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GB2117279A - A method of manufacturing a positive electrode for a lead acid electric storage cell - Google Patents

A method of manufacturing a positive electrode for a lead acid electric storage cell Download PDF

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Publication number
GB2117279A
GB2117279A GB08222739A GB8222739A GB2117279A GB 2117279 A GB2117279 A GB 2117279A GB 08222739 A GB08222739 A GB 08222739A GB 8222739 A GB8222739 A GB 8222739A GB 2117279 A GB2117279 A GB 2117279A
Authority
GB
United Kingdom
Prior art keywords
positive electrode
lead dioxide
lead
electric storage
storage cell
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.)
Withdrawn
Application number
GB08222739A
Inventor
Dr Patrick Timothy Moseley
Nevill Bridger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Atomic Energy Authority
Original Assignee
UK Atomic Energy Authority
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB08208326A external-priority patent/GB2117278A/en
Application filed by UK Atomic Energy Authority filed Critical UK Atomic Energy Authority
Priority to GB08222739A priority Critical patent/GB2117279A/en
Priority to EP83301558A priority patent/EP0089842B1/en
Priority to DE198383301558T priority patent/DE89842T1/en
Priority to CA000424027A priority patent/CA1199059A/en
Priority to DE8383301558T priority patent/DE3381915D1/en
Priority to GB08307762A priority patent/GB2124521B/en
Priority to US06/477,776 priority patent/US4507855A/en
Publication of GB2117279A publication Critical patent/GB2117279A/en
Withdrawn legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/14Electrodes for lead-acid accumulators
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01GWEIGHING
    • G01G21/00Details of weighing apparatus
    • G01G21/02Arrangements of bearings
    • G01G21/08Bearing mountings or adjusting means therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A positive electrode 10 for a lead acid electric storage cell 24 (Fig. 2) is made by chemically preparing lead dioxide. The lead dioxide is then applied to a support structure 14 with a binder, or poured into a permeable, tubular container located about a current collecting rod. <IMAGE>

Description

SPECIFICATION A method of manufacturing a positive electrode for a lead acid electric storage cell This invention relates to a lead acid electric storage cell, and more particularly to a method of manufacturing a positive electrode therefor.
In a well known method of manufacturing a positive electrode for a lead acid electric storage cell, lead monoxide (PbO) is mixed with water and sulphuric acid to form an active mass which is then pressed into a lead grid. The grid with the active mass is subsequently held in an environment of controlled humidity for 2-3 days - the "curing" process, and then subjected to a low charging current for a further 2-3 days to convert the active mass electrochemically to lead dioxide (PbO2) - the "formation" process. This known method is time consuming and relatively costly, and thus the invention is concerned with providing an alternative, much shorter method of manufacturing the positive electrode.
According to the present invention, a method of manufacturing a positive electrode for a lead acid electric storage cell comprises, chemically preparing particulate lead dioxide, and supporting the lead dioxide with a carrier therefor adapted to be located in the cell.
The carrier may comprise a permeable, electrically insulating, tubular container for the lead dioxide, into which container a current collecting means extends. Alternatively, the carrier may comprise an electrically conductive support structure.
Preferably, the lead dioxide is manufactured by reacting Pb304 with (3-6)M nitric acid at a temperature of about 950C.
The method may include mixing with the lead dioxide a particulate, electrically conductive material inert to the electrochemical reactions inside the cell. In some applications of the invention the lead dioxide may be mixed with a binder therefor, the binder preferably comprising polytetrafluoroethylene (hereinafter referred to as "PTFE") but desirably not exceeding 20% by weight of the mixture. However, the proportion of lead dioxide in the mixture is,desirably at least 50% by weight.
The positive electrode may with some advantage be subjected to an initial relatively short electric charge, to improve the electrical capacity of the positive electrode.
It will be understood that the invention includes a positive electrode made by the method of the invention, and also includes a lead acid electric storage cell incorporating said positive electrode.
The invention will be further described by way of example only with reference to the accompanying drawings, in which.~ Figure 1 shows a partly broken away side view of a representation Of a positive electrode for a lead acid electric storage cell; Figure 2 shows a diagrammatic sectional representation of a lead acid electric storage cell including the positive electrode of Figure 1; and Figure 3 shows a graphical representation of a charge/discharge cycle of the positive electrode of Figure 1.
Referring now to Figure 1, a positive electrode 10 shown comprises, a conventional lead support grid 14 having a multiplicity of rectangular recesses 16 and to both sides of which (only one is shown in Figure 1) active material 18 has been applied. A tab 20 of the support grid 14 provides a terminal for current collection when, as shown in Figure 2, the positive electrode 10 is incorporated in an electric cell 24 having a spongy lead negative electrode 26 and containing sulphuric acid as an electrolyte 28.
The active material 18 comprises lead dioxide mixed with PTFE as an inert binder. The active material 18 can be made by suspending red lead (Pb304) in nitric acid (3-6)M at a temperature of between about 80#1000C, preferably about 950C, the lead dioxide particulate product subsequently being filtered and washed. The lead dioxide is then mixed with an aqueous slurry of PTFE, for example ICI "FLUON" Grade GP 1, and the mixture pressed about the sides of the support grid 14 to form the positive electrode 10. In some applications graphite powder, for example Hopkins s Williams No.
445000, might be mixed with the lead dioxide and PTFE.
Some results obtained using positive electrodes 10 of different compositions are shown in Table 1 below: TABLE 1 Composition (grammes) Discharge Capacity Percentage of Lead Dioxide PTFE Graphite Theoretical Capacity 24 8 7 15 24 5 0 12 48 10 18 4 During subsequent cycling of about 40 deep discharge/charge cycles, the discharge capacities remained substantially constant, and the active material 18 adhered well to the support grid 14. A typical discharge/charge cycle for the positive electrode 10 is illustrated in Figure 3 to which reference, may be made.
The effect on discharge capacity of varying the temperature of the nitric acid when forming the lead dioxide can be seen in Table 2 below.~ TABLE 2 Nitric Acid Temperature Time at Discharge Capacity Strength of Nitric Temperature Percentage of (M) Acid (mins) Theoretical Capacity 5 95 15 15 6 95 15 16 3 95 15 18 5 80 15 8 5 100 15 14 In each of the examples in Table 2, the active material 18 comprised 1 7 grammes chemically prepared lead dioxide, 7 grammes graphite powder, and 10 grammes PTFE. It can be observed that an optimum temperature is reached at about 950C. In each example the grain size of the lead dioxide was of the order of 500A.
The proportion of the PTFE in the active material 15 may be varied without affecting the discharge capacity of the active material 1 8 to any significant extent, as shown in Table 3 below.
TABLE 3 Percentage by Discharge Capacity Percentage by Weight Graphite Percentage of Weight PTFE Powder Theoretical Capacity 0 19 19* 2 20 19 3 20 12 5 20 9 10 20 13 20 20 15 * The active material 18 was shed from the support grid 14 after one complete cycle. However even a relatively low proportion (e.g. 0.2% by weight) of PTFE has been found sufficient to retain the active material 18 on the support grid 14 during cycling.
As an alternative to mixing the chemically prepared lead dioxide with the PTFE and the graphite powder to form an active mass 1 8 to be applied to a support grid 14, the lead dioxide may be used in the well known tubular plate (or Ironclad) lead acid electric storage battery - see for example, "Standard Handbook for Electrical Engineers", pp. 24-3 and 4, 1 0th Edition, published by the McGraw-Hill Book Company, and incorporated by reference herein. In the tubular plate battery, a plurality of parallel lead alloy current collecting rods integral with a cross-piece project vertically downwards into respective permeable tubular containers filled with lead dioxide to form a positive electrode. The tubular containers are usually made from woven glass filaments, or from woven or sintered plastics material, such as Terylene polyester or PTFE. Thus the lead dioxide is poured into the annular space between the container wall and the current collecting rod in each tubular container.
It has been observed that variations in the discharge capacity of the positive electrode may be influenced by differences in the microstructure of the active material 18.

Claims (14)

1. A method of manufacturing a positive electrode for a lead acid electric storage cell, comprising chemically preparing particulate lead dioxide, and supporting the lead dioxide with a carrier therefor adapted to be located in the cell.
2. A method as claimed in Claim 1, wherein the carrier comprises a permeable, electrically insulating tubular container for the lead dioxide, and into which container a current collecting means extends.
3. A method as claimed in Claim 1, wherein the carrier comprises an electrically conductive support structure.
4. A method as claimed in any one of the preceding claims, wherein the lead dioxide is mixed with a binder therefor.
5. A method as claimed in Claim 4, wherein the binder comprises PTFE.
6. A method as claimed in Claim 5, wherein the PTFE does not exceed more than 20% by weight of the mixture.
7. A method as claimed in Claim 6, wherein the PTFE does not exceed 2% by weight of the mixture.
8. A method as claimed in any one of the preceding claims, wherein the lead dioxide is mixed with a particulate, electrically conductive material inert to the electrochemical reactions inside the cell.
9. A method as claimed in Claim 8, wherein the conductive material comprises graphite powder.
10. A method as claimed in Claim 8 or Claim 9, wherein the proportion of said lead dioxide is at least 50% by weight of the mixture.
11. A method as claimed in any one of the preceding claims, wherein the lead dioxide is prepared by reacting Pb304 with (3-6)M nitric acid at a temperature of about 950C.
12. A positive electrode manufactured by the method as claimed in any one of the preceding claims.
13. A lead acid electric storage cell incorporating the positive electrode of Claim 12.
14. A lead acid electric storage cell substantially as hereinbefore described with reference to Figures 1 to 3 of the accompanying drawings.
GB08222739A 1982-03-22 1982-08-06 A method of manufacturing a positive electrode for a lead acid electric storage cell Withdrawn GB2117279A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
GB08222739A GB2117279A (en) 1982-03-22 1982-08-06 A method of manufacturing a positive electrode for a lead acid electric storage cell
EP83301558A EP0089842B1 (en) 1982-03-22 1983-03-21 Lead acid electric storage cell and a positive electrode therefor
DE198383301558T DE89842T1 (en) 1982-03-22 1983-03-21 BLEISAURE ELECTRICAL STORAGE CELL AND POSITIVE ELECTRODE DAFUER.
CA000424027A CA1199059A (en) 1982-03-22 1983-03-21 Lead acid electric storage cell and a positive electrode therefor
DE8383301558T DE3381915D1 (en) 1982-03-22 1983-03-21 BLEISAURE ELECTRICAL STORAGE CELL AND POSITIVE ELECTRODE DAFUER.
GB08307762A GB2124521B (en) 1982-03-22 1983-03-21 Lead acid electric storage cell and a method of manufacturing a positive electrode therefor
US06/477,776 US4507855A (en) 1982-08-06 1983-03-22 Lead acid electric storage cell and a positive electrode therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB08208326A GB2117278A (en) 1982-03-22 1982-03-22 A method of manufacturing a positive electrode for a lead acid electric storage cell
GB08222739A GB2117279A (en) 1982-03-22 1982-08-06 A method of manufacturing a positive electrode for a lead acid electric storage cell

Publications (1)

Publication Number Publication Date
GB2117279A true GB2117279A (en) 1983-10-12

Family

ID=26282327

Family Applications (1)

Application Number Title Priority Date Filing Date
GB08222739A Withdrawn GB2117279A (en) 1982-03-22 1982-08-06 A method of manufacturing a positive electrode for a lead acid electric storage cell

Country Status (1)

Country Link
GB (1) GB2117279A (en)

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