JPH08264183A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH08264183A JPH08264183A JP7094352A JP9435295A JPH08264183A JP H08264183 A JPH08264183 A JP H08264183A JP 7094352 A JP7094352 A JP 7094352A JP 9435295 A JP9435295 A JP 9435295A JP H08264183 A JPH08264183 A JP H08264183A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- lithium secondary
- secondary battery
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000011149 active material Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 abstract description 47
- 239000000843 powder Substances 0.000 abstract description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 20
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 239000011737 fluorine Substances 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002033 PVDF binder Substances 0.000 abstract description 2
- 239000006230 acetylene black Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 229910003005 LiNiO2 Inorganic materials 0.000 abstract 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 11
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 10
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- -1 iS 2 Chemical class 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
【０００１】[0001]
【産業上の利用分野】本発明はリチウム二次電池に係わ
り、詳しくは充放電サイクル特性に優れたリチウム二次
電池を提供することを目的とした、正極活物質の粒子表
面の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to improvement of the particle surface of a positive electrode active material for the purpose of providing a lithium secondary battery having excellent charge / discharge cycle characteristics.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池が、高エネルギー密度を有する電池と
して、注目されている。この電池では、リチウムが水と
容易に反応し易いことから、電解質として有機溶媒を含
有する非水電解質が使用される。2. Description of the Related Art In recent years,
Lithium secondary batteries have attracted attention as batteries having high energy density. In this battery, a non-aqueous electrolyte containing an organic solvent is used as an electrolyte because lithium easily reacts with water.
【０００３】また、この電池の正極活物質としては、Ｔ
ｉＳ2 、ＭｏＳ2 、ＮｂＳｅ3 等の金属カルコゲン化
物、Ｃｒ2 Ｏ5 、Ｖ2 Ｏ5 等の金属酸化物、ＬｉＭｎ2
Ｏ4 、ＬｉＮｉＯ2 、ＬｉＣｏＯ2 、Ｌｉ2 ＮｉＣｏＯ
4 等のリチウム−遷移金属複合酸化物などがよく知られ
ている。The positive electrode active material of this battery is T
Metal chalcogenides such as iS 2 , MoS 2 and NbSe 3 , metal oxides such as Cr 2 O 5 and V 2 O 5 , LiMn 2
O 4 , LiNiO 2 , LiCoO 2 , Li 2 NiCoO
Lithium 4 etc. - are well known and transition metal composite oxide.
【０００４】しかしながら、従来のリチウム二次電池に
は、充放電を繰り返すと、正極側で非水電解質中の有機
溶媒が分解することに起因して電池容量が比較的短サイ
クル裡に減少するという問題があった。However, in the conventional lithium secondary battery, when the charge and discharge are repeated, the battery capacity is relatively reduced in a short cycle due to the decomposition of the organic solvent in the non-aqueous electrolyte on the positive electrode side. There was a problem.
【０００５】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、充放電サイ
クル特性に優れたリチウム二次電池を提供するにある。The present invention has been made to solve this problem, and an object of the present invention is to provide a lithium secondary battery having excellent charge / discharge cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウム二次電池（本発明電池）は、正
極と、負極と、有機溶媒を含有する非水電解質とを備え
るリチウム二次電池であって、前記正極の活物質が、粒
子表面に金属フッ化物からなる被膜を有するものであ
る。A lithium secondary battery according to the present invention (a battery according to the present invention) for achieving the above object comprises a positive electrode, a negative electrode, and a non-aqueous electrolyte containing an organic solvent. In the secondary battery, the active material of the positive electrode has a coating film made of metal fluoride on the surface of particles.
【０００７】本発明における金属フッ化物としては、Ｌ
ｉＦ、ＮａＦ等のアルカリ金属のフッ化物、ＭｇＦ2 、
ＣａＦ2 等のアルカリ土類金属のフッ化物、ＣｏＦ2 、
ＦｅＦ3 等の遷移金属のフッ化物が例示される。なかで
も、充放電サイクル特性に優れたリチウム二次電池を得
る上で、ＬｉＦが好ましい。The metal fluoride used in the present invention is L
Fluorides of alkali metals such as iF and NaF, MgF 2 ,
Fluoride of alkaline earth metal such as CaF 2 , CoF 2 ,
Illustrative are transition metal fluorides such as FeF 3 . Among them, LiF is preferable for obtaining a lithium secondary battery having excellent charge / discharge cycle characteristics.
【０００８】本発明における正極活物質としては、リチ
ウム二次電池用として従来提案されている種々のものを
使用することができる。具体例としては、ＴｉＳ2 、Ｍ
ｏＳ2 、ＮｂＳｅ3 等の金属カルコゲン化物、Ｃｒ2 Ｏ
5 、Ｖ2 Ｏ5 等の金属酸化物、ＬｉＭｎ2 Ｏ4 、Ｌｉx
Ｎｉ1-y Ｃｏy Ｏz （但し、０＜ｘ＜１．３、０≦ｙ≦
１、１．８＜ｚ＜２．２）等のリチウム−遷移金属複合
酸化物を挙げることができる。なかでも、内部抵抗が小
さいこと、また充放電を繰り返した際の容量減少が小さ
いことから、Ｌｉx Ｎｉ1-y Ｃｏy Ｏz が好ましい。特
に、ＬｉＦの被膜を粒子表面に形成したＬｉx Ｎｉ1-y
Ｃｏy Ｏz を使用すれば、充放電を繰り返した際の容量
減少が極めて小さい、充放電サイクル特性に極めて優れ
たリチウム二次電池を得ることができる。As the positive electrode active material in the present invention, various materials conventionally proposed for lithium secondary batteries can be used. Specific examples include TiS 2 and M
Metal chalcogenides such as oS 2 and NbSe 3 , Cr 2 O
5 , metal oxides such as V 2 O 5 , LiMn 2 O 4 , Li x
Ni 1-y Co y O z (where 0 <x <1.3, 0 ≦ y ≦
Examples of the lithium-transition metal composite oxide include 1, 1.8 <z <2.2). Among them, Li x Ni 1-y Co y O z is preferable because it has a small internal resistance and a small capacity decrease when charging and discharging are repeated. In particular, Li x Ni 1-y with a LiF coating formed on the surface of the particles
By using Co y O z , it is possible to obtain a lithium secondary battery having extremely small charge and discharge cycle characteristics and a very small capacity reduction when repeated charging and discharging.
【０００９】金属フッ化物の正極活物質に対する好適な
割合（被覆量）は、金属フッ化物の種類によって若干異
なる。ＬｉＦの場合は、正極活物質に対して０．１〜２
０モル％の範囲が好ましい。ＬｉＦが０．１モル％未満
の場合は、正極活物質の粒子表面の被覆量が不十分とな
り非水電解質中の有機溶媒の正極側での分解を有効に抑
制することができなくなる。一方、ＬｉＦが２０モル％
を越えた場合は、ＬｉＦの電導性が低いことに起因して
電池の内部抵抗が上昇するとともに、放電時の正極内で
のリチウムの拡散が悪くなるため充放電効率が低下す
る。A suitable ratio (coating amount) of the metal fluoride to the positive electrode active material is slightly different depending on the kind of the metal fluoride. In the case of LiF, 0.1 to 2 relative to the positive electrode active material
The range of 0 mol% is preferred. If the LiF content is less than 0.1 mol%, the amount of coating on the surface of the particles of the positive electrode active material becomes insufficient, and the decomposition of the organic solvent in the non-aqueous electrolyte on the positive electrode side cannot be effectively suppressed. On the other hand, LiF is 20 mol%
If it exceeds, the internal resistance of the battery rises due to the low conductivity of LiF, and the diffusion of lithium in the positive electrode during discharge deteriorates, resulting in a decrease in charge / discharge efficiency.
【００１０】本発明の特徴は、充放電を繰り返した際の
電池容量の減少を抑制するために、粒子表面に金属フッ
化物からなる被膜を有する正極活物質使用した点にあ
る。それゆえ、負極材料、有機溶媒を含有する非水電解
質など、電池を構成する他の部材については、従来リチ
ウム二次電池用として提案され、或いは実用されている
種々の材料を特に制限なく用いることが可能である。A feature of the present invention is that a positive electrode active material having a coating film made of a metal fluoride on the surface of particles is used in order to suppress a decrease in battery capacity when charging and discharging are repeated. Therefore, for other members constituting the battery, such as the negative electrode material and the non-aqueous electrolyte containing the organic solvent, various materials conventionally proposed or practically used for lithium secondary batteries should be used without particular limitation. Is possible.
【００１１】例えば、負極材料としては、リチウムイオ
ンを電気化学的に吸蔵及び放出することができる物質、
金属リチウムなどを使用することが可能である。リチウ
ムイオンを電気化学的に吸蔵及び放出することができる
物質としては、リチウム合金（リチウム−アルミニウム
合金、リチウム−鉛合金、リチウム−錫合金など）、炭
素材料（黒鉛、コークス、有機物焼成体など）、金属酸
化物（ＬｉＮｂ2 Ｏ5など）が例示される。For example, as the negative electrode material, a substance capable of electrochemically absorbing and desorbing lithium ions,
It is possible to use metallic lithium or the like. Materials capable of electrochemically absorbing and desorbing lithium ions include lithium alloys (lithium-aluminum alloys, lithium-lead alloys, lithium-tin alloys, etc.), carbon materials (graphite, coke, organic substance calcined products, etc.). , And metal oxides (LiNb 2 O 5 and the like) are exemplified.
【００１２】また、非水電解質の有機溶媒としては、エ
チレンカーボネート、ビニレンカーボネート、プロピレ
ンカーボネートなどの高誘電率溶媒や、これらとジエチ
ルカーボネート、ジメチルカーボネート、１，２−ジメ
トキシエタン、１，２−ジエトキシエタン、エトキシメ
トキシエタンなどの低沸点溶媒との混合溶媒が、同溶質
としては、ＬｉＰＦ6 、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ
3 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＢＦ4 、ＬｉＡｓ
Ｆ6 が、それぞれ例示される。なお、本発明における有
機溶媒を含有する非水電解質には、ゲル状固体電解質
（擬似固体電解質）も含まれる。As the organic solvent for the non-aqueous electrolyte, a high dielectric constant solvent such as ethylene carbonate, vinylene carbonate or propylene carbonate, or diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane or 1,2-dicarbonate may be used. A mixed solvent with a low-boiling-point solvent such as ethoxyethane or ethoxymethoxyethane has the same solute as LiPF 6 , LiClO 4 , LiCF 3 SO 4 .
3 , LiN (CF 3 SO 2 ) 2 , LiBF 4 , LiAs
Each of F 6 is exemplified. The non-aqueous electrolyte containing an organic solvent in the present invention also includes a gelled solid electrolyte (pseudo solid electrolyte).
【００１３】[0013]
【作用】正極活物質の粒子表面に金属フッ化物からなる
被膜が形成されてその表面活性が低減されているので、
充放電サイクル時の正極側での有機溶媒（非水電解液中
の有機溶媒又はゲル状固体電解質中の有機溶媒）の分解
が起こりにくくなる。[Function] Since a film made of a metal fluoride is formed on the surface of the particles of the positive electrode active material to reduce the surface activity,
Decomposition of the organic solvent (organic solvent in the non-aqueous electrolytic solution or organic solvent in the gelled solid electrolyte) on the positive electrode side during the charge / discharge cycle is less likely to occur.
【００１４】[0014]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the following examples, and various modifications may be made without departing from the scope of the invention. Is possible.
【００１５】（実施例１〜５） 〔正極〕ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮ
ｉＯ2 、ＬｉＣｏＯ2 の各粉末をフッ素（Ｆ2 ）ガス中
に１分間曝して表面部をフッ素化し、粒子表面に、それ
ぞれＴｉＦ4 、ＶＦ5 、ＭｎＦ2 、ＮｉＦ2 、ＣｏＦ2
からなる被膜を有する５種類の正極活物質を作製した。
各被膜の同定は、Ｘ線光電子分光法（X-ray Photoelect
ron Spectroscopy) により定性分析して行った。また、
正極活物質（フッ素化された表面部を除く部分）に対す
る金属フッ化物の割合を赤外分光分析法により調べたと
ころ、いずれも１モル％であった。(Examples 1 to 5) [Positive electrode] TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiN
Each of the powders of iO 2 and LiCoO 2 was exposed to a fluorine (F 2 ) gas for 1 minute to fluorinate the surface portion, and TiF 4 , VF 5 , MnF 2 , NiF 2 and CoF 2 were formed on the particle surfaces, respectively.
Five kinds of positive electrode active materials having a coating film made of were prepared.
The identification of each film is performed by X-ray photoelectrometry (X-ray Photoelect
ron Spectroscopy) for qualitative analysis. Also,
When the ratio of the metal fluoride to the positive electrode active material (portion excluding the fluorinated surface portion) was examined by infrared spectroscopy, all were 1 mol%.
【００１６】次いで、各正極活物質と、導電剤としての
アセチレンブラックと、結着剤としてのポリフッ化ビニ
リデンとを、重量比９０：６：４で混合して正極合剤を
調製し、この正極合剤を成型圧２トン／ｃｍ2 で直径２
０ｍｍの円盤状に加圧成型し、２５０°Ｃで２時間熱処
理して、５種類の正極を作製した。Next, each positive electrode active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder are mixed at a weight ratio of 90: 6: 4 to prepare a positive electrode mixture, and this positive electrode is prepared. diameter mixture at a molding pressure 2 tons / cm 2 2
Five types of positive electrodes were produced by pressure molding into a 0 mm disk shape and heat treatment at 250 ° C. for 2 hours.
【００１７】〔負極〕所定の厚みを有する金属リチウム
圧延板を直径２０ｍｍの円盤状に打ち抜いて負極を作製
した。[Negative Electrode] A negative electrode was produced by punching a rolled metal lithium plate having a predetermined thickness into a disk shape having a diameter of 20 mm.
【００１８】〔非水電解液〕プロピレンカーボネートと
１，２−ジメトキシエタンとの体積比１：１の混合溶媒
に、過塩素酸リチウムを１Ｍ（モル／リットル）の割合
で溶かして非水電解液を調製した。[Non-Aqueous Electrolyte] Lithium perchlorate is dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane at a volume ratio of 1: 1 at a ratio of 1 M (mol / liter) to prepare a non-aqueous electrolyte. Was prepared.
【００１９】〔電池の組立〕以上の正極、負極及び非水
電解液を用いて、正極活物質のみが異なる扁平型のリチ
ウム二次電池（本発明電池ＢＡ１〜ＢＡ５）を組み立て
た（電池寸法：直径２４．０ｍｍ、厚さ３．０ｍｍ）。
なお、セパレータとしては、ポリプロピレン製の微多孔
膜を使用し、これに非水電解液を含浸させた。[Battery Assembly] Using the above positive electrode, negative electrode and non-aqueous electrolyte, flat lithium secondary batteries (invention batteries BA1 to BA5) having different positive electrode active materials were assembled (battery size: Diameter 24.0 mm, thickness 3.0 mm).
As the separator, a polypropylene microporous film was used and impregnated with the non-aqueous electrolyte.
【００２０】図１は、作製した本発明電池ＢＡ１を模式
的に示す断面図であり、図示の本発明電池ＢＡ１は、正
極１、負極２、これら両電極１，２を互いに離間するセ
パレータ３、正極缶４、負極缶５、正極集電体６、負極
集電体７及びポリプロピレン製の絶縁パッキング８など
からなる。FIG. 1 is a cross-sectional view schematically showing the produced battery BA1 of the present invention. The illustrated battery BA1 of the present invention includes a positive electrode 1, a negative electrode 2, a separator 3 for separating both electrodes 1 and 2 from each other, It comprises a positive electrode can 4, a negative electrode can 5, a positive electrode current collector 6, a negative electrode current collector 7, an insulating packing 8 made of polypropylene, and the like.
【００２１】正極１及び負極２は、非水電解液を含浸し
たセパレータ３を介して対向して正極缶４及び負極缶５
が形成する電池ケース内に収納されており、正極１は正
極集電体６を介して正極缶４に、又負極２は負極集電体
７を介して負極缶５に接続され、電池内部に生じた化学
エネルギーを正極缶４及び負極缶５の両端子から電気エ
ネルギーとして外部へ取り出し得るようになっている。The positive electrode 1 and the negative electrode 2 are opposed to each other with the separator 3 impregnated with the non-aqueous electrolytic solution interposed therebetween, and the positive electrode can 4 and the negative electrode can 5 are provided.
The positive electrode 1 is connected to the positive electrode can 4 via the positive electrode current collector 6 and the negative electrode 2 is connected to the negative electrode can 5 via the negative electrode current collector 7 in the battery case formed by The generated chemical energy can be taken out as electric energy from both terminals of the positive electrode can 4 and the negative electrode can 5.
【００２２】（実施例６〜１０）正極活物質としてのＴ
ｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、Ｌ
ｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にてモ
ル比１：０．１で混合し、乾燥空気雰囲気下にて４５０
°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯＨ
で被覆した。次いで、これらの各粉末をフッ素（Ｆ2 ）
ガス中に１分間曝して、粒子表面にＬｉＦからなる被膜
を有する５種類の正極活物質を作製した。正極活物質に
対するＬｉＦの割合は、いずれも１モル％であった。こ
れらの正極活物質を使用したこと以外は実施例１〜５と
同様にして、本発明電池ＢＡ６〜ＢＡ１０を組み立て
た。(Examples 6 to 10) T as a positive electrode active material
iS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 , L
Each powder of iCoO 2 and LiOH powder were mixed in a mortar at a molar ratio of 1: 0.1, and were mixed in a dry air atmosphere at 450
After heat treatment at ° C for 2 hours, the surface of each powder particle is LiOH
Coated with. Then, each of these powders is treated with fluorine (F 2 )
It was exposed to gas for 1 minute to prepare five kinds of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material was 1 mol% in all cases. Inventive batteries BA6 to BA10 were assembled in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
【００２３】（比較例１〜５）正極の作製において、Ｔ
ｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、Ｌ
ｉＣｏＯ2 の各粉末をそのまま正極活物質として使用し
たこと以外は実施例１〜５と同様にして、比較電池ＢＣ
１〜ＢＣ５を組み立てた。(Comparative Examples 1 to 5) In the production of the positive electrode, T
iS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 , L
Comparative battery BC was prepared in the same manner as in Examples 1 to 5 except that each powder of iCoO 2 was used as it was as the positive electrode active material.
1 to BC5 were assembled.
【００２４】〔充放電サイクル試験〕本発明電池ＢＡ１
〜ＢＡ１０及び比較電池ＢＣ１〜ＢＣ５について、充電
電流密度１ｍＡ／ｃｍ2 で４．３Ｖまで充電した後、放
電電流密度３ｍＡ／ｃｍ2 で２．５Ｖまで放電する工程
を１サイクルとする充放電サイクル試験を行い、１サイ
クル目の放電容量に対する１５０サイクル目の放電容量
の容量劣化率〔容量劣化率（％）＝｛（１サイクル目の
放電容量−１５０サイクル目の放電容量）／１サイクル
目の放電容量｝×１００〕を求めた。結果を表１に示
す。[Charge / Discharge Cycle Test] Battery BA1 of the Present Invention
For ~BA10 and Comparative Batteries BC1～BC5, it was charged to 4.3V at a charging current density of 1 mA / cm 2, the charge-discharge cycle test of the step of discharging at a discharging current density of 3mA / cm 2 to 2.5V and 1 cycle The capacity deterioration rate of the discharge capacity at the 150th cycle relative to the discharge capacity at the first cycle [capacity deterioration rate (%) = {(discharge capacity at the first cycle−discharge capacity at the 150th cycle) / discharge at the first cycle Capacity} × 100] was determined. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１より、粒子表面に金属フッ化物からな
る被膜を有する正極活物質を用いた本発明電池ＢＡ１〜
ＢＡ１０は、従来公知の正極活物質をそのまま用いた比
較電池ＢＣ１〜ＢＣ５に比べて、１５０サイクル目の容
量劣化率が小さく、充放電サイクル特性に優れているこ
とが分かる。本発明電池ＢＡ１〜ＢＡ１０の中では本発
明電池ＢＡ６〜ＢＡ１０の容量劣化率が特に小さい。こ
のことから、被膜形成材料たる金属フッ化物としてはＬ
ｉＦが好ましいことが分かる。From Table 1, the batteries BA1 to BA1 of the present invention using the positive electrode active material having a coating made of a metal fluoride on the surface of the particles are shown.
It can be seen that BA10 has a smaller capacity deterioration rate at the 150th cycle and is superior in charge / discharge cycle characteristics, as compared with comparative batteries BC1 to BC5 using the conventionally known positive electrode active material as it is. Among the batteries BA1 to BA10 of the present invention, the capacity deterioration rates of the batteries BA6 to BA10 of the present invention are particularly small. From this, as a metal fluoride as a film forming material, L
It can be seen that iF is preferred.
【００２７】（実施例１１〜１５）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．１で混合し、乾燥空気雰囲気下にて４５
０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯ
Ｈで被覆した。次いで、これらの各粉末をフッ化窒素
（ＮＦ3 ）ガス中に１分間曝して、粒子表面にＬｉＦか
らなる被膜を有する５種類の正極活物質を作製した。正
極活物質に対するＬｉＦの割合は、いずれも０．０５モ
ル％であった。これらの正極活物質を使用したこと以外
は実施例１〜５と同様にして、本発明電池ＢＡ１１〜Ｂ
Ａ１５を組み立てた。(Examples 11 to 15) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as the positive electrode active material,
LiCoO 2 powders and LiOH powders were mixed in a mortar at a molar ratio of 1: 0.1, and then mixed in a dry air atmosphere at 45
After heat treatment at 0 ° C for 2 hours, the particle surface of each powder is LiO
Coated with H. Next, each of these powders was exposed to nitrogen fluoride (NF 3 ) gas for 1 minute to prepare five types of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material was 0.05 mol% in each case. Inventive batteries BA11 to B were prepared in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
A15 was assembled.
【００２８】（実施例１６〜２０）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．１で混合し、乾燥空気雰囲気下にて４５
０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯ
Ｈで被覆した。次いで、これらの各粉末をフッ化窒素
（ＮＦ3 ）ガス中に５分間曝して、粒子表面にＬｉＦか
らなる被膜を有する５種類の正極活物質を作製した。正
極活物質に対するＬｉＦの割合は、いずれも０．１モル
％であった。これらの正極活物質を使用したこと以外は
実施例１〜５と同様にして、本発明電池ＢＡ１６〜ＢＡ
２０を組み立てた。(Examples 16 to 20) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as the positive electrode active material,
LiCoO 2 powders and LiOH powders were mixed in a mortar at a molar ratio of 1: 0.1, and then mixed in a dry air atmosphere at 45
After heat treatment at 0 ° C for 2 hours, the particle surface of each powder is LiO
Coated with H. Next, each of these powders was exposed to nitrogen fluoride (NF 3 ) gas for 5 minutes to prepare five types of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material was 0.1 mol% in all cases. Inventive batteries BA16 to BA were carried out in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
Twenty assembled.
【００２９】（実施例２１〜２５）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．１で混合し、乾燥空気雰囲気下にて４５
０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯ
Ｈで被覆した。次いで、これらの各粉末をフッ素
（Ｆ2 ）ガス中に３分間曝して、粒子表面にＬｉＦから
なる被膜を有する５種類の正極活物質を作製した。正極
活物質に対するＬｉＦの割合は、いずれも２モル％であ
った。これらの正極活物質を使用したこと以外は実施例
１〜５と同様にして、本発明電池ＢＡ２１〜ＢＡ２５を
組み立てた。(Examples 21 to 25) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as the positive electrode active material,
LiCoO 2 powders and LiOH powders were mixed in a mortar at a molar ratio of 1: 0.1, and then mixed in a dry air atmosphere at 45
After heat treatment at 0 ° C for 2 hours, the particle surface of each powder is LiO
Coated with H. Next, each of these powders was exposed to a fluorine (F 2 ) gas for 3 minutes to prepare five types of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material was 2 mol% in all cases. Inventive batteries BA21 to BA25 were assembled in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
【００３０】（実施例２６〜３０）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．１で混合し、乾燥空気雰囲気下にて４５
０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯ
Ｈで被覆した。次いで、これらの各粉末をフッ素
（Ｆ2 ）ガス中に１０分間曝して、粒子表面にＬｉＦか
らなる被膜を有する５種類の正極活物質を作製した。正
極活物質に対するＬｉＦの割合は、いずれも１０モル％
であった。これらの正極活物質を使用したこと以外は実
施例１〜５と同様にして、本発明電池ＢＡ２６〜ＢＡ３
０を組み立てた。(Examples 26 to 30) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as the positive electrode active material,
LiCoO 2 powders and LiOH powders were mixed in a mortar at a molar ratio of 1: 0.1, and then mixed in a dry air atmosphere at 45
After heat treatment at 0 ° C for 2 hours, the particle surface of each powder is LiO
Coated with H. Next, each of these powders was exposed to a fluorine (F 2 ) gas for 10 minutes to prepare five types of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material is 10 mol% in each case.
Met. Inventive batteries BA26 to BA3 were carried out in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
Assembled 0.
【００３１】（実施例３１〜３５）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．２で混合し、乾燥空気雰囲気下にて４５
０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉＯ
Ｈで被覆した。次いで、これらの各粉末をフッ素
（Ｆ2 ）ガス中に１０分間曝して、粒子表面にＬｉＦか
らなる被膜を有する５種類の正極活物質を作製した。正
極活物質に対するＬｉＦの割合は、いずれも２０モル％
であった。これらの正極活物質を使用したこと以外は実
施例１〜５と同様にして、本発明電池ＢＡ３１〜ＢＡ３
５を組み立てた。(Examples 31 to 35) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as a positive electrode active material,
LiCoO 2 powder and LiOH powder were mixed in a mortar at a molar ratio of 1: 0.2, and the mixture was dried in an atmosphere of dry air at 45
After heat treatment at 0 ° C for 2 hours, the particle surface of each powder is LiO
Coated with H. Next, each of these powders was exposed to a fluorine (F 2 ) gas for 10 minutes to prepare five types of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material is 20 mol% in each case
Met. Inventive batteries BA31 to BA3 were carried out in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
Assembled 5.
【００３２】（実施例３６〜４０）正極活物質としての
ＴｉＳ2 、Ｖ2 Ｏ5 、ＬｉＭｎ2 Ｏ4 、ＬｉＮｉＯ2 、
ＬｉＣｏＯ2 の各粉末と、ＬｉＯＨ粉末とを、乳鉢にて
モル比１：０．２２で混合し、乾燥空気雰囲気下にて４
５０°Ｃで２時間熱処理して、各粉末の粒子表面をＬｉ
ＯＨで被覆した。次いで、これらの各粉末をフッ素（Ｆ
2 ）ガス中に１０分間曝して、粒子表面にＬｉＦからな
る被膜を有する５種類の正極活物質を作製した。正極活
物質に対するＬｉＦの割合は、いずれも２２モル％であ
った。これらの正極活物質を使用したこと以外は実施例
１〜５と同様にして、本発明電池ＢＡ３６〜ＢＡ４０を
組み立てた。(Examples 36 to 40) TiS 2 , V 2 O 5 , LiMn 2 O 4 , LiNiO 2 as the positive electrode active material,
LiCoO 2 powder and LiOH powder were mixed in a mortar at a molar ratio of 1: 0.22, and then mixed in a dry air atmosphere at 4
After heat treatment at 50 ° C for 2 hours, the particle surface of each powder is Li
Coated with OH. Then, each of these powders is treated with fluorine (F
2 ) It was exposed to gas for 10 minutes to prepare five kinds of positive electrode active materials having a coating film made of LiF on the particle surface. The ratio of LiF to the positive electrode active material was 22 mol% in all cases. Inventive batteries BA36 to BA40 were assembled in the same manner as in Examples 1 to 5 except that these positive electrode active materials were used.
【００３３】〔充放電サイクル試験〕本発明電池ＢＡ１
１〜ＢＡ４０について先と同じ条件の充放電サイクル試
験を行い、各電池の容量劣化率を求めた。結果を表２に
示す。[Charge / Discharge Cycle Test] Battery BA1 of the Invention
A charge-discharge cycle test was performed on 1 to BA40 under the same conditions as above, and the capacity deterioration rate of each battery was obtained. Table 2 shows the results.
【００３４】[0034]
【表２】 [Table 2]
【００３５】表２に示すように、本発明電池ＢＡ１１〜
ＢＡ４０のうちＢＡ１６〜ＢＡ３０の容量劣化率が６％
以下と特に小さい。このことから、ＬｉＦの正極活物質
に対する割合は０．１〜２０モル％の範囲が好ましいこ
とが分かる。また、本発明電池ＢＡ１６〜ＢＡ３０のう
ちＢＡ１９，ＢＡ２０，ＢＡ２４，ＢＡ２５，ＢＡ２
９，ＢＡ３０，ＢＡ３４，ＢＡ３５の容量劣化率が４％
以下と極めて小さいことから、被膜形成材料としてＬｉ
Ｆを使用し、且つ正極活物質としてＬｉＮｉＯ2及びＬ
ｉＣｏＯ2 に代表されるＬｉx Ｎｉ1-y Ｃｏy Ｏz を使
用することが最も好ましいことが分かる。As shown in Table 2, the batteries BA11 to BA11 of the present invention.
The capacity deterioration rate of BA16 to BA30 of BA40 is 6%
The following is particularly small. From this, it is understood that the ratio of LiF to the positive electrode active material is preferably in the range of 0.1 to 20 mol%. Further, among the batteries BA16 to BA30 of the present invention, BA19, BA20, BA24, BA25, BA2
9, BA30, BA34, BA35 capacity deterioration rate is 4%
Since it is extremely small as below, Li as a film forming material
F is used, and LiNiO 2 and L are used as the positive electrode active material.
It can be seen most preferred to use a Li x Ni 1-y Co y O z typified iCoO 2.
【００３６】[0036]
【発明の効果】充放電サイクル時に正極側で有機溶媒の
分解が起こりにくいために、本発明電池は充放電サイク
ル特性に優れる。EFFECT OF THE INVENTION Since the organic solvent is less likely to be decomposed on the positive electrode side during the charge / discharge cycle, the battery of the present invention has excellent charge / discharge cycle characteristics.
【図１】実施例で組み立てた扁平型のリチウム二次電池
（本発明電池）の断面図である。FIG. 1 is a cross-sectional view of a flat type lithium secondary battery (the battery of the present invention) assembled in an example.
ＢＡ１ 扁平型のリチウム二次電池（本発明電池） １ 正極 ２ 負極 ３ セパレータ BA1 flat type lithium secondary battery (battery of the present invention) 1 positive electrode 2 negative electrode 3 separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Nishio 2-5-5 Keihan Hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Toshihiko Saito 2-chome, Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd.
Claims (5)
電解質とを備えるリチウム二次電池であって、前記正極
の活物質が、粒子表面に金属フッ化物からなる被膜を有
していることを特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte containing an organic solvent, wherein the active material of the positive electrode has a coating made of metal fluoride on the surface of particles. A lithium secondary battery characterized in that
Ｆ5 、ＭｎＦ2 、ＮｉＦ2 又はＣｏＦ2 である請求項１
記載のリチウム二次電池。2. The metal fluoride is LiF, TiF 4 , V
It is F 5 , MnF 2 , NiF 2 or CoF 2.
The lithium secondary battery described.
記載のリチウム二次電池。3. The metal fluoride is LiF.
The lithium secondary battery described.
０．１〜２０モル％である請求項３記載のリチウム二次
電池。4. The lithium secondary battery according to claim 3, wherein the ratio of the LiF to the active material is 0.1 to 20 mol%.
z （但し、０＜ｘ＜１．３、０≦ｙ≦１、１．８＜ｚ＜
２．２）である請求項３又は４記載のリチウム二次電
池。5. The active material is Li x Ni 1-y Co y O.
z (However, 0 <x <1.3, 0 ≦ y ≦ 1, 1.8 <z <
The lithium secondary battery according to claim 3 or 4, which is 2.2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09435295A JP3157413B2 (en) | 1995-03-27 | 1995-03-27 | Lithium secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09435295A JP3157413B2 (en) | 1995-03-27 | 1995-03-27 | Lithium secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JPH08264183A true JPH08264183A (en) | 1996-10-11 |
| JP3157413B2 JP3157413B2 (en) | 2001-04-16 |
Family
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|---|---|---|---|
| JP09435295A Expired - Lifetime JP3157413B2 (en) | 1995-03-27 | 1995-03-27 | Lithium secondary battery |
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| JP (1) | JP3157413B2 (en) |
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