CA1285318C - Non-aqueous secondary cell - Google Patents

Non-aqueous secondary cell

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Publication number
CA1285318C
CA1285318C CA000550739A CA550739A CA1285318C CA 1285318 C CA1285318 C CA 1285318C CA 000550739 A CA000550739 A CA 000550739A CA 550739 A CA550739 A CA 550739A CA 1285318 C CA1285318 C CA 1285318C
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CA
Canada
Prior art keywords
lithium
cell
manganese dioxide
heat
mixture
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 - Lifetime
Application number
CA000550739A
Other languages
French (fr)
Inventor
Nobuhiro Furukawa
Toshihiko Saito
Toshiyuki Nohma
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Sanyo Electric Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

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

Abstract

Abstract of the Disclosure A non-aqueous secondary cell is provided which is repeatedly chargeable and dischargeable. This cell comprises, as main components thereof, a negative electrode, a positive electrode, and a separator disposed between the negative and positive electrode and impregnated with an electrolyte. The negative electrode has lithium or lithium alloy as the active material. The positive electrode has manganese dioxide as the active material and contains Li2MnO3.

Description

~L21~3~3 NON-AQUEOUS SECONDARY CELL l Background of the Invention (1~ Field of the Invention The present invention relates to a non-aqueous secondary cell in which lithium or lithium alloy is used as the active material for the negative electrode, and particularly to an improvement in the positive electrode. Brief Description of the Drawings Figs. 1a-1e are views showing diffraction patterns where charges and discharges are repeated on a cell having a positive electrode formed of y-~ MnO2, wherein Fig. 1a shows a diffraction pattern prior to charging and discharging, FigsO 1b and 1c show diffraction patterns at a 1Oth discharge and a subsequent charge, respectively, and Figs. ld and le show diffraction patterns at a 100th discharge and a subsequent charge, respectively, Fig. 2 is a half section of a cell according to the present invention, Fig. 3 is a view showing charge and discharge characteristics of the cell, Figs. 4a--4e are views showing diffraction patterns where charging and discharging are repeated -- 1 -- ~2~i3~3 l on the cell according to the present invention, wherein Fig. 4a shows a diffraction pattern prior to charging and discharging, Figs. 4b and 4c show diffraction patterns at a 1Oth discharge and a subsequent charge, respectively, and Figs. 4d and 4e show diffraction patterns at a 100th discharge and a subsequent charge, respectively, Figs. 5 through 9 are views showing diffraction patterns for checking heat treatment temperature conditions for preparing Li2MnO3, where heat treatment is effected at temperatures of 250C, 300C, 375C, 430C, and 500C, respectively, and Figs. 10 through 16 are views showing diffraction patterns for checkiny molar ratios between ~i and Mn for producing Li2MnO3, where Li and Mn are mixed in the ratios of 5:95, 10:90, 20:80, 30:70, 50:50, 70:30, and 85:15, respectively. (2) Description of the Prior Art Molybdenum trioxide, vanadium pentoxide and niobic sulfide have been proposed as the active material for the positive electrode of this type of secondary cell, but these substances have not been put to practical use to date. For the positive electrode of the non-aqueous primary cell, on the other hand, manganese dioxide and carbon fluoride are known to be typical examples of active material and are actually employed for the l purpose. Manganese dioxide has the advantages of being excellent in storage characteristics, abundant in the earth and inexpensive. As the crystal structure of manganese dioxide suited for the positive electrode, y -~ MnO2 heat- treated at temperatures of 250-350C has been proposed as in Japanese Patent Publication No. 49-25571. This r-~ MnO2,however, is unsatisfactory in reversibility and has the problem of lowering charge and discharge characteristics. The reason will be explained with reference to Figs. 1a-1e of the accompanying drawings showing X-ray diffraction patterns. Fig. 1a shows a diffraction pattern prior to charging and discharging. Figs. 1b and 1c show lS diffraction patterns at a 10th discharge and charge, respectively. Compared with the pattern of Fig. 1a, it will be seen that the patterns of Figs. 1b and 1c show the angles of diffraction shifting to a lower side and the peaks becoming less sharp. These trends are more conspicuous and the peaks are almost leveled out in the patterns at a 100th discharge and charge shown in Figs. 1d and 1e, respectively. It may be deduced from the above that a repetition of charges and discharges results in widening of the bond length between manganese and oxygen and in loosening of the crystal structure of manganese dioxide. Consequently, the manganese dioxide has poor reversibility and charge and discharge characteristics. -- 3 -- 5~8 l This applies also to ~ -MnO2 heat-treated at temperatures of 350-430C as disclosed in U.S. Patent 4,133,856. Thus, manganese dioxide is desirable as the active material for the positive electrode of the non- aqueous secondary cell, but involves difficulties in practice. Summary of the Invention The object of the present invention, therefore, is to improve the reversibility of manganese dioxide without impairing the advantages of manganese dioxide, i.e. excellent storage characteristics, availability in abundance and low cost, thereby to improve charge and discharge cycle characteristics of the non-aqueous lS manganese dioxide-lithium secondary cell. The above object is fulfilled by a repeatedly chargeable and dischargeable non-aqueous secondary cell comprising a negative electrode having lithium or lithium alloy as an active matsrial, a positive electrode having manganese dioxide as an active material, the positive electrode including Li2MnO3, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte. The above Li2MnO3 is obtained by heat-treating a mixture of manganese dioxide and lithium salt. ~s~ 1 Specifically, the lithium salt is selected from the group consisting of lithium hydroxide, lithium nitrate, lithium phosphate, lithium carbonate and lithium oxide. in a lithium-manganese molar ratio range of 10:90 to 70:30~ The mixture of manganese dioxide and lithium salt is heat-treated in a temperature range of 300-430C, preferably 350-430C. The positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce manganese dioxide and Li2MnO3, thereafter adding a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture. The positive electrode may also be formed by heat-treating a mixture of manganese dioxide and lithium salt to produce manganese dioxide and Li2MnO3, thereafter adding further manganese dioxide, a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture. Alternatively, the positive electrode may be formed by heat-treating a mixture of manganese dioxide and lithium salt to produce Li2MnO3, thereafter adding manganese dioxide, a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture~ 1 According to the present invention, the positive electrode lncludes Li2MnO3 in addition to manganese dioxide constituting the actlve material. This composition prevents widening of the bond length between manganese and oxygen in the manganese dioxide and loosening of the crystal structure of the manganese dioxide. Thus, the present invention provides an improvement in the reversibility and charge and discharge characteristics. ~n Detailed Description of the Invention EXAMPLE 1 A first example embodying the present invention will be described hereinafter with reference to a flat type non-aqueous secondary cell as shown in Fig. 2. The illustrated cell comprises positive and negative cans 1 and 2 formed of stainless steel and separated from each other by an insulating packing 3 formed of polypropylene. Number 4 indicates a positive electrode constituting the gist of this invention, which is pressed upon a positive collector 5 secured to a bottom inside surface of the positive i3~8 can 10 Number 6 indicates a negative elect~ode pressed upon a negative collector 7 secured to a bottom inside surface of the negative can 2. Number 8 indicates a separator comprising a porous membrane of polypropylene. This cell employs an electrolyte comprising l.ithium perchlorate di~solved in 1 mol/liter in a solve~t mixture of propylene carbonate and dimethoxyethane~ The positive and negative electrodes ar~ prepared as follows: 80 grams of chemical manganese dioxide having an average particle size not exceeding 30 micron and 20 grams of lithium hydroxide are first mixed in a mortar, and then heat-t.reated in the air at 375C for twenty hours. This heat treatment produces a mixture in which manganese dioxide and Li2MnO3 coexist. The reaction formula for the Li2MnO3 productic,n i5 as follows: MnO2 ~ 2LiGH ~ Li2MnO3 ~ H2O ... (1) Next, the active material powder thus obtained is mixed with acetylene black acting as conductive agent and fluoric resin powder acting as binder in a weight ratio of 90:6:4 to produce a blend for forming the positive electrode. This blend is molded under a pressure of 2 tons/cm2 into a shape having a 20mm diameter, and then heat-treated at 250C, whereby the ;3~1~ positive electrode is completed. The negative electrode, on the othex hand, is prepared by punching a piece 20mm in diamPter out of a lithium foil having a selected thickness. Incidentally, the cell is 24.0mm in diameter and 3.0mm in thickness. This cell em~odying the present invention is hereinafter referred to as Cell A1. EXAMPLE 2 A positive electrode is produced in the same way as in EXAMPLE 1 except that 60 grams of lithium carbonate are used instead of the 20 grams o~ lithium hydroxide. This cell is hereinafter referred to as Cell A2. The reaction formula for the I.i2MnO3 production in this example is as rollows: ~n2 + Li2C03 ~ Li2MnO3 ~ CO2 COMPARATIVE EXAMPLE 1 A positive electrode i5 produced in the same way as in EXAMPLE 1 except that the lithium salt Is not added. This cell produced for comparison purposes is hereinafter referred to as Cell B1. COMPARATIVE EXAMPLE 2 Manganese dio~ide is added and mixed with lithium hydroxide as in EXAMPLE 1 but, as distinct .rom EXAMPLE ~, the mixture is not heat-treated here. ~he cell thus produced is hereinafter referred to as Cell - 8 - ~2~5;~ B2. Fig. 3 shows charge and discharge cycle characteristics of these cells. The data were obtained from the conditions that the discharge was carried out in a curr~nt of 3mA for four hours, the charge in the current of 3mA, and the charge ending voltage was 400V. It will be seen rrom Fig. 3 that discharge ~nding ~oltages of Cells B1 and B~ drop sharply around the 100th cycle whereas those of Cells A1 and A2 emb~dying the preserlt inven-tion do not show sharp drops up to the ~icinity of 150 cycles. This demonstrates an improvement in the cycle characteristics. From the characteristics of Cells B1 and B2 produced for compar:ison purposes, it is understo3d that the addition of lithium salt would not produce a sat:isfactory result for improving the cycl~ characteristics unless it is present in the positlve electrode in the form of Li2MnO3. The reason for the improvement in the cycle characteristics will be explained next with reference to Figs. 4a-4e. Compared with the a diffraction pattern 2rior t~ charging and discharging shown in Fig. 4a. diffraction patterns at a 1Oth cycle discharge and a subsequent char~e shown in Figs. 4b and 4c indicate no wea~ening ~213~i3~ of the peaks and no shift of diffxaction angles. This ~s true also of diffraction patterns at a 100th cyc~e discharye and a subsequent charge shown in Figs. 4d an~ 4e. This demonstrates that the bon~ length between manganese and oxygen does not increase and the crystal structuxe of manganese dioxide does not ~ecome loose with a repetition of charges and discharges~ Thus, the cells according to the present invention have improved reversibility and charge and discharge characteristics. Heat treatment temperatures for producing Li2MnO~ have been checked, and the results will be ~escribed hereinafter referring to the X-ray diffraction patterns shown in Figs. 5 through 9. In these tests lithium and manganese were mixed in a fixed ratio of 30 70l and LiOH was used as the lithium salt ard MnO2 as the manganese oxide. When the heat treatment was carried out at 250C, Li2~lnO3 was not produced at all as shown in Fig. 5. The reason is considered that no reaction takes place between LiOH and MnO2 at this temperature. Consequently, the heat treatment at this temperature is inadequate for the purpose of the present invention. When ths heat txeatment was arried out at 300C, 375C and 430C, Li2MnO3 was produced and MnO2 remained as shown in Figs. 6 through 8, respectively. - 10 - L3~3 I~ appears that~ in this temperature range, a reaction as expressed in the foregoing formula (1) takes place between LiOH and MnO~, and only ~nO2 remains ater all LiOH has reacted with MnO2. Consequently, the heat treatment in the temperature range of 300-~30C produces the effect of the invention tv the full. Further, when the heat treatment was carried out at 500C, Li2MnO3 was produced and MnO2 remained, but Mn2O3 which is an undesirable cell materia]. was produced as a result of decomposition of MnO2 as shown in FigO 9~ Consequently the heat treatment at this temperature fail.s to produce the effect oE the invention. The above test results prove that the desirable temperature range for the heat treatment i5 from 3.00~C to 430C. The heat treatment carried out in the tempe:!ature range of 300-430C has the advantage of proclucing Li2MnO3 and dehydrating MnO2 acting as the actiYe material. Where the heat treatment for producing Li2MnO3 is aimed at removal of combined water in manganese d.ioxide, it is desirable to carry out the heat treatment in the temperature range of 350 430C. Furthermore, molar ratios between lithium and manganese for producing Li2MnO3 were checked and the results will be described hereinafter referring to the X-ray diffraction patterns shown in Figs. 10 through 1 60 In these tests the heat treatment temperature was fixed to 375C, and LiOH was used as the lithium salt and MnO2 as the manganese oxideO When lithium and manganese were mixe~ in a molar ratio of 5:95, Li2MnO3 was not produced at all as shown in FigO 1 0~ Consequently, the molar rat:io of 5:95 between lithium and manganese does not accomplish the purpose of the present invention. When the lithium and manganese were mixed in molar ratios of 10:90~ 20:80, 30:70, 50:50, and 70:30, Li2~nO3 was produced as shown in Figs. 11 through 15~ respectively. This is because, in this range of mixing ratios, the reaction expressed in the formula - (1) takes place between LiOH and MnO2. Consequently, mixing of lithium and manganese in the molar ratio of 10:90 to 70.30 produces the effect of the invention to the full. Further, when the lithium and manganese were mixed in a molar ratio of 85:15, Li2MnO3 was produced but LiOH which is an undesirable cell material remained as shown in Fig. 16. Consequently the mixing lithium and manganese in this molar ratio fails to produce the effect of the inven~ion. The above test results prove that the desirable molar ratio range between lithium and manganese is - 12 - from 10:90 to 70:30. When lithium and manganese were mixed in the molar ratio of 70~30, Li2MnO3 was produced but MnO2 was not as shown in Fig. 15O Even sc, the purpose of the invention will be fulfilled by adding MnO2 after producing Li2MnO3O Further, it is possible to vary the ratio between Li2MnO3 and MnO2 by mixing l~thium and manganese in the molar ratio range of 10 90 to 70:30 to produce Li2MnO3 and thereafter adding MnO2. In obtaining Li2MnO3 by heat-treating the mixture of manganese dioxide and lithium salt as in this invention, the lithium salt is not limited to those given in the foregoing examples but may comprise lithium nitrate, lithium phosphate or lithium oxide. The type of manganese dioxide is not limitéd to chemical manganese dioxide but may of course ccmprise natural manganese dioxide or electrolytic manganese dioxide. Furthermore, the present invention is app:Licable not only to the non-aqueous electrolyte cell but to the solid electrolyte cell also~ - 13 -

Claims (19)

  1. What is claimed is: 1. A repeatedly chargeable and dischargeable non- aqueous secondary cell comprising; a negative electrode having lithium or lithium alloy as an active material, a positive electrode having manganese dioxide as an active material, said positive electrode including Li2MnO3, a separator disposed between said positive electrode and said negative electrode, and a non-aqueous electrolyte.
  2. 2. A cell as claimed in claim 1 wherein said Li2MnO3 is obtained by heat-treating a mixture of manganese dioxide and lithium salt.
  3. 3. A cell as claimed in claim 2 wherein said lithium salt is selected from the group consisting of lithium hydroxide, lithium nitrate, lithium phosphate, lithium carbonate and lithium oxide.
  4. 4. A cell as claimed in claim 2 wherein said lithium salt and manganese dioxide are mixed in a lithium- manganese molar ratio range of 10:90 to 70:30. - 14 -
  5. 5. A cell as claimed in claim 2 wherein said mixture of manganese dioxide and lithium salt is heat-treated in a temperature range of 300-430.degree.C, preferably 350- 430.degree.C.
  6. 6. A cell as claimed in claim 1 wherein said positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce manganese dioxide and Li2MnO3, thereafter adding a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture.
  7. 7. A cell as claimed in claim 1 wherein said positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce manganese dioxide and Li2MnO3, thereafter adding further manganese dioxide, a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture.
  8. 8. A cell as claimed in claim 1 wherein said positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce Li2MnO3, thereafter adding manganese dioxide, a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture. - 15 -
  9. 9. A cell as claimed in claim 1 wherein said negative electrode is selected from the group consisting of pure lithium, lithium-aluminum alloy and lithium- magnesium alloy.
  10. 10. A cell as claimed in claim 1 wherein said separator comprises a porous membrane of polypropylene.
  11. 11. A cell as claimed in claim 1 wherein said electrolyte comprises a liquid mixture formed by dissolving lithium perchlorate in a solvent mixture of propylene carbonate and dimethoxyethane.
  12. 12. A cell as claimed in claim 1 wherein said positive electrode is pressed upon a positive collector secured to a bottom inside surface of a positive terminal can.
  13. 13. A cell as claimed in claim 1 wherein said negative electrode is pressed upon a negative collector secured to a bottom inside surface of a negative terminal can.
  14. 14. A repeatedly chargeable and dischargeable non- aqueous secondary cell comprising; - 16 - a negative electrode having lithium or lithium alloy as an active material, a positive electrode having a mixture in which manganese dioxide as an active material and Li2MnO3 coexist, a separator disposed between said positive electrode and said negative electrode, and a non-aqueous electrolyte.
  15. 15. A cell as claimed in claim 14 wherein said positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce manganese dioxide and Li2MnO3, thereafter adding a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture.
  16. 16. A cell as claimed in claim 14 wherein said positive electrode is formed by heat-treating a mixture of manganese dioxide and lithium salt to produce Li2MnO3, thereafter adding manganese dioxide, a conductive agent and a binder, and pressurizing and heat-treating a resulting mixture.
  17. 17. A cell as claimed in claim 14 wherein said negative electrode is selected from the group consisting of pure lithium, lithium-aluminum alloy and - 17 - lithium-magnesium alloy.
  18. 18. A cell as claimed in claim 14 wherein said separator comprises a porous membrane of polypropylene.
  19. 19. A cell as claimed in claim 14 wherein said electrolyte comprises a liquid mixture formed by dissolving lithium perchlorate in a solvent mixture of propylene carbonate and dimethoxyethane. - 18 -
CA000550739A 1986-10-30 1987-10-30 Non-aqueous secondary cell Expired - Lifetime CA1285318C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61258940A JPH0746608B2 (en) 1986-10-30 1986-10-30 Non-aqueous secondary battery
JP61-258940 1986-10-30

Publications (1)

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CA1285318C true CA1285318C (en) 1991-06-25

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US (1) US4758484A (en)
EP (1) EP0265950B1 (en)
JP (1) JPH0746608B2 (en)
CA (1) CA1285318C (en)
DE (1) DE3769587D1 (en)

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US4758484A (en) 1988-07-19
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EP0265950B1 (en) 1991-04-24
JPH0746608B2 (en) 1995-05-17

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