# US 5,708,349 A · Alkaline secondary battery manufacturing method, alkaline secondary battery positive electrode, alkaline secondary battery, and a method of manufacturing an initially charged alkaline secondary battery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,708,349 A - Document ID: US5708349A - Status: Granted - Kind: A - Application number: 08/604,795 - Filed: 1996-02-23 - Granted: 1998-01-13 - Earliest claimed: 1995-02-23 - Assignees: Kabushiki Kaisha Toshiba; Toshiba Battery Co., Ltd. - Inventors: Hiroyuki Hasebe; Shinji Tsuruta; Hideki Yoshida; Masaaki Yamamoto; Ken-ichi Kanno; Kiyoshi Ishitsuka; Ken Komiyama; Hidekazu Oppata - Web page: https://patentgrep.com/patent/US5708349A ## CPC - H01M 4/242: {Hydrogen storage electrodes} - H01M 4/383: {Hydrogen absorbing alloys} - H01M 10/44: Methods for charging or discharging (circuits for charging H02J7/00) - Y02E 60/10: Energy storage using batteries - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - Y10T 29/49115: including coating or impregnating - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Disclosed is a method of manufacturing an alkaline secondary battery improved in the positive electrode utilization, the large-current discharge characteristic, the discharge capacity, and the capacity recovery ratio after storage. This method of manufacturing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, a negative electrode and an alkaline electrolyte, the method comprising the step of performing initial charging which comprises a charging process of supplying a current I (mA) satisfying the following Inequality (1): 50<(T.times.C.sup.2)/(I.times.S)<2000 (1) where C is a electrochemical capacity (mAh) of the cobalt compound contained in the positive electrode, which is calculated on the basis of a electrochemical equivalent of the cobalt compound, T is a temperature (.degree.C.) at which the charging process is performed, and S is an area (cm.sup.2) of the positive electrode. ## Claims ### Claim 1 A method of manufacturing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, negative electrode and an alkaline electrolyte, said method comprising the step of performing initial charging which comprises a charging process of supplying a current I (mA) satisfying the following Inequality (1): 50<(T.times.C.sup.2)/(I.times.S)<2000 (1) where C is an electrochemical capacity (mAh) of said cobalt compound contained in said positive electrode, which is calculated on the basis of an electrochemical equivalent of said cobalt compound, T is a temperature (.degree.C.) at which said charging process is performed, and S is an area (cm.sup.2) of said positive electrode. ### Claim 2 (depends on 1) The method according to claim 1, wherein said charging process supplies a current I (mA) satisfying the following Inequality (2): 200<(T.times.C.sup.2)/(I.times.S)<2000 (2) ### Claim 3 (depends on 1) The method according to claim 1, wherein the temperature (T) at which said charging process is performed is 40.degree. to 120.degree. C. ### Claim 4 (depends on 1) The method according to claim 1, wherein said charging process is maintained until a charged electricity quantity Q (mAh) reaches a range of Inequality (3) below: 0.1<Q/C<3 (3) ### Claim 5 (depends on 1) The method according to claim 1, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 6 (depends on 5) The method according to claim 5, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 7 A method of manufacturing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, a negative electrode and an alkaline electrolyte, said method comprising the step of performing initial charging which comprises a charging process of supplying a current I (mA) satisfying the following Inequality (1), and a process of lowering a temperature after a charged electricity quantity Q (mAh) reaches a range of Inequality (3) below: 50<(T.times.C.sup.2)/(T.times.S)<2000 (1) 0.1<Q/C<3 (3) where C is an electrochemical capacity (mAh) of said cobalt compound contained in said positive electrode, which is calculated on the basis of an electrochemical equivalent of said cobalt compound, T is a temperature (.degree.C.) at which said charging process is performed, and S is an area (cm.sup.2) of said positive electrode. ### Claim 8 (depends on 7) The method according to claim 7, wherein said charging process supplies a current I (mA) satisfying the following Inequality (2): 200<(T.times.C.sup.2)/(I.times.S)<2000 (2) ### Claim 9 (depends on 7) The method according to claim 7, wherein the temperature (T) at which said charging process is performed is 40.degree. to 120.degree. C. ### Claim 10 (depends on 7) The method according to claim 7, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 11 (depends on 10) The method according to claim 10, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 12 A method of manufacturing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, a negative electrode and an alkaline electrolyte, said method comprising the step of performing initial charging which comprises a charging process of supplying a current I (mA) satisfying the following Inequality (1), and a process of increasing the current after a charged electricity quantity Q (mAh) reaches a range of Inequality (3) below: 50<(T.times.C.sup.2)/(I.times.S)<2000 (1) 0.1<Q/C<3 (3) where C is an electrochemical capacity (mAh) of said cobalt compound contained in said positive electrode, which is calculated on the basis of an electrochemical equivalent of said cobalt compound, T is a temperature (.degree.C.) at which said charging process is performed, and S is an area (cm.sup.2) of said positive electrode. ### Claim 13 (depends on 12) The method according to claim 12, wherein said charging process supplies a current I (mA) satisfying the following Inequality (2): 200<(T.times.C.sup.2)/(I.times.S)<2000 (2) ### Claim 14 (depends on 12) The method according to claim 12, wherein the temperature (T) at which said charging process is performed is 40.degree. to 120.degree. C. ### Claim 15 (depends on 12) The method according to claim 12, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 16 (depends on 15) The method according to claim 15, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 17 A method of manufacturing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, a negative electrode and an alkaline electrolyte, said method comprising the step of performing initial charging which comprises a charging process of supplying a current I (mA) satisfying the following Inequality (1), and a process of lowering a temperature and increasing the current after a charged electricity quantity Q (mAh) reaches a range of Inequality (3) below: 50<(T.times.C.sup.2)/(I.times.S)<2000 (1) 0.1<Q/C<3 (3) where C is an electrochemical capacity (mAh) of said cobalt compound contained in said positive electrode, which is calculated on the basis of an electrochemical equivalent of said cobalt compound, T is a temperature (.degree.C.) at which said charging process is performed, and S is an area (cm.sup.2) of said positive electrode. ### Claim 18 (depends on 17) The method according to claim 17, wherein said charging process supplies a current I (mA) satisfying the following Inequality (2): 200<(T.times.C.sup.2)/(I.times.S)<2000 (2) 19. ### Claim 19 (depends on 17) The method according to claim 17, wherein the temperature (T) at which said charging process is performed is 40.degree. to 120.degree. C. ### Claim 20 (depends on 17) The method according to claim 17, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 21 (depends on 20) The method according to claim 20, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 22 An alkaline secondary battery positive electrode containing a nickel compound and a cobalt compound, wherein assuming that said cobalt compound is cobalt oxyhydroxide and an electrochemical capacity of said cobalt oxyhydroxide calculated on the basis of an electrochemical equivalent of said cobalt oxyhydroxide is C (mAh), when said positive electrode is discharged with a current value of C/100 (mA), said positive electrode has a discharge capacity of C/20 (mAh) or more while a positive electrode potential decreases from 200 mV to -200 mV with respect to a mercury/mercuric oxide reference electrode. ### Claim 23 (depends on 22) The positive electrode according to claim 22, wherein the discharge capacity is not less than C/10. ### Claim 24 An alkaline secondary battery comprising: a positive electrode containing a nickel compound and a cobalt compound; a negative electrode; and an alkaline electrolyte, wherein assuming that said cobalt compound is cobalt oxyhydroxide and an electrochemical capacity of said cobalt oxyhydroxide calculated on the basis of an electrochemical equivalent of said cobalt oxyhydroxide is C (mAh), when said positive electrode is discharged with a current value of C/100 (mA), said positive electrode has a discharge capacity of C/20 (mAh) or more while a positive electrode potential decreases from 200 mV to -200 mV with respect to a mercury/mercuric oxide reference electrode. ### Claim 25 (depends on 24) The secondary battery according to claim 24, wherein the discharge capacity is not less than C/10. ### Claim 26 (depends on 25) The secondary battery according to claim 25, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 27 (depends on 26) The secondary battery according to claim 26, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 28 An alkaline secondary battery comprising: a positive electrode containing a nickel compound and a cobalt compound; a negative electrode; and an alkaline electrolyte, wherein assuming that said cobalt compound is cobalt oxyhydroxide, when said battery is discharged at 45.degree. C. by causing a short using a 2-.OMEGA. resistance, said battery has a quantity of electricity which flows while a voltage decreases from 100 mV to 20 mV and which is not less than 20% of an electrochemical capacity of said cobalt oxyhydroxide calculated on the basis of an electrochemical equivalent of said cobalt oxyhydroxide. ### Claim 29 (depends on 28) The secondary battery according to claim 28, wherein the quantity of electricity is not less than 30% of the electrochemical capacity. ### Claim 30 (depends on 28) The secondary battery according to claim 28, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 31 (depends on 30) The secondary battery according to claim 30, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y Co.sub.x A.sub.y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0y.gtoreq.2.0, respectively. ### Claim 32 An alkaline secondary battery comprising: a positive electrode containing a nickel compound and a cobalt compound; a negative electrode; and an alkaline electrolyte, wherein said battery has a recovery voltage which rises from 10 mV to 30 mV within one hour or less after said battery has been discharged at 45.degree. C. by causing a short using a 2-.OMEGA. resistance for 48 hours and rendered not short-circuited at 25.degree. C. ### Claim 33 (depends on 32) The secondary battery according to claim 32, wherein the time within which a voltage rises from 10 mV to 30 mV is not more than 45 minutes. ### Claim 34 (depends on 33) The secondary battery according to claim 33, wherein said negative electrode contains a hydrogen-absorbing alloy. ### Claim 35 (depends on 34) The secondary battery according to claim 34, wherein said hydrogen-absorbing alloy is represented by RNi.sub.t-x-y CoxA.sub.Y wherein R represents at least one element selected from the group consisting of rare earth elements containing La and Y, A represents at least one element selected from the group consisting of Al, Mn, Ti, Cu, Zn, Zr, Cr, and P, and t, x, and y represent atomic ratios satisfying 4.5.ltoreq.t.ltoreq.5.5, x.gtoreq.0.4, and 0.ltoreq.y.ltoreq.2.0, respectively. ### Claim 36 A method of manufacturing an initially charged alkaline secondary battery, comprising the steps of: preparing an alkaline secondary battery comprising a positive electrode containing a nickel compound and a cobalt compound, a negative electrode and an alkaline electrolyte, performing initial charging of said battery at a high temperature of 40.degree. to 120.degree. C.; and performing heat exchange between said initially charged battery and a battery to be initially charged, thereby cooling said initially charged battery and heating said battery to be initially charged.