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WO2000076013A1 - Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe - Google Patents

Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe Download PDF

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Publication number
WO2000076013A1
WO2000076013A1 PCT/IT2000/000229 IT0000229W WO0076013A1 WO 2000076013 A1 WO2000076013 A1 WO 2000076013A1 IT 0000229 W IT0000229 W IT 0000229W WO 0076013 A1 WO0076013 A1 WO 0076013A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
liquid
electrolyte
environment
external
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/IT2000/000229
Other languages
English (en)
Inventor
Fernando Zocchi
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.)
Ala Elettronica Srl Also Known As Ala Elettronica Srl
Consiglio Nazionale delle Richerche CNR
Original Assignee
Ala Elettronica Srl Also Known As Ala Elettronica Srl
Consiglio Nazionale delle Richerche CNR
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 Ala Elettronica Srl Also Known As Ala Elettronica Srl, Consiglio Nazionale delle Richerche CNR filed Critical Ala Elettronica Srl Also Known As Ala Elettronica Srl
Priority to EP00940740A priority Critical patent/EP1188194A1/fr
Priority to AU55638/00A priority patent/AU5563800A/en
Priority to CA002375418A priority patent/CA2375418A1/fr
Publication of WO2000076013A1 publication Critical patent/WO2000076013A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/317—Re-sealable arrangements
    • H01M50/325—Re-sealable arrangements comprising deformable valve members, e.g. elastic or flexible valve members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/383—Flame arresting or ignition-preventing means
    • 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

  • the present invention relates to batteries for underwater use provided with liquid means for separating the internal electrochemical environment and the external liquid environment therebetween.
  • Primary batteries as well as storage batteries, can be used as power sources in underwater engineering, to operate motors, for lighting, to power-feed electrical apparatuses and the like.
  • secondary (storage) batteries mainly of the lead/sulphuric acid type, and in some instances nickel-iron or nickel-cadmium batteries having an alkaline electrolyte, are widely used.
  • Non-sealed batteries have plugs provided with a gas vent. Both battery types, although provided with satisfactorily insulated liquid-tight clips, cannot directly be immersed at sea or lake depths, as salty, brackish or fresh water would enter the non-sealed batteries, entailing the leaking of the electrolyte, whereas sealed batteries would collapse under the external environment pressure. Both instances would entail a voltage drop and a permanent damage of the electrodes, not to mention the relevant environmental damage. Therefore, the state of the art discloses the use of heavy and expensive steel casings, containing, in case of non-sealed batteries, platinum catalysts for hydrogen and oxygen recombination.
  • the subject matter of the present invention is a system that provides the filling of the recess located above the electrolyte of the cell units of a battery with a liquid meeting specific requisites.
  • An object of the present invention is that of providing an arrangement for liquid electrolyte batteries allowing the immersion thereof even at great depths, without the occurrence of the above-mentioned drawbacks, up to date solely avoidable by means of costly devices .
  • an assembly exploiting the near-incompressibility of the liquids and using a non-ionised liquid separating layer, non-reactive with the battery electrolyte and with the aqueous environment.
  • the separating layer is arranged in the recess located above the electrolyte solution level in the cell units of the battery, thereby allowing the assembly to be pressurised even at great depths due to the immersion, without introducing significant stresses inside the battery casing.
  • FIG. 1 is a schematic view of a multiple-cell or element battery provided with liquid separating means (layer) according to the invention and with free apertures, at the top of the individual cell units, communicating with the external liquid environment
  • FIG. 2 is a schematic view analogous to that of FIG. 1 and referring to a second embodiment, in which check valves are provided at the apertures at the top of the individual cells or cell units, toward the external liquid environment
  • FIG. 3 shows a third embodiment of a battery assembly in which a manifold is provided between the vents of the individual cell units of the battery, the manifold being provided, at the top portion thereof, with a check valve at an individual aperture communicating with the external liquid environment;
  • FIG. 4 schematically shows a further embodiment of the battery according to the present invention, in which a multiple-cell battery is housed into a container filled up with the liquid separating means (layer) and the container being provided, at the top portion thereof, with a check valve at an individual aperture communicating with the external liquid environment;
  • FIGS. 5, 6 and 7 show voltage/time charts for batteries according to the invention under a closed circuit voltage condition.
  • the object of the present invention is based on the liquid near-incompressibility principle, and it provides a liquid separating layer according to the already outlined conditions.
  • the liquid separating layer performs the following tasks : a) it allows the escape of the gases evolved within the battery towards the external environment; b) it avoids short circuit current between the electrodes of different battery cells.
  • the electrolyte solution of the battery will be indicated with S
  • a liquid floating onto the solution S will be indicated with A
  • the water of the external environment (sea, lake, etc.)
  • E the densities of S
  • a and E will be indicated with d s , d A , d E , respectively.
  • d A can be lower or equal to d E (d A ⁇ d E ) .
  • FIGS. 1, 2, 3 and 4 show schematic views of such embodiments, that are to be construed as non-limiting illustrative examples of the invention itself .
  • FIGS. 1-3 are mere sketches, in which a highlighting of the thickness of the battery casing was omitted.
  • FIG. 1 schematically shows a longitudinal section of the battery according to a first embodiment thereof.
  • the battery comprises a casing, globally indicated with 10, partitioned into six cell units by partitions 11 extending from the bottom panel 12 of the battery to the top panel 13.
  • Positive and negative plates 14 and 15 are housed within the six cell units, in case spaced apart by known spacers, not shown.
  • the positive and negative plates 14, 15 are interconnected by jumpers 16, sealingly bridging the partitions 11.
  • the space described by the individual cell units or elements is filled up to a height hi with an electrolyte S.
  • the solution S is made of a H 2 0/H 2 S0 4 solution.
  • the electrolyte S is exposed to air which contains H 2 and is enriched with 0 2 , the various gas ratios thereof being variable and depending on the operating conditions of the battery, as it is well-known to those skilled in the art.
  • a liquid separating layer A of a thickness h 2 , non-ionised and non-reactive with the electrolyte S or with the external liquid environment (salty, brackish or fresh water) , is located on the electrolyte S.
  • the battery is also provided with terminals 17 and 18 for the connection to an electric load (not shown) and, if needed, to a well-known battery recharger.
  • the terminals 17 and 18 are insulated from the external environment, e.g., with silicone or epoxy resins.
  • elements 19 for communicating the layer A and the external environment E therebetween, comprising an expansion chamber 20 delimited by chokes 21 and 22, are located.
  • the communication elements 19 allow a pressure compensation of the external environment E with the internal environment of the battery S+A.
  • the presence of the chambers 20 and of the chokes 21 and 22 enables to prevent the external leaking of S+A in case the battery is tilted during the handling or the use.
  • the walls of the battery casing have to be elastic rather than stiff, in order to adapt to the volumetric changes in the battery content, essentially due to the volumetric changes of S+A at the increase of the external environment pressure.
  • 100 atm changes in the external pressure yield volumetric changes lower than 1%, typically of 0.4-0.5%.
  • liquids are not strictly incompressible, the compressibility value thereof depending on their nature.
  • different liquids such as E and the S+A complex could have slightly different compressibility, and also the volumetric changes due to such differences are assessable at 0.4-0.5% for pressure changes equal to 100 atm, therefore such as to easily be compensated by the elasticity of the walls of the battery casing.
  • a cubic battery having a 20 cm corner would undergo linear dimension changes in the order of the millimetre.
  • non-stiff walls are not required for the battery casing, since, according to the Pascal principle, the internal pressure of each individual cell battery equals that of the external environment .
  • check valves Vi, V ⁇ arranged so as to allow the escape of the gases that might evolve from the electrodes 14 and 15 during the battery operation, while preserving the hydrostatic balance among S, A, and E as already indicated, are provided.
  • the top end of the elements 19 is connected to a manifold pipe network, globally indicated with 23, provided with branches, 24, 25, 26, 27, 28, 29, converging towards a common connection spot 30, at which a check valve VK, having the same purpose of the valves V x , ... V 6 of FIG. 2, is arranged.
  • the arrangement of the various branchings allows the gas produced from the battery to converge to the collection vertex 30.
  • the casing of the battery 10 is accommodated within a watertight case 31.
  • Said watertight case 31 is provided with a perimetric lip 32 registered with a corresponding perimetric lip 33 onto the bottom portion of an upwards-tapered pyramid-shaped element 34 for collecting the gases evolved at the electrodes 14 and 15 of the various cell units of the battery.
  • a check valve VN is located at the apex of the pyramid-shaped element 34 .
  • a seal 35 is located at the lips 32 and 33, fastened therebetween with bolts 36.
  • seal feedthroughs 37 and 38 for the passage of connection cables to the terminals 17 and 18 of the battery are provided.
  • the entire space around and above the battery casing 10, as well as the space over the electrolyte S is filled up with the separating liquid A, having the already described characteristics and that will hereinafter be better detailed.
  • the battery housed within the case 31 as shown in FIG. 4 could be replaced by a number of batteries.
  • the liquid forming the separating layer A (liquid separating means) between the electrolyte S and the external environment E will hereinafter be disclosed.
  • the liquid A must be non-ionised in order to be insulating.
  • the density of the electrolyte solution of a lead/sulphuric acid battery depends on the battery type and charge.
  • the electrolyte density in an electric car battery during the discharge ranges from 1.33 to 1.21 g/ml
  • the density in a battery for stationary plants ranges from 1.225 to 1.08 g/ml.
  • the density in a nickel-iron battery with an alkaline electrolyte (20-30% KOH, 50 g/1 LiOH) the density usually exceeds 1.16 g/ml.
  • a separating liquid A having a density ranging from 1.04 to 1.07 g/ml, immiscible with aqueous solutions and non-reactive in an acidic or alkaline environment proves to be an all-purpose separating liquid for storage batteries with an acidic or alkaline electrolyte, to be used according to the embodiment sketched in FIG. 1.
  • a liquid A, immiscible and non reactive with the electrolyte solution, having a density smaller than the minimum density evidenced by said solution during the discharge process, yet greater than that of the external environment water can always be found.
  • Substances useful as separating liquid A, covering the electrolyte solution, in the embodiment of FIG. 1 can be selected also from the following substance classes: chlorinated hydrocarbons, like, e.g., 1,1,1- trichloroethane, chlorobenzene, 1,1,2,2- tetrachloroethane, 1, 2-dichlorobenzene, carbon tetrachloride, trichloroethylene, 2-chlorotoluene, 4- chlorotoluene; bromidrated hydrocarbons, like, e.g., 1-bromodecane, bromobenzene, 1-bromohexane, bromocyclohexane; nitroderivatives of hydrocarbons, like, e.g., nitrobenzene; silicones, like, e.g., the silicone oil 710.
  • chlorinated hydrocarbons like, e.g., 1,1,1- trichloroethane, chlorobenzene, 1,1,
  • check valves are provided, preventing the external environment water from entering the battery, as a covering liquid A, besides the substances belonging to the above-mentioned groups, immiscible and non-reactive liquids, the density of which being lower than that of the external environment water, like, e.g., a hydrocarbon mixture like oil, naphtha, kerosene, Nujol or liquid paraffin, (with a density being generally comprised in the range 0.76-0.88 g/ml) or their mixtures can suitably be utilised.
  • the discharge curves, i.e. the CCV (closed circuit voltage) versus time, of some batteries available on the market modified according to the present invention are shown in FIGS. 5-7.
  • FIG. 5-7 The discharge curves, i.e. the CCV (closed circuit voltage) versus time, of some batteries available on the market modified according to the present invention are shown in FIGS. 5-7.
  • FIG. 5-7 The discharge curves, i.e. the CCV (
  • FIG. 5 shows the discharge of a 12V/35Ah lead/sulphuric acid battery, connected to a water-cooled 0.33 ohm/300 W load resistor, the electrolyte solution thereof having been covered according to the embodiment of FIG. 1 with a liquid mixture of several substances belonging to the aforementioned groups, by way of demonstration of the compatibility of said substances with the electrolyte.
  • FIG. 6 shows the discharge of a 1.3V/5Ah nickel-iron battery connected to a 1.74 ohm/4 W load resistor
  • FIG. 7 shows the discharge of a cadmium-nickel battery, made of seven 1.2V/3Ah cell units, connected to a 12 ohm/20 W load resistor. Both batteries were of the alkaline electrolyte type, and were filled with liquid paraffin according to the embodiments of FIGS. 2 and 4, respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Filling, Topping-Up Batteries (AREA)

Abstract

L'invention concerne une batterie pour utilisation sous-marine, comprenant une pluralité d'éléments, chacun d'eux ayant une électrode positive (14) et une électrode négative (15) dans un électrolyte liquide, caractérisée en ce que lesdits éléments sont des séries connectées, et en ce que chaque élément comporte une ouverture (19) communiquant avec l'environnement liquide externe (E), et en ce qu'il est prévu des moyens liquides (A) pour la séparation de l'électrolyte et de l'environnement liquide externe, lesdits moyens liquides comprenant un liquide non ionisé, ne réagissant pas avec ledit électrolyte ainsi qu'avec ledit environnement liquide externe.
PCT/IT2000/000229 1999-06-03 2000-06-05 Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe Ceased WO2000076013A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP00940740A EP1188194A1 (fr) 1999-06-03 2000-06-05 Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe
AU55638/00A AU5563800A (en) 1999-06-03 2000-06-05 Underwater batteries provided with liquid separating means between internal electrochemical environment and external liquid environment
CA002375418A CA2375418A1 (fr) 1999-06-03 2000-06-05 Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM99A000355 1999-06-03
IT1999RM000355A IT1306570B1 (it) 1999-06-03 1999-06-03 Batterie elettriche per impiego subacqueo munite di mezzi liquidi diseparazione tra ambiente elettrochimico interno e ambiente liquido

Publications (1)

Publication Number Publication Date
WO2000076013A1 true WO2000076013A1 (fr) 2000-12-14

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Application Number Title Priority Date Filing Date
PCT/IT2000/000229 Ceased WO2000076013A1 (fr) 1999-06-03 2000-06-05 Batteries sous-marines munies de moyens de separation entre l'environnement electrochimique interne et l'environnement liquide externe

Country Status (5)

Country Link
EP (1) EP1188194A1 (fr)
AU (1) AU5563800A (fr)
CA (1) CA2375418A1 (fr)
IT (1) IT1306570B1 (fr)
WO (1) WO2000076013A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2218632C1 (ru) * 2002-04-25 2003-12-10 Федеральное Государственное Унитарное Предприятие "Санкт-Петербургское Морское Бюро Машиностроения "Малахит" Погружная аккумуляторная батарея
EP1998344A1 (fr) * 2007-05-29 2008-12-03 Siemens Aktiengesellschaft Composant électronique, en particulier un condensateur, pour des applications dans des environnements haute pression
WO2014139710A1 (fr) * 2013-03-11 2014-09-18 Robert Bosch Gmbh Système de dégazage pour modules de batterie

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553018A (en) * 1968-09-26 1971-01-05 Esb Inc Pressure equalized deep submergence battery having gas bubble-electrolyte scrubbing means beneath the cover
US3589940A (en) * 1968-09-26 1971-06-29 Esb Inc Deep submergence battery having gas bubble-electrolyte scrubbing vent cap
US3925592A (en) * 1973-03-15 1975-12-09 British Petroleum Co Holder for electrical equipment
US5876872A (en) * 1996-11-08 1999-03-02 Feezor; Michael D. Underwater rechargeable battery and method of manufacture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3553018A (en) * 1968-09-26 1971-01-05 Esb Inc Pressure equalized deep submergence battery having gas bubble-electrolyte scrubbing means beneath the cover
US3589940A (en) * 1968-09-26 1971-06-29 Esb Inc Deep submergence battery having gas bubble-electrolyte scrubbing vent cap
US3925592A (en) * 1973-03-15 1975-12-09 British Petroleum Co Holder for electrical equipment
US5876872A (en) * 1996-11-08 1999-03-02 Feezor; Michael D. Underwater rechargeable battery and method of manufacture

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2218632C1 (ru) * 2002-04-25 2003-12-10 Федеральное Государственное Унитарное Предприятие "Санкт-Петербургское Морское Бюро Машиностроения "Малахит" Погружная аккумуляторная батарея
EP1998344A1 (fr) * 2007-05-29 2008-12-03 Siemens Aktiengesellschaft Composant électronique, en particulier un condensateur, pour des applications dans des environnements haute pression
WO2008145639A1 (fr) * 2007-05-29 2008-12-04 Siemens Aktiengesellschaft Condensateur arrangé dans un environnement haute pression
US8400756B2 (en) 2007-05-29 2013-03-19 Siemens Aktiengesellschaft Capacitor arranged in a high pressure environment
WO2014139710A1 (fr) * 2013-03-11 2014-09-18 Robert Bosch Gmbh Système de dégazage pour modules de batterie
CN105027323A (zh) * 2013-03-11 2015-11-04 罗伯特·博世有限公司 用于电池模块的排气系统

Also Published As

Publication number Publication date
ITRM990355A1 (it) 2000-12-03
EP1188194A1 (fr) 2002-03-20
IT1306570B1 (it) 2001-06-18
ITRM990355A0 (it) 1999-06-03
AU5563800A (en) 2000-12-28
CA2375418A1 (fr) 2000-12-14

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