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WO2005081354A1 - A method of manufacturing a battery - Google Patents

A method of manufacturing a battery Download PDF

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Publication number
WO2005081354A1
WO2005081354A1 PCT/GB2005/000574 GB2005000574W WO2005081354A1 WO 2005081354 A1 WO2005081354 A1 WO 2005081354A1 GB 2005000574 W GB2005000574 W GB 2005000574W WO 2005081354 A1 WO2005081354 A1 WO 2005081354A1
Authority
WO
WIPO (PCT)
Prior art keywords
pgm
battery
hydrogen storage
hydrogen
storage alloy
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.)
Ceased
Application number
PCT/GB2005/000574
Other languages
French (fr)
Inventor
David Alan Boyd
Allin Sidney Pratt
David Benjamin Willey
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.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of WO2005081354A1 publication Critical patent/WO2005081354A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • H01M4/385—Hydrogen absorbing alloys of the type LaNi5
    • 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

Definitions

  • a METHOD OF MANUFACTURING A BATTERY The present invention concerns the activation of batteries of the hydrogen-storage type.
  • PGM platinum group metal
  • WO98/50968 discloses PGM loadings of 0.02 to about 8wt%, preferably from
  • the present invention provides a method of manufacturing a battery comprising assembling a hydrogen storage battery using dry hydrogen storage alloy or pasted hydrogen storage alloy to construct a hydrogen storage alloy electrode, filling the assembled battery with electrolyte, and sealing and charging the battery wherein hydrogen is generated at the surface of the hydrogen storage alloy electrode during charging and is stored within the alloy bulk by diffusion, characterised in that the electrolyte comprises one or more reducible PGM precursor compound.
  • the charging procedure generates hydrogen which is stored within the hydrogen storage alloy.
  • the invention further provides a battery-filling composition comprising an electrolyte of an alkali metal hydroxide, optionally KOH or NaOH, solution in combination with an effective amount of one or more reducible PGM precursor compound.
  • the PGM precursor compounds may be capable of being reduced by hydrogen to metallic PGM form.
  • the PGM precursor compounds may be selected from one or more of Pd, Ru and Pt compounds.
  • the method of the invention permits reduction of the PGM-precursor compound in situ to form discontinuous PGM metal deposits on the hydrogen storage alloy. Accordingly, the actual battery manufacturing method is unchanged, permitting easy integration into conventional manufacturing lines.
  • the PGM precursor will be reduced at the available (i.e. wetted) surface of the hydrogen storage alloy electrode during charging, at the most active sites.
  • the method of the invention permits the activation by PGM of the outer surface of the electrode; this permits a minimisation of PGM usage, and avoids PGM deposits being buried within the electrode. It is believed that activation at the surface is completely adequate since hydrogen diffusion within the bulk of the electrode is extremely fast.
  • Suitable hydrogen storage alloy electrode materials may be selected from AB 5 , AB 2 or AB battery alloys, e.g. LaNi 5 , Al doped LaNi 5 , CeNi 5 , Al doped CeNis, CaNi 5 , Mn doped CaNi 5 , ZrV 2 , Zr(V 0 . 3 3Ni 0 . 67 ) 2 , TiNMn, Zr doped TiCrMn, Zr doped TiCr 2 , Co doped TiN 2 , Ti ⁇ i, TiMn, TiFe, TiZr, Ti(MnN) and Ti(MnCr).
  • Electrodes for hydrogen storage batteries are typically made using either ⁇ i or a PTFE/carbon mix to cause the particles of hydrogen storage alloy to bond under pressure together or to bond under pressure to a substrate such as porous ⁇ i.
  • the ⁇ i or PTFE/carbon mix tends to fill pores between the hydrogen storage alloy particles, thus reducing ingress of the electrolyte comprising PGM precursor compound(s), and promoting the deposition of metallic PGM and reduced PGM compound(s) on the outermost surface of the electrode.
  • a battery filling composition comprising an alkali metal hydroxide electrolyte solution in admixture with the appropriate quantity of PGM precursor compound is used.
  • Suitable compositions cannot readily be defined in terms of wt%, because of widely different battery designs and requirements but may probably best be described as being sufficient to give a desired PGM loading in terms of mg/m 2 of geometric electrode area.
  • the surface concentration may be in a range equivalent to 0.02 to 2 wt% of PGM in the bulk alloy.
  • the level of PGM surface concentration will vary with application and intended operating regime.
  • the present invention is flexible enough to permit improved activation across the range of applications, and an appropriate loading for a given battery design and for specific power/charge/discharge requirements may be determined by conventional optimisation techniques.
  • PGM metal concentrations may suitably be in the ranges for the above varied types of battery of 0.2 to 4.0 g/m 2 PGM, which might be 0.1 to 2.0 g/m 2 for each of two PGMs or some other mix of two or more PGMs.
  • Precursor compounds may be selected for their solubility in the solvent being used for the electrolyte, for example an aqueous medium containing, optionally, KOH or NaOH. Examples include:
  • Pd(diaminoethane) 2 Cl 2 also known as Pd(en) Cl 2 H 2 Pt(OH) 6 Pt(NO 3 ) 2 Ru(NO)(NO 3 ) Ru(NO)Cl
  • PGM precursor compounds are usually chosen from palladium, ruthenium and platinum systems and may be used singly, in pairs or together.
  • Typical compositions comprise Pd Ru, Pt/Ru and Pd Pt. Of these, in one particular embodiment, the Pd/Ru pair is used with the Pd to Ru ratio range from 1 : 10 to 1 :1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A method of manufacturing a battery comprises assembling a hydrogen storage battery using dry hydrogen storage alloy or pasted hydrogen storage alloy to construct a hydrogen storage alloy electrode, filling the assembled battery with electrolyte, and sealing and charging the battery, wherein hydrogen is generated at the surface of the hydrogen storage alloy electrode during charging and is stored within the alloy bulk by diffusion, characterised by the electrolyte comprising one or more reducible platinum group metal ('PGM') precursor compounds.

Description

A METHOD OF MANUFACTURING A BATTERY The present invention concerns the activation of batteries of the hydrogen-storage type.
We have previously described novel platinum group metal ("PGM") interface- activated hydride-forming metallic particles in WO98/50968. Such activated materials particularly show improved performance in batteries in charging and discharging. The methods of activation disclosed therein are effective to deposit a discontinuous or partial deposit of one or more PGMs on hydride-forming metallic particles such as AB5, AB2 or AB. Desirably, hydrogen is introduced into the metal particles, then the hydrogen-loaded particles are contacted with a solution of the PGM and the composition is dehydrogenated. The particles may then be pasted up and made into the hydrogen electrode of a battery in the conventional manner. (Throughout this description and claims, the term "battery" is used as being the commonly used expression instead of "cell".) WO 98/50968 discloses PGM loadings of 0.02 to about 8wt%, preferably from
0.08 to about 2wt%.
It would be desirable to develop methods of activation that are easy and safe to incorporate into conventional battery manufacturing processes and which offer the possibility to minimise the usage of expensive PGMs and avoid the costs associated with the activation step as described in WO98/50968.
Accordingly, the present invention provides a method of manufacturing a battery comprising assembling a hydrogen storage battery using dry hydrogen storage alloy or pasted hydrogen storage alloy to construct a hydrogen storage alloy electrode, filling the assembled battery with electrolyte, and sealing and charging the battery wherein hydrogen is generated at the surface of the hydrogen storage alloy electrode during charging and is stored within the alloy bulk by diffusion, characterised in that the electrolyte comprises one or more reducible PGM precursor compound. The charging procedure generates hydrogen which is stored within the hydrogen storage alloy. The invention further provides a battery-filling composition comprising an electrolyte of an alkali metal hydroxide, optionally KOH or NaOH, solution in combination with an effective amount of one or more reducible PGM precursor compound. The PGM precursor compounds may be capable of being reduced by hydrogen to metallic PGM form. The PGM precursor compounds may be selected from one or more of Pd, Ru and Pt compounds.
It is believed that the method of the invention permits reduction of the PGM-precursor compound in situ to form discontinuous PGM metal deposits on the hydrogen storage alloy. Accordingly, the actual battery manufacturing method is unchanged, permitting easy integration into conventional manufacturing lines.
Further, it is believed that the PGM precursor will be reduced at the available (i.e. wetted) surface of the hydrogen storage alloy electrode during charging, at the most active sites. Thus the method of the invention permits the activation by PGM of the outer surface of the electrode; this permits a minimisation of PGM usage, and avoids PGM deposits being buried within the electrode. It is believed that activation at the surface is completely adequate since hydrogen diffusion within the bulk of the electrode is extremely fast.
Suitable hydrogen storage alloy electrode materials may be selected from AB5, AB2 or AB battery alloys, e.g. LaNi5, Al doped LaNi5, CeNi5, Al doped CeNis, CaNi5, Mn doped CaNi5, ZrV2, Zr(V0.33Ni0.67)2, TiNMn, Zr doped TiCrMn, Zr doped TiCr2, Co doped TiN2, TiΝi, TiMn, TiFe, TiZr, Ti(MnN) and Ti(MnCr).
Electrodes for hydrogen storage batteries are typically made using either Νi or a PTFE/carbon mix to cause the particles of hydrogen storage alloy to bond under pressure together or to bond under pressure to a substrate such as porous Νi. The Νi or PTFE/carbon mix tends to fill pores between the hydrogen storage alloy particles, thus reducing ingress of the electrolyte comprising PGM precursor compound(s), and promoting the deposition of metallic PGM and reduced PGM compound(s) on the outermost surface of the electrode. Although it is feasible to fill the battery with electrolyte and separately fill, before or after the electrolyte, with PGM precursor compound, in a particular embodiment, a battery filling composition comprising an alkali metal hydroxide electrolyte solution in admixture with the appropriate quantity of PGM precursor compound is used. Suitable compositions cannot readily be defined in terms of wt%, because of widely different battery designs and requirements but may probably best be described as being sufficient to give a desired PGM loading in terms of mg/m2 of geometric electrode area. Suitably the surface concentration may be in a range equivalent to 0.02 to 2 wt% of PGM in the bulk alloy. Since battery design varies with the intended application from button cell design for high capacity low power applications and wound ("Swiss roll") cells for high power applications, the level of PGM surface concentration will vary with application and intended operating regime. The present invention is flexible enough to permit improved activation across the range of applications, and an appropriate loading for a given battery design and for specific power/charge/discharge requirements may be determined by conventional optimisation techniques.
PGM metal concentrations (rather than precursor compound concentrations) may suitably be in the ranges for the above varied types of battery of 0.2 to 4.0 g/m2 PGM, which might be 0.1 to 2.0 g/m2 for each of two PGMs or some other mix of two or more PGMs. Precursor compounds may be selected for their solubility in the solvent being used for the electrolyte, for example an aqueous medium containing, optionally, KOH or NaOH. Examples include:
Pd(diaminoethane)2Cl2 , also known as Pd(en) Cl2 H2Pt(OH)6 Pt(NO3)2 Ru(NO)(NO3) Ru(NO)Cl The PGM precursor compounds are usually chosen from palladium, ruthenium and platinum systems and may be used singly, in pairs or together. Typical compositions comprise Pd Ru, Pt/Ru and Pd Pt. Of these, in one particular embodiment, the Pd/Ru pair is used with the Pd to Ru ratio range from 1 : 10 to 1 :1. The invention will now be further described by way of illustration only, by reference to the following working examples.
Various Ru precursors were dissolved in 6M KOH solution. An initial assessment was performed by cyclic voltammetry using a typical AB5 battery alloy as an electrode, and the results plotted in Fig 1. The precursor compounds tested were:
Precursor No. Compound 1 ammonium trisoxalato Ru(III) 2 hydrogen trisoxalato Ru(III) 3 Ru(NO)(NO3) 4 Ru(NO)Cl 5 Ru((NH3)5Cl)Cl 2 6 Ru(NH3)6Cl3
Reviewing the plots, clearly precursor compounds Nos. 3 and 4 look most promising because of their lower overpotential. Similar tests were carried out for Pt (from hexahydroxyplatinic acid) and mixtures of Pt + Ru precursor compounds (from hexahydroxyplatinic acid and potassium ruthenate), and attached plots Figs 2 and 3 show the respective cyclic voltamograms, indicating the reduction peaks for Ru and Pt.
Sample commercial batteries were inoculated with precursor compound-loaded KOH and charged and then discharged. Fig 4 shows a typical discharge curve.

Claims

1. A method of manufacturing a battery comprising assembling a hydrogen storage battery using dry hydrogen storage alloy or pasted hydrogen storage alloy to construct a hydrogen storage alloy electrode, filling the assembled battery with electrolyte, and sealing and charging the battery, wherein hydrogen is generated at the surface of the hydrogen storage alloy electrode during charging and is stored within the alloy bulk by diffusion, characterised in that the electrolyte comprises one or more reducible platinum group metal ("PGM") precursor compound.
2. A method according to claim 1, wherein the or each reducible PGM precursor compound is capable of being reduced by hydrogen to metallic PGM form.
3. A method according to claim 1 or 2, wherein the hydrogen storage alloy electrode comprises an AB5, AB or AB battery alloy.
4. A method according to claim 1, 2 or 3, wherein the PGM precursor compound is a compound selected from compounds comprising one or more of Pd, Ru and Pt.
5. A method according to claim 4, wherein the battery is filled with an electrolyte comprising the PGM precursor in solution.
6. A method according to claim 5, wherein the electrolyte comprises a solution of an alkali metal hydroxide, optionally KOH or NaOH,
7. A method according to any one of the preceding claims, wherein the quantity of PGM precursor is such as to yield 0.02 to 2 wt% of metallic PGM measured in the bulk alloy.
8. A method according to any one of claims 1 to 6, wherein the quantity of PGM precursor is such as to give an amount of PGM in the form of a discontinuous surface deposit on the surface of the hydrogen storage alloy electrode totalling 0.2 to 4.0 gPGM/m2.
9. A battery-filling composition for use in a method according to any preceding claim comprising an alkali metal hydroxide, optionally KOH or NaOH, solution and one or more reducible PGM precursor compounds, capable of being reduced by hydrogen to metallic PGM form.
10. A battery-filling composition according to claim 9, wherein the or each reducible PGM precursor compound is capable of being reduced by hydrogen to metallic PGM form.
11. A battery-filling composition according to claim 9 or 10, wherein the or each reducible PGM precursor compound is selected from the group consisting of Pd(diaminoethane)2Cl2, H2Pt(OH)6, Pt(NO3)2, Ru(NO)(NO3) and Ru(NO)Cl.
12. A battery-filling composition according to claim 11, wherein the or each reducible PGM precursor compound comprises a combination of Pd/Ru, Pt/Ru or Pd/Pt.
13. A battery-filling composition according to claim 12, wherein the or each reducible PGM precursor compound comprises Pd/Ru with the Pd to Ru ratio ranging from 1:10 to 1:1.
PCT/GB2005/000574 2004-02-18 2005-02-18 A method of manufacturing a battery Ceased WO2005081354A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0403577.0 2004-02-18
GBGB0403577.0A GB0403577D0 (en) 2004-02-18 2004-02-18 Activation of batteries

Publications (1)

Publication Number Publication Date
WO2005081354A1 true WO2005081354A1 (en) 2005-09-01

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050968A1 (en) * 1997-05-01 1998-11-12 Johnson Matthey Public Limited Company Hydrogen storage materials

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050968A1 (en) * 1997-05-01 1998-11-12 Johnson Matthey Public Limited Company Hydrogen storage materials

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