CA1090878A - Lead crystal storage cells and storage devices made therefrom - Google Patents
Lead crystal storage cells and storage devices made therefromInfo
- Publication number
- CA1090878A CA1090878A CA291,524A CA291524A CA1090878A CA 1090878 A CA1090878 A CA 1090878A CA 291524 A CA291524 A CA 291524A CA 1090878 A CA1090878 A CA 1090878A
- Authority
- CA
- Canada
- Prior art keywords
- lead
- cadmium
- cells
- layer
- storage
- 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
Links
- 210000000352 storage cell Anatomy 0.000 title claims abstract description 35
- 238000003860 storage Methods 0.000 title claims abstract description 22
- 239000005355 lead glass Substances 0.000 title abstract description 25
- 210000004027 cell Anatomy 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 25
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 claims description 56
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 27
- 229910052787 antimony Inorganic materials 0.000 claims description 22
- 239000004020 conductor Substances 0.000 claims description 18
- 230000001464 adherent effect Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- -1 cadmium fluoroborate Chemical compound 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012943 hotmelt Substances 0.000 claims description 7
- 239000012811 non-conductive material Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910000925 Cd alloy Inorganic materials 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940075103 antimony Drugs 0.000 claims 11
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 3
- 239000002253 acid Substances 0.000 abstract description 32
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910020159 Pb—Cd Inorganic materials 0.000 description 17
- 229940032330 sulfuric acid Drugs 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 12
- 238000010276 construction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910000464 lead oxide Inorganic materials 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IJJWOSAXNHWBPR-HUBLWGQQSA-N 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]-n-(6-hydrazinyl-6-oxohexyl)pentanamide Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)NCCCCCC(=O)NN)SC[C@@H]21 IJJWOSAXNHWBPR-HUBLWGQQSA-N 0.000 description 1
- 102100035683 Axin-2 Human genes 0.000 description 1
- 101700047552 Axin-2 Proteins 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- 244000025221 Humulus lupulus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940075911 depen Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 108010052322 limitin Proteins 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
LEAD CRYSTAL STORAGE CELLS AND
STORAGE DEVICES MADE THEREFROM
ABSTRACT OF THE DISCLOSURE
A unique storage cell is provided in which the active mass on the positive electrode is a mixture of crystalline and polycrystalline lead superoxide (PbO2). These cells are characterized, inter alia, by their remarkably lower internal resistance, higher activity, better charging and discharging characteristics, lower sulphatization, higher storage capacity and greater ability to draw larger amounts of electric current in a considerably shorter period of time as compared with conventional lead-acid storage cells. Storage devices (e.g., a battery) made from such cells also exhibit superior performance characteristics as compared with storage devices made from the conventional lead-acid cells. Batteries made from such cells will be referred to as "lead-crystal" batteries.
Also, several methods are described for making the polycrystalline and crystalline lead superoxide (active Mass).
STORAGE DEVICES MADE THEREFROM
ABSTRACT OF THE DISCLOSURE
A unique storage cell is provided in which the active mass on the positive electrode is a mixture of crystalline and polycrystalline lead superoxide (PbO2). These cells are characterized, inter alia, by their remarkably lower internal resistance, higher activity, better charging and discharging characteristics, lower sulphatization, higher storage capacity and greater ability to draw larger amounts of electric current in a considerably shorter period of time as compared with conventional lead-acid storage cells. Storage devices (e.g., a battery) made from such cells also exhibit superior performance characteristics as compared with storage devices made from the conventional lead-acid cells. Batteries made from such cells will be referred to as "lead-crystal" batteries.
Also, several methods are described for making the polycrystalline and crystalline lead superoxide (active Mass).
Description
87~1 Field of Invention:
This invention relates yenerally to improved storage cells and to devices, including storage batteries, which incorpor-ate such cells in their construction. More specifically, the pre-sent invention is concerned with the active mass used in making the electrodes of such cells, wherein said active mass is a mix-ture of crystalline and polycrystalline lead superoxide, and to themethods of making the active mass.
The Prior Art:
. The construction and operation of a cell is generally well known. A cell, whether primary or secondary, is an electro-chemical device which consists of two plates of conducting material immersed in an electrolyte. A primary cell is designed to develop an electric potential and to convert chemical energy into electri-cal energy irreversibly. A secondary cell, however, is reversible in its function and can transform chemical energy into electrical energy, or vice versa. Secondary cells are more commonly called "storage cells".
When a storage cell is supplying electric energy, the cell is said to be "discharging" and chemical energy is being con-verted to electrical energy~ and when the storage cell is supplied with electrical energy, the process is reversed and the cell is said to be "charging".
This invention relates yenerally to improved storage cells and to devices, including storage batteries, which incorpor-ate such cells in their construction. More specifically, the pre-sent invention is concerned with the active mass used in making the electrodes of such cells, wherein said active mass is a mix-ture of crystalline and polycrystalline lead superoxide, and to themethods of making the active mass.
The Prior Art:
. The construction and operation of a cell is generally well known. A cell, whether primary or secondary, is an electro-chemical device which consists of two plates of conducting material immersed in an electrolyte. A primary cell is designed to develop an electric potential and to convert chemical energy into electri-cal energy irreversibly. A secondary cell, however, is reversible in its function and can transform chemical energy into electrical energy, or vice versa. Secondary cells are more commonly called "storage cells".
When a storage cell is supplying electric energy, the cell is said to be "discharging" and chemical energy is being con-verted to electrical energy~ and when the storage cell is supplied with electrical energy, the process is reversed and the cell is said to be "charging".
- 2 -B ~
7~
, I
,1 .
1 I ~o or more cells connected together, in series or in ¦
parallel, constitute a battery and a battery made from connectirg I
several storage cells is known as a storage battery. There are . Itwo common types of storage bat-teries; the lead-acid type battery,¦
¦or as it is simply called, the lead battery, and the nickel- ¦
alkaline or Edison type battery, popularly called the alkaline ¦battery. It is with the former type battery that the present in-¦vention is concerned.
¦ The cells in the lead-acid battery consist of a posi-¦tive plate of lead oxide and a negative plate of spongy lead whlch i are immersed in a diluted solution of sulfuric acid (electrolyte).
~The active mass or material of bach plate is that part which un-- ¦
¦dergoes a chemical change when electricity flows through the ba}-¦tery. This active mass is supported by a frame or grid of pure ¦lead or lead alloy, e.g., an alloy of lead and antimony, which serves the dual function of carrying the active mass and conductin~
the electric current. It is with a novel, unique and improved ac-¦
tive mass that the present invention is more specifically con- ¦
¦cerned.
¦ The charging and discharging cycles of a typical l~ad-i ¦acid type battery may be represented by the following reversible Ireaction:
¦ Charge Discharge PbO2+2H2s04~pb c ---- ~ 2PbS04+2H20 + plate - plate i Tne active material of the positive plate is brown, !Porous lead oxide, while the active mass on the neyative plate 1s yray r spongy and porous lead, in pure form.
_3_ 30~7~
1 I The lead-acid batteries which are currently available on the mar~etplace exhibit limited performance capabilities, and numerous attempts and suggestions have here-tofore been made to ~improve them. Thus, improvemen~s in charging and discharying Icharacteristics of these batteries, increasing their current dis-Icharye rate and reduction in the in-ternal resistance of the bat-Itery cells are but few of the numerous properties which have re-¦ceived considerable attention of the prior art workers in this ¦field. Some have focused their attention on the electrodes while ¦others have suggested a variety of electrolytes in order to im-Iprove the overall performance of the cells, and the devices which ¦incorporate such cells.
Thus, U.S. 2,933,547 describes a battery made fro~. ~
plurallty of solid state electric cells consisting of silver and ~inc electrodes and a solid, so~vated cation-exchange resin meM-brane which is sandwiched between the electrodes.
U.S. 3,468,719 discloses a solid state ionic conductor made of a polycrystalline material in which the structural lat~ce¦
is composed of ions of aluminum and oxygen in combination, and : sodium ions whiah migrate in relation to the crystal lattice under the influence of an electric field. This material is employed 39 a half-cell separator in the construction of batteries as more fully described in example 3 of said patent.
I U.S. 3j499,796 discloses a ceramic sandwich between a ¦pair of elec-trochemically and cationically-conductive crystalline objects which are in cation exchanye relationship and separated by a cationicelly-conductive, electrcnically nnn-conductive cryLtdl- ¦
I
l I
7~
, I
,1 .
1 I ~o or more cells connected together, in series or in ¦
parallel, constitute a battery and a battery made from connectirg I
several storage cells is known as a storage battery. There are . Itwo common types of storage bat-teries; the lead-acid type battery,¦
¦or as it is simply called, the lead battery, and the nickel- ¦
alkaline or Edison type battery, popularly called the alkaline ¦battery. It is with the former type battery that the present in-¦vention is concerned.
¦ The cells in the lead-acid battery consist of a posi-¦tive plate of lead oxide and a negative plate of spongy lead whlch i are immersed in a diluted solution of sulfuric acid (electrolyte).
~The active mass or material of bach plate is that part which un-- ¦
¦dergoes a chemical change when electricity flows through the ba}-¦tery. This active mass is supported by a frame or grid of pure ¦lead or lead alloy, e.g., an alloy of lead and antimony, which serves the dual function of carrying the active mass and conductin~
the electric current. It is with a novel, unique and improved ac-¦
tive mass that the present invention is more specifically con- ¦
¦cerned.
¦ The charging and discharging cycles of a typical l~ad-i ¦acid type battery may be represented by the following reversible Ireaction:
¦ Charge Discharge PbO2+2H2s04~pb c ---- ~ 2PbS04+2H20 + plate - plate i Tne active material of the positive plate is brown, !Porous lead oxide, while the active mass on the neyative plate 1s yray r spongy and porous lead, in pure form.
_3_ 30~7~
1 I The lead-acid batteries which are currently available on the mar~etplace exhibit limited performance capabilities, and numerous attempts and suggestions have here-tofore been made to ~improve them. Thus, improvemen~s in charging and discharying Icharacteristics of these batteries, increasing their current dis-Icharye rate and reduction in the in-ternal resistance of the bat-Itery cells are but few of the numerous properties which have re-¦ceived considerable attention of the prior art workers in this ¦field. Some have focused their attention on the electrodes while ¦others have suggested a variety of electrolytes in order to im-Iprove the overall performance of the cells, and the devices which ¦incorporate such cells.
Thus, U.S. 2,933,547 describes a battery made fro~. ~
plurallty of solid state electric cells consisting of silver and ~inc electrodes and a solid, so~vated cation-exchange resin meM-brane which is sandwiched between the electrodes.
U.S. 3,468,719 discloses a solid state ionic conductor made of a polycrystalline material in which the structural lat~ce¦
is composed of ions of aluminum and oxygen in combination, and : sodium ions whiah migrate in relation to the crystal lattice under the influence of an electric field. This material is employed 39 a half-cell separator in the construction of batteries as more fully described in example 3 of said patent.
I U.S. 3j499,796 discloses a ceramic sandwich between a ¦pair of elec-trochemically and cationically-conductive crystalline objects which are in cation exchanye relationship and separated by a cationicelly-conductive, electrcnically nnn-conductive cryLtdl- ¦
I
l I
3~ 7~3 ~
I
1 , line object, and to storage devices comprising the same.
¦~ U.S. 3,709,820 discloses an organic solid electrolyte , which is a crystalline electron donor-acceptor complex comprising ¦ ionic crystals of 7,7,8,8-tetracyanoquinodimethane, an aromatic lamine, and a liquid impregnated in the ionic crystal lattice. The¦
electrolyte described in this patent is employed in eapacitors to ¦
¦lower their resistivity.
U S 3,765,915 describes the uses of Beta-alu~ina Ipolycrystalline ceramics for use as electrolyte in the construction of cells or batteries of the sodium~sulfur type.
The foregoing patents are but a few of the plethora f¦
Ipatents which represent the research and activities which have ¦been expended in this art. Nevertheless, however, the basic con- ¦
struction of the lead-acid battery and its constituent cells re-main essentially unchanged. Today, as it was made several decades ago, lead-acid batteries are made by serial connection of a plu-rality of cells (usually 3 or 6) wherein porous lead o~ide is the lactive mass on the positive plate and spongy, porous lead is the Inegative plate, and dilute sulfuric acid is the electrolyte oF
Ichoice.
¦ Accordingly, it is an object of the present invention !
to provide improved storage cells and devices which are made from ¦
Isuch cells.
I It is a further object of this invention to provide a I
storage battery in which the active mass on the positive electrode !
is a unique material made from crystalline and polycrystalline 37~3 1 llead oxide. Such batteries will hereinafter be referred ~o as "lead-crystal" batteries to distinguish them from the conventional lead-acid batteries.
' It is another object of this invention to provide novel and unique lead-crystal batteries which have superior per-formance characteristics as compared with the conventional lead I batteries .
It is also an object of this invention to provide such llead-crystal batteries which exhibit lower internal resistance and ¦higher potential difference (electromotive force) than the con-ventional lead batteries.
It is still another object of this invention to pro-vide lead-crystal batteries which exhibit higher current charge land discharge capacity and which can be charged at a considerah'y ¦
Ifaster rate than the conventional lead battery.
It is a further object of this invention to provide ~lead-crystal batte~ies which exhibit considerably lower:sulphati-zation as compared with the lead-acid battery.
¦ It is also an object of this invention to provide a ¦method of making crystalline and polycrystalline lead oxide as the active mass.
It is yet another object of this invention to provlde ¦
~a unique positive plate for the construction of storage cells and ¦
batteries made from such cells.
¦ I~ is also an ob~ect of this invention to provide such I
~positive plates which comprise a carrier plate such as lead, an alloy of lead with antimony, or a non-conductive carrier material with a conductive coating, and lead oxide in crystalline and I
I
polycrystalline form applied to the surface of the carrier plate.
The foregoing and other objects of this invention will be more readily comprehended from the following detailed description of the invention taken in conjunction with the accompanying drawings which form a part of this application.
SUMMARY OF THE INVENTION
Thus the present invention provides a solid state conductor for use in storage cells comprised of a carrier plate made from a material selected from the group consisting of lead, an alloy of lead with antimony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and a uniform, adherent and durable layer of an active mass on said carrier plate, said active mass consisting essentially of crystalline and polycrystalline lead superoxide in which lead is at its maximum valence of four.
In another embodiment the present invention provides a storage cell comprised of a dilute solution of sulfuric acid, at least one negative electrode and at least one positive electrode, each made from a material selected from the group consisting of lead, an alloy of lead with antimony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and wherein said positive electrode is coated with a uniform, adherent and durable layer of polycrystalline and crystalline lead superoxide in which lead is at its maximum valence of four. A preferred embodiment of such a storage cell is provided wherein said electrodes are an inert, non-conductive material coated with lead, or an alloy of lead with antimony.
In another embodiment the present invention provides a method of making a solid state conductor for use in storage cells which comprises: (a) forming a uniform and adherent layer 7~3 of lead and cadmium on a carrier plate made from lead, an alloy of lead with antimony or an inert, non-conductive material coated with lead or an alloy of lead with antimonyi (b) immersing the resulting carrier plate in a container containing a dilute solution of sulfuric acid and a lead plate;
(c) connecting said carrier plate to the positive terminal of an emf source and connecting lead plate to the negative terminal of said emf source, thereby causing electric current to flow through said plates; and (d) causing said cadmium in said lead~cadmium layer to react with sulfuric acid to form cadmium sulfate which is deposited on said lead plate, and simultaneously oxidizing said lead in said lead-cadmium layer thereby forming a mixture of crystalline and polycrystalline lead superoxide, in which lead is at its maximum valence of four. In one embodiment there is disclosed a method of making such a solid state conductor wherein, in step (a) said uniform and adherent layer of lead and cadmium is formed by making a relatively thin paste of lead and cadmium mixture in a reducing organic liquid, depositing said paste on said carrier plate and evaporating said solvent from the paste.
In a further embodiment the present invention provides a method of making a solid state conductor wherein, in step (a), said uniform and adherent layer of lead and cadmium is formed on the surface of said carrier plate by an electroplating process which comprises immersing, in an electrolytic bath, two conductors, a cathode made from an alloy of lead and antimony and an anode made from lead and cadmium, wherein said electrolytic bath comprises lead fluoroborate, metallic lead, fluoroboric acid, boric acid, cadmium fluoroborate, metallic cadmium, ammonium fluoroborate and water, connecting said cathode and said anode, respectively, - 7(a) -.~
7i~3 to the negative and positive terminals of an emf source, andcausing an electric current to flow through said electrodes.
In accordance with this invention, a storage cell i5 provided in which the active mass OII the positive electrode of the cell is a mixture of crystal:Line and polycrystalline lead superoxide (PbO2). Thus, a mixture of lead and cadmium is first deposited, or otherwise conveniently applied, as a uniform, adherent layer, on a carrier plate made of lead, an alloy of lead with antimony, or a suitable inert and non-conductive material which is coated with lead or an alloy oflead with antimony. The lead-cadmium mixture may be deposited on the carrier plate by hot-spraying, so-called "powdered metallurgy" technique or by electroplating, all as hereinafter described in the ensuing detailed description of the invention.
The carrier plate which has been coated with lead and cadmium as aforesaid is then immersed in a container containing a dilute solution of sulfuric acid (electrolyte) and a lead plate or sheet which serves as the cathode. The carrier plate is then connected to the positive terminal of an emf source and the lead sheet is connected to the negative terminal of said source. The passage of electric current through the plates causes the oxidation - 7(b) -j, 1 I,of lead (in the lead-cadmium layer) to lead superoxide, in the Eorm of crystalline and polycrystalline mass, while the cadmium reacts with sulfuric acid to form cadmium sulfate which is de-Iposited on the lead sheet as a spongy material. The carrier plate lis then removed from the solution, rin.sed clean with water and dried.
Three carrier plates made as aforesaid are thereafter immersed in a second container containing a dilute solution of Isulfuric acid. The middle carrier plate is connected to the posi-Itive terminal of an emf source while the other two carrier plates lare jointly connected to the negative terminal of said emf source.
¦Upon the passage of electric current, the middle carrier plate ¦will be positively charged and the lead superoxide will remain lunchanged while the lead oxide on the other two carrier plates is ¦reduc~d to lead and becomes negatively charged.
After a few minutes the emf source is removed and the emf within the cell drops from 2.9 volts to approximately 2.4 !
¦volts and remains essentially constant at this level. The cell is Inow charged and is storing energy for subsequent release.
¦ Three or more such cells may be connected in series to ¦form the lead-crystal battery of this invention.
! ~RIEF DESCRIPTION OF THE DRAWINGS
i Figure 1 is a schematic representation illustrating the method of formation oE the active mass, i~e., the crystalline and polycrystalline lead oxide, in accordance with this invention;l , . I
I
I -8~
~I.vsslt37a 1 ~I E'igure 2 is anot~ier schematic diagram illustrating the formation of the positive and negative plates and the cell ¦icomprising such plates; and ¦I Figure 3 shows two curves which compare the discharge ¦Icharacteristics of a lead-crystal cell made in accordance with ¦Ithis invention with a conventional lead-acid type cell.
DETAILED DESCRIPTION OF THE INVENTION
1 It has now been unexpectedly discovered that the per-Iformance of storage cells can be xemarkably improved by providing ¦the cells with a unique positive plate comprising crystalline and polycrystalline lead oxide in the form of Pb02 as the active mass.
Conse~uently, lead-cr~stal batteries made from such cells exhibit superior performance characteristics as compared with the con-¦ventibnal lead-acid batteries.
In the ensuing description, the present invention will ~be described in detail with particular reference to the construc~
tion of a storage cell, and a battery made from such cells. Such description, however, is not to be taken as limitin~ the scope of this invention as there are other storage devices which can be constructed on the basis of the principles set forth herein and which are, therefore, comprehended, contemplated and included Iwithin this disclosuxe.
~ It has been discovered that a storage cell constructed lin accordance ~ith this invention exhibits properties which have . Iheretofore been unattainable in the prior art type storage cells, and conse~uently, devlces, e.g , storaqe batteries, made by the 7~
.
1 ' serial connection of such cells, also exhibit superior perform~
i ance characteristics as compared with the conventional lead bat-teries. Such improved properties include, althoughthey are not I limited to, lower internal resistance, higher activity, lower sul-I phatization, better char~ing and discharging characteristics, greater storage capacity, faster charging rates and higher em~
per cell.
The unique active mass which is formed in accordance I with the method of this invention is composed essentially of ¦ crystalline and polycrystalline lead oxide (PbO2) in which lead has its maximum electron valence of four, and which is sometimes ¦ referred to as lead superoxide to distinguish it from PbO in ¦ which lead has its lower electron valence of two.
The term "polycrystalline" as used herein denotes an aggregation of single crystalline masses of lead superoxide, wherein such crystals are at varying stages of growth and develop-ment. Thus, the active mass of this invention is a mixture of ¦ single crystalline masses of PbO2 together with such polycrystal-¦ line aggregates.
¦ In accordance with one embodiment of this invention, and with particular reference first to Fig. 1, a carrier plate 1 ¦ which is typically made of pure lead (Pb) or an alloy of lead I with antimony (Pb-Sb), coated with a layer of Pb-Cd as hereinafter described, is immersed in a dilute solution of sulfuric acid (electrolyte~ in a container 3. The carrier plate used herein is ¦
conveniently a foil of approximately 0.2mm thickness and is made ... l .
1.
l I
~0~:3~i7E~
of an alloy of lead and antimony. The thickness of the carrier plate, however, may vary somewhat depending on the particular construction and intended use of the storage device.
Prior to immersing the carrier plate 1 in the sul-furic acid solutlon, a hot melt of lead and cadmium is sprayed on the surface of the foil by means of a conventional spray gun, or some other suitable spraying device, to deposit a uniform and adherent layer of lead and cadmium on both sur-faces of the foil. A reducing gas such as, for example, hydrogen is used in conjunction with the spraying of the hot melt on the foil's surface, and spraying is discontinued when the thickness of the deposited layer reaches approxi-mately 0.5mm on each surface. Again, this thickness may vary somewhat depending on the particular construction, the required resistivity and the intended use of the device.
Generally, the thickness of Pb-Cd layer on each surface may vary from about 0.1 to 2mm, preferably from about 0.5 to about 1.2mm and is most preferably about lmm.
The Pb-Cd melt is prepared by coating a cadmium wire of approximately lmm thickness electroyltically or by plating to obtain an approximately 1:1 ratio by weight of lead to cadmium, and the resulting wire is then melted, sprayed onto the surface of the foil as hereinbefore des-cribed at a temperature which is higher than the melting points of lead and cadmium, but lower than the temperature which will~cause significant melting of the particular alloy of lead and antimony from which the carrier plate is made, .' .
ll 1 , thus causing sinterization of the Pb-Cd on the surface of the I carrier plate.
¦ In order to improve the adhesion of the Pb-Cd layer to ~ I the surface o~ the carrier pl~te 1, the carrier plate (foil) may ¦ first be sandblasted for several minutes to create a roughened surEace so that the sinterized Pb-Cd mixture will be better bonded to the foil's surface. It must be understood that the terms "foil", "carrier plate" and "collector plate" are used in-terchangeably throughout this application to refer to the Pb-Sb carrier plate.
Referring again to,Fig. 1, there is shown the con-tainer 3 made from a non-conductive material (e.g., glass, plas-tic, etc.) and containing a dilute solution of sulfuric acid , (electrolyte) having approximately the same specific gravity as the sulfuric acid solutions employed in ordinary lead-acid type ¦~ storage batteries. The container 3 is also provided with a lead plate or lead sheet 5 which serves as -the negative electrode (ca-thode). The collector or carrier plate 1 which has been made as aforesaid is immersed in the electrolyte as shown in Fig. 1 and is connected to the positive terminal of a 3 volt emf source 7 (e.g., a battery) while the lead sheet 5 is connected to the nega-tive terminal of said 3 volt emf source. ~lthough more than one carrier plate may be immersed in the electrolyte and suitably connected to the emf source, the invention will be describe~ and I illustrated with reference to the preparation of one positive plate only for the sake of simplicity of illustration.
. i , l I
lU'~ 7~
1 When the circuit is closed as hereinbefore described, the cadmium from the Pb-Cd layer on the carrier plate will react j with sulfuric acid to form cadmium sulEate which is deposited as I a porous; s~on~y mass on the lead sheet 5. Water is dissociated I into hydrogen (H2) and oxygen ~2) Hydrogen appears as gas bub-! bles on the surface on the negative elec-trode while oxy~en com-¦ bines with lead, rapidly and continuously, to form lead Super-¦ oxide (PbO2) in the form of crystalline and polycrystalline mass.
¦ The formation of the active mass is thus completed within minutes ~ and the carrier plate is removed, rinsed clean and dried. It is now ready to be used in the construction of the lead-crystal hat-tery or cell of this invention.
¦ The lead superoxide crystalline and polycrystalline I active mass is a dark brown to black material. It is hard, homo-¦ geno~s, highly porous and has remarkably low internal resistance.
In preparing a carrier plate having crystalline and polycrystalline lead superoxide as the active mass, it is cri~ica~
to the formation of such mass that the Pb-Sb plate be coated with - Pb-Cd that is sinterized. Thus, care must be taken to avoid the formation of Pb-Cd alloy during sinterization or hot spraying on the carrier plate in this embodiment of the invention. The pre-sence of Cd in the sinterized mass is also critical since it aids ¦ or promotes the formation of PbO2 crystals and polycrystals. Ad-ditionally, it must be noted that even though cadmium reacts with the sulfuric acid in container 3 to form cadmium sulfate and it is removed from this container, trace amounts of cadmium . l I
Il .
I ` -13- ~
l 1 lnever~lleless remain in the active mass.
In order to construct a lead crystal cell in a~cord- !
ance with this invention, three identical carrier plates la, lb ¦and lc whiah have been made by the aforedescribed procedure are limmersed in a container 9 as shown in Fig. 2. Container 9 is 5 Isimilar in structure to the cell of a lead-acid battery and con-tains a dilute solution of sulfuric acid which is conventionally employed in such batteries. Carrier plates la and lc are joined together by conductor 11 and connected by conductor 13 to the 'negative terminal of a 3 volt emf source 15 (e.g., a battery, a Ibattery charger, etc.) while carrier plate lb is connected to ,the positive terminal of the emf source 15 via conductor 17.
,~Jhen the circuit is thus closed, the PbO2 on -the carrier plates la and lc is reducea to Pb and the plates become negatively !charged, whereas the PbO2 on the carrier plate lb remains chemi-¦cally unchanged and will become positively charged. Thus, thelead plates will serve as the negative electrodes (cathode) and Ithe lead superoxide plate will serve as the positive electrode ¦(anode).
j After a few minutes when the cell has been fully charged, the emf source 15 is removed and the emf within the cell thus drops from 2.9 volts to approximately 2.4 volts, and re-mains essentially constant at this level. The cell is now charged and is storing energy for later release.
, When a cell made as hereinbefore described is con-Inected in series with other cells (e.g., 3 cells in all), each icontaining several plates (usually 17 or 19) connected in parallel, . 1.
.
0~7~
1 la lead-crystal battery is formed which may contain 51 or 57 ~plates depen~ing on the number of cells and the number of plates ir I each cell. It is obvious, however, that more than 3 cells (e.g., i 6 cells, etc.) may be connectecl in series, if desired.
Lead crystal batteries incorporating the unique fea-~tures of this invention exh~bit superior performance character-istics as compared with lead-acid batteries. Thus, because of lits lower internal resistance, a lead crystal battery comprising ¦,51 or 57 plates can accept about 10 to about 15 times as much ~electric current as the lead-acid battery. Consequently, the llead-crystal ~attery can be charged at much faster rates than the lead-acid battery. Similarly, the discharge rate of the lead-crystal battery is considerably improved since i-t can supply electric current at a considerably more accelerated rate than the llead-acid battery.
I The discharge curve of a lead-crystal cell made in ¦accordance with this invention is compared in Fig. 3 with the ¦discharge curve for a typical lead-acid cell. The solid curve i~
¦this figure represents the discharge curve for the lead-crystai Icell and the dotted curve represents the discharge curve for khe lead-acid cell. A comparison of these two curves indicates that ¦during the first 16 minutes (i.e., during approximately 80~ of ¦the discharge cycle), the emf oE the lead-crystal cell remains con~
stant, then dropping very slightly from 2.32 to approximately ~2.3 volts, whereas the emf of the lead-acid cell decreases Isteadily and constantly during the same period, dropping from 2.1 ¦
Ito approximately 2.0 volts. This difference is particularly sig- ¦
i . I . I
-15- ~
nificant in batteries made from such cells, and indicates that the lead-crystal battery can maintain a higher emf level than the lead acid battery, and, therefore, exhibits superior performance characteristics.
Additionally, the lead-crystal batteries of this invention exhibit from about 25 to about 30 per cen-t higher capacity than the conventional lead-acid batteries. Moreover, the lead-crystal cell is capable of a far more complete charge and discharge, with no after-reaction or self-charge, as compared with a lead-acid cell; consequently, the lead-crystal battery exhibits far greater storage capacity than a lead-acid battery of comparable weight and volume. Cells made in accordance with the principles set forth herein are capable of developing from about O.l to about 0.2 volt higher emf than conventional storage cells from which the lead~acid batteries are made.
In the foregoing description, sinterized lead and cadmium was applied to the surface of the collector plates by hot spraying to deposit a homogenous, uniform and adherent layer of Pb-Cd thereon. Two additional methods will now be - described for depositing such layer of Pd-Cd on the surface of the Pb-Sb carrier plate.
In another embodiment of this invention, a soft, granular, 1:1 mixture of lead and cadmium, wherein the size of the granules is from about 100 to a-lmost 500 microns, is dissolved in a suitable organic liquid such as, for example, methanol (or ethanol) to prepare a paste which is then deposited on the surface of the carrier plate by a suitable sieve. The methanol `7~
1 is thereater evaporated; the plate is dried, and the Pb-Cd is sinkerized in a press at a témperature of Erom about 300C. to about 400C. for approximately 3 seconds. Once again, the ternp-I erature and pressure during sinteriza-tion must be carefully con-~ trolled so as to prevent the formation of the Pb-Cd 'alloy.
i The thickness of the Pb-Cd layer on the carrier plate¦
¦ may be controlled by the selection of the proper sieve and by de-¦
positing the appropriate amount of paste ~iformly on the surface I of the plate. Thus, a Pb-Cd layer of approximately 0.5~m thick-I ness may be deposited on both sides of the carrier plates.
I After depositing the desired coatin~ thickness, th~
¦ carrier plate is immersed in a container comprising a dilute solutlon of sulfuric acid and a lead plate as hereinbefore de-I scribed in connection with Fig. 1 and crystalline and polycrystal line lead superoxide (Pb02) is once a~ain formed on the surface o~
the carrier plate in the same manner. The cadmium from the Pb~Cd ¦ layer reacts with sulfuric acid and is deposited in the form Gf ¦ CdS04 from which the cadmium can be recovered and reused, and the ¦ carrier plate or plates then used to construct a lead-crystal cell as heretofore described in connection with Fig. 2.
In another embodiment of the invention a hard; com-~ pact alloy of lead and cadmium was deposited on the carr1er plate ~ by electroplating in a fluoroboratebath. Thus, two electrodes, ¦ one made from an alloy of lead with antimony (cathode) and the ! other ~rom a 1:1 alloy o~ lead and cadmium (anode) were immersed ., ~ I
. I
I
l l l I
~v9~7 1~ l Il I
1 1 in a rluorborate bath havin~J the following composition: l ¦' !
Lead Fluoroborate, Pb (BF4)2 119 oz.
Metallic Lead, Pb 65 oz.
Fluoroboric Acid HBF41.0 oz. I
Boric Acid 8.0 oz.
Cadmium Fluoroborate Cd(BF ) 32.5 oz.
j Cadmium Metal, Cd 412.0 oz.
5 ~ ~mmonium Fluoroborate8.0 oz.
WateE 1 gallon The electrodes were then connected to the positive ¦and negative terminals of a 5 volt emf source for 1 hour until a ¦uniform layer of cadmium and lead of approximately O.lmm thick- I
Iness was deposited on each surface of the cathode. The emf sourcel was then disconnected, the cathode removed from the bath, rinsed clean with water and dried. I
I In order to produce three carrier plates with cry~
,talline and polycrystalline lead superoxide on their surfaces, ,three cathodic carrier plates made by this procedure were immersedl in a dilute sulfuric acid electrolyte and subjected to the same operation as hereinabove described in connection with Fig. 1.
¦The resulting carrier plates were then used to construct a lead-Icrystal cell as hereinbefore described in connection with Fig. 2. 1 ¦ It is evident from the foregoing detailed descrip~ion¦
that the lead-crystal battery of this invention is remarkably superior to the lead-acid battery. In addition to the several uni~ue features which were described supra, the lead-crystal bat- ¦
tery is usually from about 15% to about 30% lighter in weight than !
~5 a lead-acid battery of comparable size and capacity, and exhibits from about 25~ to about 30% greater capacity as compared to a lead-acid battery of comparable size and weight. The ability to ~draw substantially larger anounts of power in a considerably shorter period of time due to its significalltly lower internal _J~ I
~' I
D~7~
resistance and higher activity makes it particularly useful in vehicles which require fast acceleration, e.g., electric vehicles and cars, and other electrically motivated power sources.
Also, the lead-crystal batteries which are made in accordance with this invention exhibit little or no sulphatiz-ation. This means that, as a practical matter, these bat-teries can discharge to a point approaching zero emf. In contrast, sulphatization is a rather common phenomenon in the lead-acid batteries, and consequently, the lead-acid batteries cannot discharge beyond about 1.5 to 1.8 volts emf, or almost irreversible sulphatization will take place in the lead grids which hold the paste of the active mass.
It must also be noted that while the invention has heretofore been described and illustrated with certain degrees of particularity, several changes and/or modifica-tions may be made which are obvious from the foregoing des-cription and which are, therefore, encompassed within the spirit and scope of this invention.
For example, instead of using Pb-Sb carrier plates, it is possible to use inert, non-co~ductive carrier plates (è.g., made from a suitable plastic such as polypropylene or cellulosic material) on which lead, or a mixture of lead with antimony, may be deposited as hereinbefore described.
Such carrier plates are considerably lighter in weight than Pb-Sb carrier plates, and consequently, the resulting batteries will be considerably lighter as well.
~)~3~
i li l I ~lso, while the inven-tion was heretofore illustrated ¦with reference to a l:l ratio by weight of Pb:Cd, this ratio 1Imay vary from about 30 to about 70 weight per cent and preferably ¦Ifrom about 45 to about 55 weight per cent; however, optimum re-1sults are obtained when an approximately equal weight ratio of 5 ¦I the two components are used. If the mixture is predominantly ¦1lead, say, 70 weight per cent, the Pb-Cd layer will be softer and less porous, whereas if the cadmium component predominates, say, 1it constitutes 70 weight per cent of the mixture, the resultiny ¦Pb-Cd layer will be harder and more porous. Optimum hardness and ¦porosity of the Pb-Cd layer are attained when the mixture is ap-proxi~ate1y ~ 1:1 ratio by weight.
l I
!
.. I , I
I
1 , line object, and to storage devices comprising the same.
¦~ U.S. 3,709,820 discloses an organic solid electrolyte , which is a crystalline electron donor-acceptor complex comprising ¦ ionic crystals of 7,7,8,8-tetracyanoquinodimethane, an aromatic lamine, and a liquid impregnated in the ionic crystal lattice. The¦
electrolyte described in this patent is employed in eapacitors to ¦
¦lower their resistivity.
U S 3,765,915 describes the uses of Beta-alu~ina Ipolycrystalline ceramics for use as electrolyte in the construction of cells or batteries of the sodium~sulfur type.
The foregoing patents are but a few of the plethora f¦
Ipatents which represent the research and activities which have ¦been expended in this art. Nevertheless, however, the basic con- ¦
struction of the lead-acid battery and its constituent cells re-main essentially unchanged. Today, as it was made several decades ago, lead-acid batteries are made by serial connection of a plu-rality of cells (usually 3 or 6) wherein porous lead o~ide is the lactive mass on the positive plate and spongy, porous lead is the Inegative plate, and dilute sulfuric acid is the electrolyte oF
Ichoice.
¦ Accordingly, it is an object of the present invention !
to provide improved storage cells and devices which are made from ¦
Isuch cells.
I It is a further object of this invention to provide a I
storage battery in which the active mass on the positive electrode !
is a unique material made from crystalline and polycrystalline 37~3 1 llead oxide. Such batteries will hereinafter be referred ~o as "lead-crystal" batteries to distinguish them from the conventional lead-acid batteries.
' It is another object of this invention to provide novel and unique lead-crystal batteries which have superior per-formance characteristics as compared with the conventional lead I batteries .
It is also an object of this invention to provide such llead-crystal batteries which exhibit lower internal resistance and ¦higher potential difference (electromotive force) than the con-ventional lead batteries.
It is still another object of this invention to pro-vide lead-crystal batteries which exhibit higher current charge land discharge capacity and which can be charged at a considerah'y ¦
Ifaster rate than the conventional lead battery.
It is a further object of this invention to provide ~lead-crystal batte~ies which exhibit considerably lower:sulphati-zation as compared with the lead-acid battery.
¦ It is also an object of this invention to provide a ¦method of making crystalline and polycrystalline lead oxide as the active mass.
It is yet another object of this invention to provlde ¦
~a unique positive plate for the construction of storage cells and ¦
batteries made from such cells.
¦ I~ is also an ob~ect of this invention to provide such I
~positive plates which comprise a carrier plate such as lead, an alloy of lead with antimony, or a non-conductive carrier material with a conductive coating, and lead oxide in crystalline and I
I
polycrystalline form applied to the surface of the carrier plate.
The foregoing and other objects of this invention will be more readily comprehended from the following detailed description of the invention taken in conjunction with the accompanying drawings which form a part of this application.
SUMMARY OF THE INVENTION
Thus the present invention provides a solid state conductor for use in storage cells comprised of a carrier plate made from a material selected from the group consisting of lead, an alloy of lead with antimony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and a uniform, adherent and durable layer of an active mass on said carrier plate, said active mass consisting essentially of crystalline and polycrystalline lead superoxide in which lead is at its maximum valence of four.
In another embodiment the present invention provides a storage cell comprised of a dilute solution of sulfuric acid, at least one negative electrode and at least one positive electrode, each made from a material selected from the group consisting of lead, an alloy of lead with antimony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and wherein said positive electrode is coated with a uniform, adherent and durable layer of polycrystalline and crystalline lead superoxide in which lead is at its maximum valence of four. A preferred embodiment of such a storage cell is provided wherein said electrodes are an inert, non-conductive material coated with lead, or an alloy of lead with antimony.
In another embodiment the present invention provides a method of making a solid state conductor for use in storage cells which comprises: (a) forming a uniform and adherent layer 7~3 of lead and cadmium on a carrier plate made from lead, an alloy of lead with antimony or an inert, non-conductive material coated with lead or an alloy of lead with antimonyi (b) immersing the resulting carrier plate in a container containing a dilute solution of sulfuric acid and a lead plate;
(c) connecting said carrier plate to the positive terminal of an emf source and connecting lead plate to the negative terminal of said emf source, thereby causing electric current to flow through said plates; and (d) causing said cadmium in said lead~cadmium layer to react with sulfuric acid to form cadmium sulfate which is deposited on said lead plate, and simultaneously oxidizing said lead in said lead-cadmium layer thereby forming a mixture of crystalline and polycrystalline lead superoxide, in which lead is at its maximum valence of four. In one embodiment there is disclosed a method of making such a solid state conductor wherein, in step (a) said uniform and adherent layer of lead and cadmium is formed by making a relatively thin paste of lead and cadmium mixture in a reducing organic liquid, depositing said paste on said carrier plate and evaporating said solvent from the paste.
In a further embodiment the present invention provides a method of making a solid state conductor wherein, in step (a), said uniform and adherent layer of lead and cadmium is formed on the surface of said carrier plate by an electroplating process which comprises immersing, in an electrolytic bath, two conductors, a cathode made from an alloy of lead and antimony and an anode made from lead and cadmium, wherein said electrolytic bath comprises lead fluoroborate, metallic lead, fluoroboric acid, boric acid, cadmium fluoroborate, metallic cadmium, ammonium fluoroborate and water, connecting said cathode and said anode, respectively, - 7(a) -.~
7i~3 to the negative and positive terminals of an emf source, andcausing an electric current to flow through said electrodes.
In accordance with this invention, a storage cell i5 provided in which the active mass OII the positive electrode of the cell is a mixture of crystal:Line and polycrystalline lead superoxide (PbO2). Thus, a mixture of lead and cadmium is first deposited, or otherwise conveniently applied, as a uniform, adherent layer, on a carrier plate made of lead, an alloy of lead with antimony, or a suitable inert and non-conductive material which is coated with lead or an alloy oflead with antimony. The lead-cadmium mixture may be deposited on the carrier plate by hot-spraying, so-called "powdered metallurgy" technique or by electroplating, all as hereinafter described in the ensuing detailed description of the invention.
The carrier plate which has been coated with lead and cadmium as aforesaid is then immersed in a container containing a dilute solution of sulfuric acid (electrolyte) and a lead plate or sheet which serves as the cathode. The carrier plate is then connected to the positive terminal of an emf source and the lead sheet is connected to the negative terminal of said source. The passage of electric current through the plates causes the oxidation - 7(b) -j, 1 I,of lead (in the lead-cadmium layer) to lead superoxide, in the Eorm of crystalline and polycrystalline mass, while the cadmium reacts with sulfuric acid to form cadmium sulfate which is de-Iposited on the lead sheet as a spongy material. The carrier plate lis then removed from the solution, rin.sed clean with water and dried.
Three carrier plates made as aforesaid are thereafter immersed in a second container containing a dilute solution of Isulfuric acid. The middle carrier plate is connected to the posi-Itive terminal of an emf source while the other two carrier plates lare jointly connected to the negative terminal of said emf source.
¦Upon the passage of electric current, the middle carrier plate ¦will be positively charged and the lead superoxide will remain lunchanged while the lead oxide on the other two carrier plates is ¦reduc~d to lead and becomes negatively charged.
After a few minutes the emf source is removed and the emf within the cell drops from 2.9 volts to approximately 2.4 !
¦volts and remains essentially constant at this level. The cell is Inow charged and is storing energy for subsequent release.
¦ Three or more such cells may be connected in series to ¦form the lead-crystal battery of this invention.
! ~RIEF DESCRIPTION OF THE DRAWINGS
i Figure 1 is a schematic representation illustrating the method of formation oE the active mass, i~e., the crystalline and polycrystalline lead oxide, in accordance with this invention;l , . I
I
I -8~
~I.vsslt37a 1 ~I E'igure 2 is anot~ier schematic diagram illustrating the formation of the positive and negative plates and the cell ¦icomprising such plates; and ¦I Figure 3 shows two curves which compare the discharge ¦Icharacteristics of a lead-crystal cell made in accordance with ¦Ithis invention with a conventional lead-acid type cell.
DETAILED DESCRIPTION OF THE INVENTION
1 It has now been unexpectedly discovered that the per-Iformance of storage cells can be xemarkably improved by providing ¦the cells with a unique positive plate comprising crystalline and polycrystalline lead oxide in the form of Pb02 as the active mass.
Conse~uently, lead-cr~stal batteries made from such cells exhibit superior performance characteristics as compared with the con-¦ventibnal lead-acid batteries.
In the ensuing description, the present invention will ~be described in detail with particular reference to the construc~
tion of a storage cell, and a battery made from such cells. Such description, however, is not to be taken as limitin~ the scope of this invention as there are other storage devices which can be constructed on the basis of the principles set forth herein and which are, therefore, comprehended, contemplated and included Iwithin this disclosuxe.
~ It has been discovered that a storage cell constructed lin accordance ~ith this invention exhibits properties which have . Iheretofore been unattainable in the prior art type storage cells, and conse~uently, devlces, e.g , storaqe batteries, made by the 7~
.
1 ' serial connection of such cells, also exhibit superior perform~
i ance characteristics as compared with the conventional lead bat-teries. Such improved properties include, althoughthey are not I limited to, lower internal resistance, higher activity, lower sul-I phatization, better char~ing and discharging characteristics, greater storage capacity, faster charging rates and higher em~
per cell.
The unique active mass which is formed in accordance I with the method of this invention is composed essentially of ¦ crystalline and polycrystalline lead oxide (PbO2) in which lead has its maximum electron valence of four, and which is sometimes ¦ referred to as lead superoxide to distinguish it from PbO in ¦ which lead has its lower electron valence of two.
The term "polycrystalline" as used herein denotes an aggregation of single crystalline masses of lead superoxide, wherein such crystals are at varying stages of growth and develop-ment. Thus, the active mass of this invention is a mixture of ¦ single crystalline masses of PbO2 together with such polycrystal-¦ line aggregates.
¦ In accordance with one embodiment of this invention, and with particular reference first to Fig. 1, a carrier plate 1 ¦ which is typically made of pure lead (Pb) or an alloy of lead I with antimony (Pb-Sb), coated with a layer of Pb-Cd as hereinafter described, is immersed in a dilute solution of sulfuric acid (electrolyte~ in a container 3. The carrier plate used herein is ¦
conveniently a foil of approximately 0.2mm thickness and is made ... l .
1.
l I
~0~:3~i7E~
of an alloy of lead and antimony. The thickness of the carrier plate, however, may vary somewhat depending on the particular construction and intended use of the storage device.
Prior to immersing the carrier plate 1 in the sul-furic acid solutlon, a hot melt of lead and cadmium is sprayed on the surface of the foil by means of a conventional spray gun, or some other suitable spraying device, to deposit a uniform and adherent layer of lead and cadmium on both sur-faces of the foil. A reducing gas such as, for example, hydrogen is used in conjunction with the spraying of the hot melt on the foil's surface, and spraying is discontinued when the thickness of the deposited layer reaches approxi-mately 0.5mm on each surface. Again, this thickness may vary somewhat depending on the particular construction, the required resistivity and the intended use of the device.
Generally, the thickness of Pb-Cd layer on each surface may vary from about 0.1 to 2mm, preferably from about 0.5 to about 1.2mm and is most preferably about lmm.
The Pb-Cd melt is prepared by coating a cadmium wire of approximately lmm thickness electroyltically or by plating to obtain an approximately 1:1 ratio by weight of lead to cadmium, and the resulting wire is then melted, sprayed onto the surface of the foil as hereinbefore des-cribed at a temperature which is higher than the melting points of lead and cadmium, but lower than the temperature which will~cause significant melting of the particular alloy of lead and antimony from which the carrier plate is made, .' .
ll 1 , thus causing sinterization of the Pb-Cd on the surface of the I carrier plate.
¦ In order to improve the adhesion of the Pb-Cd layer to ~ I the surface o~ the carrier pl~te 1, the carrier plate (foil) may ¦ first be sandblasted for several minutes to create a roughened surEace so that the sinterized Pb-Cd mixture will be better bonded to the foil's surface. It must be understood that the terms "foil", "carrier plate" and "collector plate" are used in-terchangeably throughout this application to refer to the Pb-Sb carrier plate.
Referring again to,Fig. 1, there is shown the con-tainer 3 made from a non-conductive material (e.g., glass, plas-tic, etc.) and containing a dilute solution of sulfuric acid , (electrolyte) having approximately the same specific gravity as the sulfuric acid solutions employed in ordinary lead-acid type ¦~ storage batteries. The container 3 is also provided with a lead plate or lead sheet 5 which serves as -the negative electrode (ca-thode). The collector or carrier plate 1 which has been made as aforesaid is immersed in the electrolyte as shown in Fig. 1 and is connected to the positive terminal of a 3 volt emf source 7 (e.g., a battery) while the lead sheet 5 is connected to the nega-tive terminal of said 3 volt emf source. ~lthough more than one carrier plate may be immersed in the electrolyte and suitably connected to the emf source, the invention will be describe~ and I illustrated with reference to the preparation of one positive plate only for the sake of simplicity of illustration.
. i , l I
lU'~ 7~
1 When the circuit is closed as hereinbefore described, the cadmium from the Pb-Cd layer on the carrier plate will react j with sulfuric acid to form cadmium sulEate which is deposited as I a porous; s~on~y mass on the lead sheet 5. Water is dissociated I into hydrogen (H2) and oxygen ~2) Hydrogen appears as gas bub-! bles on the surface on the negative elec-trode while oxy~en com-¦ bines with lead, rapidly and continuously, to form lead Super-¦ oxide (PbO2) in the form of crystalline and polycrystalline mass.
¦ The formation of the active mass is thus completed within minutes ~ and the carrier plate is removed, rinsed clean and dried. It is now ready to be used in the construction of the lead-crystal hat-tery or cell of this invention.
¦ The lead superoxide crystalline and polycrystalline I active mass is a dark brown to black material. It is hard, homo-¦ geno~s, highly porous and has remarkably low internal resistance.
In preparing a carrier plate having crystalline and polycrystalline lead superoxide as the active mass, it is cri~ica~
to the formation of such mass that the Pb-Sb plate be coated with - Pb-Cd that is sinterized. Thus, care must be taken to avoid the formation of Pb-Cd alloy during sinterization or hot spraying on the carrier plate in this embodiment of the invention. The pre-sence of Cd in the sinterized mass is also critical since it aids ¦ or promotes the formation of PbO2 crystals and polycrystals. Ad-ditionally, it must be noted that even though cadmium reacts with the sulfuric acid in container 3 to form cadmium sulfate and it is removed from this container, trace amounts of cadmium . l I
Il .
I ` -13- ~
l 1 lnever~lleless remain in the active mass.
In order to construct a lead crystal cell in a~cord- !
ance with this invention, three identical carrier plates la, lb ¦and lc whiah have been made by the aforedescribed procedure are limmersed in a container 9 as shown in Fig. 2. Container 9 is 5 Isimilar in structure to the cell of a lead-acid battery and con-tains a dilute solution of sulfuric acid which is conventionally employed in such batteries. Carrier plates la and lc are joined together by conductor 11 and connected by conductor 13 to the 'negative terminal of a 3 volt emf source 15 (e.g., a battery, a Ibattery charger, etc.) while carrier plate lb is connected to ,the positive terminal of the emf source 15 via conductor 17.
,~Jhen the circuit is thus closed, the PbO2 on -the carrier plates la and lc is reducea to Pb and the plates become negatively !charged, whereas the PbO2 on the carrier plate lb remains chemi-¦cally unchanged and will become positively charged. Thus, thelead plates will serve as the negative electrodes (cathode) and Ithe lead superoxide plate will serve as the positive electrode ¦(anode).
j After a few minutes when the cell has been fully charged, the emf source 15 is removed and the emf within the cell thus drops from 2.9 volts to approximately 2.4 volts, and re-mains essentially constant at this level. The cell is now charged and is storing energy for later release.
, When a cell made as hereinbefore described is con-Inected in series with other cells (e.g., 3 cells in all), each icontaining several plates (usually 17 or 19) connected in parallel, . 1.
.
0~7~
1 la lead-crystal battery is formed which may contain 51 or 57 ~plates depen~ing on the number of cells and the number of plates ir I each cell. It is obvious, however, that more than 3 cells (e.g., i 6 cells, etc.) may be connectecl in series, if desired.
Lead crystal batteries incorporating the unique fea-~tures of this invention exh~bit superior performance character-istics as compared with lead-acid batteries. Thus, because of lits lower internal resistance, a lead crystal battery comprising ¦,51 or 57 plates can accept about 10 to about 15 times as much ~electric current as the lead-acid battery. Consequently, the llead-crystal ~attery can be charged at much faster rates than the lead-acid battery. Similarly, the discharge rate of the lead-crystal battery is considerably improved since i-t can supply electric current at a considerably more accelerated rate than the llead-acid battery.
I The discharge curve of a lead-crystal cell made in ¦accordance with this invention is compared in Fig. 3 with the ¦discharge curve for a typical lead-acid cell. The solid curve i~
¦this figure represents the discharge curve for the lead-crystai Icell and the dotted curve represents the discharge curve for khe lead-acid cell. A comparison of these two curves indicates that ¦during the first 16 minutes (i.e., during approximately 80~ of ¦the discharge cycle), the emf oE the lead-crystal cell remains con~
stant, then dropping very slightly from 2.32 to approximately ~2.3 volts, whereas the emf of the lead-acid cell decreases Isteadily and constantly during the same period, dropping from 2.1 ¦
Ito approximately 2.0 volts. This difference is particularly sig- ¦
i . I . I
-15- ~
nificant in batteries made from such cells, and indicates that the lead-crystal battery can maintain a higher emf level than the lead acid battery, and, therefore, exhibits superior performance characteristics.
Additionally, the lead-crystal batteries of this invention exhibit from about 25 to about 30 per cen-t higher capacity than the conventional lead-acid batteries. Moreover, the lead-crystal cell is capable of a far more complete charge and discharge, with no after-reaction or self-charge, as compared with a lead-acid cell; consequently, the lead-crystal battery exhibits far greater storage capacity than a lead-acid battery of comparable weight and volume. Cells made in accordance with the principles set forth herein are capable of developing from about O.l to about 0.2 volt higher emf than conventional storage cells from which the lead~acid batteries are made.
In the foregoing description, sinterized lead and cadmium was applied to the surface of the collector plates by hot spraying to deposit a homogenous, uniform and adherent layer of Pb-Cd thereon. Two additional methods will now be - described for depositing such layer of Pd-Cd on the surface of the Pb-Sb carrier plate.
In another embodiment of this invention, a soft, granular, 1:1 mixture of lead and cadmium, wherein the size of the granules is from about 100 to a-lmost 500 microns, is dissolved in a suitable organic liquid such as, for example, methanol (or ethanol) to prepare a paste which is then deposited on the surface of the carrier plate by a suitable sieve. The methanol `7~
1 is thereater evaporated; the plate is dried, and the Pb-Cd is sinkerized in a press at a témperature of Erom about 300C. to about 400C. for approximately 3 seconds. Once again, the ternp-I erature and pressure during sinteriza-tion must be carefully con-~ trolled so as to prevent the formation of the Pb-Cd 'alloy.
i The thickness of the Pb-Cd layer on the carrier plate¦
¦ may be controlled by the selection of the proper sieve and by de-¦
positing the appropriate amount of paste ~iformly on the surface I of the plate. Thus, a Pb-Cd layer of approximately 0.5~m thick-I ness may be deposited on both sides of the carrier plates.
I After depositing the desired coatin~ thickness, th~
¦ carrier plate is immersed in a container comprising a dilute solutlon of sulfuric acid and a lead plate as hereinbefore de-I scribed in connection with Fig. 1 and crystalline and polycrystal line lead superoxide (Pb02) is once a~ain formed on the surface o~
the carrier plate in the same manner. The cadmium from the Pb~Cd ¦ layer reacts with sulfuric acid and is deposited in the form Gf ¦ CdS04 from which the cadmium can be recovered and reused, and the ¦ carrier plate or plates then used to construct a lead-crystal cell as heretofore described in connection with Fig. 2.
In another embodiment of the invention a hard; com-~ pact alloy of lead and cadmium was deposited on the carr1er plate ~ by electroplating in a fluoroboratebath. Thus, two electrodes, ¦ one made from an alloy of lead with antimony (cathode) and the ! other ~rom a 1:1 alloy o~ lead and cadmium (anode) were immersed ., ~ I
. I
I
l l l I
~v9~7 1~ l Il I
1 1 in a rluorborate bath havin~J the following composition: l ¦' !
Lead Fluoroborate, Pb (BF4)2 119 oz.
Metallic Lead, Pb 65 oz.
Fluoroboric Acid HBF41.0 oz. I
Boric Acid 8.0 oz.
Cadmium Fluoroborate Cd(BF ) 32.5 oz.
j Cadmium Metal, Cd 412.0 oz.
5 ~ ~mmonium Fluoroborate8.0 oz.
WateE 1 gallon The electrodes were then connected to the positive ¦and negative terminals of a 5 volt emf source for 1 hour until a ¦uniform layer of cadmium and lead of approximately O.lmm thick- I
Iness was deposited on each surface of the cathode. The emf sourcel was then disconnected, the cathode removed from the bath, rinsed clean with water and dried. I
I In order to produce three carrier plates with cry~
,talline and polycrystalline lead superoxide on their surfaces, ,three cathodic carrier plates made by this procedure were immersedl in a dilute sulfuric acid electrolyte and subjected to the same operation as hereinabove described in connection with Fig. 1.
¦The resulting carrier plates were then used to construct a lead-Icrystal cell as hereinbefore described in connection with Fig. 2. 1 ¦ It is evident from the foregoing detailed descrip~ion¦
that the lead-crystal battery of this invention is remarkably superior to the lead-acid battery. In addition to the several uni~ue features which were described supra, the lead-crystal bat- ¦
tery is usually from about 15% to about 30% lighter in weight than !
~5 a lead-acid battery of comparable size and capacity, and exhibits from about 25~ to about 30% greater capacity as compared to a lead-acid battery of comparable size and weight. The ability to ~draw substantially larger anounts of power in a considerably shorter period of time due to its significalltly lower internal _J~ I
~' I
D~7~
resistance and higher activity makes it particularly useful in vehicles which require fast acceleration, e.g., electric vehicles and cars, and other electrically motivated power sources.
Also, the lead-crystal batteries which are made in accordance with this invention exhibit little or no sulphatiz-ation. This means that, as a practical matter, these bat-teries can discharge to a point approaching zero emf. In contrast, sulphatization is a rather common phenomenon in the lead-acid batteries, and consequently, the lead-acid batteries cannot discharge beyond about 1.5 to 1.8 volts emf, or almost irreversible sulphatization will take place in the lead grids which hold the paste of the active mass.
It must also be noted that while the invention has heretofore been described and illustrated with certain degrees of particularity, several changes and/or modifica-tions may be made which are obvious from the foregoing des-cription and which are, therefore, encompassed within the spirit and scope of this invention.
For example, instead of using Pb-Sb carrier plates, it is possible to use inert, non-co~ductive carrier plates (è.g., made from a suitable plastic such as polypropylene or cellulosic material) on which lead, or a mixture of lead with antimony, may be deposited as hereinbefore described.
Such carrier plates are considerably lighter in weight than Pb-Sb carrier plates, and consequently, the resulting batteries will be considerably lighter as well.
~)~3~
i li l I ~lso, while the inven-tion was heretofore illustrated ¦with reference to a l:l ratio by weight of Pb:Cd, this ratio 1Imay vary from about 30 to about 70 weight per cent and preferably ¦Ifrom about 45 to about 55 weight per cent; however, optimum re-1sults are obtained when an approximately equal weight ratio of 5 ¦I the two components are used. If the mixture is predominantly ¦1lead, say, 70 weight per cent, the Pb-Cd layer will be softer and less porous, whereas if the cadmium component predominates, say, 1it constitutes 70 weight per cent of the mixture, the resultiny ¦Pb-Cd layer will be harder and more porous. Optimum hardness and ¦porosity of the Pb-Cd layer are attained when the mixture is ap-proxi~ate1y ~ 1:1 ratio by weight.
l I
!
.. I , I
Claims (43)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A solid state conductor for use in storage cells comprised of a carrier plate made from a material selected from the group consisting of lead, an alloy of lead with anti-mony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and a uniform, adherent and durable layer of an active mass on said carrier plate, said active mass consisting essentially of crystalline and poly-crystalline lead superoxide in which lead is at its maximum valence of four.
2. A conductor as in Claim 1 wherein said carrier plate is lead.
3. A conductor as in Claim 1 wherein said carrier plate is an alloy of lead with antimony.
4. A conductor as in Claim 1 wherein said carrier plate is an inert, non-conductive material coated with lead, or an alloy of lead with antimony.
5. A storage cell comprised of a dilute solution of sulfuric acid, at least one negative electrode and at least one positive electrode, each made from a material selected from the group consisting-of lead, an alloy of lead with anti-mony and an inert, non-conductive substance coated with lead or an alloy of lead with antimony, and wherein said positive electrode is coated with a uniform, adherent and durable lay-er of polycrystalline and crystalline lead superoxide in which lead is at its maximum valence of four.
6. A storage cell as in Claim 5 wherein said elec-trodes are lead.
7. A storage cell as in Claim 5 wherein said electrodes are an alloy of lead with antimony.
8. A storage cell as in Claim 5 wherein said electrodes are an inert, non-conductive material coated with lead, or an alloy of lead with antimony.
9. A storage device comprised of a plurality of serially connected storage cells as defined in Claim 5.
10. A storage device comprised of a plurality of serially connected storage cells as defined in Claim 6.
11. A storage device comprised of a plurality of serially connected storage cells as defined in Claim 7.
12. A storage device comprised of a plurality of serially connected storage cells as defined in Claim 8.
13. A storage battery made by serially connecting a plurality of cells as defined in Claim 5.
14. A storage battery made by serially connecting a plurality of cells as defined in Claim 6.
15. A storage battery made by serially connecting a plurality of cells as defined in Claim 7.
16. A storage battery made by serially connecting a plurality of cells as defined in Claim 8.
17. A storage cell as in Claim 5 comprised of a plurality of positive electrodes connected in parallel and a plurality of negative electrodes connected in parallel.
18. A storage cell as in Claim 6 comprised of a plurality of positive electrodes connected in parallel and a plurality of negative electrodes connected in parallel.
19. A storage cell as in Claim 7 comprised of a plurality of positive electrodes connected in parallel and a plurality of negative electrodes connected in parallel.
20. A storage cell as in Claim 8 comprised of a plurality of positive electrodes connected in parallel and a plurality of negative electrodes connected in parallel.
21. A method of making a solid state conductor for use in storage cells which comprises:
(a) forming a uniform and adherent layer of lead and cadmium on a carrier plate made from lead, an alloy of lead with antimony or an inert, non-conductive material coated with lead or an alloy of lead with antimony, (b) immersing the resulting carrier plate in a container containing a dilute solution of sulfuric acid and a lead plate, (c) connecting said carrier plate to the positive terminal of an emf source and connecting lead plate to the negative terminal of said emf source, thereby causing electric current to flow through said plates, and (d) causing said cadmium in said lead-cadmium layer to react with sulfuric acid to form cadmium sulfate which is deposited on said lead plate, and simultaneously oxidizing said lead in said lead-cadmium layer thereby form-ing a mixture of crystalline and polycrystalline lead super-oxide, in which lead is at its maximum valence of four.
(a) forming a uniform and adherent layer of lead and cadmium on a carrier plate made from lead, an alloy of lead with antimony or an inert, non-conductive material coated with lead or an alloy of lead with antimony, (b) immersing the resulting carrier plate in a container containing a dilute solution of sulfuric acid and a lead plate, (c) connecting said carrier plate to the positive terminal of an emf source and connecting lead plate to the negative terminal of said emf source, thereby causing electric current to flow through said plates, and (d) causing said cadmium in said lead-cadmium layer to react with sulfuric acid to form cadmium sulfate which is deposited on said lead plate, and simultaneously oxidizing said lead in said lead-cadmium layer thereby form-ing a mixture of crystalline and polycrystalline lead super-oxide, in which lead is at its maximum valence of four.
22. A method of making a solid state conductor as in Claim 21 wherein, in step (a), said uniform and adher-ent layer lead and cadmium is formed by spraying a hot melt mixture of lead and cadmium on the surface of the carrier plate under a reducing atmosphere, and causing said hot melt mixture to sinterize on the surface of the carrier plate without forming an alloy of lead and cadmium.
23. A method as in Claim 22 wherein said hot melt mixture consists of from about 30 to about 70 weight percent lead.
24. A method as in Claim 22 wherein said hot melt mixture consists of from about 45 to about 55 weight per cent lead.
25. A method as in Claim 22 wherein said hot melt mixture is an approximately 1:1 ratio by weight, of lead to cadmium
26. A method of making a solid state conductor as in Claim 21 wherein, in step (a) said uniform and adherent layer of lead and cadmium is formed by making a relatively thin paste of lead and cadmium mixture in a reducing organic liquid, depositing said paste on said carrier plate and evaporating said solvent from the paste.
27. A method as in Claim 26 wherein said reducing organic liquid is methanol.
28. A method as in Claim 26 wherein said reducing organic liquid is ethanol.
29. A method as in Claim 26 wherein said layer of lead and cadmium consists of from about 30 to about 70 weight per cent lead.
30. A method as in Claim 26 wherein said layer of lead and cadmium consists of from about 45 to about 55 weight per cent lead.
31. A method as in Claim 26 wherein said layer of lead and cadmium is an approximately 1:1 ratio by weight, of lead to cadmium.
32. A method as in Claim 27 wherein said layer of lead and cadmium consists of from about 30 to about 70 weight per cent lead.
33. A method as in Claim 27 wherein said layer of lead and cadmium consists of from about 45 to about 55 weight per cent lead.
34. A method as in Claim 27 wherein said layer of lead and cadmium is an approximately 1:1 ratio by weight, of lead to cadmium.
\
\
35. A method as in Claim 28 wherein said layer of lead and cadmium consists of from about 30 to about 70 weight per cent lead.
36. A method as in Claim 28 wherein said layer of lead and cadmium consists of from about 45 to about 55 weight per cent lead.
37. A method as in Claim 28 wherein said layer of lead and cadmium is an approximately 1:1 ratio by weight, of lead to cadmium.
38. A method of making a solid state conductor as in Claim 21 wherein, in step (a), said uniform and adherent layer of lead and cadmium is formed on the surface of said carrier plate by an electroplating process which comprises immersing, in an electrolytic bath, two conductors, a cathode made from an alloy of lead and antimony and an anode made from lead and cadmium, wherein said electrolytic bath com-prises lead fluoroborate, metallic lead, fluoroboric acid, boric acid, cadmium fluoroborate, metallic cadmium, ammonium fluoroborate and water, connecting said cathode and said anode, respectively, to the negative and positive terminals of an emf source, and causing an electric current to flow through said electrodes.
39. A method as in Claim 38 wherein said anode consists of from about 30 to about 70 weight per cent lead.
40. A method as in Claim 38 wherein said anode consists of from about 45 to about 55 weight percent lead.
41. A method as in Claim 38 wherein said anode consists of an approximately 1:1 ratio by weight, of lead to cadmium.
42. A composition of matter useful as the active mass of positive electrodes in storage cells, said composition consisting essentially of crystalline and polycrystalline lead superoxide in which lead is at its maximum valence of four.
43. A composition as in Claim 42 further including trace amounts of metallic cadmium.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76890977A | 1977-02-15 | 1977-02-15 | |
| US768,909 | 1977-02-15 | ||
| US78176277A | 1977-03-28 | 1977-03-28 | |
| US781,762 | 1977-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090878A true CA1090878A (en) | 1980-12-02 |
Family
ID=27118100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA291,524A Expired CA1090878A (en) | 1977-02-15 | 1977-11-23 | Lead crystal storage cells and storage devices made therefrom |
Country Status (18)
| Country | Link |
|---|---|
| AT (1) | AT368323B (en) |
| AU (1) | AU517857B2 (en) |
| BR (1) | BR7708182A (en) |
| CA (1) | CA1090878A (en) |
| CH (1) | CH636483A5 (en) |
| CS (1) | CS214885B2 (en) |
| DE (1) | DE2750596C3 (en) |
| ES (1) | ES473868A1 (en) |
| FR (1) | FR2380645A1 (en) |
| GB (1) | GB1597033A (en) |
| HK (1) | HK20583A (en) |
| IE (1) | IE46174B1 (en) |
| IL (1) | IL53476A (en) |
| IT (1) | IT1114690B (en) |
| MX (1) | MX148202A (en) |
| NL (1) | NL182266C (en) |
| NO (1) | NO155318C (en) |
| SE (1) | SE443261B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU196533B (en) * | 1984-06-04 | 1988-11-28 | Ivan Lipovetz | Lead accumulator, preferably for long-lasting uniform employment |
| FR2682817A1 (en) * | 1991-10-22 | 1993-04-23 | Gorodskoi Studenchesko Molodez | Method of manufacture of an electrode for a lead accumulator and lead accumulator comprising such an electrode |
| CN107768672A (en) * | 2016-08-15 | 2018-03-06 | 深圳市光鼎超导精密技术有限公司 | Lead-acid battery said positive-pole plate structure |
| CN107768681A (en) * | 2016-08-15 | 2018-03-06 | 深圳市光鼎超导精密技术有限公司 | Lead-acid battery cathode harden structure |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB29228A (en) * | 1908-12-14 | |||
| FR655340A (en) * | 1927-05-24 | 1929-04-17 | Ig Farbenindustrie Ag | Manufacturing process for lead electrodes for accumulators |
| DE475242C (en) * | 1927-05-25 | 1929-04-22 | I G Farbenindustrie Akt Ges | Process for the production of accumulator plates |
| FR657502A (en) * | 1927-09-27 | 1929-05-23 | Ig Farbenindustrie Ag | Process for preparing negative electrodes for accumulators |
| DE746830C (en) * | 1941-07-23 | 1944-08-25 | Dr Med Max Riese | Electrode plate for electrical collectors |
| GB963760A (en) * | 1962-01-16 | 1964-07-15 | Chloride Batteries Ltd | Improvements relating to lead-acid type electric accumulators |
| DE1571926B2 (en) * | 1964-05-25 | 1973-12-06 | Ab Tudor, Stockholm | Lead accumulator |
| GB1307221A (en) * | 1969-01-20 | 1973-02-14 | Bosch Gmbh Robert | Lead plate batteries |
-
1977
- 1977-11-10 FR FR7733901A patent/FR2380645A1/en active Granted
- 1977-11-11 DE DE2750596A patent/DE2750596C3/en not_active Expired
- 1977-11-23 CA CA291,524A patent/CA1090878A/en not_active Expired
- 1977-11-28 IE IE2410/77A patent/IE46174B1/en unknown
- 1977-11-28 NO NO774065A patent/NO155318C/en unknown
- 1977-11-28 CH CH1451377A patent/CH636483A5/en not_active IP Right Cessation
- 1977-11-28 IL IL53476A patent/IL53476A/en unknown
- 1977-11-29 SE SE7713522A patent/SE443261B/en not_active IP Right Cessation
- 1977-12-02 IT IT30354/77A patent/IT1114690B/en active
- 1977-12-05 AU AU31206/77A patent/AU517857B2/en not_active Expired
- 1977-12-08 MX MX171621A patent/MX148202A/en unknown
- 1977-12-09 BR BR7708182A patent/BR7708182A/en unknown
- 1977-12-12 CS CS778311A patent/CS214885B2/en unknown
- 1977-12-14 NL NLAANVRAGE7713836,A patent/NL182266C/en not_active IP Right Cessation
-
1978
- 1978-01-13 AT AT0024478A patent/AT368323B/en not_active IP Right Cessation
- 1978-01-25 GB GB3097/78A patent/GB1597033A/en not_active Expired
- 1978-10-02 ES ES473868A patent/ES473868A1/en not_active Expired
-
1983
- 1983-06-23 HK HK205/83A patent/HK20583A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU517857B2 (en) | 1981-09-03 |
| CH636483A5 (en) | 1983-05-31 |
| IT1114690B (en) | 1986-01-27 |
| DE2750596B2 (en) | 1980-07-03 |
| AU3120677A (en) | 1979-06-14 |
| GB1597033A (en) | 1981-09-03 |
| FR2380645A1 (en) | 1978-09-08 |
| SE443261B (en) | 1986-02-17 |
| AT368323B (en) | 1982-10-11 |
| NL7713836A (en) | 1978-08-17 |
| NO774065L (en) | 1978-08-16 |
| ES473868A1 (en) | 1979-07-16 |
| IE46174L (en) | 1978-08-15 |
| SE7713522L (en) | 1978-08-16 |
| FR2380645B1 (en) | 1983-08-26 |
| NL182266C (en) | 1988-02-01 |
| BR7708182A (en) | 1979-07-03 |
| IL53476A (en) | 1982-04-30 |
| IE46174B1 (en) | 1983-03-23 |
| MX148202A (en) | 1983-03-18 |
| DE2750596A1 (en) | 1978-09-07 |
| DE2750596C3 (en) | 1981-04-30 |
| ATA24478A (en) | 1982-01-15 |
| NO155318B (en) | 1986-12-01 |
| NL182266B (en) | 1987-09-01 |
| CS214885B2 (en) | 1982-06-25 |
| HK20583A (en) | 1983-07-01 |
| NO155318C (en) | 1987-03-11 |
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