JPH04171659A - Nonaqueous-electrolyte secondary battery - Google Patents
Nonaqueous-electrolyte secondary batteryInfo
- Publication number
- JPH04171659A JPH04171659A JP2300767A JP30076790A JPH04171659A JP H04171659 A JPH04171659 A JP H04171659A JP 2300767 A JP2300767 A JP 2300767A JP 30076790 A JP30076790 A JP 30076790A JP H04171659 A JPH04171659 A JP H04171659A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- battery
- discharge
- electrolyte secondary
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000011149 active material Substances 0.000 description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 229910032387 LiCoO2 Inorganic materials 0.000 description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
高電圧でかつ高エネルギー密度という特長をもつ非水電
解液二次電池はカムコーダー、ポータプルＴＶ、携帯電
話なとのポータプル電子機器の騨動用電源として有望で
ある。[Detailed Description of the Invention] Industrial Applications Non-aqueous electrolyte secondary batteries, which are characterized by high voltage and high energy density, are promising as power sources for portable electronic devices such as camcorders, portable TVs, and mobile phones. It is.
本発明は、この非水電解液二次電池のサイクル特性およ
び保存特性の改善に関するものである。The present invention relates to improvements in the cycle characteristics and storage characteristics of this non-aqueous electrolyte secondary battery.
従来の技術
従来より非水電解液二次電池は正極活物質に二硫化モリ
ブデン（ＭｏＳ２）、二硫化チタン（ＴｉＳ：）、二酸
化マンガフ （ＭｎＯ： ）、五酸化バナジウムい〜０
．）なとの遷移金属硫化物もしくは酸化物を用い、負極
には金属リチウムやリチウムイオンを吸蔵、放出する合
金、例えばウッド合金やリチウムアルミニウム合金なと
を用いた電池系が知られている。Conventional technology Traditionally, non-aqueous electrolyte secondary batteries use molybdenum disulfide (MoS2), titanium disulfide (TiS: ), mangaf dioxide (MnO: ), vanadium pentoxide as positive electrode active materials.
．． ), a battery system is known in which a negative electrode is made of metallic lithium or an alloy that occludes and releases lithium ions, such as a wood alloy or a lithium aluminum alloy.
また非水電解液二次電池の電解液にはリチウム塩を溶解
したプロピレンカーボネイト（ＰＣ）。In addition, the electrolyte of non-aqueous electrolyte secondary batteries is propylene carbonate (PC) in which lithium salt is dissolved.
エチレンカーボネイト（ＥＣ）、 ガンマブチロラク
トン（ＧＢＬ）、 ジメトキシエタン（ＤＭＥ）。Ethylene carbonate (EC), gamma butyrolactone (GBL), dimethoxyethane (DME).
２−メチルテトラヒドロフラグ（ＭＴＨＦ’）なとがよ
く用いられている。2-methyltetrahydroflag (MTHF') is often used.
このような正・負極および電解液からなる非水電解液二
次電池で最近放電平均電圧が約４■を示す電池系が注目
を集めている。その正極活物質はリチウムコバルトオキ
サイド（ＬｉＣｏ０２）やリチウマンガンオキサイド（
Ｌ ｉ Ｍｎ： ０４ ）などのリチウム複合酸化物で
ある。リチウムコバルトオキサイドはリチウムマンガン
オキサイドよりも反応電子数が多いため、容量が大きく
、エネルギー密度の大きい電池が得られる可能性が高い
。しかし反応電子数を０．４電子／金属以上とした時の
サイクルに伴う容量劣化が大きいことや充電状態で高温
保存した時の自己放電並びに容量劣化が激しいなど改善
しなければならない点が多い。Recently, a battery system that exhibits an average discharge voltage of about 4 cm has been attracting attention among non-aqueous electrolyte secondary batteries comprising positive and negative electrodes and an electrolyte. Its positive electrode active materials are lithium cobalt oxide (LiCo02) and lithium manganese oxide (
It is a lithium composite oxide such as L i Mn: 04). Lithium cobalt oxide has a larger number of reactive electrons than lithium manganese oxide, so there is a high possibility that a battery with larger capacity and energy density can be obtained. However, there are many points that need to be improved, such as large capacity deterioration due to cycling when the number of reaction electrons is 0.4 electrons/metal or more, and severe self-discharge and capacity deterioration when stored at high temperatures in a charged state.
発明が解決しようとする課題
正極活物質にリチウムコバルトオキサイドを用いること
により高エネルギー密度の非水電解液二次電池が得られ
ることがわかったが、先に述へたような反応電子数を０
，４電子／金属以上とした時にリチウムコバルトオキサ
イドの層状の結晶構造を支えるリチウムが４０％以上抜
けてしまうため結晶構造が破壊され、サイクルに伴う容
量劣化率が大きくなる。また充電状態すなわちリチウム
が抜けた状態で高温保存した時にも結晶構造の破壊が起
こり、自己放電並びに容量劣化が激しくなるなどの課題
がある。Problems to be Solved by the Invention It has been found that a non-aqueous electrolyte secondary battery with high energy density can be obtained by using lithium cobalt oxide as a positive electrode active material.
, 4 electrons/metal or more, 40% or more of the lithium supporting the layered crystal structure of lithium cobalt oxide is lost, destroying the crystal structure and increasing the rate of capacity deterioration with cycling. Furthermore, when stored at high temperatures in a charged state, that is, in a state in which lithium has been removed, the crystal structure is destroyed, causing problems such as self-discharge and severe capacity deterioration.
課題を解決するための手段
上記課題を解決するため、本発明はアルカリ土類金属を
その炭酸塩、硝酸塩、硫酸塩や水酸化物の形で添加量が
Ｍの１原子当たり０．５原子以下となるように加え合成
した活物質を非水電解液二次電池の正極材料として用い
る。Means for Solving the Problems In order to solve the above problems, the present invention provides alkaline earth metals in the form of carbonates, nitrates, sulfates, and hydroxides in an amount of 0.5 or less per atom of M. The active material synthesized by adding the following is used as a positive electrode material for a non-aqueous electrolyte secondary battery.
作用
上記正極材料を用いることにより、充電時にリチウムイ
オンが０，４電子／金属以上抜けても結晶格子中にアル
カリ土類金属が存在するため、安定な結晶格子を作り出
し、充放電サイクルにおいてもサイクル劣化率が小さく
、また充電状態での高温保存においても自己放電や容量
劣化の小さい非水電解液二次電池が得られることとなる
。Effect By using the above cathode material, even if lithium ions lose 0.4 electrons/metal or more during charging, the presence of alkaline earth metals in the crystal lattice creates a stable crystal lattice, and the cycle is maintained even during charge/discharge cycles. A non-aqueous electrolyte secondary battery with a low rate of deterioration and low self-discharge and low capacity deterioration even when stored at high temperatures in a charged state can be obtained.
実施例
以下、本発明の一実施例を第１図〜第４図に基づき説明
する。EXAMPLE Hereinafter, an example of the present invention will be explained based on FIGS. 1 to 4.
第１図は本発明に係わる非水電解液二次電池の一部断面
図であり、例えば直径１５ｍ＋ｎ、高さが５０師の電池
である。FIG. 1 is a partial sectional view of a non-aqueous electrolyte secondary battery according to the present invention, and is, for example, a battery with a diameter of 15 m+n and a height of 50 mm.
第１図中、１は正極合剤で封口板１２にチタン製正極リ
ード３で結線されたチタン製正極集電体２に充填されて
いる。６は有機溶媒（以下溶媒という）にＰＣとＥＣの
体積比１：１の混合溶媒に支持電解質を調合し、しみこ
ませたポリプロピレン（以下ＰＰと略す）製セパレータ
である。セパレータ６はリチウム金属４と正極合剤１に
挟まれている。４は負極活物質としてのリチウム金属で
あり、ニッケルメッキした鉄製ケース１０にニッケル製
負極リード７で結線されているニッケル製一 ４ −
負極集電体５に圧着固定されている。負極、セパレータ
と正極で構成された群は上部絶縁板８と底部絶縁板９で
ケース内に固定されている。］１はＰＰ製ガスケットで
ある。In FIG. 1, a positive electrode mixture 1 is filled in a titanium positive electrode current collector 2 connected to a sealing plate 12 with a titanium positive electrode lead 3. 6 is a separator made of polypropylene (hereinafter abbreviated as PP) in which a supporting electrolyte is prepared and impregnated with an organic solvent (hereinafter referred to as solvent) and a mixed solvent of PC and EC in a volume ratio of 1:1. Separator 6 is sandwiched between lithium metal 4 and positive electrode mixture 1. 4 is a lithium metal as a negative electrode active material, which is crimped and fixed to a nickel negative electrode current collector 5 which is connected to a nickel plated iron case 10 with a nickel negative electrode lead 7. A group consisting of a negative electrode, a separator, and a positive electrode is fixed in the case by an upper insulating plate 8 and a bottom insulating plate 9. ] 1 is a PP gasket.
なお、正極合剤１は、例えば組成が重量部で正極活物質
の１００に対し、カーボンブラック７゜フン素樹脂系結
着剤４とし、充填容量が１４００ｍＡｈとなるようにさ
れている。The positive electrode mixture 1 has a composition of, for example, 100 parts by weight of the positive electrode active material, 7 parts carbon black, and 4 parts of the fluorine resin binder, and has a filling capacity of 1400 mAh.
本発明の正極活物質の製造方法は例えば酸化コバルトの
コバルト１原子に対し、リチウムとマグネシウムの原子
比がそれぞれ０．５〜１．０ 〜０．５になるように炭
酸リチウムと炭酸マグネ／ラムを秤量し、十分混合した
後６００〜９００°Ｃの温度域で数回反応させるもので
ある。以下に示したような特長を備える活物質としては
コバルト化合物の他にニッケル化合物や鉄化合物および
コバルト化合物を含めたニッケル、鉄化合物との複合物
とマグネシウムを含んだアルカリ土類金属の炭酸塩、硫
酸塩、硝酸塩、水酸化物であった。The method for producing the positive electrode active material of the present invention includes, for example, lithium carbonate and magnesium carbonate/lamb such that the atomic ratio of lithium and magnesium to one cobalt atom of cobalt oxide is 0.5 to 1.0 to 0.5, respectively. are weighed, thoroughly mixed, and then reacted several times in a temperature range of 600 to 900°C. In addition to cobalt compounds, active materials with the features shown below include nickel compounds, iron compounds, nickel and iron compounds containing cobalt compounds, carbonates of alkaline earth metals containing magnesium, They were sulfates, nitrates, and hydroxides.
鉄、ニッケル、コバルトは複合酸化物を作り、この製造
方法に適合していた。またアルカリ土類金属の塩化物を
除く主な化合物である炭酸塩、硫酸塩、硝酸塩、水酸化
物は反応した後に塩化物のような電池の保存特性に影響
を与える塩素か残らないため、有効であった。Iron, nickel, and cobalt form composite oxides that are compatible with this manufacturing method. In addition, carbonates, sulfates, nitrates, and hydroxides, which are the main compounds of alkaline earth metals other than chlorides, are effective because they do not leave behind chlorine, which affects the storage characteristics of batteries like chlorides, after they react. Met.
上記の構成の電池を用いて、正極活物質に本発明の活物
質とＬｉＭＯ： （１，９＜Ｚ＜２．１）の−例であ
るＬｉＣＯＯ２を用いた電池のサイクル特性を対比させ
たものを第２図に示した。充電は電流７０ｍＡで４．３
Ｖまで、放電は電流２３３ｍＡで３，０■までの充放電
条件とした。A comparison of the cycle characteristics of a battery using the active material of the present invention and LiCOO2, which is an example of LiMO: (1,9<Z<2.1), as the positive electrode active material using a battery with the above configuration. is shown in Figure 2. Charging is 4.3 with a current of 70mA
The conditions for discharging up to 3.0 V were set at a current of 233 mA.
また、正極活物質に本発明の活物質とＬｉＣＯＯ２を用
いた電池の６０℃で２０日間充電状態で保存した後の充
放電曲線を第３図に示し、第４図にそのサイクル特性を
示した。保存は１０サイクルの充放電の後、充電状態で
保存した。充放電条件は上記と同様である。In addition, Fig. 3 shows the charge-discharge curve of a battery using the active material of the present invention and LiCOO2 as the positive electrode active material after being stored in a charged state at 60°C for 20 days, and Fig. 4 shows its cycle characteristics. . The battery was stored in a charged state after 10 cycles of charging and discharging. The charging and discharging conditions are the same as above.
第２図中、ＡはＬ ｉ Ｃｏ ０２単独の活物質を正極
材料とした電池のサイクル特性であり、Ｂ、Ｃ，Ｄはア
ルカリ土類金属の一例であるマグネシウムを添加剤とし
て用いたときの活物質を正極材料とした電池のサイクル
特性である。Ｂ、Ｃ，ＤはＭ１原子に対しＬ ｉ ＋
Ｍ ｇをそれぞれ（０，７５０，２５） 、 （０，
５０： ０１５０）、（０，２５０，７５）原子の量を
添加したものである。In Figure 2, A is the cycle characteristics of a battery using Li Co 02 alone as an active material as the positive electrode material, and B, C, and D are the cycle characteristics when magnesium, an example of an alkaline earth metal, is used as an additive. This is the cycle characteristics of a battery using an active material as a positive electrode material. B, C, and D are Li + for M1 atom
M g (0,750,25) and (0,
50: 0150), (0,250,75) atoms added.
第２図からもわかるようにマグネシウムを添加した活物
質を用いた電池はサイクル特性かＬｉＣｏＯ２単独の活
物質を用いた電池よりも良好であることが言える。しか
し添加量か０７５原子では充放電に寄与するリチウム原
子か減少するため、放電容量か低くなり、高エネルギー
密度化が不可能であることがわかった。従って以下には
マグネシウム添加量を０．２５，０．５０原子／Ｍつい
てのみ記した。リチウム添加量は上記と同様である。ま
た第３図でＥはＬｉＣＯＯ：：単独の活物質を正極材料
とした電池の保存前の放電曲線であり、ＦはＬｉＣｏＯ
２単独の活物質を正極材料とした電池を充電状態で６０
°Ｃｌ２Ｏ日保存した後の放電曲線である。Ｇ、ＨはＭ
１原子に対しそれぞれマグネシウム０．２５．０．５０
原子の岱を添加した活物質を正極材料とした電池を上記
と同様な条件で保存した後の放電曲線である。As can be seen from FIG. 2, it can be said that the battery using the active material to which magnesium is added has better cycle characteristics than the battery using the active material containing only LiCoO2. However, it was found that when the amount of addition is 0.75 atoms, the number of lithium atoms contributing to charging and discharging decreases, resulting in a low discharge capacity and making it impossible to achieve high energy density. Therefore, in the following, only the amounts of magnesium added of 0.25 and 0.50 atoms/M are described. The amount of lithium added is the same as above. Furthermore, in Fig. 3, E is the discharge curve before storage of a battery using LiCOO:: a single active material as the positive electrode material, and F is LiCoO
2 A battery using a single active material as a positive electrode material is charged for 60 hrs.
This is a discharge curve after storage in °Cl2O for days. G, H are M
Magnesium 0.25 and 0.50 per atom respectively
This is a discharge curve after a battery using an active material added with Atomic Radium as a positive electrode material was stored under the same conditions as above.
第３図かられかるように６０℃で２０日間保存した後の
放電曲線で、ＦのＬｉＣｏＯ２単独の活物質を正極材料
とした電池は他のマグネ／ラムを添加している活物質を
用いた電池（Ｇ、Ｈ）の放電曲線と異なり、活物質の結
晶構造が崩壊しているような形状を示した。それ対し、
他のマグネシウムを添加している活物質を用いた電池（
Ｇ、Ｈ）は保存前の放電曲線に類似し、結晶構造が崩壊
せず、安定しているような形状を示した。それを自己放
電としてみると、ＬｉＣｏＯ２単独の活物質を正極材料
とした電池で約５０％、マグネシウムを添加している活
物質を用いた電池（Ｇ、Ｈ）で約１０〜１３％となり、
やはりマグネシウムを添加した活物質を用いた電池の方
が自己放電も少なく安定した電池特性を示すことがわか
った。As can be seen from Figure 3, the discharge curve after storage at 60°C for 20 days shows that the battery using F's LiCoO2 active material alone as the positive electrode material used other active materials containing Magne/Lam. Unlike the discharge curves of batteries (G, H), the crystal structure of the active material appeared to have collapsed. On the other hand,
Batteries using active materials containing other magnesium (
G, H) were similar to the discharge curves before storage, and the crystal structure did not collapse and showed a stable shape. Looking at this as self-discharge, it is approximately 50% in batteries using LiCoO2 alone as an active material as the positive electrode material, and approximately 10-13% in batteries using active materials containing magnesium (G, H).
It was found that batteries using active materials containing magnesium had less self-discharge and exhibited more stable battery characteristics.
第４図でＩはＬｉＣｏＯ２単独の活物質を正極材料とし
た電池のサイクル特性で１１サイクル目に充電状態での
保存を行い、その後も充放電サイ−９＝
クルを行ったものである。In FIG. 4, I indicates the cycle characteristics of a battery using LiCoO2 alone as an active material as a positive electrode material, which was stored in a charged state at the 11th cycle, and was then subjected to 9 charge/discharge cycles.
Ｊ、にはＭ１原子に対しそれぞれマグネ／ラム０．２５
．０．５０原子の量を添加した活物質を正極材料とした
電池を上記と同様な条件で試験した時のサイクル特性で
ある。J, has 0.25 magne/lam for each M1 atom.
．． This is the cycle characteristic when a battery using an active material added in an amount of 0.50 atoms as a positive electrode material was tested under the same conditions as above.
第４図かられかるように保存した後のサイクル特性は■
のＬｉＣｏＯ２単独の活物質を正極利料止した電池では
容量劣化が約５０％と大きく、また保存後も劣化が大き
いことがわかる。これに対し、マグネシウムを添加した
Ｊ、には保存後の容量劣化が約７〜１０％と小さく、か
つ保存後の容量劣化が小さいことかわかる。As shown in Figure 4, the cycle characteristics after storage are ■
It can be seen that in a battery in which LiCoO2 alone as an active material is used as a positive electrode, the capacity deterioration is as large as about 50%, and the deterioration is large even after storage. On the other hand, it can be seen that the capacity deterioration after storage of J containing magnesium was as small as about 7 to 10%, and the capacity deterioration after storage was also small.
これらの現象は反応に寄与しないマグネシウムが結晶構
造の崩壊を防ぎ、保存における自己放電やその後の容量
劣化を低減したと思われる。These phenomena appear to be due to the fact that magnesium, which does not contribute to the reaction, prevents the crystal structure from collapsing, reducing self-discharge during storage and subsequent capacity deterioration.
以」−の実施例かられかるようにマグネ／ラムを添加す
ることによりサイクル特性が無添加のものより向上し、
かつ保存後の自己放電や容量劣化も小さい非水電解液二
次電池か得られた。これらの傾向はマグネシウム以外の
アルカリ土類金属に共通してみられ、また添加されるリ
チウム複合酸化物もコバルト以外に本発明中にあるニン
ケル、鉄のリチウム複合酸化物にも見られた。As can be seen from the examples below, by adding Magne/Ram, the cycle characteristics are improved compared to those without additives,
In addition, a non-aqueous electrolyte secondary battery was obtained with little self-discharge and capacity deterioration after storage. These trends are common to alkaline earth metals other than magnesium, and the lithium composite oxides added are also found in the lithium composite oxides of nickel and iron in the present invention, in addition to cobalt.
なお、ここでは負極に自己放電の小さいリチウム金属を
用いたが、そのほか負極にはリチウム合金、炭素材等も
使用できる。Although lithium metal with low self-discharge is used for the negative electrode here, lithium alloys, carbon materials, etc. can also be used for the negative electrode.
発明の効果
以」二の発明から明らかなように本発明によれば、従来
のものと比較し、高エネルギー密度を維持し、サイクル
特性が向上し、かつ保存後の自己放電、容量劣化が小さ
いという特長を有するリチウム二次電池が得られる。Effects of the Invention As is clear from the second invention, the present invention maintains high energy density, improves cycle characteristics, and exhibits less self-discharge and capacity deterioration after storage than conventional products. A lithium secondary battery having the following characteristics can be obtained.
第１図は本発明の一実施例における非水電解液二次電池
の一部断面図、第２図は本発明の一実施例における非水
電解液二次電池のサイクル特性を示した図である。第３
図は同非水電解液二次電池の充電状態で保存した後の放
電曲線を示した図である。第４図は同非水電解液二次電
池の保存前後のサイクル特性を示した図である。
１・・・・・・正極合剤、４・・・・・リチウム全屈、
６・・・セパレータ。FIG. 1 is a partial cross-sectional view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention, and FIG. 2 is a diagram showing cycle characteristics of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention. be. Third
The figure shows a discharge curve of the non-aqueous electrolyte secondary battery after it was stored in a charged state. FIG. 4 is a diagram showing the cycle characteristics of the non-aqueous electrolyte secondary battery before and after storage. 1... Positive electrode mixture, 4... Lithium total bending,
6...Separator.
Claims (2)
ルカリ金属イオンを出し入れすることのできる正極およ
び負極からなる電池において、正極材料がＬｉＭＯ＿Ｚ
（１．９＜Ｚ＜２．１）の化学式で示されるリチウム複
合酸化物でリチウムの一部がアルカリ土類金属で置換さ
れ、かつＭがコバルト、鉄、ニッケルのうちのいずれか
一つ以上からなるものであることを特徴とする非水電解
液二次電池。(1) In a battery consisting of a non-aqueous electrolyte containing alkali metal ions, a positive electrode and a negative electrode through which the alkali metal ions can be taken in and taken out, the positive electrode material is LiMO_Z.
A lithium composite oxide represented by the chemical formula (1.9<Z<2.1) in which a portion of lithium is replaced with an alkaline earth metal, and M is one or more of cobalt, iron, and nickel. A non-aqueous electrolyte secondary battery comprising:
、水酸化物の形で、そのうちの少なくとも一つ以上添加
したものである特許請求の範囲第１項記載の非水電解液
二次電池。（３）前記アルカリ土類金属の添加量がＭの
１原子当たり０．５原子以下であることを特徴とする特
許請求の範囲第１項記載の非水電解液二次電池。(2) The nonaqueous electrolyte secondary according to claim 1, wherein the alkaline earth metal is in the form of carbonate, sulfate, nitrate, or hydroxide, and at least one of them is added. battery. (3) The nonaqueous electrolyte secondary battery according to claim 1, wherein the amount of the alkaline earth metal added is 0.5 atoms or less per 1 atom of M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2300767A JP2797693B2 (en) | 1990-11-05 | 1990-11-05 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2300767A JP2797693B2 (en) | 1990-11-05 | 1990-11-05 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04171659A true JPH04171659A (en) | 1992-06-18 |
| JP2797693B2 JP2797693B2 (en) | 1998-09-17 |
Family
ID=17888850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2300767A Expired - Fee Related JP2797693B2 (en) | 1990-11-05 | 1990-11-05 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2797693B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712172A2 (en) | 1994-11-09 | 1996-05-15 | Toray Industries, Inc. | Cathode material, method of preparing it and non-aqueous solvent type secondary battery having a cathode comprising it |
| WO2002054511A1 (en) * | 2000-12-27 | 2002-07-11 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for nonaqueous electrolyte secondary cell and cell using the same |
| US6921609B2 (en) | 2001-06-15 | 2005-07-26 | Kureha Chemical Industry Co., Ltd. | Gradient cathode material for lithium rechargeable batteries |
| US7563538B2 (en) | 2007-01-23 | 2009-07-21 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| US8415058B2 (en) | 2006-10-26 | 2013-04-09 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery comprising at least two lithium-containing transition metal oxides of different average particle sizes |
| US8795884B2 (en) | 2008-05-07 | 2014-08-05 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery and electronic device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6855461B2 (en) | 2001-06-15 | 2005-02-15 | Kureha Chemical Industry Co., Ltd. | Cathode material for lithium rechargeable batteries |
-
1990
- 1990-11-05 JP JP2300767A patent/JP2797693B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712172A2 (en) | 1994-11-09 | 1996-05-15 | Toray Industries, Inc. | Cathode material, method of preparing it and non-aqueous solvent type secondary battery having a cathode comprising it |
| EP0712172A3 (en) * | 1994-11-09 | 1996-07-17 | Toray Industries | Cathode material, method of preparing it and non-aqueous solvent type secondary battery having a cathode comprising it |
| WO2002054511A1 (en) * | 2000-12-27 | 2002-07-11 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for nonaqueous electrolyte secondary cell and cell using the same |
| US6991752B2 (en) | 2000-12-27 | 2006-01-31 | Matsushita Electric Industrial Co., Ltd. | Positive electrode active material for non-aqueous electrolyte secondary cell and cell using the same |
| US6921609B2 (en) | 2001-06-15 | 2005-07-26 | Kureha Chemical Industry Co., Ltd. | Gradient cathode material for lithium rechargeable batteries |
| US8415058B2 (en) | 2006-10-26 | 2013-04-09 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery comprising at least two lithium-containing transition metal oxides of different average particle sizes |
| US8691446B2 (en) | 2006-10-26 | 2014-04-08 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery and method of using the same |
| US9350019B2 (en) | 2006-10-26 | 2016-05-24 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery and method of using the same |
| US7563538B2 (en) | 2007-01-23 | 2009-07-21 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| US8795884B2 (en) | 2008-05-07 | 2014-08-05 | Hitachi Maxell, Ltd. | Nonaqueous secondary battery and electronic device |
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| Publication number | Publication date |
|---|---|
| JP2797693B2 (en) | 1998-09-17 |
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