JP3921836B2 - Organic electrolyte secondary battery - Google Patents
Organic electrolyte secondary battery Download PDFInfo
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- JP3921836B2 JP3921836B2 JP27482198A JP27482198A JP3921836B2 JP 3921836 B2 JP3921836 B2 JP 3921836B2 JP 27482198 A JP27482198 A JP 27482198A JP 27482198 A JP27482198 A JP 27482198A JP 3921836 B2 JP3921836 B2 JP 3921836B2
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- positive electrode
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- lithium
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- 239000005486 organic electrolyte Substances 0.000 title claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 25
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 22
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 19
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 229910013716 LiNi Inorganic materials 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 230000007246 mechanism Effects 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 description 47
- 239000000203 mixture Substances 0.000 description 26
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910016230 LiNi0.9Co0.1Sr0.002O2 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910011723 LiNi0.8 CO0.2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000009782 nail-penetration test Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- 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
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- Gas Exhaust Devices For Batteries (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は有機電解液二次電池の安全性の向上に関するものである。
【０００２】
【従来の技術】
リチウム二次電池に代表される有機電解液二次電池は、高エネルギー密度であるため、ＶＴＲ一体型カメラ、ノート型パソコン、携帯電話などのポータブル機器に使用されている。なお、負極に金属リチウムを用いたリチウム二次電池は、充電時にデンドライト状のリチウムイオンの負極に析出し、正極と内部短絡を起こすなどの問題点がある。そこで、リチウムイオンの吸蔵・放出が可能な炭素材料を負極に用いたリチウムイオン二次電池が普及している。
【０００３】
最近では、前記したリチウムイオン二次電池の高容量化が強く要求されている。その要望に応じるべく、正極活物質材料及び負極活物質材料の高容量化が急ピッチで進められている。そして、正極活物質の容量として、従来から使用されていた145〜150mAh/g程度のコバルト酸リチウム(LiCoO2)に替わり、180〜200mAh/g程度のニッケル酸リチウム(LiNiO2)の開発が積極的に進められている。なお、LiNiO2は充放電を繰り返すと結晶構造が崩壊しやすいため、サイクル寿命が短いという問題点がある。この問題点を解決するために、結晶構造中のLiサイトやNiサイトの一部を、１種類以上の他の金属元素で置換する方法が提案されており、サイクル寿命特性の向上に効果が得られている。例えば特開平9-17430号公報、特開平10-27610号公報及び特開平8-185863号公報では、第１の置換元素としてSr、Mg、Baに代表されるようなアルカリ土類金属、第２の置換元素としてCoに代表されるような、Ni以外の遷移金属元素で置換することにより、充放電サイクル特性が向上することが開示されている。
【０００４】
一方、放電特性、保存特性及び充放電サイクル寿命特性等の向上を目的とし、特開平4-95362号公報、特開平4-169075号公報、特開平6-84542号公報、特開平8-96852号公報等では電解液中にビニレンカーボネート(以下、ＶＣと略す）を添加することが開示されており、効果が認められている。
【０００５】
しかしながら、正極にLiNiO2を使用した有機電解液二次電池は、LiCoO2を使用したものに比べて、充電状態の電池を火中に投入した場合などの過酷な加熱試験や、釘刺し試験などにおいて発火しやすく、安全性の点で劣るという問題点がある。
【０００６】
【発明が解決しようとする課題】
本発明はリチウムニッケル複合酸化物を正極用活物質に用いた場合において、発火しにくく、安全性の高い有機電解液二次電池を提供するものである。
【０００７】
【課題を解決するための手段】
上記した課題を解決するために、第一の発明では一般式LiNixCoySrzO2（0.7≦ｘ≦0.9、0.1≦ｙ≦0.3、ｘ＋ｙ≒1、0.001≦ｚ≦0.02）で示されるリチウムイオンの吸蔵・放出が可能なリチウムニッケル複合酸化物を活物質とする正極と、リチウムイオンの吸蔵・放出が可能な負極と、リチウムイオンの移動が可能な有機電解液とが密閉容器内に収納されており、該密閉容器には所定圧力よりも高い内部圧力で作動する弁機構を有する有機電解液二次電池において、前記有機電解液にはビニレンカーボネートを１〜２０重量％含有し、溶質として 0.75 〜 2.5mol/l の LiPF 6 を含有することを特徴とする。
【０００９】
第二の発明では、前記正極に燐酸リチウムを0.5〜5重量％含有することを特徴とする。
【００１０】
【発明の実施の形態】
以下に本発明の実施の形態を説明する。図１は本発明を実施した円筒形リチウム二次電池の断面図である。
１．リチウムニッケル複合酸化物の調製
以下において、原材料として市販されている高純度試薬を用いた。水酸化リチウム(LiOH)、水酸化ニッケル(Ni(OH)2)及び水酸化コバルト(Co(OH)2)を混合する。この混合物に水酸化ストロンチウム・8水和物(Sr(OH)2・8H2O)、または水酸化マグネシウム(Mg(OH)2)のいずれかを混合した後、アルミナ製の皿に充填し、600℃の酸素気流中で10時間保持して予備焼成をする。そして、室温まで冷却した後、自動乳鉢で粉砕し、二次粒子の凝集を解きほぐした。この粉末を予備焼成に用いた、アルミナ製の皿に充填し、750℃の酸素気流中に12時間保持して本焼成をし、室温まで冷却する。そして、自動乳鉢で粉砕し、篩にかけ、粒径70μm以上の粒子は除去した。前記した原材料の配合比を変えることで、以下に示す12種類の組成の異なるリチウムニッケル複合酸化物を得た。なお、作成したリチウムニッケル複合酸化物の組成比はＩＣＰ分析によって、ほぼ所望の組成比になっていることを確認した。
【００１１】
（正極活物質Ａ）LiNi0.65Co0.35Sr0.002O2
（正極活物質Ｂ）LiNi0.7Co0.3Sr0.002O2
（正極活物質Ｃ）LiNi0.8Co0.2Sr0.002O2
（正極活物質Ｄ）LiNi0.9Co0.1Sr0.002O2
（正極活物質Ｅ）LiNi0.95Co0.05Sr0.002O2
（正極活物質Ｆ）LiNi0.9Co0.1Sr0.0005O2
（正極活物質Ｇ）LiNi0.9Co0.1Sr0.001O2
（正極活物質Ｈ）LiNi0.9Co0.1Sr0.005O2
（正極活物質Ｉ）LiNi0.9Co0.1Sr0.01O2
（正極活物質Ｊ）LiNi0.9Co0.1Sr0.02O2
（正極活物質Ｋ）LiNi0.9Co0.1Sr0.03O2
（正極活物質Ｌ）LiNi0.9Co0.1Mg0.002O2
２．正極の作製
前記した正極活物質である各種のリチウムニッケル複合酸化物、導電剤として平均粒径約０．５μｍのグラファイト、結着剤としてポリフッ化ビニリデン（商品名：ＫＦ＃１1２０、呉羽化学工業（株）製、以下ＰＶｄＦと略す）とを混合した後、後述する所定量のLi3PO4を加えて、溶媒であるＮ−メチル−２−ピロリドン（以下、ＮＭＰと略す）に分散させてスラリを作製する。このスラリを正極集電体１である厚みが20μmのアルミニウム箔の両面にロールｔｏロール法転写により塗布し、乾燥した後、プレスして一体化する。正極の厚さは144±4μmとし、正極活物質層２の密度を約3.2g/cm3 とした。その後、幅が55mm、長さが450mmに切断して短冊状の正極を作製した。以下、正極活物質、黒鉛、燐酸リチウム及びＰＶｄＦの混合物を正極合剤と呼ぶ。今回、以下に示す７種類の組成の正極合剤を用いた。
【００１２】
（正極合剤Ａ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝83：10：0：7
（正極合剤Ｂ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝82.7：10：0.3：7
（正極合剤Ｃ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝82.5：10：0.5：7
（正極合剤Ｄ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝82：10：1：7
（正極合剤Ｅ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝80：10：3：7
（正極合剤Ｆ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝78：10：5：7
（正極合剤Ｇ）正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝77：10：6：7
３．負極の作製
リチウムイオンの吸蔵、放出が可能な平均粒径20μmの黒鉛粉末と、結着剤としてＰＶｄＦとを重量比で９０：１０で混合した後、溶媒であるＮＭＰを適量加えて十分に混練してスラリにする。このスラリを負極集電体３として用いる厚みが10μmの銅箔の両面にロールｔｏロール法転写により塗布、乾燥後、プレスして一体化する。負極の厚さは190〜200μmであり、負極活物質層の密度は約1.4g／cm3である。その後、幅が56mm、長さが490mmに切断して短冊状の負極を作製した。なお、負極活物質の放電時の容量が280mAh/gとなるように、正極活物質量及び負極活物質量のバランスを調整した。
【００１３】
４．電解液の調整
エチレンカーボネート（ＥＣ）とジメチルカーボネート（ＤＭＣ）とジエチルカーボネート（ＤＥＣ）を３０：５０：２０の体積比で混合した後、溶質として1 Mol/l（以下、濃度の単位であるmol/lを Ｍ と略す）のLiPF6を溶解させて電解液とする。この電解液に、後述する量のビニレンカーボネート（ＶＣ）を添加する。今回、以下の１３種類の組成の異なる電解液を用いた。
【００１４】
（電解液Ａ）ＥＣ：ＤＭＣ＝１：１、ＶＣ添加なし、1M LiPF6
（電解液Ｂ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：０．５重量％、1M LiPF6
（電解液Ｃ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：１重量％、1M LiPF6
（電解液Ｄ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、1M LiPF6
（電解液Ｅ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：１０重量％、1M LiPF6
（電解液Ｆ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：２０重量％、1M LiPF6
（電解液Ｇ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：２５重量％、1M LiPF6
（電解液Ｈ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、0.5M LiPF6
（電解液Ｉ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、0.75M LiPF6
（電解液Ｊ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、1.5M LiPF6
（電解液Ｋ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、2M LiPF6
（電解液Ｌ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、2.5M LiPF6
（電解液Ｍ）ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、1M LiBF4
５．電池の組立て
作製した短冊状の正極と負極とを、厚さが25μm、幅が58mmのポリエチレン多孔膜からなるセパレータ５を介して渦巻き状に巻いて電極群を作製する。正極と負極の厚さの和は345±5μmとした。正極と負極の厚さの和が350μmを超えると、捲回体の径が大きくなり負極缶６に挿入できない。一方、正極と負極の厚さの和が340μm未満では、捲回体の直径が負極缶６の内径よりも小さくなり、電池としての容量が十分得られないためである。なお、後述する各種の電池を作製するにあたり、正極活物質となるリチウムニッケル複合酸化物と、負極活物質となる黒鉛の充電容量を実験セルにて予め測定した。そして、負極活物質１ｇあたりの充電容量と正極活物質１ｇあたりの充電容量の比率が１．１となるように正極活物質量と負極活物質量を調整した。
【００１５】
この電極群を電池缶６に挿入し、負極集電体３の端子を電池缶６の底部に溶接した。電池缶６内に、前記した電解液のいずれかを5ml注液した。正極タブ端子８の一方を正極集電体１に溶接した後、他の一方を正極キャップ７に溶接する。正極キャップ７を絶縁性のガスケット９を介して電池缶６の上部に配置し、この部分をかしめて密閉する。正極キャップ７内には、電池の内部圧力の上昇に応じて作動する電流遮断機構（圧力スイッチ）と、この圧力よりも高い圧力で開放作動する安全弁が組み込まれている。本実施例では作動圧が9kgf/cm2の電流遮断機構と、作動圧が20kgf/cm2の安全弁の２種類を用いた。
【００１６】
６．電池の試験
作製した有機電解液二次電池は、周囲温度25℃、4.2Vの定電圧（ただし、制限電流320mA）で8時間充電した後、1Aの定電流で終止電圧2.5Vまで放電して初期の放電容量を確認した。充放電サイクル寿命特性試験は、放電と充電の間に休止時間10分間を設け、前記した条件で行った。
【００１７】
この電池を前記した条件で再び充電した後、ＵＬ１６４２規格に示されているプロジェクタイルテストに準拠し、バーナによる加熱試験で合否を判定した。すなわち、電池をバーナで加熱し、電池が発火しても、アルミニウム製の網から電池の部品等の構成物が飛び出さない状態を合格とした。安全性に劣る電池を、バーナで加熱試験を実施した場合には、電池が破裂して正極キャップ７や負極缶が網を突き破る可能性が高い。そこで今回は、前記した条件で合否を判定するだけでなく、試験体である電池から1m離れた場所での発火時における音量を測定した。すなわち、発火時の音量が大きい電池ほど網を突き破る可能性が高いと考えて、安全性に劣る電池と判断した。
【００１８】
【実施例】
（実施例１〜７、比較例１〜５）
リチウムニッケル複合酸化物として前記した（正極活物質Ａ〜Ｌ）を用い、正極合剤配合比Ａ（正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝83：10：0：7、すなわち、正極活物質層に燐酸リチウムを含まないもの）の正極を作製した。また、電解液の組成として、電解液Ｄ（ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、１Ｍ LiPF6）を用いた。そして、表１に示す仕様の電池を作成し、初期の放電容量と１００サイクル目の容量保持率（初期の放電容量に対する、１００サイクル目の放電容量の百分率）の測定及びバーナ加熱試験をした。初期の放電容量は、（実施例３）の電池の放電容量を１００とした場合の比較で示した。
【００１９】
（実施例１〜７）の電池においては、すべてバーナ加熱試験に合格し、初期の放電容量と１００サイクル目の容量保持率が高い。
（比較例１）の電池は、バーナ加熱試験に合格しているものの、実施例３の電池に対して初期の放電容量が２０％低い。したがって、正極活物質のNiの組成比が０．７未満となると初期の放電容量が低下することを示している。
（比較例２、３）の電池では、バーナ加熱試験に不合格（×印）であり、１００サイクル目の容量保持率が低い。
（比較例４）の電池では、バーナ加熱試験に合格しているものの、初期の放電容量が１８％低い。これは、Srの置換量が多いため、放電反応を阻害したためと推察している。
（比較例５）の電池では、Sr以外のMg等のアルカリ土類金属で置換すると、バーナ加熱試験に合格しないことを示している。
以上の結果から、一般式LiNixCoySrzO2(0.7≦ｘ≦0.9、0.1≦y≦0.3、ｘ＋ｙ≒１、0.001≦z≦0.02)で示されるリチウムニッケル複合酸化物を正極活物質に用いると安全性の高い電池が得られる。
【００２０】
【表１】
正極活物質として用いる、リチウムニッケル複合酸化物として正極活物質Ｄ（LiNi0.9Co0.1Sr0.002O2)を用いた。正極の活物質層として、正極合剤配合比Ａ（正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝83：10：0：7、すなわち、正極活物質層に燐酸リチウムを含まないもの）を用いた。そして電解液中のLiPF6量を１Ｍとし、表２に示すようにＶＣ量の異なる電池を作成した。その他の試験条件等は、前述したものである。
【００２２】
（実施例８、３、９、１０）の電池は、バーナ加熱試験に合格し、初期の放電容量、１００サイクル目の容量保持率が高い。
（比較例６、７）の電池は、バーナ加熱試験において不合格である。この理由は、電解液中にＶＣ添加がないことや、また添加量が少なすぎるためと考えられる。
（比較例８）の電池は、バーナ加熱試験に合格しているものの、初期の放電容量が低い。この理由は、ＶＣの過剰添加によって電解液の導電率が低下したためと考えられる。
【００２３】
【表２】
正極活物質として用いる、リチウムニッケル複合酸化物として正極活物質Ｄ(LiNi0.9Co0.1Sr0.002O2)を用いた。正極活物質層を形成する正極合剤配合比Ａ（正極活物質：黒鉛：燐酸リチウム：ＰＶｄＦ＝83：10：0：7、すなわち、正極活物質層に燐酸リチウムを含まないもの）を用いた。そして表３に示すように、電解液中のＶＣ量を５重量％とし、LiPF6量の異なる電解液を用いた。その他の試験条件等は、前述したものである。
【００２５】
表３では省略したが、これらの電池はすべてバーナ加熱試験に合格した。
（実施例１２、３、１３、１４、１５）、すなわち電解液の溶質がLiPF6を用い、かつLiPF6の濃度が０．７５〜２．５Ｍの範囲のものが発火時の音量が小さく、初期放電容量や容量保持率が高い。
電解液の溶質にLiBF4を用いた実施例１６の電池では、同濃度のLiPF6を用いた実施例３に比べて、初期放電容量が若干低いこと、100サイクル目の容量保持率の低下が大きく好ましくない。
【００２６】
【表３】
（実施例３、１７〜２２）
正極活物質として用いる、リチウムニッケル複合酸化物として正極活物質Ｄ(LiNi0.9Co0.1Sr0.002O2)を用い、正極合剤に添加する燐酸リチウムの配合比を表４に示す変えた、７種類の仕様の電池を作成した。なお、電解液Ｄ（ＥＣ：ＤＭＣ＝１：１、ＶＣ：５重量％、1M LiPF6)を用いた。その他の試験条件等は、前述したものである。
【００２８】
（実施例３、１７〜２２）のすべての電池でバーナ加熱試験に合格した。なお、（実施例１８〜２１）の電池、すなわち正極合剤中の燐酸リチウムの量が０．５〜５重量％の電池では、初期の放電容量の低下も少なく、発火時の音量も小さく好ましい。一方、燐酸リチウムの量が６重量％の（実施例２２）では、初期の放電容量と100サイクル目の容量保持率の低下が認められた。
【００２９】
【表４】
本発明において、正極合剤中の導電剤としてグラファイト、および負極活物質の炭素材として黒鉛を用いた実施例を示したが、これらに材料に限定されるものではない。
【００３１】
【発明の効果】
本発明による電池では、初期の放電容量や１００サイクル目の容量保持率が高く、火中投下などの加熱時において、安全性の高い有機電解液二次電池を提供できる点で優れている。
【図面の簡単な説明】
【図１】本発明を実施した円筒形有機電解液二次電池の断面図である。
【符号の説明】
１：正極集電体、 ２：正極活物質、 ３：負極集電体、 ４：負極活物質、
５：セパレータ、 ６：電池缶、 ７：正極キャップ、 ８：正極タブ端子、
９：ガスケット。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improvement in safety of an organic electrolyte secondary battery.
[0002]
[Prior art]
Organic electrolyte secondary batteries typified by lithium secondary batteries have high energy density, and are therefore used in portable devices such as VTR integrated cameras, notebook computers, and mobile phones. In addition, the lithium secondary battery using metallic lithium for the negative electrode has a problem that it deposits on the negative electrode of dendritic lithium ions during charging and causes an internal short circuit with the positive electrode. Therefore, lithium ion secondary batteries using a carbon material capable of occluding and releasing lithium ions as a negative electrode have become widespread.
[0003]
Recently, there has been a strong demand for higher capacity of the lithium ion secondary battery. In order to meet the demand, higher capacities of the positive electrode active material and the negative electrode active material are being rapidly advanced. The positive electrode active material has a capacity of about 180 to 200 mAh / g lithium nickelate (LiNiO 2 ) instead of about 145 to 150 mAh / g lithium cobaltate (LiCoO 2 ). Is underway. In addition, LiNiO 2 has a problem that the cycle life is short because the crystal structure is likely to collapse when repeated charge and discharge are performed. In order to solve this problem, a method has been proposed in which part of the Li site or Ni site in the crystal structure is replaced with one or more other metal elements, which is effective in improving cycle life characteristics. It has been. For example, in Japanese Patent Application Laid-Open Nos. 9-17430, 10-27610, and 8-185863, alkaline earth metals such as Sr, Mg, and Ba are used as the first substitution element. It is disclosed that the charge / discharge cycle characteristics are improved by substituting with a transition metal element other than Ni, as represented by Co, as a replacement element.
[0004]
On the other hand, for the purpose of improving discharge characteristics, storage characteristics, charge / discharge cycle life characteristics, etc., JP-A-4-95362, JP-A-4-69075, JP-A-6-84542, JP-A-8-96852 The publications and the like disclose that vinylene carbonate (hereinafter abbreviated as VC) is added to the electrolytic solution, and the effect is recognized.
[0005]
However, organic electrolyte secondary batteries that use LiNiO 2 for the positive electrode are more severe than those using LiCoO 2 such as a harsh heating test when a charged battery is put into the fire, a nail penetration test, etc. It is easy to ignite and is inferior in safety.
[0006]
[Problems to be solved by the invention]
The present invention provides an organic electrolyte secondary battery that is difficult to ignite and has high safety when a lithium nickel composite oxide is used as a positive electrode active material.
[0007]
[Means for Solving the Problems]
In order to solve the above-described problem, the first invention is represented by the general formula LiNi x Co y Sr z O 2 (0.7 ≦ x ≦ 0.9, 0.1 ≦ y ≦ 0.3, x + y≈1, 0.001 ≦ z ≦ 0.02). A positive electrode using a lithium nickel composite oxide capable of occluding and releasing lithium ions as an active material, a negative electrode capable of occluding and releasing lithium ions, and an organic electrolyte capable of moving lithium ions are contained in a sealed container. An organic electrolyte secondary battery having a valve mechanism that is stored in the sealed container and operates at an internal pressure higher than a predetermined pressure. The organic electrolyte contains 1 to 20% by weight of vinylene carbonate, and is a solute. characterized in that it contains of LiPF 6 0.75 ~ 2.5 mol / l as.
[0009]
In the second invention, the positive electrode contains 0.5 to 5% by weight of lithium phosphate.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below. FIG. 1 is a cross-sectional view of a cylindrical lithium secondary battery embodying the present invention.
1. Preparation of lithium nickel composite oxide In the following, a high-purity reagent commercially available as a raw material was used. Lithium hydroxide (LiOH), nickel hydroxide (Ni (OH) 2 ) and cobalt hydroxide (Co (OH) 2 ) are mixed. After mixing this mixture with either strontium hydroxide octahydrate (Sr (OH) 2 / 8H 2 O) or magnesium hydroxide (Mg (OH) 2 ), it is filled into an alumina dish, Pre-baking is held for 10 hours in an oxygen stream at 600 ° C. And after cooling to room temperature, it grind | pulverized with the automatic mortar and the aggregation of the secondary particle was loosened. This powder is filled in an alumina dish used for pre-baking, held in an oxygen stream at 750 ° C. for 12 hours for main baking, and cooled to room temperature. And it grind | pulverized with the automatic mortar, it sieved, and the particle | grains with a particle size of 70 micrometers or more were removed. By changing the mixing ratio of the raw materials described above, lithium nickel composite oxides having the following 12 different compositions were obtained. The composition ratio of the prepared lithium nickel composite oxide was confirmed to be almost the desired composition ratio by ICP analysis.
[0011]
(Positive electrode active material A) LiNi 0.65 Co 0.35 Sr 0.002 O 2
(Positive electrode active material B) LiNi 0.7 Co 0.3 Sr 0.002 O 2
(Positive electrode active material C) LiNi 0.8 Co 0.2 Sr 0.002 O 2
(Positive electrode active material D) LiNi 0.9 Co 0.1 Sr 0.002 O 2
(Positive electrode active material E) LiNi 0.95 Co 0.05 Sr 0.002 O 2
(Positive electrode active material F) LiNi 0.9 Co 0.1 Sr 0.0005 O 2
(Positive electrode active material G) LiNi 0.9 Co 0.1 Sr 0.001 O 2
(Positive electrode active material H) LiNi 0.9 Co 0.1 Sr 0.005 O 2
(Positive electrode active material I) LiNi 0.9 Co 0.1 Sr 0.01 O 2
(Positive electrode active material J) LiNi 0.9 Co 0.1 Sr 0.02 O 2
(Positive electrode active material K) LiNi 0.9 Co 0.1 Sr 0.03 O 2
(Positive electrode active material L) LiNi 0.9 Co 0.1 Mg 0.002 O 2
2. Production of Positive Electrode Various lithium nickel composite oxides which are the positive electrode active materials described above, graphite having an average particle size of about 0.5 μm as a conductive agent, and polyvinylidene fluoride as a binder (trade name: KF # 1120, Kureha Chemical Industry ( Co., Ltd., hereinafter abbreviated as PVdF), a predetermined amount of Li 3 PO 4 described later is added, and dispersed in N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) as a solvent to prepare a slurry. Is made. This slurry is applied to both surfaces of a 20 μm thick aluminum foil as the positive electrode current collector 1 by roll-to-roll method transfer, dried, and then pressed to be integrated. The thickness of the positive electrode was 144 ± 4 μm, and the density of the positive electrode active material layer 2 was about 3.2 g / cm 3 . After that, a strip-shaped positive electrode was produced by cutting it to a width of 55 mm and a length of 450 mm. Hereinafter, a mixture of the positive electrode active material, graphite, lithium phosphate and PVdF is referred to as a positive electrode mixture. This time, a positive electrode mixture having the following seven compositions was used.
[0012]
(Positive electrode mixture A) Positive electrode active material: graphite: lithium phosphate: PVdF = 83: 10: 0: 7
(Positive electrode mixture B) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 82.7: 10: 0.3: 7
(Positive electrode mixture C) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 82.5: 10: 0.5: 7
(Positive electrode mixture D) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 82: 10: 1: 7
(Positive electrode mixture E) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 80: 10: 3: 7
(Positive electrode mixture F) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 78: 10: 5: 7
(Positive electrode mixture G) Positive electrode active material: Graphite: Lithium phosphate: PVdF = 77: 10: 6: 7
3. Preparation of negative electrode After mixing graphite powder with an average particle diameter of 20 μm capable of occlusion and release of lithium ions and PVdF as a binder at a weight ratio of 90:10, an appropriate amount of NMP as a solvent is added and kneaded sufficiently. And make it a slurry. This slurry is applied as a negative electrode current collector 3 on both sides of a 10 μm thick copper foil by roll-to-roll method transfer, dried, and then pressed to be integrated. The thickness of the negative electrode is 190 to 200 μm, and the density of the negative electrode active material layer is about 1.4 g / cm 3 . After that, a strip-shaped negative electrode was produced by cutting to a width of 56 mm and a length of 490 mm. The balance between the amount of the positive electrode active material and the amount of the negative electrode active material was adjusted so that the capacity of the negative electrode active material during discharge was 280 mAh / g.
[0013]
4). Preparation of electrolyte solution After mixing ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a volume ratio of 30:50:20, 1 mol / l (hereinafter referred to as a unit of concentration mol) as a solute. (Li is abbreviated as M) LiPF 6 is dissolved to obtain an electrolyte. An amount of vinylene carbonate (VC) described later is added to this electrolytic solution. At this time, the following 13 types of electrolytic solutions having different compositions were used.
[0014]
(Electrolyte A) EC: DMC = 1: 1, no VC added, 1M LiPF 6
(Electrolyte B) EC: DMC = 1: 1, VC: 0.5 wt%, 1M LiPF 6
(Electrolyte C) EC: DMC = 1: 1, VC: 1 wt%, 1M LiPF 6
(Electrolyte D) EC: DMC = 1: 1, VC: 5% by weight, 1M LiPF 6
(Electrolyte E) EC: DMC = 1: 1, VC: 10% by weight, 1M LiPF 6
(Electrolyte F) EC: DMC = 1: 1, VC: 20 wt%, 1M LiPF 6
(Electrolytic Solution G) EC: DMC = 1: 1, VC: 25% by weight, 1M LiPF 6
(Electrolytic Solution H) EC: DMC = 1: 1, VC: 5% by weight, 0.5M LiPF 6
(Electrolyte I) EC: DMC = 1: 1, VC: 5% by weight, 0.75M LiPF 6
(Electrolytic Solution J) EC: DMC = 1: 1, VC: 5% by weight, 1.5M LiPF 6
(Electrolyte K) EC: DMC = 1: 1, VC: 5% by weight, 2M LiPF 6
(Electrolyte L) EC: DMC = 1: 1, VC: 5 wt%, 2.5M LiPF 6
(Electrolyte M) EC: DMC = 1: 1, VC: 5% by weight, 1M LiBF 4
5. A strip-like positive electrode and negative electrode assembled and fabricated in a battery are spirally wound through a separator 5 made of a polyethylene porous film having a thickness of 25 μm and a width of 58 mm to produce an electrode group. The sum of the thickness of the positive electrode and the negative electrode was 345 ± 5 μm. When the sum of the thicknesses of the positive electrode and the negative electrode exceeds 350 μm, the diameter of the wound body increases and cannot be inserted into the negative electrode can 6. On the other hand, when the sum of the thicknesses of the positive electrode and the negative electrode is less than 340 μm, the diameter of the wound body becomes smaller than the inner diameter of the negative electrode can 6, and a sufficient capacity as a battery cannot be obtained. In preparing various types of batteries described later, the charge capacities of a lithium nickel composite oxide serving as a positive electrode active material and graphite serving as a negative electrode active material were measured in advance in an experimental cell. And the amount of positive electrode active materials and the amount of negative electrode active materials were adjusted so that the ratio of the charge capacity per gram of negative electrode active material and the charge capacity per gram of positive electrode active material was 1.1.
[0015]
This electrode group was inserted into the battery can 6, and the terminal of the negative electrode current collector 3 was welded to the bottom of the battery can 6. In the battery can 6, 5 ml of any one of the above electrolytes was injected. After welding one of the positive
[0016]
6). Battery test Organic electrolyte secondary batteries were charged at an ambient temperature of 25 ° C and a constant voltage of 4.2V (limited current of 320mA) for 8 hours, and then discharged to a final voltage of 2.5V at a constant current of 1A. The initial discharge capacity was confirmed. The charge / discharge cycle life characteristic test was performed under the above-described conditions with a 10 minute rest period between discharge and charge.
[0017]
After recharging the battery under the above-mentioned conditions, the acceptance / rejection was determined by a heating test using a burner in accordance with the projectile test shown in the UL 1642 standard. That is, the battery was heated with a burner, and even when the battery ignited, a state where components such as battery parts did not jump out of the aluminum net was regarded as acceptable. When a battery with poor safety is subjected to a heating test with a burner, the battery is likely to burst and the positive electrode cap 7 and the negative electrode can break through the net. Therefore, this time, not only the pass / fail was determined under the above-mentioned conditions, but also the sound volume at the time of ignition in a place 1 m away from the battery as a test body was measured. That is, a battery with a louder volume at the time of ignition is considered to have a lower possibility of breaking through the net, and thus determined to be a battery with lower safety.
[0018]
【Example】
(Examples 1-7, Comparative Examples 1-5)
The above-described (positive electrode active materials A to L) were used as the lithium nickel composite oxide, and the positive electrode mixture mixture ratio A (positive electrode active material: graphite: lithium phosphate: PVdF = 83: 10: 0: 7, that is, the positive electrode active material A positive electrode having no lithium phosphate in the layer was prepared. As the composition of the electrolytic solution, electrolytic solution D (EC: DMC = 1: 1, VC: 5% by weight, 1M LiPF 6 ) was used. Then, the batteries having the specifications shown in Table 1 were prepared, and the initial discharge capacity and the capacity retention ratio at the 100th cycle (percentage of the discharge capacity at the 100th cycle with respect to the initial discharge capacity) and the burner heating test were performed. The initial discharge capacity is shown as a comparison when the discharge capacity of the battery of Example 3 is 100.
[0019]
In the batteries of Examples 1 to 7, all passed the burner heating test, and the initial discharge capacity and the capacity retention rate at the 100th cycle were high.
Although the battery of (Comparative Example 1) passed the burner heating test, the initial discharge capacity was 20% lower than that of the battery of Example 3. Therefore, when the composition ratio of Ni of the positive electrode active material is less than 0.7, the initial discharge capacity is reduced.
In the battery of (Comparative Examples 2 and 3), the burner heating test was rejected (x mark), and the capacity retention rate at the 100th cycle was low.
In the battery of Comparative Example 4, although the burner heating test was passed, the initial discharge capacity was 18% lower. This is presumed to be because the discharge reaction was hindered because of the large amount of substitution of Sr.
In the battery of (Comparative Example 5), when the alkaline earth metal such as Mg other than Sr is substituted, it does not pass the burner heating test.
From the above results, the lithium nickel composite oxide represented by the general formula LiNi x Co y Sr z O 2 (0.7 ≦ x ≦ 0.9, 0.1 ≦ y ≦ 0.3, x + y≈1, 0.001 ≦ z ≦ 0.02) is used as the positive electrode active material. A battery with high safety can be obtained when used for.
[0020]
[Table 1]
The positive electrode active material D (LiNi 0.9 Co 0.1 Sr 0.002 O 2 ) was used as the lithium nickel composite oxide used as the positive electrode active material. As the positive electrode active material layer, the positive electrode mixture mixture ratio A (positive electrode active material: graphite: lithium phosphate: PVdF = 83: 10: 0: 7, ie, the positive electrode active material layer does not contain lithium phosphate) was used. . Then, the amount of LiPF 6 in the electrolytic solution was set to 1M, and batteries having different VC amounts were prepared as shown in Table 2. Other test conditions are as described above.
[0022]
The batteries of Examples 8, 3, 9, and 10 pass the burner heating test, and the initial discharge capacity and the capacity retention rate at the 100th cycle are high.
The batteries of (Comparative Examples 6 and 7) failed in the burner heating test. The reason for this is considered that there is no addition of VC in the electrolytic solution and that the addition amount is too small.
Although the battery of (Comparative Example 8) passed the burner heating test, the initial discharge capacity was low. The reason for this is considered that the electrical conductivity of the electrolytic solution was lowered by the excessive addition of VC.
[0023]
[Table 2]
The positive electrode active material D (LiNi 0.9 Co 0.1 Sr 0.002 O 2 ) was used as the lithium nickel composite oxide used as the positive electrode active material. A positive electrode material mixture ratio A (positive electrode active material: graphite: lithium phosphate: PVdF = 83: 10: 0: 7, ie, the positive electrode active material layer does not contain lithium phosphate) was used to form the positive electrode active material layer. . Then, as shown in Table 3, the amount of VC in the electrolyte solution and 5 wt%, using different electrolyte of LiPF 6 amount. Other test conditions are as described above.
[0025]
Although omitted in Table 3, all of these batteries passed the burner heating test.
(Examples 12, 3, 13, 14, 15), that is, the electrolyte solute uses LiPF 6 and the concentration of LiPF 6 in the range of 0.75 to 2.5 M has a low volume during ignition, High initial discharge capacity and capacity retention.
In the battery of Example 16 using LiBF 4 as the solute of the electrolytic solution, the initial discharge capacity is slightly lower and the capacity retention rate at the 100th cycle is lower than Example 3 using LiPF 6 of the same concentration. Large and undesirable.
[0026]
[Table 3]
(Example 3, 17-22)
Seven types of cathode active material D (LiNi 0.9 Co 0.1 Sr 0.002 O 2 ) used as the positive electrode active material and the mixing ratio of lithium phosphate added to the positive electrode mixture as shown in Table 4 were used. A battery with specifications was created. Electrolyte D (EC: DMC = 1: 1, VC: 5% by weight, 1M LiPF 6 ) was used. Other test conditions are as described above.
[0028]
All the batteries of Examples 3 and 17 to 22 passed the burner heating test. In addition, in the batteries of Examples 18 to 21, that is, the battery in which the amount of lithium phosphate in the positive electrode mixture is 0.5 to 5% by weight, the initial discharge capacity is hardly decreased, and the volume during ignition is small and preferable. . On the other hand, when the amount of lithium phosphate was 6% by weight (Example 22), the initial discharge capacity and the capacity retention at the 100th cycle were reduced.
[0029]
[Table 4]
In the present invention, examples have been shown in which graphite is used as the conductive agent in the positive electrode mixture and graphite is used as the carbon material of the negative electrode active material. However, the present invention is not limited to these materials.
[0031]
【The invention's effect】
The battery according to the present invention is excellent in that it has a high initial discharge capacity and a capacity retention ratio at the 100th cycle, and can provide a highly safe organic electrolyte secondary battery during heating such as dropping in a fire.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a cylindrical organic electrolyte secondary battery embodying the present invention.
[Explanation of symbols]
1: positive electrode current collector, 2: positive electrode active material, 3: negative electrode current collector, 4: negative electrode active material,
5: Separator, 6: Battery can, 7: Positive electrode cap, 8: Positive electrode tab terminal,
9: Gasket.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27482198A JP3921836B2 (en) | 1998-09-29 | 1998-09-29 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27482198A JP3921836B2 (en) | 1998-09-29 | 1998-09-29 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000106210A JP2000106210A (en) | 2000-04-11 |
| JP3921836B2 true JP3921836B2 (en) | 2007-05-30 |
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| JP27482198A Expired - Fee Related JP3921836B2 (en) | 1998-09-29 | 1998-09-29 | Organic electrolyte secondary battery |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9929698D0 (en) * | 1999-12-15 | 2000-02-09 | Danionics As | Non-aqueous electrochemical cell |
| AU4692901A (en) * | 2000-04-17 | 2001-10-30 | Ube Industries, Ltd. | Non-aqueous electrolyte and lithium secondary battery |
| TW531924B (en) | 2000-05-26 | 2003-05-11 | Sony Corp | Nonaqueous electrolyte secondary battery |
| CN104600360A (en) | 2008-02-29 | 2015-05-06 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery |
| JP2019079745A (en) * | 2017-10-26 | 2019-05-23 | トヨタ自動車株式会社 | Lithium secondary battery |
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