CA1294587C - Method and apparatus for filling containers with a gelled composition and applications thereof in electric accumulators - Google Patents
Method and apparatus for filling containers with a gelled composition and applications thereof in electric accumulatorsInfo
- Publication number
- CA1294587C CA1294587C CA000589423A CA589423A CA1294587C CA 1294587 C CA1294587 C CA 1294587C CA 000589423 A CA000589423 A CA 000589423A CA 589423 A CA589423 A CA 589423A CA 1294587 C CA1294587 C CA 1294587C
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- CA
- Canada
- Prior art keywords
- composition
- container
- filling
- chamber
- fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B39/00—Nozzles, funnels or guides for introducing articles or materials into containers or wrappers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Filling, Topping-Up Batteries (AREA)
- Basic Packing Technique (AREA)
Abstract
METHOD AND APPARATUS FOR FILLING CONTAINERS
WITH A GELLED COMPOSITION AND
APPLICATIONS THEREOF IN ELECTRIC ACCUMULATORS
A B S T R A C T
The apparatus comprises a hollow body (10) for con-ducting a gelled composition and a nozzle (20) for injecting a propelling fluid such as compressed air.
This nozzle and the body are disposed in such manner as to define for example a venturi for producing turbulence.
The gelled composition with upon entry a viscosity on the order of 300 000 cP, issues from the apparatus with a temporary apparent viscosity in the neighbourhood of that of water for filling the container. Application in the filling of sealed lead accumulator containers, the precharged plates of which bathe in a gelled electrolyte based on sulphuric acid and silicic acid.
Single Figure.
WITH A GELLED COMPOSITION AND
APPLICATIONS THEREOF IN ELECTRIC ACCUMULATORS
A B S T R A C T
The apparatus comprises a hollow body (10) for con-ducting a gelled composition and a nozzle (20) for injecting a propelling fluid such as compressed air.
This nozzle and the body are disposed in such manner as to define for example a venturi for producing turbulence.
The gelled composition with upon entry a viscosity on the order of 300 000 cP, issues from the apparatus with a temporary apparent viscosity in the neighbourhood of that of water for filling the container. Application in the filling of sealed lead accumulator containers, the precharged plates of which bathe in a gelled electrolyte based on sulphuric acid and silicic acid.
Single Figure.
Description
Method and apparatus for filling containers with a gelled composition and applications thereof in electric accumulators The present invention relates to sealed electric accu-mulators, and more particularly to lead and acid accumulators and concerns especially the filling of the latter by means of a gelled electrolyte.
Sealed electric accumulators, in particular employing lead with a solidi:fied set electrolyte are known. This ty~e of accumu -lator is for example disclosed in French patent 1 280 180.
As explained, an electrolyte composition is employedwhich is immobilized in the form of a gel and is constituted by a mixture of sulphuric acid and salicic acid, in parti-cular.
In the conventional way, electric accumulators are constituted by sealed containers in which are disposed active plates associated with porous separators interposed there-between.
When accumulators of medium and large size of this type are employed, a notable difficulty appears in arranging that the electrolyte fill all the interstices without forming bubbles or empty spaces. The existence of filling defects is particularly harmful to the life and performance of this type of accumulator.
To obtain the maximum sealing, it is advisable to employ an electrolyte of very high viscosity, but the higher the viscosity, the more delicate is the filling.
lZ~ 5~7 To overcome this type of difficulty in which contradic-tory requlrements must be conciliated, various solutions have already been proposed.
For example, the German document DE 1 671 693 proposes incorporating in the electrolyte based on sulphuric acid and phosphoric acid, a silicon gel which is progressively added while permanently shaking so as to maintain a certain flui-dity by stirring. By means of this technique, it is possi-ble to fill more or less well sealed accumulators or batte-ries whose electrodes are dry and charged, with a partiallysolidified electrolyte whose viscosity is notable and on the order of 1 500 cP.
Another technique has been proposed by the French document FR 2 493 608. In this technique, an electrolyte of low concentration is used and poured into the containers in which are initially placed the previously discharged pla-tes. There is then brought into effect an extremely complex procedure during which various filling, emptying and charging stages occur.
According to another method disclosed in the German patent DE 3 539 834, there is employed an electrolyte to which is added a gelling agent having two components which react physically and/or chemically on each other inside the containers so that the viscosity gradually increases after filling and consequently solidifies in the form of a very consistant electrolyte gel.
All these methods permit filling sealed electric accumulcltors or batteries with an electrolyte which i5 gel-led, but they are delicate to carry out and do not give full satisfaction since they are long, complicated or employ expensive constituents.
An object of the invention is to overcome these draw-backs by means of a relatively simple method which is easy to carry out.
The invention concerns in particular the manufacture of lead accumulators, for example having tubular positive pla-tes or planar positive plates, in which the filling and working electrolyte is based on a composition obtained from a mixture of sulphuric acid and silicic acid forming ~ gel for obtaining sealed accumulators, termed gas recombination accumulators, having good aptitudes for working in cycles for theuse as a traction battery and good aptitudes for working at a floating voltage for use in stationary batte-ries. Floating voltage is intended to mean in the art the constant voltage of predetermined value as a function of the type and nature of the battery to which it is applied, main-tained at the terminals of a battery so as to pass throughthe battery a current which compensates for the spontaneous discharge of the active materials and thus permits perma-nently maintaining the battery in a state of maximum charge.
The invention provides a method and an apparatus and their application in the filling of sealed accumulator con-tainers provided with at least a part of their internal constituents, in particular their definitively formed plates, directly with an-electrolyte composition gelled in operation having a relatively high viscosity. ~
In the filling method according to the invention, the gelled composition is introduced in a container by means of a propelling fluid injected within said composition and creating therein such turbulence that initially the visco-sity of the composition is on the order of about 300 000 cP
and in such manner that upon entry in the container, the viscosity is in the neighbourhood of that of water, and the rate at which the composition flows into the container is so adjusted that it is on the order of 2 cu.m/h and a pro-pelling fluid such as air is employed whose pressure is between 0.1 and 7 hPa.
The apparatus for filling, in particular according to the method just defined, comprises a longilinear hollow body for conducting the gelled composition in which is pro-vided a compartment onto which open an inlet orifice and an outlet orifice between which is provided an intermediate constriction in the region of a chamber having a conical wall, and a tapered nozzle for injecting a fluid which is disposed at least partly in the hollow body and 1 s provided with an axial duct at one of the ends of which is located a terminal connector outside the hollow body and at the other end of which is provided a jet opening out substantially in the region of the constriction and having conical sides in alignment with the chamber so as to define an annular passage between the chamber and the sides.
451~7 By IlleallS oE ttle inv~ntion, it is possible to efEect the filling of large or small accumulators the active material of the plates of which has been previously formed eitherin the final containers or in auxiliary containers. In par-ticular, owing to the invention, it can be arrangd that theactive materials of the plates are formed in the final containers by means of a forming electrolyte u~,-ch is re-moved by pouring before the containers are filled with the definitive gelled electrolyte composition based on sulphu-ric acid and silicic acid.
By means of the invention, it is also possible to employa final gelled electrolyte composition comprising phospho-ric acid so as to improve the aptitude for work in cycles.
Other features of the invention will be apparent from the following description and claims with reference to the accompanying drawing which is given solely by way of exam-ple and in which the single Figure is an axial sectional view of an embodiment of an apparatus according to the in-vention, in particular for carrying out the method defined hereinbefore.
Sealed accumulators, in particular those in which there is used for the electrolyte a composition based on sulphu-ric acid gelled by silicic acid, are well known in the art.
This is why only that which concerns the invention will be described. For the rest, the person skilled in the consi-dered art will draw from the current conventional solutions at his disposal to meet the particular problems with which he is confronted.
5~7 ~s is know, the physical properties and the surface cha-racterictics of the pyrogenation silica impart thereto the ap-titude to thicken the liquids to which it is added and to adjust the thyxotropy.
When the silicic acid is dispersed in a liquid composition, aggregates in the form of chains are united and give a network structure. The aptitude of the liquid composition to flow is in this way reduced, whence an increase in the viscosity or thicke-ning and even on at least artial solidification or setting into a maSs-Each of the particles of the chain has hydroxylated groupsfixed on the silica atoms on the surface, the hydrogen atom on a particle has an affinity for the oxygen atom of a neighbouring particle. When these particles approach each other, thev form a bond between tAese two atoms, which phenomenon is known under the name of hydrogen bond.
If the quantity of silicic acid dispersed in a liquid composition is very small, only a limited number of hydrogen bonds are formed, since the chains are generally too far away from each other to unite into a closely knit network ; the viscosity remains at a low value.
On the other hand, if a larger quantity of dispersed silicic acid is used, and if the acid concentration of the mixture is al~greater, a large number of hydrogen bonds are formed, whence a notable increase in the viscosity, or thickening, termed thy~otro~y.
It has been found that the factors acting on the -thyxo~ropy are principally the n~ture of the liquid, the con-centration of silicic acid, the value of the pH, the nature of the additives, the degree of dispersion, the type of sili-cic employed, bearing in mind the relative concentrations of silicic acid and sulphuric acid employed.
When lead accumulators are manufactured whose electro-lyte is a composition consisting of a mixture of sulphuric acid and silicic acid acting as a gel-forming agent, a compo-sition of high viscosity is obtained which renders the intro-duction of this composition almost impossible in the accumu-lator and above all when the accumulator is of large si~e.
One of the methods employed, as recalled hereinbefore, consists in arranging that the composition for filling the accumulator has a low th'~otropyl i.e. high fluidity, by nota-bly decreasing the acid concentration of the filling com-position by a prior discharge of the plates or by the addi-tion of additives acting asthyxotropy retarding means, i.e.
means for retarding the gelling.
That which characterizes the filling method accord-ing to the invent:ion is the fact that the filling electro-lyte composition contains the quantity of silicic acid re-quired for the forming of the gel and the concentration of sulphuric acid required for the discharge of the accumulator and which corresponds to the acid concentration of a fully charged accumulator. This gelled compositionhas for example an acid concentration which may vary from about 22 % to about 40 % with silicic acid put on the mar~et un~er the 5~7 reference "AEROSIL 20C" by the German Firm DEG~SSA AG in pro-portions on the order of 3 tolO~ by weight of the filling electrolyte. ~here may also be used that put on the market under the reference "CAB-O-SIL" by the French Firm CABOT
FRANCE. There is used a composition obtained in this way which has a high viscosity, on the order of about 300 000 cP.
In order to ensure that this composition is capable of fil-ling all the free interstices existing between the internal constituents, for example the plates and the spaces of the accumulator, its aptitude to flow, is physically increased, i.e. its apparent viscosity is momentarily reduced , only in the Eilling stage proper.
According to the method of the invention, the structure of the network of the electrolyte composition is temporarily modified by creating a turbulence by means of a propelling fluid injected under pressure within the electrolyte composi-tion having high viscosity, for example by means of an ejector whose conEiguration reminds one of a venturi.
As can be seen in the Figure of the drawing, shown substantially to scale, the apparatus in particular for carry-ing out the-method according to the invention comprises a relatively longilinear hollow body 10 for conducting the electrolyte composition which is supplied for example by means of a conventional metering pump (not shown) ~hereby itisFossible adjust the rate of flow and/or the supply pressure of the electrolyte composition.
This body 10 has a compartment 11 which communicates lZ~5~7 with the inlet oriEice 12 and the outlet orifice 13. As can be seen, an intermediate constriction or throttle is provided.
This constriction is preceded by a chamber 15 having a coni-cal wall and preferably of revolution.
Placed in this body 10 is a tapered nozzle 20 for in-jecting a propelling fluid. This propelling fluid is for example compressed air. For example,there is used compressed air distributed by the distribution network usually found in industrial premises. If need be, a pressure reducer is inter-posed between the compressor and the nozzle. Compressed air is preferably employed which has a pressure of between 0.1 and 7 hPa.
This nozzle 20 is disposed at least partly in the hollow body , as illustrated. This nozzle 20 is provided with a duct 21 which terminates at one of its ends in an exterior terminal connection 22 and at the other end in a jet 23 opening out substantially in alignment with the constric-tion 14. As can be seen, this nozzle has conical sides in the region o~ the chamber 15. The chamber and the nozzle which are approximately coaxial in this way deEine an annular passage 25.
The body is also provided with a tapped hole 26 in which may be engaged a screw (not shown) for adjusting the longitudinal postiion of the nozzle 20 in the chamber 14.
The exterior terminal connector 22 of the nozzle 20 and the orifices 12 and 13 of the hollow body 10 are prVided with appropriate connectors suitably adapted for connecting 3'7 them to the conduits, pipings and accumulator containers.
This is convelltional and this is why no more details will be given.
The materials of this apparatus are so chosen as to resist and be compatible with the electrolyte composition and the propelling fluid.
For the illustrated embodiment, the jet 23 extends beyond the constriction 14 by about 8 mm and has an inside diameter of about 4 mm. The annular passage 25 has an outside diameter of about 24 mm and an inside diameter of about 7 mm.
The angles of the cones of the chamber and nozzle are prefe-rably on the order of those of the drawing.
The apparatus according to the invention is used in such manner that its inlet orifice 12 receives the electrolyte composition which issues therefrom through its outlet orifice 13 connected to the sealed accumulator container. The pro-pelling fluid is ejected through the exterior terminal connec-tor 22 and is,sues through the jet23 within the electrolyte with which it becomes mixed for reducing the viscosity.
The propelli,ng fluid, here c o m p r e s s e d a i r , thereafter escapes from the sealed container through the other openings of the latter which are lert open.
By employing, if necessary, a plurality of apparatus-according to the invention, mounted in cascade, one behind the other, it is possible to start with an electrolyte compo-sition consisting of a mixture of sulphuric acid and silicic acid whcse concentration of sulphuric acid corresponds to the opera-tion of an accumulator whose plates are lnitially formed and charged. When it enters the apparatus,the elec-trolyte composition has a very high viscosity,on the order of about 300 000 cP,whereas when it arrives in the container the viscosity of the electrolyte is in the neighbourhood of that o f water. Thus, it will be understood that with such a viscosity which is in this way temporarily lowered, there is no longer any difficulty for filling thc container with the electrolyte including within the narrowest intersti-ces, of a few tenths of a millimetre, which exist betweenthe materials of the plates and the porous separator elements facing them. The composition of the electro:Lyte which has just been notably fluidified temporarily is again gelled so as to resume its initial viscosity which is practically un-modified.
The whole importance of the invention wlll therefore be realized, since it permits avoiding practically all the dif-ficulties inherent in the prior known methods some of which have been briefly recalled.
As can be observed, by means of the invention it is possible, on one hand~to manufacture lead accumulato~, in particular having tubular positive plates or planar positive plates, of small or large sizes, the active materials of which plates have been either previously formed electrochemi-cally in separate containers which are not the containers of utilization of the accumulator, or formed in the definitive containers of utilization of the accumulator, and, on the lZ~4~87 other hand, to fill containers containing in particular the plates thus completely charged with an electrolyte composi-tion containing sulphuric acid at a high concentration cor-responding to the concentration of the fully charged accumu-lator, and silicic acid with the concentration requiredfor the formation of a gel of very high viscosity permitting the immobilization of the sulphuric acid while ensuring that the properties of the gel thus obtained allow the transfer of the oxygen to the negative plate according to the requi-red prescriptionsfor gas recombination accumulators.
Sealed electric accumulators, in particular employing lead with a solidi:fied set electrolyte are known. This ty~e of accumu -lator is for example disclosed in French patent 1 280 180.
As explained, an electrolyte composition is employedwhich is immobilized in the form of a gel and is constituted by a mixture of sulphuric acid and salicic acid, in parti-cular.
In the conventional way, electric accumulators are constituted by sealed containers in which are disposed active plates associated with porous separators interposed there-between.
When accumulators of medium and large size of this type are employed, a notable difficulty appears in arranging that the electrolyte fill all the interstices without forming bubbles or empty spaces. The existence of filling defects is particularly harmful to the life and performance of this type of accumulator.
To obtain the maximum sealing, it is advisable to employ an electrolyte of very high viscosity, but the higher the viscosity, the more delicate is the filling.
lZ~ 5~7 To overcome this type of difficulty in which contradic-tory requlrements must be conciliated, various solutions have already been proposed.
For example, the German document DE 1 671 693 proposes incorporating in the electrolyte based on sulphuric acid and phosphoric acid, a silicon gel which is progressively added while permanently shaking so as to maintain a certain flui-dity by stirring. By means of this technique, it is possi-ble to fill more or less well sealed accumulators or batte-ries whose electrodes are dry and charged, with a partiallysolidified electrolyte whose viscosity is notable and on the order of 1 500 cP.
Another technique has been proposed by the French document FR 2 493 608. In this technique, an electrolyte of low concentration is used and poured into the containers in which are initially placed the previously discharged pla-tes. There is then brought into effect an extremely complex procedure during which various filling, emptying and charging stages occur.
According to another method disclosed in the German patent DE 3 539 834, there is employed an electrolyte to which is added a gelling agent having two components which react physically and/or chemically on each other inside the containers so that the viscosity gradually increases after filling and consequently solidifies in the form of a very consistant electrolyte gel.
All these methods permit filling sealed electric accumulcltors or batteries with an electrolyte which i5 gel-led, but they are delicate to carry out and do not give full satisfaction since they are long, complicated or employ expensive constituents.
An object of the invention is to overcome these draw-backs by means of a relatively simple method which is easy to carry out.
The invention concerns in particular the manufacture of lead accumulators, for example having tubular positive pla-tes or planar positive plates, in which the filling and working electrolyte is based on a composition obtained from a mixture of sulphuric acid and silicic acid forming ~ gel for obtaining sealed accumulators, termed gas recombination accumulators, having good aptitudes for working in cycles for theuse as a traction battery and good aptitudes for working at a floating voltage for use in stationary batte-ries. Floating voltage is intended to mean in the art the constant voltage of predetermined value as a function of the type and nature of the battery to which it is applied, main-tained at the terminals of a battery so as to pass throughthe battery a current which compensates for the spontaneous discharge of the active materials and thus permits perma-nently maintaining the battery in a state of maximum charge.
The invention provides a method and an apparatus and their application in the filling of sealed accumulator con-tainers provided with at least a part of their internal constituents, in particular their definitively formed plates, directly with an-electrolyte composition gelled in operation having a relatively high viscosity. ~
In the filling method according to the invention, the gelled composition is introduced in a container by means of a propelling fluid injected within said composition and creating therein such turbulence that initially the visco-sity of the composition is on the order of about 300 000 cP
and in such manner that upon entry in the container, the viscosity is in the neighbourhood of that of water, and the rate at which the composition flows into the container is so adjusted that it is on the order of 2 cu.m/h and a pro-pelling fluid such as air is employed whose pressure is between 0.1 and 7 hPa.
The apparatus for filling, in particular according to the method just defined, comprises a longilinear hollow body for conducting the gelled composition in which is pro-vided a compartment onto which open an inlet orifice and an outlet orifice between which is provided an intermediate constriction in the region of a chamber having a conical wall, and a tapered nozzle for injecting a fluid which is disposed at least partly in the hollow body and 1 s provided with an axial duct at one of the ends of which is located a terminal connector outside the hollow body and at the other end of which is provided a jet opening out substantially in the region of the constriction and having conical sides in alignment with the chamber so as to define an annular passage between the chamber and the sides.
451~7 By IlleallS oE ttle inv~ntion, it is possible to efEect the filling of large or small accumulators the active material of the plates of which has been previously formed eitherin the final containers or in auxiliary containers. In par-ticular, owing to the invention, it can be arrangd that theactive materials of the plates are formed in the final containers by means of a forming electrolyte u~,-ch is re-moved by pouring before the containers are filled with the definitive gelled electrolyte composition based on sulphu-ric acid and silicic acid.
By means of the invention, it is also possible to employa final gelled electrolyte composition comprising phospho-ric acid so as to improve the aptitude for work in cycles.
Other features of the invention will be apparent from the following description and claims with reference to the accompanying drawing which is given solely by way of exam-ple and in which the single Figure is an axial sectional view of an embodiment of an apparatus according to the in-vention, in particular for carrying out the method defined hereinbefore.
Sealed accumulators, in particular those in which there is used for the electrolyte a composition based on sulphu-ric acid gelled by silicic acid, are well known in the art.
This is why only that which concerns the invention will be described. For the rest, the person skilled in the consi-dered art will draw from the current conventional solutions at his disposal to meet the particular problems with which he is confronted.
5~7 ~s is know, the physical properties and the surface cha-racterictics of the pyrogenation silica impart thereto the ap-titude to thicken the liquids to which it is added and to adjust the thyxotropy.
When the silicic acid is dispersed in a liquid composition, aggregates in the form of chains are united and give a network structure. The aptitude of the liquid composition to flow is in this way reduced, whence an increase in the viscosity or thicke-ning and even on at least artial solidification or setting into a maSs-Each of the particles of the chain has hydroxylated groupsfixed on the silica atoms on the surface, the hydrogen atom on a particle has an affinity for the oxygen atom of a neighbouring particle. When these particles approach each other, thev form a bond between tAese two atoms, which phenomenon is known under the name of hydrogen bond.
If the quantity of silicic acid dispersed in a liquid composition is very small, only a limited number of hydrogen bonds are formed, since the chains are generally too far away from each other to unite into a closely knit network ; the viscosity remains at a low value.
On the other hand, if a larger quantity of dispersed silicic acid is used, and if the acid concentration of the mixture is al~greater, a large number of hydrogen bonds are formed, whence a notable increase in the viscosity, or thickening, termed thy~otro~y.
It has been found that the factors acting on the -thyxo~ropy are principally the n~ture of the liquid, the con-centration of silicic acid, the value of the pH, the nature of the additives, the degree of dispersion, the type of sili-cic employed, bearing in mind the relative concentrations of silicic acid and sulphuric acid employed.
When lead accumulators are manufactured whose electro-lyte is a composition consisting of a mixture of sulphuric acid and silicic acid acting as a gel-forming agent, a compo-sition of high viscosity is obtained which renders the intro-duction of this composition almost impossible in the accumu-lator and above all when the accumulator is of large si~e.
One of the methods employed, as recalled hereinbefore, consists in arranging that the composition for filling the accumulator has a low th'~otropyl i.e. high fluidity, by nota-bly decreasing the acid concentration of the filling com-position by a prior discharge of the plates or by the addi-tion of additives acting asthyxotropy retarding means, i.e.
means for retarding the gelling.
That which characterizes the filling method accord-ing to the invent:ion is the fact that the filling electro-lyte composition contains the quantity of silicic acid re-quired for the forming of the gel and the concentration of sulphuric acid required for the discharge of the accumulator and which corresponds to the acid concentration of a fully charged accumulator. This gelled compositionhas for example an acid concentration which may vary from about 22 % to about 40 % with silicic acid put on the mar~et un~er the 5~7 reference "AEROSIL 20C" by the German Firm DEG~SSA AG in pro-portions on the order of 3 tolO~ by weight of the filling electrolyte. ~here may also be used that put on the market under the reference "CAB-O-SIL" by the French Firm CABOT
FRANCE. There is used a composition obtained in this way which has a high viscosity, on the order of about 300 000 cP.
In order to ensure that this composition is capable of fil-ling all the free interstices existing between the internal constituents, for example the plates and the spaces of the accumulator, its aptitude to flow, is physically increased, i.e. its apparent viscosity is momentarily reduced , only in the Eilling stage proper.
According to the method of the invention, the structure of the network of the electrolyte composition is temporarily modified by creating a turbulence by means of a propelling fluid injected under pressure within the electrolyte composi-tion having high viscosity, for example by means of an ejector whose conEiguration reminds one of a venturi.
As can be seen in the Figure of the drawing, shown substantially to scale, the apparatus in particular for carry-ing out the-method according to the invention comprises a relatively longilinear hollow body 10 for conducting the electrolyte composition which is supplied for example by means of a conventional metering pump (not shown) ~hereby itisFossible adjust the rate of flow and/or the supply pressure of the electrolyte composition.
This body 10 has a compartment 11 which communicates lZ~5~7 with the inlet oriEice 12 and the outlet orifice 13. As can be seen, an intermediate constriction or throttle is provided.
This constriction is preceded by a chamber 15 having a coni-cal wall and preferably of revolution.
Placed in this body 10 is a tapered nozzle 20 for in-jecting a propelling fluid. This propelling fluid is for example compressed air. For example,there is used compressed air distributed by the distribution network usually found in industrial premises. If need be, a pressure reducer is inter-posed between the compressor and the nozzle. Compressed air is preferably employed which has a pressure of between 0.1 and 7 hPa.
This nozzle 20 is disposed at least partly in the hollow body , as illustrated. This nozzle 20 is provided with a duct 21 which terminates at one of its ends in an exterior terminal connection 22 and at the other end in a jet 23 opening out substantially in alignment with the constric-tion 14. As can be seen, this nozzle has conical sides in the region o~ the chamber 15. The chamber and the nozzle which are approximately coaxial in this way deEine an annular passage 25.
The body is also provided with a tapped hole 26 in which may be engaged a screw (not shown) for adjusting the longitudinal postiion of the nozzle 20 in the chamber 14.
The exterior terminal connector 22 of the nozzle 20 and the orifices 12 and 13 of the hollow body 10 are prVided with appropriate connectors suitably adapted for connecting 3'7 them to the conduits, pipings and accumulator containers.
This is convelltional and this is why no more details will be given.
The materials of this apparatus are so chosen as to resist and be compatible with the electrolyte composition and the propelling fluid.
For the illustrated embodiment, the jet 23 extends beyond the constriction 14 by about 8 mm and has an inside diameter of about 4 mm. The annular passage 25 has an outside diameter of about 24 mm and an inside diameter of about 7 mm.
The angles of the cones of the chamber and nozzle are prefe-rably on the order of those of the drawing.
The apparatus according to the invention is used in such manner that its inlet orifice 12 receives the electrolyte composition which issues therefrom through its outlet orifice 13 connected to the sealed accumulator container. The pro-pelling fluid is ejected through the exterior terminal connec-tor 22 and is,sues through the jet23 within the electrolyte with which it becomes mixed for reducing the viscosity.
The propelli,ng fluid, here c o m p r e s s e d a i r , thereafter escapes from the sealed container through the other openings of the latter which are lert open.
By employing, if necessary, a plurality of apparatus-according to the invention, mounted in cascade, one behind the other, it is possible to start with an electrolyte compo-sition consisting of a mixture of sulphuric acid and silicic acid whcse concentration of sulphuric acid corresponds to the opera-tion of an accumulator whose plates are lnitially formed and charged. When it enters the apparatus,the elec-trolyte composition has a very high viscosity,on the order of about 300 000 cP,whereas when it arrives in the container the viscosity of the electrolyte is in the neighbourhood of that o f water. Thus, it will be understood that with such a viscosity which is in this way temporarily lowered, there is no longer any difficulty for filling thc container with the electrolyte including within the narrowest intersti-ces, of a few tenths of a millimetre, which exist betweenthe materials of the plates and the porous separator elements facing them. The composition of the electro:Lyte which has just been notably fluidified temporarily is again gelled so as to resume its initial viscosity which is practically un-modified.
The whole importance of the invention wlll therefore be realized, since it permits avoiding practically all the dif-ficulties inherent in the prior known methods some of which have been briefly recalled.
As can be observed, by means of the invention it is possible, on one hand~to manufacture lead accumulato~, in particular having tubular positive plates or planar positive plates, of small or large sizes, the active materials of which plates have been either previously formed electrochemi-cally in separate containers which are not the containers of utilization of the accumulator, or formed in the definitive containers of utilization of the accumulator, and, on the lZ~4~87 other hand, to fill containers containing in particular the plates thus completely charged with an electrolyte composi-tion containing sulphuric acid at a high concentration cor-responding to the concentration of the fully charged accumu-lator, and silicic acid with the concentration requiredfor the formation of a gel of very high viscosity permitting the immobilization of the sulphuric acid while ensuring that the properties of the gel thus obtained allow the transfer of the oxygen to the negative plate according to the requi-red prescriptionsfor gas recombination accumulators.
Claims (10)
1. A method for filling a sealed container, for exam-ple of an accumulator provided with at least one part of its internal constituents, in particular its plates, with a composition of a relatively high viscosity, said method comprising introducing in the container the composition by means of a propelling fluid injected within the composition and creating therein turbulence and regulating the flows and the pressures of the composition and propelling fluid in such manner that upon entry in the container the visco-sity of the composition is notably reduced.
2. A method according to claim 1, wherein the compo-sition has initially a viscosity on the order of 300 000 cp and a viscosity in the neighbourhood of that of water upon its introduction in the container.
3. A method according to claim 1, wherein the propel-ling fluid is a gas.
4. A method according to claim 3, wherein the propel-ling fluid is air.
5. A method according to claim 1, wherein the pressure of the propelling fluid is between about 0.1 and about 7 hPa.
6. An apparatus for filling a sealed container, for example an accumulator provided with at least a part of its internal constituents, in particular its plates prefera-bly preformed, with an electrolyte composition having an ini-tially relatively high viscosity, said apparatus comprising a hollow longilinear body for conducting the electrolyte composition, a compartment provided in the body onto which compartment open an inlet orifice and an outlet orifice between which there is provided an intermediate constriction in the region of a chamber having a conical wall, and a tapered fluid-injecting nozzle disposed at least partly in the hollow body and provided with an axial duct, there being provided at one of the ends of the duct a terminal connector outside the hollow body and at the other end of the duct a jet which opens out substantially in the region of the constriction and has conical sides in alignment with the chamber so as to define an annular passage between the chamber and the sides.
7. An apparatus according to claim 6, wherein the body is provided with a tapped hole for adjusting the posi-tion of the nozzle in the body.
8. An apparatus according to claim 6, wherein the body and the nozzle are provided with connectors.
9. A method for filling a container of a previously-charged lead accumulator with an electrolyte composition based on sulphuric acid and silicic acid, said method com-prising introducing in the container the composition by means of a propelling fluid injected within the composition and creating therein turbulence and regulating the flows and the pressures of the composition and propelling fluid in such manner that upon entry in the container the visco-sity of the composition is notably reduced.
10. A method for filling a container of a previously-charged lead accumulator with an electrolyte composition based on sulphuric acid and silicic acid, said method com-prising using an apparatus comprising a hollow longilinear body for conducting the electrolyte composition, a compart-ment provided in the body onto which compartment open an inlet orifice and an outlet orifice between which there is provided an intermediate constriction in the region of a chamber having a conical wall, and a tapered fluid-injecting nozzle disposed at least partly in the hollow body and provided with an axial duct, there being provided at one of the ends of the duct a terminal connector outside the hollow body and at the other end of the duct a jet which opens out substantially in the region of the constriction and has conical sides in alignment with the chamber so as to define an annular passage between the chamber and the sides.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8801528A FR2627014B1 (en) | 1988-02-09 | 1988-02-09 | PROCESS AND APPARATUS FOR FILLING CONTAINERS WITH A GEL COMPOSITION AND THEIR APPLICATION TO ELECTRIC ACCUMULATORS |
| FR8801528 | 1988-02-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1294587C true CA1294587C (en) | 1992-01-21 |
Family
ID=9363101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000589423A Expired - Lifetime CA1294587C (en) | 1988-02-09 | 1989-01-27 | Method and apparatus for filling containers with a gelled composition and applications thereof in electric accumulators |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0329506B1 (en) |
| KR (1) | KR950012944B1 (en) |
| CA (1) | CA1294587C (en) |
| DE (1) | DE68905634T2 (en) |
| ES (1) | ES2039884T3 (en) |
| FR (1) | FR2627014B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5829476A (en) * | 1997-07-21 | 1998-11-03 | Tetra Laval Holdings & Finance, Sa | Dual-stream filling valve |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE88241C (en) * | ||||
| US1640945A (en) * | 1926-04-28 | 1927-08-30 | Magnus Fruit Products Co | Dispensing faucet |
| BE432980A (en) * | 1939-03-07 | |||
| US2508492A (en) * | 1942-12-14 | 1950-05-23 | Dole Valve Co | Drink dispensing device |
| GB785848A (en) * | 1955-09-09 | 1957-11-06 | Pritchett & Gold & E P S Co | Improvements relating to lead-acid electric accumulators |
| US2920579A (en) * | 1957-02-01 | 1960-01-12 | Dole Valve Co | Variable concentrate proportioner |
| US3305396A (en) * | 1965-03-30 | 1967-02-21 | Marc Illinois Inc | Method of producing secondary dry cells with lead electrodes and sulfuric acid electrolyte |
| DE1904014C3 (en) * | 1969-01-28 | 1974-06-20 | Noll Maschinenfabrik Gmbh, 4950 Minden | Device for continuously combining beverage components in an adjustable proportion |
| GB1364438A (en) * | 1970-08-18 | 1974-08-21 | Electric Power Storage Ltd | Lead acid batteries |
| US3776779A (en) * | 1972-04-28 | 1973-12-04 | Elpower Corp | Gelled battery electrolyte containing a polyglycol polymer and a process for locating same within a lead-acid cell |
-
1988
- 1988-02-09 FR FR8801528A patent/FR2627014B1/en not_active Expired - Lifetime
-
1989
- 1989-01-27 CA CA000589423A patent/CA1294587C/en not_active Expired - Lifetime
- 1989-01-30 EP EP89400254A patent/EP0329506B1/en not_active Expired - Lifetime
- 1989-01-30 DE DE8989400254T patent/DE68905634T2/en not_active Expired - Lifetime
- 1989-01-30 ES ES198989400254T patent/ES2039884T3/en not_active Expired - Lifetime
- 1989-02-04 KR KR1019890001346A patent/KR950012944B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE68905634T2 (en) | 1993-09-09 |
| KR950012944B1 (en) | 1995-10-23 |
| EP0329506B1 (en) | 1993-03-31 |
| KR890013824A (en) | 1989-09-26 |
| FR2627014A1 (en) | 1989-08-11 |
| FR2627014B1 (en) | 1990-07-20 |
| EP0329506A1 (en) | 1989-08-23 |
| ES2039884T3 (en) | 1993-10-01 |
| DE68905634D1 (en) | 1993-05-06 |
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