CA1191544A - Halogen hydrate storage device for mobile zinc- chloride battery systems - Google Patents
Halogen hydrate storage device for mobile zinc- chloride battery systemsInfo
- Publication number
- CA1191544A CA1191544A CA000420731A CA420731A CA1191544A CA 1191544 A CA1191544 A CA 1191544A CA 000420731 A CA000420731 A CA 000420731A CA 420731 A CA420731 A CA 420731A CA 1191544 A CA1191544 A CA 1191544A
- Authority
- CA
- Canada
- Prior art keywords
- store
- cell
- gas
- electrolyte
- hydrate
- 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
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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/64—Constructional details of batteries specially adapted for electric vehicles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/015—Chlorine hydrates; Obtaining chlorine therefrom
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Sustainable Energy (AREA)
- Transportation (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Secondary Cells (AREA)
- Glass Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
HALOGEN HYDRATE STORAGE DEVICE FOR MOBILE ZINC-CHLORIDE BATTERY SYSTEM ABSTRACT OF THE DISCLOSURE A metal halogen battery system, said system having the following construction, a store means constructed in the form of a container which includes a generally unitary filter means extending around most of the inside surface of the container and with the filter means being spaced a predetermined distance away from said surface a form spacing between the filter means and the inside surface, said filter means being operative to separate the hydrate formed from the liquid electrolyte, a hydrate former-gas pulp means associated with the store means and being operative to intermix halogen gas from the battery cell with aqueous electro-lyte from the store means and from the cell, a gas space means being maintained at the top of the store means with the hydrate former-pump means exhausting into the proximity of the gas space, said gas space means being operative to reduce transfer of liquid from the store to the cell, exit conduit-means generally adjacent the top of the store means for trans-mitting fluid containing halogen gas to the cell, and second exit conduit means generally adjacent the bottom of the store means for recirculating filtered electrolyte to the battery system.
Description
JACX~ROUN~ OF THE INVENT~O~
~ ~he present inv~ntion ~elstcs ~o impr~Ye~ents in ~e~al hal~g~n bat~ry syst~ms. ~ore particul~rly ~he ln~en~ion relates to ~ DeW hydrate 3tor~g~ de~ice ~r z;nr-chloride battery ~yst~ms. ~he ~nv~n2i~n he~ein i~ parti~ularly u~eful for mobil~
b~tery appli~8~ion5, e.g.~ for el~ctric ~ehicl~s.
The electrical cnergy storage sys~ems of the type referred ~o herein ~e.g., ~ zinc chlo~ine bat~ery sys~em or other Det~l-halogen b~t~ery system3 u~ilize a halogen hydra~e as the source of ~ h~logen component for r~duction at a normally posi-~ive clectrode, and an oxidiz~ble met~l ~dap~ed to become oxidized at ~ ~ormally negative el c~rode during th~ normal dischar~e of ~he storage system. An aqueDu.s ~lectrolyte is employed or replenish-in~ the supply ~,f the hslogen components as it becomes reduced at lS the positi~e electrode. ~he electrolyte cont~ins the dissolYed ~ons of the oxidized ~etal and ~he red~cet halogen and i~ eir-culatea be~wee~ ~he electrode ~rea ~nd gl s~orage area con~aining ha:logen hydr~te, which progressive:ly decomposes during a noTmal dischar~e of ~he elec~rical energy syste~ libersting addi~ional ¢lemen~l halogen ~o be consumed a~ the posi~ive electrode.
The state of the ~rt in electrical energy stor~ge systems ~r b~2ry systems Df ~his type is described in p~ents owned by ~he s~me assignee ~s ~he present ~nven~ion, such as SymoDs ~.5. Pa~ent 3D713j8B8; 5~ons ~.S. Patent 3,8D9D5~8 enti~led
~ ~he present inv~ntion ~elstcs ~o impr~Ye~ents in ~e~al hal~g~n bat~ry syst~ms. ~ore particul~rly ~he ln~en~ion relates to ~ DeW hydrate 3tor~g~ de~ice ~r z;nr-chloride battery ~yst~ms. ~he ~nv~n2i~n he~ein i~ parti~ularly u~eful for mobil~
b~tery appli~8~ion5, e.g.~ for el~ctric ~ehicl~s.
The electrical cnergy storage sys~ems of the type referred ~o herein ~e.g., ~ zinc chlo~ine bat~ery sys~em or other Det~l-halogen b~t~ery system3 u~ilize a halogen hydra~e as the source of ~ h~logen component for r~duction at a normally posi-~ive clectrode, and an oxidiz~ble met~l ~dap~ed to become oxidized at ~ ~ormally negative el c~rode during th~ normal dischar~e of ~he storage system. An aqueDu.s ~lectrolyte is employed or replenish-in~ the supply ~,f the hslogen components as it becomes reduced at lS the positi~e electrode. ~he electrolyte cont~ins the dissolYed ~ons of the oxidized ~etal and ~he red~cet halogen and i~ eir-culatea be~wee~ ~he electrode ~rea ~nd gl s~orage area con~aining ha:logen hydr~te, which progressive:ly decomposes during a noTmal dischar~e of ~he elec~rical energy syste~ libersting addi~ional ¢lemen~l halogen ~o be consumed a~ the posi~ive electrode.
The state of the ~rt in electrical energy stor~ge systems ~r b~2ry systems Df ~his type is described in p~ents owned by ~he s~me assignee ~s ~he present ~nven~ion, such as SymoDs ~.5. Pa~ent 3D713j8B8; 5~ons ~.S. Patent 3,8D9D5~8 enti~led
2~ "Process for ~ormin~ ~nd Storing Halogen Hydr~t~ Bsttery''g Bjorkm<~ .S. 1~a~e~1lt 3,~:19,~30 entitled "Fllte~r/Store For Electric EncrcJy Storc1ge Devi.ce"; and Bjorkman U.S. patent 4,~86,:L~0. Such systems are ~:1so describecl :in published repor-ts prepared by the assig:nee herein such as "Zinc-Chloricle Elec-tric ~ngine ~nit For Four Passenger Elec-tric Vehicle"
by J. Kiwalle et al of Eneryy Developmerl-t Associates Reference is also rnade to U.S. patent 4,4l4,292 en~i-tled "Me-tal Halogen Ba-ttery System".
The basic operation of a zinc chloride ba-ttery system is as follows. In charge, an electrolyte pump delivers aqueous elec-troly-te to pockets between pairs of porous graphite-chlorine electrodes in a battery stack comprise~d of a plurality of cells. The electrolyte passes through the porous chlorine electrodes into a chamber be-tween opposite polarity electrocles, flows up be-tween the elec-trodes, -then flows back in-to the bat-tery sump. Chlorine gas libera-ted from porous graphite electrode subs-trates is pumped by ~
gas pump, and before entering -the gas pump, the chlorine is mixed with electroly-te chilled hy a chiller uni-t. The chlorlne and chilled electrolyte are mixed in the gas pump, chlorine hydrate forms, and the chlorine hydrate-electr~lyte mixture is deposited in -the store. In discharge, chlor~ne is liberated from hydrate by decomposition of chlorine hydrate in the store by injection of warm electrolyte from the sump. On development of kh/~
by J. Kiwalle et al of Eneryy Developmerl-t Associates Reference is also rnade to U.S. patent 4,4l4,292 en~i-tled "Me-tal Halogen Ba-ttery System".
The basic operation of a zinc chloride ba-ttery system is as follows. In charge, an electrolyte pump delivers aqueous elec-troly-te to pockets between pairs of porous graphite-chlorine electrodes in a battery stack comprise~d of a plurality of cells. The electrolyte passes through the porous chlorine electrodes into a chamber be-tween opposite polarity electrocles, flows up be-tween the elec-trodes, -then flows back in-to the bat-tery sump. Chlorine gas libera-ted from porous graphite electrode subs-trates is pumped by ~
gas pump, and before entering -the gas pump, the chlorine is mixed with electroly-te chilled hy a chiller uni-t. The chlorlne and chilled electrolyte are mixed in the gas pump, chlorine hydrate forms, and the chlorine hydrate-electr~lyte mixture is deposited in -the store. In discharge, chlor~ne is liberated from hydrate by decomposition of chlorine hydrate in the store by injection of warm electrolyte from the sump. On development of kh/~
3 ~ 3 ~he required ~hl~rine g~ pressure in ~he stoTe, ~he chl~rino ~s injected and ~ixed with ana dissol~ed .in the olectrolyt~
which i5 then fed to ~he poro-ls electrodes ;n the battesy sta~k.
The b~ttery ~t~ck is then discharged, wher~in the elect~ode dissolution of zinc DCcUrs at the 2inc electr~de, ~ed~ction of the dissolYed ~hlorine occurs at the chlorine electrode, pow~r is availsble from ~he bats~ry ~erminals, and zinc chl~Jide is fDrm~d in the electroly~e by reac~iDn o* zinc and chlorine to form zinc chlorid~.
There have been certain weaknesses in prior sys~ems direc~ed toward hydra~e storage deYices for mobile metal-hal~gen battery applications. For ~xample, prior designs and concepts for hydrate storage in mobile sys~ems employed multiple no7zles and multiple filters that ~re staged for operatiDn at various pressures, 1~ and Yarious liquid/gas sepaTation me~hods Although these prio~
designs accomplished reasonably effective hydra~e storage, they also had operational ~hortc~mings as applied to mobile applications.
These shoTscomings were: ~l)excessi~e liquid transfeT frcm thP
hydrate store to the stack compartment duTing the charg~ ~ycl~
resulting in floodia~ ~f the stack sump; (2)insufficient gas-liqu.id separatioD ~esul~ing in periodic gas-Dut of ~he hydrate forma~ion pump; (3)the multiple nozzles concept employed resulted, in many instances, in partial plugging which resul~ed in operational difi-culties ~nd reduced hydr~te stora~e density; snd, (4)st~ged multiple ~ ers increased ~he functional complexi~y of ~he prior devices ~ ~n~ also led ~o improper liquid separation and ~assing problems~
Accordingly it i5 Dne ob~ec~ of ~his invention ~o pro-Yide ~ novel and unique halogen hydrate s~DJa~e device for mobile battery systems. Other ob~e~ts, eatures and advantages of th~
~L ~
in~ention will become ~pparent rom the descriptioD he~oinD
from the drawings, ~nd frOJn th~ ~ppended cl~ims.
BRIEF DESCRIPTION O~ THE ~RAWINGS
FIGURE 1 illustrates a schematic of the halogeD
bydrate S~OTage device in accordance wi~h ~he invention herein, ~ith the device bein~ shown installed in a schematic ba~ter~
system;
FIGURE 2 illustratcs a ~Dre detailed dr~wing Df hydrate storage deYice of FIG. l; ~d . 10 FI~URE 3 illustra~es ~ different embodiment ~f hydrate store de~ic~ in accordance with the invPn~ion.
SUMMARY OF THE INVENTION
The invention hereih is concerned wi~h a novsl metal halogen battery system which includes a new and unique halogen hydrate stor~. The technique of the present inYentiDn differs from other store concPp~s in tha~: (1) A singl~ or generally uni~ary functisnal fil~er arrangemen~ is employPd wi~h ~ecirculat;on liquid gener~lly leaving the 5tore ~t the bottom thereof. This effects good liquid-gas separation ~nd prevents ~0 gas-out in the hydra~e forma~ion pump, as well as reduci~ the design complexity. (2) A significant gas space is maintained at the top of ~he store with the hydrate forming gas pump exhausting into ~he gas space. This ~educes store ~o s~ack l;quid ~ransfer without reducing the hydrate ~torage ~apability. ~3~ A hydr~te former with ~ single nozzle design ~ay be employed which p~o~ides ~ood hydrste orm~ion charac~eristics and reduces oper~ional problems inheren~ in multipl~ ~ozzl~O
., ; :~
-~ ? ,3;
r9 DESCRIPTION ~ PREFERRED EMBODIMENTS
The drawing FI5URE 1 illustrates ~ schematic ~
a zinc-chlorine battery system wherein ~eans nr~ provided tD
~chieve the desired ~lows of chlorine9 electTolyte, and he~t.
The ziDc-chloride battery consists of three basio pn~ts, the stack~ the ~ump, and the store, as shown in FlGURE 1. The st~ck 10 consists of ~ plurali~y of cells made up, for example, of solid-graphite .zinc electrodes and porous-graphi~e chlorine electrodes. F.ach cell has the pntential uf two volts (2hus 0 giYing a stack nrran~ement with 60 cells ~ 120-~lt potenti21~.
The sump means is designated 20 and is csmprised of an electro-lyte reservoir 22 and ~he elec~roly~e pump P-l to circulat2 ~he electrolyte 210 The novel halogen hydrate store means is designated 30 and incl~des ~ ~as pump P-2 and a generally unit~ry filte~
means 3Z. The store functions to store the chlorine reactant in the form of chloriDe hydrate, which is a brillian~ yell3w solid th~t decomposes ~o chlorine gas and electrolyte a~ ~empera~ures abo~e 9.6~C ~t ~mbient Qtmospheric preSSuTe.
The centriugal pump P-l circ~lates the electrolyte 21 from the reservoir 22 to the i~dividual porous electrodes rnot shown~ in the stnck through the conduit ~4 9 from which electroly~e returns ~o the reserv~ir ~hrough ~he condui~ 25. The small quAn~i~y ~f hydro~en ~vnlved during bnttery operation is combined with the 2~ chlorine in ~n ultr~violet light-~ctivated r~actDr designated 40 to form hyd~ogen fhloride9 ~hich is subsequently s~urned ~o ~he e1ectrolyte reser~oir ~s will be described hereln.
As shown9 there aro two locations ~ ultr~Yiolet lights, sne iDside the reservoir Bas space indic~ted ~ 419 i~
-~ith the ~.V. light 41 being ~cti~ated during ch~rge ~nly; a~d, *~o ~re U.V~ hts .~nside ~eactor 4D which ~re sctiv~t~d both during thar~e and discharge ~f the bat~eryO ~n order to gener~
~te suc~ion ~i~hin ~he ~eac~or 40 neeessary to ~nduce flow ~f gas ~rom r~serY~ir 2~ in~o ~he Teac~or 40 and back ints ~eser-Yoir 22~ ~ jet pump construction design~ted sn is ~mploy~d~
A small quanti~y of elec~rolyte from electroly~e pump P-l is diverted into *he jet pump 50 ~hrough ~he tonduits 51~52 ~o act as 8 driving force fcr ~he jet pump. ~h~n the electrolyte pump P-l is in bperati~n, ~he stre~m of liquid elec~rolyte passing through the j et pump fr~m conduit 52 causes a suction whçreby ~he gases from the reserYoir 22 and from ~he uppeT part of the reac*or ~0 ~re drawn into ~he je~ pump through the conduit SDl, and the gas s are then mixed in with the liquid stream exiting from the no~zle 502 near the point S03. Thereafter the inter-mixture ~f g~s and liquid is re~ur~led ~o ~he sump 20 via the condui~ 5D4.
Ba~tery Chargin~
During ~harge o~ the batt~ry system, chlorine i~
liberated from *he pcr~us-graphi~e ~hlorine electrode s~b-strates, while ~inc ls deposit~d on the solid-graphite electrodes.
The chlorine which is liberated in the stack 10 i5 subsequently drawn through cDnduit 54 ~o the s~ore 30 Yia ~he ~acuum crea~ed by the gas pump P-2 within the store 30. The heat exchan~er HX-l operates to provide cooling ~or Ihe electrolyte in ~he sump during operation of the bat~ery.
A small ~mount of ~lectrolyte, from ~he ou~put o~ tho cent~ifugal pump P-l~ is ~Iso diverted through condui~ ~5 t~
heat exchanger ~X-2 and chilled to approximately O~C. Shi~
chill~d elec~soly~ ~ont~cts chlorine gas ~Yia c~ndui~ 54~
drawn f~om the stac~ ~y ~he ~BCuum ~t the intake 56 to the gAS
- pump P 2, ~nd chlosine hydra~e i5 foTmed at the ~utlet port of pump P-2. Hydr~e is il~ered-~ut in ~he s~ore in 8 fashion si~ilar ~3 ~ fil~ering press by ~he fil~er ~ean~ 32.
The ~orma~ion of chlorine hydrate from the ~queous elects31yte leads ~o an increasing concentra~ion of zinc ~hloride within the store 30, and the electsolysis of the zinc chloride in the stack 10 ~educes the zinc-chloride eoncentration in it.
lD Therefor~, by in~erchanging elec~roly~e between ~he s~ack and ~torep the use of inc chloride is optimized in the system. The elec~roly~e interchan~e be~ween ~he s~ack 10 and stoTe 30 is accomplished by pumping warm electrolyte ~about 30DC~ ~ia the ~entrifugal pump P-l and c~nduit 55 from the sump seservoir 22 into the st~re 3D 9 and returning cold elec~rolyte (about O~C) ~hrou~h conduit 57 from ~he store 30 to the stack at point 58 on the high pressure side of pump P-l, and ~hen via conduit 24 to the stack lOo ~he flow rates of both solutions are approx-imately equalO If ~he fluid 10w pressuTe in conduit 57 exceeds approxi~ately 25 psia ~hen the fluid by-passes valve 60 and f1DWS
through the relief ~alve 9~ ~o conduit 614 which leads ~o the high pressure side of the electroly~e pump P~l a~ point 5B.
System pressure during çharge represents a balance between the rate of chlorine generation and the ra~e Df hydrate forma~ion. Therefore~ when ~he s~ack pressure increase~ ~boYe ~
predetermined level~ mOT~ c~olant is required f~r hydra~e forma~ion and Yi ce versa D
, --7~-~J~ r~
~attery Di~c~ r~e ~UI`in~ dischargeb drop in T)ressure inside sto~e 30 5t~ 's gea-r plllnp P-2 inject.ing warm electrolyte from th~
~eservoir (throLIgh pump P 1~ conauit 55 ~nd HX-2) urlti~ desired s~sre pressure is ~estored~ This action decomposes ~ po~tion o ~he chloTine hydra-~.e w;thin ~he s~ore, thereby 3ibera~ing ohlor.lne ~nd inCTe~sing ~he internal pressuTe in the sto-re~ This ~h70rlne is injected in~o the dischaTge por~ of the centrifugal ~mp P-l at point 53, and then circulated through ~he s~ack.
1~ Cv:n~rol is maintaine~ by monitoTing the pressure of the store~
which indicates the balance be~ween t~e rate of chlorine con-sl~ptio~ în ~he stack and ~he ~a~e o~ chlorine decomposi~ion in the s~ore~ This~ in ~urn, is con~rolled by ~he rate ~f ~n3ec~ing warm elec~r~lyte into the store.
The demand or power ~rom the battery ean c~a-~ge rapidly but dl~e ~o ~he la~ge thermal mass within the sto~e3 ~lution ~ chlorine tracks demand only approximately. There-~o~e ~ diaphragm operated, 2-position-l7nidirectional 10w valYe .is u~ ed as designated ~.~ 6D with th e ~alve ~;ng normall~-in ~he closed p~s;tion~ This pr~ssure sensi~ive valve 6~ ~orms no ~art of the present inYentlOn, however3 it is shswn i~ more deta;l in u.~. Ra~ent 4,414~292.
~ The val~e i5 cons~ruçted as a vzriar.t ~f spool valve~ and i~ pro~ldes rO~`
cl~se control of chlorine demand nd bubble ~igh~ isol~on of ~he st~re fr~m ~he stack. A lar~e ~emand o power f~om ~he batt~ry ~ esult in ~ large demand of chlorine~ an~ ~hi5 will lower ~he pressure in the reservoir 22~ ~he r~seTvoi~ p~essuIe is fed ~o ~he valYe 60 through ~he condul~ 602. The di~phr.agm _~.
(;~ ;i3 ~not shown~ of th~ Y~l~e ~0 i5 ~cted ~pon by reserYoi~ pre3sur~, ~nd ambient atmospheri~ pressur~ also oper~tes on the Y~
diaphragm. Lowerin~ ~f the pressure in reser~o.ir 22 bel~w ~mbient atmospheric pr~ssure causes ~peniDg of ~he valve 60, and 5 this ~llows hlorine frqm the s~ore ~i~ eo~duit 57 to be tr~ns-~itted ~hrough c~ndui~ 614 ~o the discharee side of pump P-l at point 5~. When store press~re exceeds smbient atmospheric pressure ~ valYe 60 shu~s tight.
The FIGURE 2 drawing represents the sto~e 30 ~of FIG. 1) in ~ battery sys~em during chasge. During charge, fil~red store ~ecirculstion electr~lyte is metered ~rom ~he lvwer portiDn of the store 30 and mixed with ~eteJed interchange electrolyte rom the ~tack at 2Dl. The mixture is cooled in the heat exchanger - HX-2 and en~ers the fo~ma~ion pump P-2 along ~i~h ~he chl~rine gas generated in the stack for storage. The liquid-~as mixture is pumped in~o the hydrate former 203 and nozzle 205 where chlorine hydrste is formed. The liquid-solid slurry along with residual chlorine ga5 and inert ~eses are discharged into the maintained gas space ~t ~he ~op of ~be store at 2070 ~he s~lid hydra~e is fil~ered ~ut and sto~ed wi~hin the filter 32 ~nd ~he ~cess gas and liquid pass ~hrough the filter. The excess Kas and inte~change liquid return to the stack through the upper interchange port 209 and the recirculstion liquid returns to the pump through the lower ~circulation port 211. E~cessive liquid transfer~ if permi~ted, from ~he store t~ the ~2ack ceuses filling of ~he s~srk sump with liquid wbi~h ~e~ult~ in severe 3perstional difficulti~sO This liquid ~Ta~s fer i~ due tv liquid displscement in the stoT~ by in rt ~nd chlorine gas bubbles trapped in the sture by the hydr~e m~ss or c~ke durin~
bat~ery ~hargingO Wi~h ~he nozzle 205 discharging into ~he ~as _9_ 5'~
~pace 213 ~ ~he tDp ~f the stoTe, good gas separatlon i~
~chie~ed~ ~s en~r~pment is ~inimi2ed and ~cessiYe liquid transfer to the stack i5 prevent~d. ln one possible embodi-~ent of the invPntion9 the Yolume ~f *he gas sp~c~ 213 is achieved by placing ~he interchan~e port 209 the desir~d distance below ~he ~Dp of ~he storeO Excessive gas en~esing ~he pump P-2 ~ia ~he recircula~ion electrolyte line 215 results in reduced formation capabilities and possible gassi~g out of the pump. The plaeemen~ Df the recirculation pDlt at the bottom of the store 30 maximizes gravi~y gas-liquid separation and minimizes gas flow in ~he reciTcula~ion liDe 215.
The gas space 213 a~ ~he top Df ~he s9~ore does no~ Teduce tD~al hydrate storage v~lume. As the battery ~harge proceeds to cDm-pletion9 the hydrate density is increased throughout the e~tire store ~nd the gas space eventually fills ~ith hydrate.
The ~lternative embodiment of FIGURE 3 (wherein like numerals indica~e like elemen~s~ shows another form of hydra~e storage device 300 in ~ccordance with the invention. ~he devioe is spherio21 in shape with the two halves.being held to~ether by a plurallty ~f bolts s~ch cs at 302~ ~nd the inside wall diameter of the store 300 is ~pproximate1y 28~ inches, with ~he inside diameter of the filter 32 being spproximately 27-7~ inches9 ~nd the vertical dividing line being shown at 304. The store 300 is quite similar iD opi~ration to thc store 30 except that in the store 300 the liquid level is ~aintained by an Dddi~ional ~onduit B00 which communica~es with ~he bat~ery sump 2Q~ Conduit 800 as also shown by do~ted lin~s in FIG. 1~ ~nd liquid flow ~hrough conduit 800 ~o ~hi2 sump 20 is controlled by the normally closed --lo~
; 3 5~
solen~id valv~ ~02 ~hich is opened by the ~ump liquid 10Yel sensor B04 wheD ~he sump liquid drops below a predet~mi~lod leYel to thereby cause ~ ~ran~er ~f electTolyte liquid f~om the store 300 over to the sump 20. In ad~it;Dn the outl~t lin~
57 fro~ the store 3D0 opesatea to transfer essenti211y only halogen ~as back tD ~he high p~essur~ side of the electTolyte p~mp P-l ~t point 5~. This gas transfeT i~ facilitated by the condui~ ~06 and valv2 308 which is opened duTing discharge sf the batteTy system. Such a coDdult-Yalve ~rrangement can also ~ptionally &nd preferably be used during discharge in the store device 3D ~of FIG. 2).
The store de~ice ~f FIGURE 2 has been used in a battery system to power a full size 4-door automobile ~nd it has performed very sa~isfactorily in numerous miles of ~est drivin~.
lS The stoTe device of FIGURE 3 has been incorporated, and has tested out very satisfactorily, in a fully built operational batteTy system in a test room at the assignee's plant.
Whil~ it will be apparent that the preferred embodime~ts o~ ~he invention disclosed are well calculated tD fulfill ~he ~bjects, benefits, and advantages nf the inventionV it will be appreciated that the invention is susceptible to modification, Yaria~ion and chan~e without depar~ing ~om ~he proper scope or fair meaning of ~he subjoined clai~s.
,
which i5 then fed to ~he poro-ls electrodes ;n the battesy sta~k.
The b~ttery ~t~ck is then discharged, wher~in the elect~ode dissolution of zinc DCcUrs at the 2inc electr~de, ~ed~ction of the dissolYed ~hlorine occurs at the chlorine electrode, pow~r is availsble from ~he bats~ry ~erminals, and zinc chl~Jide is fDrm~d in the electroly~e by reac~iDn o* zinc and chlorine to form zinc chlorid~.
There have been certain weaknesses in prior sys~ems direc~ed toward hydra~e storage deYices for mobile metal-hal~gen battery applications. For ~xample, prior designs and concepts for hydrate storage in mobile sys~ems employed multiple no7zles and multiple filters that ~re staged for operatiDn at various pressures, 1~ and Yarious liquid/gas sepaTation me~hods Although these prio~
designs accomplished reasonably effective hydra~e storage, they also had operational ~hortc~mings as applied to mobile applications.
These shoTscomings were: ~l)excessi~e liquid transfeT frcm thP
hydrate store to the stack compartment duTing the charg~ ~ycl~
resulting in floodia~ ~f the stack sump; (2)insufficient gas-liqu.id separatioD ~esul~ing in periodic gas-Dut of ~he hydrate forma~ion pump; (3)the multiple nozzles concept employed resulted, in many instances, in partial plugging which resul~ed in operational difi-culties ~nd reduced hydr~te stora~e density; snd, (4)st~ged multiple ~ ers increased ~he functional complexi~y of ~he prior devices ~ ~n~ also led ~o improper liquid separation and ~assing problems~
Accordingly it i5 Dne ob~ec~ of ~his invention ~o pro-Yide ~ novel and unique halogen hydrate s~DJa~e device for mobile battery systems. Other ob~e~ts, eatures and advantages of th~
~L ~
in~ention will become ~pparent rom the descriptioD he~oinD
from the drawings, ~nd frOJn th~ ~ppended cl~ims.
BRIEF DESCRIPTION O~ THE ~RAWINGS
FIGURE 1 illustrates a schematic of the halogeD
bydrate S~OTage device in accordance wi~h ~he invention herein, ~ith the device bein~ shown installed in a schematic ba~ter~
system;
FIGURE 2 illustratcs a ~Dre detailed dr~wing Df hydrate storage deYice of FIG. l; ~d . 10 FI~URE 3 illustra~es ~ different embodiment ~f hydrate store de~ic~ in accordance with the invPn~ion.
SUMMARY OF THE INVENTION
The invention hereih is concerned wi~h a novsl metal halogen battery system which includes a new and unique halogen hydrate stor~. The technique of the present inYentiDn differs from other store concPp~s in tha~: (1) A singl~ or generally uni~ary functisnal fil~er arrangemen~ is employPd wi~h ~ecirculat;on liquid gener~lly leaving the 5tore ~t the bottom thereof. This effects good liquid-gas separation ~nd prevents ~0 gas-out in the hydra~e forma~ion pump, as well as reduci~ the design complexity. (2) A significant gas space is maintained at the top of ~he store with the hydrate forming gas pump exhausting into ~he gas space. This ~educes store ~o s~ack l;quid ~ransfer without reducing the hydrate ~torage ~apability. ~3~ A hydr~te former with ~ single nozzle design ~ay be employed which p~o~ides ~ood hydrste orm~ion charac~eristics and reduces oper~ional problems inheren~ in multipl~ ~ozzl~O
., ; :~
-~ ? ,3;
r9 DESCRIPTION ~ PREFERRED EMBODIMENTS
The drawing FI5URE 1 illustrates ~ schematic ~
a zinc-chlorine battery system wherein ~eans nr~ provided tD
~chieve the desired ~lows of chlorine9 electTolyte, and he~t.
The ziDc-chloride battery consists of three basio pn~ts, the stack~ the ~ump, and the store, as shown in FlGURE 1. The st~ck 10 consists of ~ plurali~y of cells made up, for example, of solid-graphite .zinc electrodes and porous-graphi~e chlorine electrodes. F.ach cell has the pntential uf two volts (2hus 0 giYing a stack nrran~ement with 60 cells ~ 120-~lt potenti21~.
The sump means is designated 20 and is csmprised of an electro-lyte reservoir 22 and ~he elec~roly~e pump P-l to circulat2 ~he electrolyte 210 The novel halogen hydrate store means is designated 30 and incl~des ~ ~as pump P-2 and a generally unit~ry filte~
means 3Z. The store functions to store the chlorine reactant in the form of chloriDe hydrate, which is a brillian~ yell3w solid th~t decomposes ~o chlorine gas and electrolyte a~ ~empera~ures abo~e 9.6~C ~t ~mbient Qtmospheric preSSuTe.
The centriugal pump P-l circ~lates the electrolyte 21 from the reservoir 22 to the i~dividual porous electrodes rnot shown~ in the stnck through the conduit ~4 9 from which electroly~e returns ~o the reserv~ir ~hrough ~he condui~ 25. The small quAn~i~y ~f hydro~en ~vnlved during bnttery operation is combined with the 2~ chlorine in ~n ultr~violet light-~ctivated r~actDr designated 40 to form hyd~ogen fhloride9 ~hich is subsequently s~urned ~o ~he e1ectrolyte reser~oir ~s will be described hereln.
As shown9 there aro two locations ~ ultr~Yiolet lights, sne iDside the reservoir Bas space indic~ted ~ 419 i~
-~ith the ~.V. light 41 being ~cti~ated during ch~rge ~nly; a~d, *~o ~re U.V~ hts .~nside ~eactor 4D which ~re sctiv~t~d both during thar~e and discharge ~f the bat~eryO ~n order to gener~
~te suc~ion ~i~hin ~he ~eac~or 40 neeessary to ~nduce flow ~f gas ~rom r~serY~ir 2~ in~o ~he Teac~or 40 and back ints ~eser-Yoir 22~ ~ jet pump construction design~ted sn is ~mploy~d~
A small quanti~y of elec~rolyte from electroly~e pump P-l is diverted into *he jet pump 50 ~hrough ~he tonduits 51~52 ~o act as 8 driving force fcr ~he jet pump. ~h~n the electrolyte pump P-l is in bperati~n, ~he stre~m of liquid elec~rolyte passing through the j et pump fr~m conduit 52 causes a suction whçreby ~he gases from the reserYoir 22 and from ~he uppeT part of the reac*or ~0 ~re drawn into ~he je~ pump through the conduit SDl, and the gas s are then mixed in with the liquid stream exiting from the no~zle 502 near the point S03. Thereafter the inter-mixture ~f g~s and liquid is re~ur~led ~o ~he sump 20 via the condui~ 5D4.
Ba~tery Chargin~
During ~harge o~ the batt~ry system, chlorine i~
liberated from *he pcr~us-graphi~e ~hlorine electrode s~b-strates, while ~inc ls deposit~d on the solid-graphite electrodes.
The chlorine which is liberated in the stack 10 i5 subsequently drawn through cDnduit 54 ~o the s~ore 30 Yia ~he ~acuum crea~ed by the gas pump P-2 within the store 30. The heat exchan~er HX-l operates to provide cooling ~or Ihe electrolyte in ~he sump during operation of the bat~ery.
A small ~mount of ~lectrolyte, from ~he ou~put o~ tho cent~ifugal pump P-l~ is ~Iso diverted through condui~ ~5 t~
heat exchanger ~X-2 and chilled to approximately O~C. Shi~
chill~d elec~soly~ ~ont~cts chlorine gas ~Yia c~ndui~ 54~
drawn f~om the stac~ ~y ~he ~BCuum ~t the intake 56 to the gAS
- pump P 2, ~nd chlosine hydra~e i5 foTmed at the ~utlet port of pump P-2. Hydr~e is il~ered-~ut in ~he s~ore in 8 fashion si~ilar ~3 ~ fil~ering press by ~he fil~er ~ean~ 32.
The ~orma~ion of chlorine hydrate from the ~queous elects31yte leads ~o an increasing concentra~ion of zinc ~hloride within the store 30, and the electsolysis of the zinc chloride in the stack 10 ~educes the zinc-chloride eoncentration in it.
lD Therefor~, by in~erchanging elec~roly~e between ~he s~ack and ~torep the use of inc chloride is optimized in the system. The elec~roly~e interchan~e be~ween ~he s~ack 10 and stoTe 30 is accomplished by pumping warm electrolyte ~about 30DC~ ~ia the ~entrifugal pump P-l and c~nduit 55 from the sump seservoir 22 into the st~re 3D 9 and returning cold elec~rolyte (about O~C) ~hrou~h conduit 57 from ~he store 30 to the stack at point 58 on the high pressure side of pump P-l, and ~hen via conduit 24 to the stack lOo ~he flow rates of both solutions are approx-imately equalO If ~he fluid 10w pressuTe in conduit 57 exceeds approxi~ately 25 psia ~hen the fluid by-passes valve 60 and f1DWS
through the relief ~alve 9~ ~o conduit 614 which leads ~o the high pressure side of the electroly~e pump P~l a~ point 5B.
System pressure during çharge represents a balance between the rate of chlorine generation and the ra~e Df hydrate forma~ion. Therefore~ when ~he s~ack pressure increase~ ~boYe ~
predetermined level~ mOT~ c~olant is required f~r hydra~e forma~ion and Yi ce versa D
, --7~-~J~ r~
~attery Di~c~ r~e ~UI`in~ dischargeb drop in T)ressure inside sto~e 30 5t~ 's gea-r plllnp P-2 inject.ing warm electrolyte from th~
~eservoir (throLIgh pump P 1~ conauit 55 ~nd HX-2) urlti~ desired s~sre pressure is ~estored~ This action decomposes ~ po~tion o ~he chloTine hydra-~.e w;thin ~he s~ore, thereby 3ibera~ing ohlor.lne ~nd inCTe~sing ~he internal pressuTe in the sto-re~ This ~h70rlne is injected in~o the dischaTge por~ of the centrifugal ~mp P-l at point 53, and then circulated through ~he s~ack.
1~ Cv:n~rol is maintaine~ by monitoTing the pressure of the store~
which indicates the balance be~ween t~e rate of chlorine con-sl~ptio~ în ~he stack and ~he ~a~e o~ chlorine decomposi~ion in the s~ore~ This~ in ~urn, is con~rolled by ~he rate ~f ~n3ec~ing warm elec~r~lyte into the store.
The demand or power ~rom the battery ean c~a-~ge rapidly but dl~e ~o ~he la~ge thermal mass within the sto~e3 ~lution ~ chlorine tracks demand only approximately. There-~o~e ~ diaphragm operated, 2-position-l7nidirectional 10w valYe .is u~ ed as designated ~.~ 6D with th e ~alve ~;ng normall~-in ~he closed p~s;tion~ This pr~ssure sensi~ive valve 6~ ~orms no ~art of the present inYentlOn, however3 it is shswn i~ more deta;l in u.~. Ra~ent 4,414~292.
~ The val~e i5 cons~ruçted as a vzriar.t ~f spool valve~ and i~ pro~ldes rO~`
cl~se control of chlorine demand nd bubble ~igh~ isol~on of ~he st~re fr~m ~he stack. A lar~e ~emand o power f~om ~he batt~ry ~ esult in ~ large demand of chlorine~ an~ ~hi5 will lower ~he pressure in the reservoir 22~ ~he r~seTvoi~ p~essuIe is fed ~o ~he valYe 60 through ~he condul~ 602. The di~phr.agm _~.
(;~ ;i3 ~not shown~ of th~ Y~l~e ~0 i5 ~cted ~pon by reserYoi~ pre3sur~, ~nd ambient atmospheri~ pressur~ also oper~tes on the Y~
diaphragm. Lowerin~ ~f the pressure in reser~o.ir 22 bel~w ~mbient atmospheric pr~ssure causes ~peniDg of ~he valve 60, and 5 this ~llows hlorine frqm the s~ore ~i~ eo~duit 57 to be tr~ns-~itted ~hrough c~ndui~ 614 ~o the discharee side of pump P-l at point 5~. When store press~re exceeds smbient atmospheric pressure ~ valYe 60 shu~s tight.
The FIGURE 2 drawing represents the sto~e 30 ~of FIG. 1) in ~ battery sys~em during chasge. During charge, fil~red store ~ecirculstion electr~lyte is metered ~rom ~he lvwer portiDn of the store 30 and mixed with ~eteJed interchange electrolyte rom the ~tack at 2Dl. The mixture is cooled in the heat exchanger - HX-2 and en~ers the fo~ma~ion pump P-2 along ~i~h ~he chl~rine gas generated in the stack for storage. The liquid-~as mixture is pumped in~o the hydrate former 203 and nozzle 205 where chlorine hydrste is formed. The liquid-solid slurry along with residual chlorine ga5 and inert ~eses are discharged into the maintained gas space ~t ~he ~op of ~be store at 2070 ~he s~lid hydra~e is fil~ered ~ut and sto~ed wi~hin the filter 32 ~nd ~he ~cess gas and liquid pass ~hrough the filter. The excess Kas and inte~change liquid return to the stack through the upper interchange port 209 and the recirculstion liquid returns to the pump through the lower ~circulation port 211. E~cessive liquid transfer~ if permi~ted, from ~he store t~ the ~2ack ceuses filling of ~he s~srk sump with liquid wbi~h ~e~ult~ in severe 3perstional difficulti~sO This liquid ~Ta~s fer i~ due tv liquid displscement in the stoT~ by in rt ~nd chlorine gas bubbles trapped in the sture by the hydr~e m~ss or c~ke durin~
bat~ery ~hargingO Wi~h ~he nozzle 205 discharging into ~he ~as _9_ 5'~
~pace 213 ~ ~he tDp ~f the stoTe, good gas separatlon i~
~chie~ed~ ~s en~r~pment is ~inimi2ed and ~cessiYe liquid transfer to the stack i5 prevent~d. ln one possible embodi-~ent of the invPntion9 the Yolume ~f *he gas sp~c~ 213 is achieved by placing ~he interchan~e port 209 the desir~d distance below ~he ~Dp of ~he storeO Excessive gas en~esing ~he pump P-2 ~ia ~he recircula~ion electrolyte line 215 results in reduced formation capabilities and possible gassi~g out of the pump. The plaeemen~ Df the recirculation pDlt at the bottom of the store 30 maximizes gravi~y gas-liquid separation and minimizes gas flow in ~he reciTcula~ion liDe 215.
The gas space 213 a~ ~he top Df ~he s9~ore does no~ Teduce tD~al hydrate storage v~lume. As the battery ~harge proceeds to cDm-pletion9 the hydrate density is increased throughout the e~tire store ~nd the gas space eventually fills ~ith hydrate.
The ~lternative embodiment of FIGURE 3 (wherein like numerals indica~e like elemen~s~ shows another form of hydra~e storage device 300 in ~ccordance with the invention. ~he devioe is spherio21 in shape with the two halves.being held to~ether by a plurallty ~f bolts s~ch cs at 302~ ~nd the inside wall diameter of the store 300 is ~pproximate1y 28~ inches, with ~he inside diameter of the filter 32 being spproximately 27-7~ inches9 ~nd the vertical dividing line being shown at 304. The store 300 is quite similar iD opi~ration to thc store 30 except that in the store 300 the liquid level is ~aintained by an Dddi~ional ~onduit B00 which communica~es with ~he bat~ery sump 2Q~ Conduit 800 as also shown by do~ted lin~s in FIG. 1~ ~nd liquid flow ~hrough conduit 800 ~o ~hi2 sump 20 is controlled by the normally closed --lo~
; 3 5~
solen~id valv~ ~02 ~hich is opened by the ~ump liquid 10Yel sensor B04 wheD ~he sump liquid drops below a predet~mi~lod leYel to thereby cause ~ ~ran~er ~f electTolyte liquid f~om the store 300 over to the sump 20. In ad~it;Dn the outl~t lin~
57 fro~ the store 3D0 opesatea to transfer essenti211y only halogen ~as back tD ~he high p~essur~ side of the electTolyte p~mp P-l ~t point 5~. This gas transfeT i~ facilitated by the condui~ ~06 and valv2 308 which is opened duTing discharge sf the batteTy system. Such a coDdult-Yalve ~rrangement can also ~ptionally &nd preferably be used during discharge in the store device 3D ~of FIG. 2).
The store de~ice ~f FIGURE 2 has been used in a battery system to power a full size 4-door automobile ~nd it has performed very sa~isfactorily in numerous miles of ~est drivin~.
lS The stoTe device of FIGURE 3 has been incorporated, and has tested out very satisfactorily, in a fully built operational batteTy system in a test room at the assignee's plant.
Whil~ it will be apparent that the preferred embodime~ts o~ ~he invention disclosed are well calculated tD fulfill ~he ~bjects, benefits, and advantages nf the inventionV it will be appreciated that the invention is susceptible to modification, Yaria~ion and chan~e without depar~ing ~om ~he proper scope or fair meaning of ~he subjoined clai~s.
,
Claims (10)
1. In a metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, sump means for the electrolyte, store means thereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former whereby the hydrate is formed in association with the store means, the improvement comprising, said store means being constructed in the form of a container which includes a generally unitary filter means extend-ing around most of the inside surface of the container and with the filter means being spaced a predetermined distance away from said surface to form spacing between the filter means and said inside surface, said filter means being operative to separate the hydrate formed from the liquid electrolyte, a hydrate former-gas pump means associated with the store means and being operative to intermix halogen gas from the cell with aqueous electrolyte from the store means and from the cell, a gas space means being maintained at the top of the store means with the hydrate former-pump means exhausting into the proximity of the gas space, said gas space means being operative to reduce transfer of liquid from the store to the cell, exit conduit means generally adjacent the top of the store means for transmitting fluid containing halogen gas to the cell, second exit conduit means generally adjacent the bottom of the store means for recirculating filtered electrolyte to the battery system.
2. The invention of claim 1 wherein, said battery is a zinc-chlorine battery using an aqueous zinc chloride electrolyte.
3. The invention of claim 2 wherein, said store means is substantially spherical in shape.
4. The invention of claim 2 wherein, said store means operates to provide good liquid/gas separation with recirculating liquid electrolyte essentially leaving the store at the bottom and gas leaving at the top, to thereby assist in preventing gassing-out of said pump means.
5. The invention of claim 2 wherein, said gas space means maintained at the top of the store operates to prevent gas build-up in the middle of the store thus preventing store liquid from being prematurely forced over to the cell.
6. The invention of claim 4 wherein, said gas space means maintained at the top of the store operates to prevent gas build-up in the middle of the store thus preventing store liquid from being prematurely forced over to the cell.
7. In a metal halogen battery system, including at least one cell having a positive electrode and a negative electrode contacted by aqueous electrolyte containing the material of said metal and halogen, sump means for the electrolyte, store means whereby halogen hydrate is formed and stored as part of an aqueous material, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas formed in the cell to a hydrate former thereby the hydrate is formed in association with the store means, the improvement comprising, said store means being constructed in the form of a container which includes a generally unitary filter means extend-ing around most of the inside surface of the container and with the filter means being spaced a predetermined distance away from said surface to form spacing between the filter means and said inside surface, said filter means being operative to separate the hydrate formed from the liquid electrolyte, a hydrate former-gas pump means associated with the store means and being operative to intermix halogen gas from the cell with aqueous electrolyte, a gas space means being maintained at the top of the store means with the hydrate former-pump means exhausting into the gas space, said gas space means being operative to minimize transfer of liquid from the store to the cell, exit conduit means generally adjacent the top of the store means for transmitting fluid containing halogen gas to the cell, second exit conduit means generally adjacent the bottom of the store means for recirculating filtered electrolyte to the battery system.
8. The invention of claim 7 wherein, said battery is a zinc-chlorine battery using an aqueous zinc chloride electrolyte.
9. In a metal halogen battery system, including at least one cell, electrolyte, store means whereby halogen hydrate is formed and stored, means for circulating electrolyte through the cell and to the store means, and conduit means for transmitting halogen gas to a hydrate former, the improvement comprising, said store means being constructed in the form of a container which includes a filter means extending around most of the inside of the container, said filter means being operative to separate the hydrate formed from the electrolyte, a hydrate former means associated with the store means and being operative to intermix halogen gas from the cell with electrolyte from the store means and from the cell, a gas space means being maintained at the top of the store means with the hydrate former exhausting into the proximity of the gas space, said gas space means being operative to minimize transfer of liquid from the store to the cell, exit conduit means near the top of the store means for transmitting gas-fluid to the cell, second exit conduit means near the bottom of the store means for recirculating filtered electrolyte to the battery system.
10. The invention of claim 9 wherein, said battery is a zinc-chlorine battery using an aqueous zinc chloride electrolyte.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US357,742 | 1982-03-12 | ||
| US06/357,742 US4400446A (en) | 1982-03-12 | 1982-03-12 | Halogen hydrate storage device for mobile zinc-chloride battery systems |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1191544A true CA1191544A (en) | 1985-08-06 |
Family
ID=23406840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000420731A Expired CA1191544A (en) | 1982-03-12 | 1983-02-02 | Halogen hydrate storage device for mobile zinc- chloride battery systems |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4400446A (en) |
| EP (1) | EP0089754B1 (en) |
| JP (1) | JPS58218776A (en) |
| AT (1) | ATE24254T1 (en) |
| CA (1) | CA1191544A (en) |
| DE (1) | DE3368352D1 (en) |
| MX (1) | MX158242A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386140A (en) * | 1982-04-16 | 1983-05-31 | Energy Development Associates, Inc. | Multiple stage multiple filter hydrate store |
| US4413040A (en) * | 1982-04-26 | 1983-11-01 | Energy Development Associates, Inc. | Hydrogen/halogen reactor system for metal halogen batteries |
| US4585709A (en) * | 1983-01-21 | 1986-04-29 | Energy Development Associates, Inc. | Method and apparatus for regulating the hydrate formation temperature in a metal-halogen battery |
| AU2010310894B2 (en) * | 2009-10-23 | 2014-08-07 | Redflow R&D Pty Ltd | Recombinator for flowing electrolyte battery |
| KR20210003457A (en) * | 2019-07-02 | 2021-01-12 | 현대자동차주식회사 | Thermal management system for vehicle |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3713888A (en) * | 1970-06-26 | 1973-01-30 | Oxy Metal Finishing Corp | Process for electrical energy using solid halogen hydrates |
| US3814630A (en) * | 1971-11-18 | 1974-06-04 | Occidental Energy Dev Co | Filter/store for electric energy storage device |
| US3823036A (en) * | 1972-05-26 | 1974-07-09 | Energy Dev Ass | Secondary battery comprising means for forming halogen hydrate solid bubble shells |
| US3993502A (en) * | 1975-10-29 | 1976-11-23 | Energy Development Associates | Metal halogen hydrate battery system |
| US4146680A (en) * | 1978-06-15 | 1979-03-27 | Energy Development Associates | Operational zinc chlorine battery based on a water store |
| US4306000A (en) * | 1980-04-29 | 1981-12-15 | Energy Development Associates, Inc. | Method of cooling zinc halogen batteries |
| US4414292A (en) * | 1982-01-29 | 1983-11-08 | Energy Development Associates, Inc. | Metal halogen battery system |
-
1982
- 1982-03-12 US US06/357,742 patent/US4400446A/en not_active Expired - Lifetime
-
1983
- 1983-02-02 CA CA000420731A patent/CA1191544A/en not_active Expired
- 1983-02-24 EP EP83300974A patent/EP0089754B1/en not_active Expired
- 1983-02-24 AT AT83300974T patent/ATE24254T1/en not_active IP Right Cessation
- 1983-02-24 DE DE8383300974T patent/DE3368352D1/en not_active Expired
- 1983-03-10 MX MX196526A patent/MX158242A/en unknown
- 1983-03-11 JP JP58039367A patent/JPS58218776A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| MX158242A (en) | 1989-01-17 |
| DE3368352D1 (en) | 1987-01-22 |
| EP0089754A1 (en) | 1983-09-28 |
| JPH0427677B2 (en) | 1992-05-12 |
| EP0089754B1 (en) | 1986-12-10 |
| JPS58218776A (en) | 1983-12-20 |
| US4400446A (en) | 1983-08-23 |
| ATE24254T1 (en) | 1986-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4414292A (en) | Metal halogen battery system | |
| US12103849B2 (en) | Method, device and fuel for hydrogen generation | |
| EP0464111B1 (en) | Metal/air battery with seeded recirculating electrolyte | |
| FI60622B (en) | BATTERY VARI HALOGEN KAN LAGRAS | |
| CN114421054B (en) | Liquid-cooled energy storage device | |
| EP1627438B1 (en) | Method for forming lead-acid batteries and plant for implementing said method. | |
| CA1191544A (en) | Halogen hydrate storage device for mobile zinc- chloride battery systems | |
| CN103296337A (en) | A metal-air battery | |
| US3823036A (en) | Secondary battery comprising means for forming halogen hydrate solid bubble shells | |
| CN115535962A (en) | Sodium-loaded replacement hydrogen fuel generator for hydrogen energy power automobile | |
| AU552820B2 (en) | Primary battery system | |
| CN212141207U (en) | Non-pressure-storage type automatic fire extinguishing device for lithium battery fire | |
| CN114583293A (en) | Liquid cooling energy storage device | |
| GB1296610A (en) | ||
| CN217887949U (en) | Prevent difluoro oxalic acid lithium borate synthesizer of reinforced jam of liquid | |
| CN217880438U (en) | Immersed inclined water fire-fighting charging cabinet | |
| US4389468A (en) | Metal halogen battery system with multiple outlet nozzle for hydrate | |
| CA2089885C (en) | Caustic-based metal battery with seeded recirculating electrolyte | |
| GB2109621A (en) | Metal halogen electrical energy storage system and method of use thereof | |
| EP0131353A2 (en) | Self-draining heat exchanger arrangement for a metal-halogen battery system, and method of putting it into practice | |
| CA1112719A (en) | Electrochemical cell using a dithionite compound of an alkaline metal as the charge transfer agent | |
| CN112875643A (en) | Aluminum-based hydrogen production material, preparation method thereof and method for preparing hydrogen by cracking water | |
| KR20240058236A (en) | Recycling apparatus of used lithium ion battery | |
| CA1114894A (en) | Electrochemical cell using a dithionite radical of an alkaline metal as the charge transfer agent | |
| HK40074404A (en) | Device for hydrogen generation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20030202 |