US1402285A - Manufacture of primary cells - Google Patents

Description

"1;402,2 5, Patented Jan. 3, 192? 'H; 0E OLANETA. MANUFACTURE OF PRIMARY CELLS.

APPLICATION FILED NOV. 26. 1919.

V 4 21 (fl Norma Q tamed in a paste or.

i To all whom it may concern:

or contain among other pyrolusite,

' present application is a. division.

HAROLD DE OLANETA, onNEw REPEATINGARMS COMPANY,

CONNECTICUT.

Oi'iginaI application filed May 24',

Be it known that I, HARoLn DE O ANErA, a citizen of the United States, residlng 1 n New Haven, New Haven county, Connecticut, have inventedcertaiu new and useful- Improvements in'the Manufacture of Primary Cells, ofwhich the followin is a full, clear, and exact description v 1 This invention relates to the manufacture of primary cells. It pertains more especially to small dry cells such aS those used inconnection with pocket flash-lights, -where manganiferous material is used as a depolarizing agent, and 'where the exciting solution, e. g.,

a solution of ammonium chloridwith or without zinc chlorid, is carried by or congelatinous substance.

- The invention is not limited,.however, to this particular application.

My present invention has particular ref-J purification of the depolariz erence to the ing material prior to its incorporation in the cell.

ganese generically designated as manganese dioxid. The manganese material may be things comminuted or manganese ore, an artificial or recovered manganese dioxid produced by hydration, or a precipitate of manganese, as described in my application Serial No. 299,522, filed May 24,-191'9, of whiph tge n t e following description Ishall assume, for

purposes of explanation only, ization is to be effected by or with a suitable manganlferous that depolarmaterial havmg or susceptible of taking up a'high content of .oxvgen for combination or'other coaction with the hydrogen which is liberated 'in the cell.

The manganese dioxid commonly used in dry cellsc'ontains in many cases a number of impurities which have a on thecell and shortens its life. I ascribe this toijthe fact that the impurities are acted upon by or soluble in the electrolyte, e. g.,sal ammoniac solution, with the result that as 'soon as. the ordinary cell is made, a local Specification of Letters Patent. 7

quantity, the cell .way to the zinc,

The depolarizer may consist of depending on the or comprise one or more compounds of manin connection.

invention deleterious action HAVEN, CONNECTICUT, ASSIGNOR ITO WINCH STER on NEW HAVEN, CONNECTICUT, A CORPORATION or MANUFACTURE OF IjRIMARY CELLS.

, action is set up which short-circuits the cell PatentedJan. 3,1922. 1 19, Serial No. 299,522: Divided and this application filed Noveni- 'bel 2c, 1919. Serial No. 340,752. I v

for example, iron is present in a substantial I will be drained in a very short time, because the iron is converted into an oxid of iron, which eventually finds its and once in contact with the zinc a. local action is setup. If, for further example, potash of any description, either free or neutralized, is present in .the manganese dioxid, the sa l ammoniac will dissolve the same and form a" salt with the zinc or with any zinc salt present, setting up a deleterious local action. These deleterious substances in the manganese often include iron, copper and phosphorus, when manganese ore or pyrolusite is used. WVhen artificial or hydrated manganese dioxid is employed, sulphur, oxids, nitrates, or chlorids will often be found,

process of hydration;

potash or the like will be impurities, and

others, when chemically combined with the manganese, are insoluble in water, and when it is attempted to separate them out by the use of acids, for example, the result will either be .that the manganese is dissolved, on the one hand, or, on the. other insoluble compounds are created.

'One of the primary objects of the present is to furnish an improved process for the manufacture of a relatively cheap but extremely eflicient and satisfactory depolarizing material for primary cells, and more particularly small dry cells.

Another objectv of my in thoseimpurities or substances 'in thefde polarizer which set up local action Ord a te other deleterious effects as a result of dissolutionin or action on the electrolyte while the cell is not in use are eliminated priorto the assembly of the cell parts.

hand, that 9b invention is to provide aamethod of manufacturing cells where of the cell, with a solution containing one or more of the salts used in" the excitin solution or paste of the battery (and pre erably .of approximately the same concentration),

whereby all deleterious impurities s'olublein the exciter are removedgprior to the-assembl of the cell.

' ore specifically, in the improvement in the manufacture of drylcells having a. manganiferous depolarizer, which resides certain procedure prek liminary "to the assembly ofthe cell, that is calculated to prevent action of the sal ammoniac on the manganiferous materialwhile the cell is on the shelf.

B my invention I also make itpossible commercially to utilize for battery manuj,facture, and more' especially for use as a 'fdep'olarizer, certain manganiferousmaterials which have hitherto not 'fully in this art.

been used success The invention also consists in other novel "features hereinafter described and claimed.

The accompanying drawing shows a dia grammatic sectional view of a dry cell of one typein connection with'which my 1nvention maybe carried into eflect.

In carrying out eating themannerin which the invention my process, I prefer to make 'use of a suitable tank of any appro riatesize, shape and material, provided wit 2a perforated or screenlike bottom. On

. the bottom of the tank is placed a suitable piece of filtering material, such as cloth. The manganese compound which is to be mployed, after having been ground' or comminuted, and sifted, is charged into the tank, leavin a certain amount of space at the top. solution of a neutral salt usually an ammonium salt, for. e ample, a

- is then poured into the top of t so1ution.of -ammoni'um chlorid, 0 any appropriate density, say, one degree Baum,

e tank onto the material andpermitted "to fpercolate through it; If itbe assumed that the manganese material takes up, say, two-thirds of the tank capacity,'the remaining on third of the tank will be filled with thesaline'solution, which 'will'pas s completely into the material under treatment. in, say, twentyfour hours. Another-similar quantity of'the quantity of solution will be poured into' solution will then be poured into the tank and allowed to pass downinto the material in; the same manner. vAfter the lapse of forty-eight hours, for example, a third the tank, and similar quantities of solution will be poured in at a proximately equal" hen the solution,

intervals, as needed.

my invention consiststom of the tank correspon .in at the top.

commences to. out of the tank at the bottom, the same is tested in any suitable manner which permits comparison with the solution being poured in at the top; I test and a decrease of density isnoted, until the solution coming out of the bottom of ethe tank has the 'samedensity as that pouredin at the top.- .No furtherlte'sts are then needed; When the material-being treated ispyrolusite, or natural manganese dioxid,

for exam 'Ie, the solution passin'goutat the b0tt0m,i its shows no difierence in Baum;

is. tested chemically, which will indicate. the

character and amount of impurities, such as metallic oxids, which are being leached out. In any case, if the best results are to be obtained, the solution is passed through the material until that flowin out at the botto that poured In" this process; which will consume a variable length of time, depending on the. kind of material treated, and the facilities available, the impurities in the material I shall now describe; one example indiwhich are soluble in the solution to be used in the assembled battery has an exciting he material remaining in the tank,

which is practically pure manganese oxids, 1s then taken out and dried and, if intended for use as a'dep'olarizing material, is permitted to take up oxygen from the air. 'The amount of oxygen absorbed will, of course,

depend to a certain extent on the amount of the lower oxids of manganese contained in the. initial material. When the impuris ties have been removed, the material will tendto absorb oxygen up to its full oxygenabsorbing. capacity. It is preferable to expose the pu'rified material to the air forse'veral: days at least, so that a maximum amount of oxygen will be taken up thereby before it is used'in the battery 'as' adepolarizer. w a

In .carrying'outv my vp ro cess,.I prefer to agent, and especially those which render use a manganese precipitate as a starting material, or any cheap waste material con- I taining manganese,'but it will be understood from what, has'been said above that the process can be carried out successfully with more expensive grades of manganese;

One of the particular advantages of my process, however, consists in the fact that i very cheap manganese containing materials,

heretofore considered waste products, may be treated successfully and economically,

feriordepolar-izers now used.-

y my invention, very low grade material can beeasily and economically converted into a high grade material which gives the very best results in the cell, increasing the E. M.

. F., and at the same time lengthening the life very considerably. The purified manganese material absorbs oxygen by a natural process, which is not only very inexpensive as compared to hydration and similar processes, but the product, containing substantially nothing but manganese and oxygen, and being in fact a very pure manganese dioxid, has much' greater depolarizing efiiciency than the substances commonly employed. The fact thatthe tests during the process of purification indicate that the ammonium chlorid' used in the cell as an exciting agent will have no chemical eflect upon the depolarizer, is also an important feature of advantage, as in this manner the possibility, of any local-action being set up from thissource, is eliminated.

Obviously, the lowering of the cost of dry cells, by the use of low grade manganesecontainlng material, is a factor of no small importance. For example, I am able to use with entire success manganese compounds comm'only occurring as waste products in the manufacture of permanganates, such as sodium permanganate, potassium permanganate and barium permanganate. In the oxidizing of manganates to produce such permanganates, there are precipitations of manganese compounds which can be purified to advantage by the above mentioned, process for the production of a very satisfactory depolarizer. Other products which can be used" are precipitations formed by agents used to remove the oxygen from permanganates.

\Vhen oxygen is eliminated from a permanganate, for the purpose, say, of oxidizing, a precipitate is thrown down which has heretofore been considered practically worthless. If, however, the method previously described is used for the purification of a precipitate of this kind, it is a simple matter to recover all of the manganese. The impurities will be largely dissolved. and removed by the ammonium salt in the manner previously described, and the resulting pure manganese material will take up oxygen, as above set forth, creating a manganese dioxid, which is very desirable for battery use. Cells made up with this material,showed on. current tests, approximatel 100% more lifethan standard cells of similar'weight found on the market. 1

An example of a precipitate such as'that above indicated would be a residue of potassome industrial floxidizing process, which residue 1s thrown down as abasis manganese nitrate or sulphate, for example. This ma-' terial is so finely divided as'to be impalpable and usually has a darkblue color.

It is not necessary in all cases to expose such material to the air subsequent toits treatment by my purification process (with a neutral saline solution), for oxidation purposes, inasmuch as, with the impurities such as potash eliminated, it --is exceptionally greedy in taking up oxygen from any available source, and the. necessary oxygen for high oxidation is furnished it either from the substances used inmixing up the' depolarizer cartridge or is material is brought into contact with the electrolyte, .on putting together the parts of the cell. H

In my process above described, the densit of the solution poured into the tank at various times should always be the same. That is, if I start out with a solution of one degree Baum, subsequent quantities of the solution used are likewise not necessary to remove all of the sal ammoniac from the material before drying and oxidizing, if the material is. to be used as a depolarizer. While it' is possible to remove the sal ammoniac by washing with water, the material, as I employ it for battery purposes, carries a trace of sal ammoniac whenplaced in the cell. a r

In the drawing I have-showna sectional enlargement of a pocket dry cell in connection with the manufactureof which my in.- vention has been practised with very good results. In this drawing, 1 denotes a zinc cup which serves one electrode, and 2, a carbon rod serving as the other electrode. The depolarizing material, which may contain other ingredients in addition to the manganiferous material hereinbefore mentioned,'is packed or rammed about the car bonelectrode in such a manner as to form a.

however, from what has been said above, that it is not essential in all cases to have the same kind of solution with which the depolarizing material is treated for the removal of impurities, present later on in a paste within the cell, for while the invention has resulted I in a marked increase in the efficiency of cells of this type, other types may be used.

taken up when the cartridge 3 covered with cheese-cloth or like i Various changes and modifications may "be made in the detailed procedure, and in other matters, without departing from the rial which comprises treatment of the .mate

rial. with a solution of a neutral salt, as claimed in my prior application hereinbefore identified, Neither do I claim herein. thenew depolarizer for electric dry cells or the method of making the same, or of making a cell containing a depolarizer around the carbon electrode, eomprising recovered manganese or, more part cularly, a mangar'i ate derivative, as claimed in'myapplicar.

tion Serial No. 360,353; nor do I claim the dry cell per se as claimed in my application Serial No. 378,456. -What I claimis: v 1. The method of making a primary cell, having a depolarizer, which comprises'treate ing the depolarizer material, prior to;the assembly ofthe cell,with. a solution containingone or more of the salts used in the elec-- trolyt'e, wherebydeleterious substances soluble in the electrolyte are removed before the cell is assembled;

2. The method (if-"making a primarycell having a depola'rizer' andg anlelectrolyte, which COIDPIISGSI treatment "of 'the 'depolarizer with electrolyte material prior to the assembly of the cell for removing impurities that are soluble in'the electrolyte.

- 3. The method of makinga primary cell having a depolarizeianjd an electrolyte,

which comprises as a p'relimin'ary step the leaching of the depolarizer. with; a solution containing electrolyte material prior to the assembly'of the cell.

' 4 The method of making a primary cell having a depolarizer and an electrolyte, such electrolyte consistingof or containing a -ne'u-. tral salt, which comprises; the treatment of the depolarizer' material riort the incorporation of, the depolarizer in-thej cell, with a solution'containing such neutral salt.

5. The method ofsmaki'ng a primary cell having a depolarizepandan electr0lyte,"sucl1.

electrolyteeonsisting of or containing a neutraltsalt,whiclrcomppises the treatment of the "dep olarizer 'mater a1 prior to the incorporation of the'dep'olarizer in the cell, with a solution containing such neutral salt, such broadly herein a process consists inleaching treatment being in the nature of lixiviation and being continued until substantially all substances in the depolarizer soluble in the electrolyte are eliminated. a i

6. The method of making a primary cell having a depolarizer and an electrolyte, which comprises leaching the de olarizing material with a solution of electro yte material prior to the assembly of the cell, such solution of electrolyte material being of approximately the same concentration as the electrolyte.

7. In the'manufacture of primary cells, having a manganiferous depolarizer, the treatment of the manganiferous material preliminary to its incorporation in the cell with a solution containing one or'more of the ingredients of the electrolyte to be used in the cell, whereby the soluble impurities whose presence in the cell is deleterious to the life and strength thereof are removed before the cell is put together.

8. The method of making a primary cell:

having a manganiferous depolarizer, which 3 I with a neutral solvent."

9."The method'of manufacturing 'a-primary cell having a manganiferous depolarizer and anelectrolyte consisting of or containing aneutral salt, which consists. in

leaching the manganiferous material prior the manganiferousma-J I vterial prior to its incorporation in the'cell to its incorporation in the cell with "asolu? I I tion' of such neutral salt. v

makinga primary cell having a mangamferous depolarizer and an 10. The method of electrolyte consistingof or contain ng a hentral ammonium salt, which consists in so;

treating the mangani ferous; 1 material, prior to the assembly of the cell, with such neutral. I

salt that impurities in' the depolarizeron which such salt would :act while the-cell is onthe shelf are eliminated before the parts of the cell are assembled.

11. The method of making a dry cell hav- I ing a imanganiferous depolarizer, a pastein proximity thereto, and a saline exciting sci lution in the paste, which comprises the leaching of the manganiferous material with a quantity of such saline solution prior to the1 j incorporation. of such material in the The method'of making a dry cell hav- .iiiga depolarizer of manganiferous' mate rial, a paste in proximity thereto, anda solution of ammoniun'rchlorid in, the paste-,; which comprises the leachin ""ganiferous material with a so ution contain ing ammonium chlorid but devoid of acid for-the removal of impurities soluble-in an ammonium chlorid solution.

13. The method of making a dry cell having adepolarizer, a paste and a'saline exciting. agent in the paste, which comprises the of. the man-r i treatment of the depolarizing material with a neutral saline substance, in the absence of acid, for the purpose ofremoving' deleteri-- ous substances.

14; In the manufacture of primary cells b wherein ammonium chlorid is used as an exc ting agent and a manganese 031d 1s employed as a depolarizer, leachlng the manganiferous material with asolution for the removal of impurities, and exposing the re- 10 suiting depolarizing material to the air for oxidation prior tothe assembly of the cell.

In witness whereof, I have hereunto set myhand on theQAth day of November, 1919.

- HAROLD 1m OLANE'IA.

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