剂。板栅使用铅钙合金。Inventors: Jache; Otto (Budingen/Oberhessen, DT) Appl. No.: 093888Filed: November 30, 1970Foreign Application Priority D
4、ataDec 01, 1967 DT A 57 56 121 Current U.S. Class: 429/300 ; 429/225Field of Search: 136/26,6,154,157,17 Primary Examiner: Curtis; A. B. Assistant Examiner: Lefevour; C. F. Parent Case TextThis application is a continuation of my copending application Ser. No. 747,974, filed July 26, 1968 now abando
5、ned, for Accumulator or Battery. ClaimsHaving thus described my invention, what I claim is:1. A lead battery comprising a housing containing spaced electrodes having lead grids free of antimony, an electrolyte comprising a mixture of sulphuric acid and phosphoric acid rendered thixotropic by admixtu
6、re of jelling material, the quantity of phosphoric acid in the electrolyte, before charging, being 20 to 35g per liter of said electrolyte so that after a lower initial capacity, the capacity of said accumulator increases and then remains substantially constant to over about 150 cycles. 2. A lead ba
7、ttery according to claim 1, wherein the jelling material is silicic acid.3. A lead battery comprising a housing containing spaced lead electrodes free of antimony, a sulphuric acid electrolyte rendered thixotropic by admixture of a jelling material, and containing a quantity of phosphoric acid, the
8、amount of phosphoric acid in the electrolyte before charging, being 20 to 35g. per liter of said electrolyte so that after a lower initial capacity, the capacity of said accumulator increases and then remains substantially constant to over about 150 cycles. 板栅采用无锑合金（PbCa 合金），磷酸添加量 20-35g/l，凝胶剂采用SIO2
9、 酸，电池初始容量低，随后升高，然后在超过 150 次循环中保持稳定。DescriptionThe invention relates to a lead battery or accumulator with improved life and improved uniformity in capacity during its cycles of charge and discharge. 本发明不仅提升电池寿命还提高电池充放电循环过程中容量的均一性。Preferably in lead accumulators, whose positive plates consist of a me
10、tallic grid and of an essentially active mass of lead suboxide, lead alloy plates are used for the electrode grids, which contain, as the essentially stabilizing part of the alloy, antimony, the antimony content being at most between 5 and 12 percent. Positive plates, with an electrode grid made fro
11、m such a lead antimony alloy, can contain if occasion arises, as a further stable part of the alloy arsenic, copper, silver, tin, etc. Such batteries have a recognized good life expectancy as regards cycles, that is, as regards continuous successive discharging and charging. Efforts have been made f
12、or quite a long time, however, to eliminate antimony completely in the production of lead accumulators, since antimony is quite expensive in proportion to lead and since with the use of electrode grids containing antimony the self-discharge of the accumulator is considerable. The introduction, thoug
13、h, of lead accumulators whose electrode grids are antimony-free has hitherto suffered from the fact that their positive plates have a very bad life. The active mass of the positive plates loses very quickly its cohesion in the course of the cycling. It loses in increasing amount its capacity to stor
14、e electrical energy, and to give up again its stored energy, that is, the capacity of the lead accumulator becomes constantly smaller. It is already known that this loss can be offset by arranging the positive plates in pockets consisting of a fleece of glass fiber or of a web of synthetic material.
15、 Thereby, however, only erosion of the positve mass is hindered; the deterioration phenomenon is still not prevented practically. It is also already known that phosphoric acid may be added to the electrolyte of lead accumulators. Through phosphoric acid addition originally it was desired to prevent
16、the harmful sulphating of accumulators having the lead-antimony alloy electrode grids. Through the addition of the phosphoric acid, moreover, better fixation of the positive mass and thereby a lessening of its spalling off during cycling, as well as a diminution of corrosive action on the grid rack
17、and current conductor can be obtained, whereby all together an improvement in the life of the accumulator can be achieved. The phosphoric acid has heretofore been supplied in different ways to the electrolyte. For example, it has been added, in a dry state in the form of one of its salts, to the lea
18、d oxide used for filling of the capillary plates, or, in fluid form, to the lead paste mixture used for stuffing the positive grid plates. Another process was to immerse the positive electrodes produced in the usual fashion, before their formation, for a longer time in a strong phosphor-containing s
19、ulphuric acid. It is also possible to add the phosphoric acid directly to the electrolyte used for activating the accumulator. The hitherto known lead accumulators with a phosphoric-acid-containing electrolyte exhibit, however, an unsatisfactory capacity and an unsatisfactory life in their cycling.
20、In the cycling after an originally brief capacity increase, a heavier capacity decline during the first ten discharges is perceptible. The decrease in capacity is in direct relation to the amount of the phosphoric acid added. With small phosphoric acid additions, the capacity decrease is not so pron
21、ounced; while with greater phosphoric acid additions the capacity can decrease up to 50 percent of the initial capacity. Accumulators are already known which contain an electrolyte with thixotropic characteristics, that is, an electrolyte converted to the thixotropic state by addition of an extremel
22、y finely divided insoluble oxide, for example, of silicic acid, or aluminum oxide. The electrodes are wrapped with a fleece or web of glass fibers or another suitable acid resistant fiber. The fleece or web on the electrode holds the electrolyte fast in the vicinity of the plates, and spreads the el
23、ectrolyte equally over the whole surface of the plates because of its wick-like action, and thereby promotes current passage and diffusion, since the pores of the active mass are filled with freely movable jell-free electrolyte. The subject matter of the invention is a lead accumulator which is char
24、acterized by the combination of the following in themselves known characteristics: 1. The grid of the electrode consists of fine lead, dispersion hardened lead or of an antimony-free lead alloy. 2. Each electrode is wrapped in a fleece or web. The term “web“ as hereinafter used is intended to includ
25、e a fleece. 3. The electrolyte consists of sulphuric acid to which 20 to 35g/l. of phosphoric acid are added and 4. The electrolyte is made thixotropic by addition of a jelling material. In an accumulator built in accordance with the present invention the capacity does not decrease suddenly during c
26、ycling but increases still further and finally does not vary any more. The invention will now be explained further with reference to the drawings in which: FIG. 1 is a section extending parallel to the plane of the plates of an accumulator made according to the invention, individual parts being brok
27、en away for better illustration; FIG. 2 is a section on the line II-II in FIG. 1; FIG. 3 is a section on the line III-III in FIG. 2; and FIG. 4 is a diagrammatic illustration of the capacity of different accumulators in dependence on the number of the cycles. The accumulator illustrated in the drawi
28、ngs consists of a housing 1 and of a cell cover 2 which are cemented or welded together. The negative electrodes 3 and the positive electrodes 3 are fastened together in sets in the usual manner by means of bridges 4 and 4. The negative terminal post 5 and the positive terminal post 5 extend through
29、 the cover 2 and carry on their upper ends contacts 6. For liquid and gas-tight sealing, the posts are mounted in seals 7 in the cover. The individual electrodes 3 and 3 are covered by a web or fiber fleece 8, 8, resulting in pockets for taking up the electrolyte 9, which preferably are open above.
30、Preferably, as shown in FIG. 2, the fiber fleeces 8 and 8 are extended about the electrodes 3 and 3 and the space between two neighboring electrodes 3, 3 is covered laterally and on its underside by an additional web 10 for the development of pockets opening only at the top. Between two adjacent ele
31、ctrodes 3 and 3 there is disposed an undulant and perforated spacer 11. The pockets built up from the fleece or web are covered by a plate 12 which has holes 13, 13 bored through it. In the center of the cover there is a valve block 14 which is secured by a fluted lip 15 against twisting or withdraw
32、al. The valve block comprises a body insert 16, the valve proper formed by an inverted cup-shaped member 17, the cover plate 18 and the protective cage 19. The valve body has shoulders 20 which in the seating of the valve proper slide under the opposed shoulders 21 provided on the cell cover in the
33、form of a bayonet joint, so that between the sealing surfaces 22 and 23 there is compressed a sealing ring 24. Thus, a sealed closure is provided between the valve insert 14 and the cell cover 2. A boss 25 provided in the cover plate 18 presses the valve body 17 down, whereby the rim 26 of member 17
34、 is sealingly engaged in a ring groove 28 of block 14, such groove being filled with a silicon oil 27. About the positive pole post 5 with the contact 6 there is built up a protecting ring 29 provided with a slot 30 which with the corresponding opposed contact insures the mounting of the accumulator
35、 in its correct position and prevents the poles from being exchanged inadvertently. The cover plate 18 is fixed in the valve block 14 by means of peripheral lugs 31 and of a ring-shaped collar 32 in such a manner that when the valve opens, the excess pressure will be relieved by the escape of gases
36、between the outer periphery of plate 18 and the insert body 14. The electrolyte consists of sulphuric acid with a density of 1.24 to 1.30, preferably approximately 1.28 at 20.degree.C. To this there are added, per liter, 20 to 35 grams of phosphoric acid; and by addition of a finely divided oxide in
37、soluble in the electrolyte, preferably silicic acid, the electrolyte is converted to a thixotropic state. The most favorable content of phosphoric acid in the electrolyte amounts approximately to 25 g/l A phosphoric acid content below 20 g/l. is unsatisfactory, while a phosphoric acid content of ove
38、r 35 g/l. results in a considerably decrease of the capacity. For converting the electrolyte to a jell state, preferably finely divided pyrolytically produced silicic acid is used having a particle size of 0.01 to 0.02 micron and a surface of 200m2 /g. For jell-building material if occasion arises,
39、other suitable metallic oxides, for example, aluminum oxide, or organic jell builders, which are sufficiently stable in the electrolyte, can be used. The amount of the added silicic acid depends on the particle size and the surface area and will be approximately from 3 to 10 percent, preferably 6 pe
40、rcent. With use of a silicic acid addition below 3 percent too long stabilizing times are required for the building up of a consistent jell, while with an addition of over 10 percent a premature alteration of the jell can take place. 酸中胶含量 3-10，低于 3会使凝胶稳定时间太长For covering the electrodes a fiber glass
41、 is preferably used, in which the thickness of an individual fiber is approximately 15 microns and the offset between the individual fibers amounts to 150 microns. Thinner glass fibers can also be used up to 10 microns or thicker up to 20 microns. Precautions should be taken, however, to insure that
42、 the pore sizes of the fleece, determining the center-to-center offset between individual fibers, is somewhere between 100 and 200 microns. The grids of the electrodes are made of fine lead, dispersion-hardened lead, or of an antimony-free lead base, preferably of a lead-calcium base produced from 0
43、.08% calcium, the rest lead. Hereinafter, when the term “lead grids“ is used, it is meant to cover any and all of these possible types of grids. It has appeared especially advantageous that the active masses of the electrodes already contain stored at the time of filling of the electrolyte their ful
44、l electrochemical energy, that is, if in the production of the accumulator dry-charged electrodes are used. In the following the preparation of the electrolyte will be explained by an example. There are placed in a mixing vessel 90 liters of sulphuric acid; and there are added little by little with
45、continuous stirring 5 kg of very finely divided silicic acid with a surface area of 200 m.sup.2 /g. Finally 1.6 liters of 85% orthophosphoric acid with a concentration of 1.7 is stirred in. The thus-produced electrolyte is flowed into the cells of the lead accumulator while being continuously stirre
46、d until they are filled. It possesses a viscosity of about 1.500 CP. It has proved especially advantageous, before filling of the electrolyte, first to evacuate the accumulator housing having the sets of electrode plates already in place therein; whereupon the electrolyte is poured in. Caution is to
47、 be taken that the electrode plates of the accumulator are brought into contact with the electrolyte as far as possible uniformly and in as brief as possible time. After filling the housing with the electrolyte the housing is exposed to air, so that the pores of the active masses are filled with ele
48、ctrolyte fluid. In this way only the fluid portions of the electrolyte press into the pores, while the silicic acid portions remain in the pockets built out of the glass fiber, and within the pockets, on the basis of the existing fluid, the jell building already sets in. Especially is it advantageou
49、s that within the fleece or web lying on the electrodes a higher jell concentration is built up. This results in an improved fixation of the jell in its area. In order to reduce the loss of water as much as possible to a minimum during the charging of an accumulator built according to the invention, the charging is stopped upon attainment of a cell voltage of at most 2.5 volts. The accumulator according to the invention is safe in any position, and can be charged and discharged in any suitable position. For proof of the advance achieved by the invention several accumulator
