CA2110024C - Non-aqueous electrolyte cell - Google Patents
Non-aqueous electrolyte cellInfo
- Publication number
- CA2110024C CA2110024C CA002110024A CA2110024A CA2110024C CA 2110024 C CA2110024 C CA 2110024C CA 002110024 A CA002110024 A CA 002110024A CA 2110024 A CA2110024 A CA 2110024A CA 2110024 C CA2110024 C CA 2110024C
- Authority
- CA
- Canada
- Prior art keywords
- positive electrode
- stainless steel
- electrode case
- cell
- electrochemical cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/545—Terminals formed by the casing of the cells
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Primary Cells (AREA)
Abstract
An electrochemical cell is disclosed wherein product cost of positive electrode cases is reduced and the productivity of the electrochemical cell improved by suppressing anodic oxidation of the positive electrode case, without an aluminum layer inside of the positive electrode case being required. For electrochemical cells with non-aqueous electrolytes, for the materials for the positive electrode case, a high grade corrosion resistant stainless steel or high corrosion resistant austenitic ferrite stainless steel is used. The cost of the high corrosion resistibility positive electrode case is decreased and a high pressure tightness electrochemical cell can be manufactured.
Description
-' ' 2 ~ 2 ~
NON-AQllEOUS ELECTROLYTE ELECTROCHEMICAL CELL
BACKGROUND OF THE INVENTION
The present invention relates to small ele-llochclllical cells of high capacity.In the prior art wet type electroche nical cells, a~ onitic ferrite stainless steel 5 (SUS329Jl) which has an alu~ layer inside of the case, is used as positive el~llode case material ~ aft~,l briefly specified as A~-SUS clod mAt~riA1~) as in J-c~ c~se laid open patent ~ nn 62-94908.
Fig. S shows an example of an electric duul~le layer r 'l'~ ;1O. as in a prior art ele~,~oc.l.~ n.i~-Al cell. Pol ~ ;on electrodes 3, 3' are of actuated carbon fiber cloth, on 10 each side of which is formed a collector 4, 4' of alu.llhluln made by plasma spraying.
The actuated carbon fiber cloth is welded on positive electrode case l, 2 and negative electrode case 7 by, for eY~mrle~ laser welding. The electrodes 3, 3' are coupled with each other by way of ~e~ OI 5, and ~ .mhled by bending the upper side of the positive electrode case inwards after an organic electrolytic liquid is poured into it. As l5 for the electrolytic liquid, a solvent is used in which, for PY~mple, a tetra-aLL~ .n.~-n~ co~ or tetra aLlcyl ~ h5l.hnl.;...,, co..~ is dissolved in for e , '~ aprotic n-butyl lac~one, ethylene c~l,o~ , propylene C;~IJO1~IC as the solvent.
When the aforesaid prior art elecllo~ 1 cell is used at a voltage range of 2 -2.8 V, ~nn-li7.in~ of the inside of the positive electrode case which is made of stainless 20 steel only, is ~cccl ~lr~, the solution of metal ions ~eCCJII1C;S more active, and then higher ~ .re in thc cell or a decrease in elec~ic capacity is observed. In order to S~l~lc~;~ the ~ n~ n, an ~ ..;.--.... layer is set inside the posi~ve electrode case.
Because of the above reason, a ~b~;..-ce of JIS standard SUS329Jl, or SUS449Jl cannot be used as the In;~ of the positive electrode case, and two - 25 l~---il--,t,d metals of stainless steel and ~l,-.";,,..." are used as m~t~-.ri~l~ for the positive electrode case. But uniform and equally ~ick ~1...";"..." layer is difflcult to . " . .
..... ~.~r~A~ and multiple lamination processes are llece~ for its production. The cost is more than several times as much as that of stainless steel.
Moreover, in the pressing process, the ~1. ,.;,.---., layer sometimes covers over the 30 upper side edge of the positive electrode case. In the assembling of the positive electrode case l, 2 and the negative electrode case by bending the positive electrode case inwards at the edge and by shielding the cell, 5~ on the inside of the '" 2il~24 positive electrode case comes o~f and small fragments of it become coupled with negative electrode 3. This c~ cause short-circuits. Even when the alul~ l layer does not cover the edge of the stainless steel, it can cause divergence between the positive electrode case and the negative electrode case as to shielding and this becomes a cause of short-circuits, also.
According to the present invention, in the use of an electrochemical cell with organic electrolytic liquid at a level of 2 - 2.8 V, ~no~ ing of the positive electrode cell without an alu.llillulll layer inside can be ~u~ ed and the product cost decreased.
Therefore the productivity can be illl~roved~
SUMMARY OF THE INVENTION
The present invention provides a small electrochemical cell having high capacity.
The present invention also provides a non-aqueous electrolyte electrochemical cell capable of operating at the highest working voltage of 2.8 V.
The present invention further provides a non-aqueous electrolyte electrochernical cell using st~inless steel of low cost as a positive electrode case.
Still filrther, the present invention provides a non-aqueous electrolyte :
electroch~mic~l cell using a stainless steel having a pitting index between 30.5 and 45 as a positive electrode case. ~
The aforesaid problems can be solved accol.lillg to the present invention in that -as the m~t~ri~1~ for the positive electrode case certain kinds of high Ni ~nct~nitic stainless steel or high pressure tightn~ tPnitic ferrite duplex stainless steel are used.
According to the present invention, an electro~h~mis~l cell at the highest working voltage of 2.8 V can be obtained.
- 25 High Ni ~ hnitic stainless steel used in this invention is high Cr. higher Mo.
n~nitic stainless steel, of which for ~y~m~le JIS standard SUS317J4L shows very good corrosion resistivity even in severe atm~-sph~res. Table 1 exhibits data relating to the rh.o.mic~l coll~on~ of high Cr. high Mo. austenitic stainless steel SUS317J4L.
.: .: . . . - .
-: . . . .
NON-AQllEOUS ELECTROLYTE ELECTROCHEMICAL CELL
BACKGROUND OF THE INVENTION
The present invention relates to small ele-llochclllical cells of high capacity.In the prior art wet type electroche nical cells, a~ onitic ferrite stainless steel 5 (SUS329Jl) which has an alu~ layer inside of the case, is used as positive el~llode case material ~ aft~,l briefly specified as A~-SUS clod mAt~riA1~) as in J-c~ c~se laid open patent ~ nn 62-94908.
Fig. S shows an example of an electric duul~le layer r 'l'~ ;1O. as in a prior art ele~,~oc.l.~ n.i~-Al cell. Pol ~ ;on electrodes 3, 3' are of actuated carbon fiber cloth, on 10 each side of which is formed a collector 4, 4' of alu.llhluln made by plasma spraying.
The actuated carbon fiber cloth is welded on positive electrode case l, 2 and negative electrode case 7 by, for eY~mrle~ laser welding. The electrodes 3, 3' are coupled with each other by way of ~e~ OI 5, and ~ .mhled by bending the upper side of the positive electrode case inwards after an organic electrolytic liquid is poured into it. As l5 for the electrolytic liquid, a solvent is used in which, for PY~mple, a tetra-aLL~ .n.~-n~ co~ or tetra aLlcyl ~ h5l.hnl.;...,, co..~ is dissolved in for e , '~ aprotic n-butyl lac~one, ethylene c~l,o~ , propylene C;~IJO1~IC as the solvent.
When the aforesaid prior art elecllo~ 1 cell is used at a voltage range of 2 -2.8 V, ~nn-li7.in~ of the inside of the positive electrode case which is made of stainless 20 steel only, is ~cccl ~lr~, the solution of metal ions ~eCCJII1C;S more active, and then higher ~ .re in thc cell or a decrease in elec~ic capacity is observed. In order to S~l~lc~;~ the ~ n~ n, an ~ ..;.--.... layer is set inside the posi~ve electrode case.
Because of the above reason, a ~b~;..-ce of JIS standard SUS329Jl, or SUS449Jl cannot be used as the In;~ of the positive electrode case, and two - 25 l~---il--,t,d metals of stainless steel and ~l,-.";,,..." are used as m~t~-.ri~l~ for the positive electrode case. But uniform and equally ~ick ~1...";"..." layer is difflcult to . " . .
..... ~.~r~A~ and multiple lamination processes are llece~ for its production. The cost is more than several times as much as that of stainless steel.
Moreover, in the pressing process, the ~1. ,.;,.---., layer sometimes covers over the 30 upper side edge of the positive electrode case. In the assembling of the positive electrode case l, 2 and the negative electrode case by bending the positive electrode case inwards at the edge and by shielding the cell, 5~ on the inside of the '" 2il~24 positive electrode case comes o~f and small fragments of it become coupled with negative electrode 3. This c~ cause short-circuits. Even when the alul~ l layer does not cover the edge of the stainless steel, it can cause divergence between the positive electrode case and the negative electrode case as to shielding and this becomes a cause of short-circuits, also.
According to the present invention, in the use of an electrochemical cell with organic electrolytic liquid at a level of 2 - 2.8 V, ~no~ ing of the positive electrode cell without an alu.llillulll layer inside can be ~u~ ed and the product cost decreased.
Therefore the productivity can be illl~roved~
SUMMARY OF THE INVENTION
The present invention provides a small electrochemical cell having high capacity.
The present invention also provides a non-aqueous electrolyte electrochemical cell capable of operating at the highest working voltage of 2.8 V.
The present invention further provides a non-aqueous electrolyte electrochernical cell using st~inless steel of low cost as a positive electrode case.
Still filrther, the present invention provides a non-aqueous electrolyte :
electroch~mic~l cell using a stainless steel having a pitting index between 30.5 and 45 as a positive electrode case. ~
The aforesaid problems can be solved accol.lillg to the present invention in that -as the m~t~ri~1~ for the positive electrode case certain kinds of high Ni ~nct~nitic stainless steel or high pressure tightn~ tPnitic ferrite duplex stainless steel are used.
According to the present invention, an electro~h~mis~l cell at the highest working voltage of 2.8 V can be obtained.
- 25 High Ni ~ hnitic stainless steel used in this invention is high Cr. higher Mo.
n~nitic stainless steel, of which for ~y~m~le JIS standard SUS317J4L shows very good corrosion resistivity even in severe atm~-sph~res. Table 1 exhibits data relating to the rh.o.mic~l coll~on~ of high Cr. high Mo. austenitic stainless steel SUS317J4L.
.: .: . . . - .
-: . . . .
3 21~0~2~
[Table 1] ~.
C Si ~In Ni Cr Mo % 24 . 00 22 . 00 5 . 000 . 170' . .
<~ . 030 ~1. 00 <1 . 0~ ~ -26 . 00 24 . 00 6 . 000 . 220 SS329J4L, which is a type of ~k;li~lic Ferrite duplex stainless steel and of which a l~lJre3~ ivt; sample is 25Cr-6Ni-3.5 Mo also shows good ~IlCS;Ol).
re~i~tibility, although it is a little bit inferior to SUS317J4L. Table 2 exhibits the data .
relating to the chernical compon~nt.~ of SUS329J4L.
[Table 23 ~-~' '.
C Si Mn Ni Cr Mo N ~ .
~6 5 . 50 24 . 00 2 . 50 0 . 08 <0 . 030 <1. 00 <1 . 50 ~ . 50 2S . ~0 3 . 50 0 . 20 ;~
Even which ~e inside surface OI each electroc.ll~.mir~l cell with positive electrode case made of both the above ..,..~ - ;AlR iS c~nt~rted directed by organic electrolytic liquid - 15 or posi~ve el~tlode, dissolution into ~e organic electrolytic liquid will be ~ e;.~d .
because of its high corrosion le~ vily.
~..
BRIEF DES(~RIPTION OF THE 13RAWINGS
Fig. 1 shows a vertical cross se~,liun showing the internal structure of a part of an electrochemical cell of the present invention.
Fig. 2 shows a graph of the dependency of corrosion potential to ~ atulc on various stainless steels.
.. i,., . ~.. - . .... ..
~ : . , 0 2 ~
Fig. 3 shows a graph of voltage/current curve of various metals.
Fig. 4 shows a graph of percentage composition of Cr and Mo in relation to pitting temperature, which is taken from the lik,la~ulc.
Fig. 5 is a vertical cross-section showing the internal ~ lU~iL~lle of an electric 5 double-layer c~p~cil-,l of a conventional ele~ och~lllical cell.
Fig. 6 shows a vertical cross-section of a tra~liticm~l positive pole case partly enlarged.
DETAILED DESC~IPTION OF THE PREFERRED EM13ODIMENTS
The present invention will be described in connection to the accolllpa(lyillg 10 drawings.
(Embodiment 1) Corrosion tests on miscellaneous stainless steels in aqueous solutions were made.
Fig. 2 shows pitting corrosion potential in relation to dirr~ll t~lllpe~ s in aqueous solutions of mi~c~ n~ous ~hl~ri~leq a and b in Fig. 2 show l~;~e~-liv~lychar~cteriqtirs of SUS317J4L and SUS329J4L according to this invention and c shows a~ cs of SUS329Jl. When the l~..p~ in(,.eases, pitting coll~Ji,;on potential of a does not change, and ~at of b decl~ases, but the corrosion resistibility of both is ' good. Pitting corrosion potential of c decreases drastically in relation to higher - -t~ p- ,1t~.e and the corrosion resistibility of c is not good.
(Ernbodirnent 2) ~ -Miqc~ n~ous stainless steels are tested as to voltage/current cl~ I;c~q of Li/Li~ ,.f~r~lce electrode on the anode and on the cathode. In this test ~llat;l~lyl tetrafluoroborate [(C2H5)4NBF4] is dissolved in propylene c~lonal~ as for a battery electrolyte.
In Fig. 3. A and B ~ sc~ s;~e~tivc;ly ~lPm~ntq of SUS317J4L stainless steel, and of SUS329J~L stainless steel, accordhlg to this invention. C and D are ~or co...l.~. ;q~-n purpose for the prior art, and show voltage/current characteristics, res~e.;liv~ly, of ~lll...i.. -ll-l~min~t~d SUS329Jl, and SUS329Jl stainless steel. Metal dissolution occurs at the anode (ca~ode as for cell). When electric voltage is ~ ng~
30 the anode reaction h~ a~s at about 1.6 V for A and 1.7 V for B in this invention, and at about +2.6 V for C and 1.2 V for D in the prior art. All the aforesaid voltages are at a current density of 1 ~Vcm2.
~t~ 1002~
Fig~ 3 shows profiles at the twelfth sweep in repetition. Since the highest voltage of cell's cathode (anode in Fig. 3) is measured +1.2 V (for the reference -1.6V at anode at cell's Ill~hllulll usage voltage 2.8 V, the dissolution reaction of A and B in positive electrode does not occur because both are at a higher position than at the cell's cathode S voltage. D is ....~ r~c~ in its usage for element because the dissolution reaction of D occurs from +1.2 V, which is equivalent to the voltage (1.2 V) on the cell's cathode.
The stalting voltage for the dissolution reaction of C is higher because an oxide film is formed on the surface of ~l,..ni...-.., at the time of the voltage sweep.
Generally spe~l~ing it is said that corrosion ~ "re of stainless steel is affected 10 more by the inclusion of Cr and Mo and less by Ni, Cu, N. Pitting index (PI) is known as an in-lir~tor of corrosion reCi~nre and is shown as PI = Cr% + 3 x Mo% + 16 xN%.
[Table 3]
Present invention Prior art SUS317J4L SUS329J4L SUS329Jl PI ~:
value 42.0 ~ 36.5 30.1 The higher the Pl value, ~e better the corrosion le~ r~ But when PI is 45-50 or more, ~e ~luce~dl,ili~ and "-~o~ it~ ;cs of the ~ are inferior, then the specification~ for the positive electrode case are not fillfilled by such -~
ms~tP.ri~1~ A different evaluation of corrosion ~ ...ce which respmhle~ that of PI is - m~.nticm~d in J. Kolts, J. B. C. Wu. P. E. M~nnin~, and A. I. ~h~h~ni, "Hig~ly 25 Alloyed ~ nitic Material for Corrosion ~ lf~ll, Corrosion Reviews, 6(4), p.279 -326 (1986).
Fig. 4 is ~ dcled from ~e above, and shows the relation of critical len~ dlu-~
for pifflng and col.lpo~ilion for Fe-Ni-Cr-Mo alloys. Corrosion of the Fe-Ni-~r-Mo alloys is tested in the solvent of 4%NaCI + 1%Fe2(SO4)3 + O.OlMHCl.
As shown in Fig. 4, the higher ~e total of Cr% + 2.4Mo%, the higher the corrosion ~ r~ e acco.ding to the calculation of pitting l~ eldlul~s of SUS317J4L
-.. , . - . . , .
. i - - - - - - -~: . . - , . -''" 2~10~2~
and SUS329J4L in this invention of which Cr% and Mo% is referred to in Fig. 4. The figure of 55 - 70 C~ is ~stim itPtl, and this expects that the corrosion may be at considerably higher ~ ldlul~s.
(E~mbodiment 3) S By a pressing process, positive electrode cases were made with SUS317J4L of high Wi austenitic stainless steel plate (0.2 mm in thickness) and SUS329J4L of high corrosion resistable austenitic Ferrite duplex stainless steel plate (0.2 mm in ll~iCk~leS~), and for co~ oses, SIJS329J1 (layer thi~knPe~ of 0.16 rnm) with Al- ~ :~
SUS3291 of alulllh~ l (layer thickness of 40 ~m) and SUS329J1 stainless steel element only (thicknP~ of 0.2 mm) as shown in Fig. 5. Using the above positive electrodecases, an ele-;ll.~ch~lllical cell (Electric double layer capacitor) shown in Fig. 1 was assembled. In more detail, first, active carbon fiber (specific surface in 2000 m2/g) for polarizable electrode is pressed in the shape of a disc; second, such disc is inserted into the inside bottom of each of the aforesaid positive electrode 11 and negative electrode 16 after an electro-conductive paste 13, 13' is applied as a film, third, the con~ lion is dried for 2 hours at a l~ c~llulc of 100~C after cl;-l~ lg. On the positive electrode ~' which is ~ w~sed as above, disc-shaped s~ o~ 14 is s~t which is made of glass fiber '~
filter tbrough the drying process for 30 minutes at a I~ Gldlulc of 200~C, and then is ;:
filled with organic electrolytic liquid in which 1 mol. boron fluoride of tetra ethylene phc srhoric acid is dissolved. The positive electrode and negative electrode areassembled in one form after polypropylene gasket 15 is forced into the negative electrode. -Co~ the cells above, Table 3 shows a decreased ratio of capacity and increased ratio o~ AC in impedance (lllea~ d at 1 kHz) after 500 hours in an - 25 ~I."osl)h~e at 70~C, 2.8 V applied, and burr occllrring ratio of stainless steel or , burr at the process of assembling a cell of positive electrode case and negative electrode case in one form and bending and ~hi~ l;n~ the edge of the aforesaid positive electrode case inwardly. A, B, C, D shows l~e~iliv~ly SUS317J4L, SUS329J4L, A~/SUS329J1, SUS329J1 which is used for the positive electrode of an ele.;l,ochel.lical cell.
. .
-'~ 2~:~0i~24 ~Table 41 Cell Decrease ratio Increase ratio of Burr occuring of capacity(%) AC impedance (~) ratio (~) A - 4.3 ~ 15 0 :
B - 5.5 + 18 0 -~
C - 8.1 + 24 9.6 D ~35.6 + 53 0 ~ ;
According to Table 4, better results are reali7ed in the,case of a positive ~ ~, 10electrode case of the present invention which is without an alu~ layer than in ~at ~ 's;
of C which has an alu,~ .l layer, and the case of ~e prior art positive electrode case which h~ no ~ .. layer shows sharp ratios of change and l~ fole shows less reliability. Burrs at the process of cell ~hi~ in~ re not found in A and B of the present invention and in the case of C observed about 10% of burr occurrin~ ration of which bars are of ~1.. ";,.. , and comes offfrom alu~ layer.
(Embodiment 4) Using an organic s~-..;r~ J~Ao, capable of releasing and absorbing anions and/orcations, polyacene as for positive and lle~livt: electrode cells, cells are assembled in ~e sarne manner and con-lition~ as those of embodiment 3, and the same items of 20 ~,1.,..,.~ ~ ,.; ~1;~s are shown in table 4, in which ~or A, B, C, D the same positive elec~ode cases as in ~e embodiment 3 are used.
[Table S]
Cell Decrease ratio Increase ratio of Burr occuring of capacity(%3- AC impedance (%) ratio (%) A - 3.5 + 14 0 B - 5.4 + 19 0 C - 9.0 + 30 7.6 D -29.1 + 61 0 ':- ' 2 ~ 2 ~
(Embodiment 5) Using polyacene as the positive electrode, and Lithium-doped polyacene and propylene c~l,on~te with 0.5 mol. lithium perchlorate dissolved therein as for negative electrode, the cells are assembled in the same manner and conditions as for embodiment -5 3. Co~ those cells, Table 5 shows the decrease in ratio of capacity and increase in ratio of AC imre-l~nre (measured at 1 kHz) after 500 hours in an atrnl~sphPre at 60~C, 3.3 V applied, and bar oc.;~ ratio. By the way, A, B, C, D in Table 5 usedthe same positive electrode cases le~e~liv~ly as in the embodirnent 3.
[Table 6] -~
Cell Decrease ratio Increase ratio of Burr occuring :~
of capacity(~) AC impedance (%) ratio (%) A - 5.9 + 18 0 ~ :~
B - 6.8 + 23 0 C - 9.7 + 34 7.1 D 28.0 + 76 0 (En-bodi~ t 6) Using ...s~ se dioxide as the positive electrode, and Lithium metal as the negative electrode and as the organic electrolyte, a liquid of a rnixed solution of 2û propylene carbonate and 1,2-dim.-th~.xy...~ P with 1 mol lithium perchlorate, the cells are ~sspmhled in the same manner and conditions as ~or embodiment 3. C-n~Prnin~
those cells, Table 6 shows the same char~ctPri~ s as in the embodiment 3, but the observation is made after 500 hours kept in an ~I---n~ at 60~C. By the way for A, B, C, D in Table 6 the same positive electrode cases lc;~e~,lively as in the embodiment 25 3 are used.
.; . - . .. --. - .-,,;: .: . - .. .. . . - . . -'' 2 ~ 2 ~
'- g [Table 73 Cell Decrease ratio Increase ratio of Burr occuring of capacity(%) AC impedance (~) ratio (%) A - 3.0 + 12 O
B - 4 . 8 + 14 0 -~
C - 6.1 + 21 10.2 ;~
D -- 7 . 5 . + 25 0 According to the present invention, it is possible to have lower cost, higher corrosion resistibility m~tt~n~l~, to improve the productivity of a cell and moreover to obtain high pressure tightn~c~ electrochPmic~l cell.
[Table 1] ~.
C Si ~In Ni Cr Mo % 24 . 00 22 . 00 5 . 000 . 170' . .
<~ . 030 ~1. 00 <1 . 0~ ~ -26 . 00 24 . 00 6 . 000 . 220 SS329J4L, which is a type of ~k;li~lic Ferrite duplex stainless steel and of which a l~lJre3~ ivt; sample is 25Cr-6Ni-3.5 Mo also shows good ~IlCS;Ol).
re~i~tibility, although it is a little bit inferior to SUS317J4L. Table 2 exhibits the data .
relating to the chernical compon~nt.~ of SUS329J4L.
[Table 23 ~-~' '.
C Si Mn Ni Cr Mo N ~ .
~6 5 . 50 24 . 00 2 . 50 0 . 08 <0 . 030 <1. 00 <1 . 50 ~ . 50 2S . ~0 3 . 50 0 . 20 ;~
Even which ~e inside surface OI each electroc.ll~.mir~l cell with positive electrode case made of both the above ..,..~ - ;AlR iS c~nt~rted directed by organic electrolytic liquid - 15 or posi~ve el~tlode, dissolution into ~e organic electrolytic liquid will be ~ e;.~d .
because of its high corrosion le~ vily.
~..
BRIEF DES(~RIPTION OF THE 13RAWINGS
Fig. 1 shows a vertical cross se~,liun showing the internal structure of a part of an electrochemical cell of the present invention.
Fig. 2 shows a graph of the dependency of corrosion potential to ~ atulc on various stainless steels.
.. i,., . ~.. - . .... ..
~ : . , 0 2 ~
Fig. 3 shows a graph of voltage/current curve of various metals.
Fig. 4 shows a graph of percentage composition of Cr and Mo in relation to pitting temperature, which is taken from the lik,la~ulc.
Fig. 5 is a vertical cross-section showing the internal ~ lU~iL~lle of an electric 5 double-layer c~p~cil-,l of a conventional ele~ och~lllical cell.
Fig. 6 shows a vertical cross-section of a tra~liticm~l positive pole case partly enlarged.
DETAILED DESC~IPTION OF THE PREFERRED EM13ODIMENTS
The present invention will be described in connection to the accolllpa(lyillg 10 drawings.
(Embodiment 1) Corrosion tests on miscellaneous stainless steels in aqueous solutions were made.
Fig. 2 shows pitting corrosion potential in relation to dirr~ll t~lllpe~ s in aqueous solutions of mi~c~ n~ous ~hl~ri~leq a and b in Fig. 2 show l~;~e~-liv~lychar~cteriqtirs of SUS317J4L and SUS329J4L according to this invention and c shows a~ cs of SUS329Jl. When the l~..p~ in(,.eases, pitting coll~Ji,;on potential of a does not change, and ~at of b decl~ases, but the corrosion resistibility of both is ' good. Pitting corrosion potential of c decreases drastically in relation to higher - -t~ p- ,1t~.e and the corrosion resistibility of c is not good.
(Ernbodirnent 2) ~ -Miqc~ n~ous stainless steels are tested as to voltage/current cl~ I;c~q of Li/Li~ ,.f~r~lce electrode on the anode and on the cathode. In this test ~llat;l~lyl tetrafluoroborate [(C2H5)4NBF4] is dissolved in propylene c~lonal~ as for a battery electrolyte.
In Fig. 3. A and B ~ sc~ s;~e~tivc;ly ~lPm~ntq of SUS317J4L stainless steel, and of SUS329J~L stainless steel, accordhlg to this invention. C and D are ~or co...l.~. ;q~-n purpose for the prior art, and show voltage/current characteristics, res~e.;liv~ly, of ~lll...i.. -ll-l~min~t~d SUS329Jl, and SUS329Jl stainless steel. Metal dissolution occurs at the anode (ca~ode as for cell). When electric voltage is ~ ng~
30 the anode reaction h~ a~s at about 1.6 V for A and 1.7 V for B in this invention, and at about +2.6 V for C and 1.2 V for D in the prior art. All the aforesaid voltages are at a current density of 1 ~Vcm2.
~t~ 1002~
Fig~ 3 shows profiles at the twelfth sweep in repetition. Since the highest voltage of cell's cathode (anode in Fig. 3) is measured +1.2 V (for the reference -1.6V at anode at cell's Ill~hllulll usage voltage 2.8 V, the dissolution reaction of A and B in positive electrode does not occur because both are at a higher position than at the cell's cathode S voltage. D is ....~ r~c~ in its usage for element because the dissolution reaction of D occurs from +1.2 V, which is equivalent to the voltage (1.2 V) on the cell's cathode.
The stalting voltage for the dissolution reaction of C is higher because an oxide film is formed on the surface of ~l,..ni...-.., at the time of the voltage sweep.
Generally spe~l~ing it is said that corrosion ~ "re of stainless steel is affected 10 more by the inclusion of Cr and Mo and less by Ni, Cu, N. Pitting index (PI) is known as an in-lir~tor of corrosion reCi~nre and is shown as PI = Cr% + 3 x Mo% + 16 xN%.
[Table 3]
Present invention Prior art SUS317J4L SUS329J4L SUS329Jl PI ~:
value 42.0 ~ 36.5 30.1 The higher the Pl value, ~e better the corrosion le~ r~ But when PI is 45-50 or more, ~e ~luce~dl,ili~ and "-~o~ it~ ;cs of the ~ are inferior, then the specification~ for the positive electrode case are not fillfilled by such -~
ms~tP.ri~1~ A different evaluation of corrosion ~ ...ce which respmhle~ that of PI is - m~.nticm~d in J. Kolts, J. B. C. Wu. P. E. M~nnin~, and A. I. ~h~h~ni, "Hig~ly 25 Alloyed ~ nitic Material for Corrosion ~ lf~ll, Corrosion Reviews, 6(4), p.279 -326 (1986).
Fig. 4 is ~ dcled from ~e above, and shows the relation of critical len~ dlu-~
for pifflng and col.lpo~ilion for Fe-Ni-Cr-Mo alloys. Corrosion of the Fe-Ni-~r-Mo alloys is tested in the solvent of 4%NaCI + 1%Fe2(SO4)3 + O.OlMHCl.
As shown in Fig. 4, the higher ~e total of Cr% + 2.4Mo%, the higher the corrosion ~ r~ e acco.ding to the calculation of pitting l~ eldlul~s of SUS317J4L
-.. , . - . . , .
. i - - - - - - -~: . . - , . -''" 2~10~2~
and SUS329J4L in this invention of which Cr% and Mo% is referred to in Fig. 4. The figure of 55 - 70 C~ is ~stim itPtl, and this expects that the corrosion may be at considerably higher ~ ldlul~s.
(E~mbodiment 3) S By a pressing process, positive electrode cases were made with SUS317J4L of high Wi austenitic stainless steel plate (0.2 mm in thickness) and SUS329J4L of high corrosion resistable austenitic Ferrite duplex stainless steel plate (0.2 mm in ll~iCk~leS~), and for co~ oses, SIJS329J1 (layer thi~knPe~ of 0.16 rnm) with Al- ~ :~
SUS3291 of alulllh~ l (layer thickness of 40 ~m) and SUS329J1 stainless steel element only (thicknP~ of 0.2 mm) as shown in Fig. 5. Using the above positive electrodecases, an ele-;ll.~ch~lllical cell (Electric double layer capacitor) shown in Fig. 1 was assembled. In more detail, first, active carbon fiber (specific surface in 2000 m2/g) for polarizable electrode is pressed in the shape of a disc; second, such disc is inserted into the inside bottom of each of the aforesaid positive electrode 11 and negative electrode 16 after an electro-conductive paste 13, 13' is applied as a film, third, the con~ lion is dried for 2 hours at a l~ c~llulc of 100~C after cl;-l~ lg. On the positive electrode ~' which is ~ w~sed as above, disc-shaped s~ o~ 14 is s~t which is made of glass fiber '~
filter tbrough the drying process for 30 minutes at a I~ Gldlulc of 200~C, and then is ;:
filled with organic electrolytic liquid in which 1 mol. boron fluoride of tetra ethylene phc srhoric acid is dissolved. The positive electrode and negative electrode areassembled in one form after polypropylene gasket 15 is forced into the negative electrode. -Co~ the cells above, Table 3 shows a decreased ratio of capacity and increased ratio o~ AC in impedance (lllea~ d at 1 kHz) after 500 hours in an - 25 ~I."osl)h~e at 70~C, 2.8 V applied, and burr occllrring ratio of stainless steel or , burr at the process of assembling a cell of positive electrode case and negative electrode case in one form and bending and ~hi~ l;n~ the edge of the aforesaid positive electrode case inwardly. A, B, C, D shows l~e~iliv~ly SUS317J4L, SUS329J4L, A~/SUS329J1, SUS329J1 which is used for the positive electrode of an ele.;l,ochel.lical cell.
. .
-'~ 2~:~0i~24 ~Table 41 Cell Decrease ratio Increase ratio of Burr occuring of capacity(%) AC impedance (~) ratio (~) A - 4.3 ~ 15 0 :
B - 5.5 + 18 0 -~
C - 8.1 + 24 9.6 D ~35.6 + 53 0 ~ ;
According to Table 4, better results are reali7ed in the,case of a positive ~ ~, 10electrode case of the present invention which is without an alu~ layer than in ~at ~ 's;
of C which has an alu,~ .l layer, and the case of ~e prior art positive electrode case which h~ no ~ .. layer shows sharp ratios of change and l~ fole shows less reliability. Burrs at the process of cell ~hi~ in~ re not found in A and B of the present invention and in the case of C observed about 10% of burr occurrin~ ration of which bars are of ~1.. ";,.. , and comes offfrom alu~ layer.
(Embodiment 4) Using an organic s~-..;r~ J~Ao, capable of releasing and absorbing anions and/orcations, polyacene as for positive and lle~livt: electrode cells, cells are assembled in ~e sarne manner and con-lition~ as those of embodiment 3, and the same items of 20 ~,1.,..,.~ ~ ,.; ~1;~s are shown in table 4, in which ~or A, B, C, D the same positive elec~ode cases as in ~e embodiment 3 are used.
[Table S]
Cell Decrease ratio Increase ratio of Burr occuring of capacity(%3- AC impedance (%) ratio (%) A - 3.5 + 14 0 B - 5.4 + 19 0 C - 9.0 + 30 7.6 D -29.1 + 61 0 ':- ' 2 ~ 2 ~
(Embodiment 5) Using polyacene as the positive electrode, and Lithium-doped polyacene and propylene c~l,on~te with 0.5 mol. lithium perchlorate dissolved therein as for negative electrode, the cells are assembled in the same manner and conditions as for embodiment -5 3. Co~ those cells, Table 5 shows the decrease in ratio of capacity and increase in ratio of AC imre-l~nre (measured at 1 kHz) after 500 hours in an atrnl~sphPre at 60~C, 3.3 V applied, and bar oc.;~ ratio. By the way, A, B, C, D in Table 5 usedthe same positive electrode cases le~e~liv~ly as in the embodirnent 3.
[Table 6] -~
Cell Decrease ratio Increase ratio of Burr occuring :~
of capacity(~) AC impedance (%) ratio (%) A - 5.9 + 18 0 ~ :~
B - 6.8 + 23 0 C - 9.7 + 34 7.1 D 28.0 + 76 0 (En-bodi~ t 6) Using ...s~ se dioxide as the positive electrode, and Lithium metal as the negative electrode and as the organic electrolyte, a liquid of a rnixed solution of 2û propylene carbonate and 1,2-dim.-th~.xy...~ P with 1 mol lithium perchlorate, the cells are ~sspmhled in the same manner and conditions as ~or embodiment 3. C-n~Prnin~
those cells, Table 6 shows the same char~ctPri~ s as in the embodiment 3, but the observation is made after 500 hours kept in an ~I---n~ at 60~C. By the way for A, B, C, D in Table 6 the same positive electrode cases lc;~e~,lively as in the embodiment 25 3 are used.
.; . - . .. --. - .-,,;: .: . - .. .. . . - . . -'' 2 ~ 2 ~
'- g [Table 73 Cell Decrease ratio Increase ratio of Burr occuring of capacity(%) AC impedance (~) ratio (%) A - 3.0 + 12 O
B - 4 . 8 + 14 0 -~
C - 6.1 + 21 10.2 ;~
D -- 7 . 5 . + 25 0 According to the present invention, it is possible to have lower cost, higher corrosion resistibility m~tt~n~l~, to improve the productivity of a cell and moreover to obtain high pressure tightn~c~ electrochPmic~l cell.
Claims (5)
1. A non-aqueous electrolyte electrochemical cell comprising:
a positive electrode case comprising a stainless steel selected from the group consisting of austenitic stainless steel and austenitic ferrite stainless steel having a pitting index between 30.5 and 45, the pitting index being calculated by a formula Cr% + 3 x Mo% + 16 x N%.
a positive electrode case comprising a stainless steel selected from the group consisting of austenitic stainless steel and austenitic ferrite stainless steel having a pitting index between 30.5 and 45, the pitting index being calculated by a formula Cr% + 3 x Mo% + 16 x N%.
2. A non-aqueous electrolyte electrochemical cell according to claim 1, wherein the stainless steel is an austenitic ferrite two phase stainless steel.
3. A non-aqueous electrolyte electrochemical cell according to claim 2, wherein the austenitic ferrite two phase stainless steel comprises 4.5 to 13% Ni, 20 to 26% Cr, 2 to 4%
Mo and 0.05 to 0.3%N.
Mo and 0.05 to 0.3%N.
4. A non-aqueous electrolyte electrochemical cell according to claim 1, wherein the stainless steel is a high Ni austenitic stainless steel.
5. A non-aqueous electrolyte electrochemical cell according to claim 4, wherein the high Ni austenitic stainless steel comprises 17 to 31% Ni, 19 to 26% Cr, 2 to 6% Mo. and 0.1 to 0.3% N.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31729692 | 1992-11-26 | ||
| JP4-317296 | 1992-11-26 | ||
| JP5-241593 | 1993-09-28 | ||
| JP24159393A JP3195475B2 (en) | 1992-11-26 | 1993-09-28 | Electrochemical cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2110024A1 CA2110024A1 (en) | 1994-05-27 |
| CA2110024C true CA2110024C (en) | 1999-06-01 |
Family
ID=26535345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002110024A Expired - Fee Related CA2110024C (en) | 1992-11-26 | 1993-11-25 | Non-aqueous electrolyte cell |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5478670A (en) |
| EP (1) | EP0599654B1 (en) |
| JP (1) | JP3195475B2 (en) |
| KR (1) | KR940008153A (en) |
| CN (1) | CN1132256C (en) |
| CA (1) | CA2110024C (en) |
| DE (1) | DE69319208T2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5656392A (en) * | 1995-03-20 | 1997-08-12 | Matsushita Electric Industrial Co., Ltd. | Organic electrolyte batteries |
| US6238971B1 (en) * | 1997-02-11 | 2001-05-29 | Micron Technology, Inc. | Capacitor structures, DRAM cell structures, and integrated circuitry, and methods of forming capacitor structures, integrated circuitry and DRAM cell structures |
| US7199997B1 (en) * | 2000-06-09 | 2007-04-03 | U.S. Nanocorp, Inc. | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| KR20000059235A (en) * | 2000-07-20 | 2000-10-05 | 라두호 | Functional custom bra x inhalation, exhaust |
| JP4437036B2 (en) * | 2003-12-26 | 2010-03-24 | パナソニック株式会社 | Case material for storage cells |
| JP4665513B2 (en) * | 2004-11-25 | 2011-04-06 | パナソニック株式会社 | Method for producing coin-type electrochemical device |
| KR100897638B1 (en) | 2004-11-25 | 2009-05-14 | 파나소닉 주식회사 | Method of producing coin-shaped electrochemical element and coin-shaped electrochemical element |
| US7465521B2 (en) * | 2004-12-08 | 2008-12-16 | Greatbatch Ltd. | Nickel-based alloys as positive electrode support materials in electrochemical cells containing nonaqueous electrolytes |
| KR100659850B1 (en) * | 2005-04-26 | 2006-12-19 | 삼성에스디아이 주식회사 | Battery exterior material using ferritic sus and secondary battery using the same |
| JP2008269972A (en) * | 2007-04-20 | 2008-11-06 | Nissan Motor Co Ltd | Non-aqueous solvent secondary battery |
| CN102332602B (en) * | 2011-01-26 | 2013-11-13 | 东莞新能源科技有限公司 | Cylindrical lithium-ion battery |
| EP2803096A1 (en) | 2012-01-13 | 2014-11-19 | Eveready Battery Company, Inc. | Lithium coin cell construction to mitigate damage from ingestion |
| JP6327633B2 (en) * | 2013-09-19 | 2018-05-23 | セイコーインスツル株式会社 | Diaphragm made of duplex stainless steel |
| CN109346627A (en) * | 2018-11-28 | 2019-02-15 | 东莞市电的电子有限公司 | Button Lithium Ion Battery |
| CN112701388A (en) * | 2020-12-28 | 2021-04-23 | 惠州亿纬创能电池有限公司 | Electrode shell of steel shell button cell, steel shell button cell comprising electrode shell and application of steel shell button cell |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5528238A (en) * | 1978-08-17 | 1980-02-28 | Matsushita Electric Ind Co Ltd | Flat battery |
| US4824745A (en) * | 1987-02-25 | 1989-04-25 | Bridgestone Corporation | Electric cell comprising a polymeric material film electrode having a collection integrated therewith |
| DE3918963A1 (en) * | 1988-06-20 | 1989-12-21 | Bridgestone Corp | Secondary cell with non-aqueous, liquid electrolyte |
| JPH02126554A (en) * | 1988-11-07 | 1990-05-15 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary cell |
| US5114811A (en) * | 1990-02-05 | 1992-05-19 | W. Greatbatch Ltd. | High energy density non-aqueous electrolyte lithium cell operational over a wide temperature range |
| US5114810A (en) * | 1990-02-05 | 1992-05-19 | Wilson Greatbatch Ltd. | Cathode current collector material for solid cathode cell |
| JP3023129B2 (en) * | 1990-02-19 | 2000-03-21 | 鐘紡株式会社 | Wet condenser using organic semiconductor |
| JPH0410365A (en) * | 1990-04-26 | 1992-01-14 | Hitachi Maxell Ltd | Lithium secondary battery |
| JP2951706B2 (en) * | 1990-09-11 | 1999-09-20 | 旭化成工業株式会社 | Battery components |
| JPH05133755A (en) * | 1991-11-13 | 1993-05-28 | Akai Electric Co Ltd | Vibratory gyroscope with diagnostic function |
-
1993
- 1993-09-28 JP JP24159393A patent/JP3195475B2/en not_active Expired - Lifetime
- 1993-11-17 US US08/153,586 patent/US5478670A/en not_active Expired - Lifetime
- 1993-11-24 KR KR1019930025149A patent/KR940008153A/en not_active Withdrawn
- 1993-11-25 CN CN93121448A patent/CN1132256C/en not_active Expired - Lifetime
- 1993-11-25 CA CA002110024A patent/CA2110024C/en not_active Expired - Fee Related
- 1993-11-26 EP EP93309441A patent/EP0599654B1/en not_active Expired - Lifetime
- 1993-11-26 DE DE69319208T patent/DE69319208T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69319208T2 (en) | 1998-10-15 |
| US5478670A (en) | 1995-12-26 |
| JP3195475B2 (en) | 2001-08-06 |
| EP0599654B1 (en) | 1998-06-17 |
| DE69319208D1 (en) | 1998-07-23 |
| CN1096136A (en) | 1994-12-07 |
| JPH06215738A (en) | 1994-08-05 |
| KR940008153A (en) | 1994-04-29 |
| EP0599654A1 (en) | 1994-06-01 |
| CN1132256C (en) | 2003-12-24 |
| CA2110024A1 (en) | 1994-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2110024C (en) | Non-aqueous electrolyte cell | |
| KR100405873B1 (en) | Laser Sealed Battery | |
| Myung et al. | Electrochemical behavior and passivation of current collectors in lithium-ion batteries | |
| Morimoto et al. | Electric double-layer capacitor using organic electrolyte | |
| US5989743A (en) | Non-aqueous battery | |
| KR101918008B1 (en) | Copper-clad steel foil, anode collector, method for producing same, and battery | |
| JP5672464B2 (en) | Secondary battery and manufacturing method thereof | |
| EP0402554B1 (en) | Method of conditioning of organic polymeric electrodes | |
| EP1043744B1 (en) | Capacitor with dual electric layer | |
| US20130149436A1 (en) | Process for preparing a solid state electrolyte used in an electrochemical capacitor | |
| EP0780920B1 (en) | Non-aqueous battery | |
| KR102823289B1 (en) | Electrode current collector and secondary battery | |
| JPH06111849A (en) | Nonaqueous battery | |
| US5437942A (en) | Lithium secondary battery | |
| US4757424A (en) | Electric double layer capacitor | |
| US20100021807A1 (en) | Energy storage device | |
| JP2011181486A (en) | Evaluation method of electrolyte for secondary battery | |
| JP3576948B2 (en) | Electrochemical cell | |
| JPH08222191A (en) | Electrochemical cell | |
| JPH01221860A (en) | Secondary battery | |
| JPH06150936A (en) | Battery member | |
| CN116818643A (en) | Method for measuring corrosion rate of aluminum foil for battery | |
| Arnaud et al. | Coupled Cyclic Voltammetry and Operando Space Charge Distribution Measurements | |
| JPH0251875A (en) | Nonaqueous electrolyte secondary battery | |
| JPH01241110A (en) | Electric double layer capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |