JPH08321326A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH08321326A JPH08321326A JP7150842A JP15084295A JPH08321326A JP H08321326 A JPH08321326 A JP H08321326A JP 7150842 A JP7150842 A JP 7150842A JP 15084295 A JP15084295 A JP 15084295A JP H08321326 A JPH08321326 A JP H08321326A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- negative electrode
- positive electrode
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 25
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 22
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 12
- 239000007774 positive electrode material Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 2
- 229910001632 barium fluoride Inorganic materials 0.000 abstract 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 abstract 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract 1
- 229910001637 strontium fluoride Inorganic materials 0.000 abstract 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 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
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- Cell Separators (AREA)
- 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、詳しくは電池缶の中にフッ化水素が発生する虞れ
があるリチウム二次電池の充放電サイクル特性を改善す
ることを目的とした、電池缶の中の部材の改良に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to improving the charge / discharge cycle characteristics of a lithium secondary battery in which hydrogen fluoride may be generated in the battery can. And the improvement of the member in the battery can.
【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、正極材料を適宜選定することによ
り高容量化が可能なことから、注目されており、高容量
化のための正極材料として、種々の金属酸化物が提案さ
れている。例えば、既に実用されているＬｉＣｏＯ2 も
その一つであり、１２０ｍＡｈ／ｇ以上の放電容量を有
するＬｉＣｏＯ2 が固相法により容易に得られている。2. Description of the Related Art In recent years,
A lithium secondary battery has attracted attention because it can have a high capacity by appropriately selecting a positive electrode material, and various metal oxides have been proposed as a positive electrode material for increasing the capacity. For example, LiCoO 2 which has already been put into practical use is one of them, and LiCoO 2 having a discharge capacity of 120 mAh / g or more is easily obtained by the solid phase method.
【０００３】ところで、リチウム二次電池においては、
一般に、非水電解質の溶質としてＬｉＰＦ6 （ヘキサフ
ルオロリン酸リチウム）、ＬｉＢＦ4 （テトラフルオロ
ホウ酸リチウム）、ＬｉＣＦ3 ＳＯ3 （トリフルオロメ
タンスルホン酸リチウム）などのフッ素化合物が、また
正極及び負極の結着剤としてＰＶｄＦ（ポリフッ化ビニ
リデン）、ＰＴＦＥ（ポリテトラフルオロエチレン）な
どのフッ素化合物が、それぞれ使用されている。By the way, in the lithium secondary battery,
Generally, a fluorine compound such as LiPF 6 (lithium hexafluorophosphate), LiBF 4 (lithium tetrafluoroborate), LiCF 3 SO 3 (lithium trifluoromethanesulfonate) is used as a solute of the non-aqueous electrolyte, and a solute of the positive electrode and the negative electrode. As a binder, a fluorine compound such as PVdF (polyvinylidene fluoride) or PTFE (polytetrafluoroethylene) is used.
【０００４】しかしながら、これらのフッ素化合物を使
用すると、これらが電池缶の中に存在する微量の水など
と反応してフッ化水素（ＨＦ）が発生し、発生したフッ
化水素が正極材料や負極材料などと反応してこれらを劣
化させる。このため、非水電解質の溶質や正極又は負極
の結着剤などにフッ素化合物を使用したリチウム二次電
池には、充放電サイクル特性が良くないという問題があ
る。この問題は、液体電解質を使用したリチウム二次電
池に限った問題ではなく、固体電解質又はゲル状電解質
を使用したリチウム二次電池にも共通する問題である。However, when these fluorine compounds are used, they react with a small amount of water or the like present in the battery can to generate hydrogen fluoride (HF), and the generated hydrogen fluoride is used as the positive electrode material or the negative electrode. It reacts with materials and degrades them. Therefore, a lithium secondary battery using a fluorine compound as a solute of a non-aqueous electrolyte or a binder of a positive electrode or a negative electrode has a problem that charge / discharge cycle characteristics are not good. This problem is not limited to a lithium secondary battery using a liquid electrolyte, but is a problem common to lithium secondary batteries using a solid electrolyte or a gel electrolyte.
【０００５】本発明は、正極、負極、非水電解質などの
電池缶の中の少なくとも一つの部材にフッ素化合物を含
有するものを使用したため、電池缶の中にフッ化水素が
発生する虞れがあるリチウム二次電池が抱える上述の問
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、電池缶の中の部材にフッ素化合物を含有す
るものが使用されているにもかかわらず、優れた充放電
サイクル特性を有するリチウム二次電池を提供するにあ
る。In the present invention, since at least one member of the battery can, such as the positive electrode, the negative electrode and the non-aqueous electrolyte, containing a fluorine compound is used, hydrogen fluoride may be generated in the battery can. It was made to solve the above-mentioned problems that a certain lithium secondary battery has, and its purpose is to use a member containing a fluorine compound as a member in a battery can. A lithium secondary battery having excellent charge / discharge cycle characteristics is provided.
【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、電
池缶の中にフッ化水素が発生する虞れがあるリチウム二
次電池において、前記電池缶の中の少なくとも一つの部
材に、ＮａＦ、ＫＦ、ＣｓＦ、ＭｇＦ2 、ＣａＦ2 、Ｓ
ｒＦ2 及びＢａＦ2 よりなる群から選ばれた少なくとも
１種の金属フッ化物を含有させたものである。電池缶内
にフッ化水素が発生する虞れがあるリチウム二次電池と
しては、正極、負極及び非水電解質の少なくとも一つに
フッ素化合物を含有する部材を使用したものが例示され
る。A lithium secondary battery according to the present invention (a battery of the present invention) for achieving the above object is a lithium secondary battery in which hydrogen fluoride may be generated in a battery can. In at least one member of the battery can, NaF, KF, CsF, MgF 2 , CaF 2 , S
It contains at least one metal fluoride selected from the group consisting of rF 2 and BaF 2 . Examples of the lithium secondary battery in which hydrogen fluoride may be generated in the battery can include those using a member containing a fluorine compound in at least one of the positive electrode, the negative electrode and the non-aqueous electrolyte.
【０００７】正極又は負極がフッ素化合物を含有する場
合としては、正極又は負極の結着剤としてＰＶｄＦ又は
ＰＴＦＥが使用されている場合が例示される。また、非
水電解質がフッ素化合物を含有する場合としては、非水
電解質の溶質としてＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＣＦ
3 ＳＯ3 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 又はＬｉＡｓＦ6
が使用されている場合が例示される。An example of the case where the positive electrode or the negative electrode contains a fluorine compound is a case where PVdF or PTFE is used as a binder for the positive electrode or the negative electrode. When the non-aqueous electrolyte contains a fluorine compound, LiPF 6 , LiBF 4 , LiCF may be used as the solute of the non-aqueous electrolyte.
3 SO 3 , LiN (CF 3 SO 2 ) 2 or LiAsF 6
Is used as an example.
【０００８】本発明電池の正極材料、負極材料及び非水
電解質の溶媒としては、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。As the positive electrode material, the negative electrode material, and the solvent of the non-aqueous electrolyte of the battery of the present invention, various ones conventionally proposed for lithium secondary batteries can be used.
【０００９】正極材料の具体例としては、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；及びＬｉx ＭＯz （Ｍは
Ｃｏ、Ｎｉ、Ｖ、Ｆｅ及びＭｎより選ばれた少なくとも
一種の遷移元素、０＜ｘ≦１．３、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。Specific examples of the positive electrode material 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 ; and Li x MO z (M is at least one transition element selected from Co, Ni, V, Fe, and Mn, 0 <x ≦ 1.3, 1.8 ≤z≤2.
Examples thereof include lithium-transition metal composite oxides such as 2).
【００１０】負極材料の具体例としては、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）、正極に対して卑な電位を示す金属酸
化物（Ｆｅ2 Ｏ3 など）及び金属硫化物（ＦｅＳなど）
等のリチウムイオンを電気化学的に吸蔵及び放出するこ
とが可能な物質及び金属リチウムを挙げることができ
る。Specific examples of the negative electrode material include lithium alloys (lithium-aluminum alloys, lithium-lead alloys, lithium-tin alloys, etc.), carbon materials (graphite, coke, organic material calcined products, etc.), and base materials for the positive electrode. Metal oxides (such as Fe 2 O 3 ) and metal sulfides (such as FeS) that show potential
Examples thereof include substances capable of electrochemically occluding and releasing lithium ions, and metallic lithium.
【００１１】非水電解質の溶媒の具体例としては、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
カーボネート等の高誘電率溶媒、これらの高誘電率溶媒
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等の低沸点溶媒との混合溶媒を挙
げることができる。なお、非水電解質として、液体電解
質の他、固体電解質又はゲル状電解質（擬似固体電解
質）を使用することもできる。Specific examples of the non-aqueous electrolyte solvent include high-dielectric constant solvents such as ethylene carbonate, vinylene carbonate and propylene carbonate, and high-dielectric constant solvents of these with diethyl carbonate, dimethyl carbonate, 1,
A mixed solvent with a low boiling point solvent such as 2-dimethoxyethane, 1,2-diethoxyethane, or ethoxymethoxyethane can be mentioned. In addition to the liquid electrolyte, a solid electrolyte or a gel electrolyte (pseudo solid electrolyte) can be used as the non-aqueous electrolyte.
【００１２】正極、負極、非水電解質又はセパレータな
どに含有させる好適な金属フッ化物の量は、電池缶の中
に発生するフッ化水素の量及び使用する金属フッ化物の
フッ化水素に対する反応性などによって変わるので一概
には言えないが、正極又は負極のいずれか一方に含有さ
せる場合は、一般的に各電極の金属フッ化物含有量を正
極合剤又は負極合剤１００重量部に対して０．１〜２０
重量部の範囲内とすることが好ましい。The preferable amount of metal fluoride contained in the positive electrode, the negative electrode, the non-aqueous electrolyte or the separator is the amount of hydrogen fluoride generated in the battery can and the reactivity of the metal fluoride used with hydrogen fluoride. Although it cannot be generally stated because it changes depending on factors such as the case, when it is contained in either the positive electrode or the negative electrode, the metal fluoride content of each electrode is generally 0 based on 100 parts by weight of the positive electrode mixture or the negative electrode mixture. 1 to 20
It is preferably within the range of parts by weight.
【００１３】[0013]
【作用】電池缶の中の部材に含まれているフッ素化合物
と、電池缶の中に存在する微量の水分等が反応して発生
したフッ化水素は、正極、負極、非水電解質、セパレー
タなどの電池缶の中の部材に含有させた金属フッ化物と
反応して、正極材料、負極材料などの電池缶の中の部材
と反応しにくい物質に変わる。このため、それらの部材
の劣化が抑制されて、充放電サイクル特性が向上する。[Function] Hydrogen fluoride generated by the reaction between the fluorine compound contained in the member inside the battery can and a small amount of water present in the battery can is used as a positive electrode, a negative electrode, a non-aqueous electrolyte, a separator, etc. When it reacts with the metal fluoride contained in the member inside the battery can, it becomes a substance that does not easily react with the member inside the battery can such as the positive electrode material and the negative electrode material. Therefore, deterioration of those members is suppressed, and charge / discharge cycle characteristics are improved.
【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】〔リチウム二次電池の作製〕正極、負極又
は非水電解質がＮａＦ、ＫＦ、ＣｓＦ、ＭｇＦ2 、Ｃａ
Ｆ2 、ＳｒＦ2 又はＢａＦ2 を含有する扁平型のリチウ
ム二次電池（本発明電池Ａ１〜Ａ２５）及び正極、負極
及び非水電解質が上記の添加剤を含有しない扁平型のリ
チウム二次電池（比較電池Ｂ１〜Ｂ６）を作製した。電
池寸法は、いずれも直径２４．０ｍｍ、厚さ３．０ｍｍ
である。セパレータとしては、ポリプロピレン製の微多
孔膜を使用した。[Production of Lithium Secondary Battery] The positive electrode, the negative electrode or the non-aqueous electrolyte is NaF, KF, CsF, MgF 2 , Ca.
Flat type lithium secondary batteries containing F 2 , SrF 2 or BaF 2 (invention batteries A1 to A25) and flat type lithium secondary batteries in which the positive electrode, the negative electrode and the non-aqueous electrolyte do not contain the above additive ( Comparative batteries B1 to B6) were produced. The battery dimensions are 24.0 mm in diameter and 3.0 mm in thickness.
Is. A polypropylene microporous film was used as the separator.
【００１６】正極は、正極材料と、導電剤としてのアセ
チレンブラックと、結着剤としてのＰＶｄＦとを、重量
比９０：５：５で混練して正極合剤を調製し、この正極
合剤を成形圧２トン／ｃｍ2 で直径２０ｍｍの円盤状に
加圧成形し、１５０°Ｃで２時間熱処理して、作製し
た。金属フッ化物を含有する正極は、上記正極合剤に金
属フッ化物を添加混合して作製した。なお、ＭｎＯ
2 は、３７５°Ｃで熱処理したものを使用した。For the positive electrode, a positive electrode material, acetylene black as a conductive agent, and PVdF as a binder are kneaded at a weight ratio of 90: 5: 5 to prepare a positive electrode mixture, and this positive electrode mixture is prepared. It was produced by press-molding into a disk shape having a diameter of 20 mm at a molding pressure of 2 ton / cm 2 and heat-treating at 150 ° C. for 2 hours. The positive electrode containing the metal fluoride was prepared by adding and mixing the metal fluoride to the positive electrode mixture. In addition, MnO
No. 2 used what was heat-processed at 375 degreeC.
【００１７】金属リチウムを負極材料とする負極は、リ
チウム圧延板を直径２０ｍｍの円盤状に打ち抜いて作製
した。Ｆｅ2 Ｏ3 又はＦｅＳを負極材料とする負極は、
負極材料と、導電剤としてのアセチレンブラックと、結
着剤としてのＰＶｄＦとを、重量比９０：５：５で混練
して負極合剤を調製し、この負極合剤を成形圧２トン／
ｃｍ2 で直径２０ｍｍの円盤状に加圧成形し、１５０°
Ｃで２時間熱処理して、作製した。黒鉛を負極材料とす
る負極は、上記負極合剤として、黒鉛と、ＰＶｄＦと
を、重量比８５：１５で混練して得たものを使用した。
金属フッ化物を含有する負極は、上記負極合剤に金属フ
ッ化物を添加混合して作製した。A negative electrode using metallic lithium as a negative electrode material was produced by punching a rolled lithium plate into a disk shape having a diameter of 20 mm. The negative electrode using Fe 2 O 3 or FeS as the negative electrode material is
A negative electrode material, acetylene black as a conductive agent, and PVdF as a binder were kneaded at a weight ratio of 90: 5: 5 to prepare a negative electrode mixture, and this negative electrode mixture was molded under a pressure of 2 tons /
It was pressed into a disc having a diameter of 20mm in cm 2, 150 °
It heat-processed in C for 2 hours, and produced. The negative electrode using graphite as the negative electrode material was obtained by kneading graphite and PVdF at a weight ratio of 85:15 as the above negative electrode mixture.
The negative electrode containing the metal fluoride was produced by adding and mixing the metal fluoride to the negative electrode mixture.
【００１８】非水電解質（液体電解質）は、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、ＬｉＢＦ4 を１Ｍ（モル／リット
ル）の割合で溶かして作製した。ＮａＦを含有する非水
電解質は、非水電解質１００重量部に対してＮａＦ１０
重量部を添加混合して作製した。The non-aqueous electrolyte (liquid electrolyte) was prepared by dissolving LiBF 4 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). The non-aqueous electrolyte containing NaF contains 10 parts by weight of NaF for 100 parts by weight of the non-aqueous electrolyte.
It was prepared by adding and mixing parts by weight.
【００１９】表１に、各電池に使用した正極材料、負極
材料、金属フッ化物の種類、添加先及び添加量を示す。
非水電解質に金属フッ化物を添加した場合の添加量は、
非水電解質１００重量部に対する重量部で示してある。
また、正極合剤又は負極合剤に金属フッ化物を添加した
場合の添加量は、正極合剤又は負極合剤１００重量部に
対する重量部で示してある。Table 1 shows the types of positive electrode materials, negative electrode materials, and metal fluorides used in each battery, the addition destination and the addition amount.
When the metal fluoride is added to the non-aqueous electrolyte, the addition amount is
It is shown in parts by weight based on 100 parts by weight of the non-aqueous electrolyte.
Further, the addition amount of the metal fluoride added to the positive electrode mixture or the negative electrode mixture is shown in parts by weight based on 100 parts by weight of the positive electrode mixture or the negative electrode mixture.
【００２０】[0020]
【表１】 [Table 1]
【００２１】〔充放電サイクル試験〕本発明電池Ａ１〜
Ａ２５及び比較電池Ｂ１〜Ｂ６について充放電サイクル
試験を行い、１サイクル目の放電容量に対する１００サ
イクル目の放電容量の比率（％）を求めて、各電池の充
放電サイクル特性の良否を調べた。但し、本発明電池Ａ
１、Ａ１４〜Ａ２５、Ｂ１、Ｂ３〜Ｂ６については、１
ｍＡで４．３Ｖまで充電した後、３ｍＡで電池電圧が
２．０Ｖに低下する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、また、本発明電池Ａ２〜
Ａ１３及び比較電池Ｂ２については、１ｍＡで３．５Ｖ
まで充電した後、３ｍＡで電池電圧が２．５Ｖに低下す
るまで放電する工程を１サイクルとする充放電サイクル
試験を行った。結果を先の表１に示す。[Charge / Discharge Cycle Test] Battery A1 of the Present Invention
A25 and comparative batteries B1 to B6 were subjected to a charge / discharge cycle test, the ratio (%) of the discharge capacity at the 100th cycle to the discharge capacity at the first cycle was determined, and the quality of the charge / discharge cycle characteristics of each battery was examined. However, the present invention battery A
1, for A14 to A25, B1, and B3 to B6, 1
After charging to 4.3 V with mA, a charging / discharging cycle test in which one cycle includes a process of discharging until the battery voltage drops to 2.0 V at 3 mA is performed.
For A13 and comparative battery B2, 3.5V at 1mA
A charge-discharge cycle test was performed in which one cycle includes a process of discharging the battery at 3 mA until the battery voltage drops to 2.5 V after charging. The results are shown in Table 1 above.
【００２２】表１に示すように、正極、負極又は非水電
解質が特定の金属フッ化物を含有する本発明電池Ａ１〜
Ａ２５は、これらの金属フッ化物を含有しない比較電池
Ｂ１〜Ｂ６に比べて、１サイクル目の放電容量に対する
１００サイクル目の放電容量の比率（％）が大きい。こ
の結果から、結着剤や非水電解質の溶質にＰＶｄＦ、Ｐ
ＴＦＥ等のフッ素化合物を使用しても、正極、負極及び
非水電解質の少なくとも一つに特定の金属フッ化物を含
有させるようにすれば、充放電サイクル特性に優れたリ
チウム二次電池が得られることが分かる。また、表１よ
り、正極又は負極の一方に金属フッ化物を含有させる場
合は、正極合剤又は負極合剤１００重量部に対して金属
フッ化物を０．１〜２０重量部の範囲で含有させること
が好ましいことが分かる。As shown in Table 1, the batteries A1 to A1 of the present invention in which the positive electrode, the negative electrode or the non-aqueous electrolyte contains a specific metal fluoride.
A25 has a large ratio (%) of the discharge capacity at the 100th cycle to the discharge capacity at the first cycle, as compared with the comparative batteries B1 to B6 that do not contain these metal fluorides. From this result, PVdF, P was added to the binder and solute of the non-aqueous electrolyte.
Even if a fluorine compound such as TFE is used, if a specific metal fluoride is contained in at least one of the positive electrode, the negative electrode and the non-aqueous electrolyte, a lithium secondary battery having excellent charge / discharge cycle characteristics can be obtained. I understand. Further, from Table 1, when the metal fluoride is contained in one of the positive electrode and the negative electrode, the metal fluoride is contained in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the positive electrode mixture or the negative electrode mixture. It turns out that it is preferable.
【００２３】上記実施例では、扁平型のリチウム二次電
池を例に挙げて説明したが、本発明は電池形状に特に制
限はない。また、結着剤としてＰＶｄＦを、非水電解質
の溶質としてＬｉＢＦ4 を使用したが、本発明は、電池
缶の中にフッ化水素が発生する虞れがあるリチウム二次
電池に広く適用可能なものである。さらに、金属フッ化
物を正極、負極及び非水電解質の少なくとも一つに含有
させた場合について効果をみたが、セパレータに含有さ
せた場合にも同様の優れた効果が得られる。In the above embodiments, the flat type lithium secondary battery has been described as an example, but the present invention is not particularly limited in battery shape. Although PVdF was used as the binder and LiBF 4 was used as the solute of the non-aqueous electrolyte, the present invention is widely applicable to lithium secondary batteries in which hydrogen fluoride may be generated in the battery can. It is a thing. Further, although the effect was observed when the metal fluoride was contained in at least one of the positive electrode, the negative electrode and the non-aqueous electrolyte, the same excellent effect was obtained when the metal fluoride was contained in the separator.
【００２４】[0024]
【発明の効果】金属フッ化物がフッ化水素と反応して、
これを、正極材料、負極材料等の電池缶の中の部材と反
応しにくい物質に変えるので、正極材料、負極材料など
の劣化が抑制される。このため、本発明電池は、電池缶
の中の部材にフッ素化合物を含有するものが使用されて
いるにもかかわらず、優れた充放電サイクル特性を有す
る。The metal fluoride reacts with hydrogen fluoride,
Since this is changed to a substance such as a positive electrode material or a negative electrode material that does not easily react with a member in the battery can, deterioration of the positive electrode material, the negative electrode material, or the like is suppressed. Therefore, the battery of the present invention has excellent charge / discharge cycle characteristics, even though the member containing the fluorine compound is used as the member in the battery can.
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Front page continuation (72) Inventor Koji Nishio 2-5-5 Keihan Hon-dori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-5-5 Keihan-hondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd.
Claims (2)
あるリチウム二次電池において、前記電池缶の中の少な
くとも一つの部材に、ＮａＦ、ＫＦ、ＣｓＦ、Ｍｇ
Ｆ2 、ＣａＦ2 、ＳｒＦ2 及びＢａＦ2 よりなる群から
選ばれた少なくとも１種の金属フッ化物を含有させてあ
るリチウム二次電池。1. In a lithium secondary battery in which hydrogen fluoride may be generated in a battery can, at least one member in the battery can has NaF, KF, CsF, Mg.
F 2, CaF 2, SrF 2 and at least one lithium secondary battery that is contain a metal fluoride selected from the group consisting of BaF 2.
つがフッ素化合物を含有するリチウム二次電池におい
て、前記正極、前記負極、前記非水電解質及びセパレー
タの少なくとも一つに、ＮａＦ、ＫＦ、ＣｓＦ、ＭｇＦ
2 、ＣａＦ2 、ＳｒＦ2 及びＢａＦ2 よりなる群から選
ばれた少なくとも１種の金属フッ化物を含有させてある
リチウム二次電池。2. A lithium secondary battery in which at least one of a positive electrode, a negative electrode and a non-aqueous electrolyte contains a fluorine compound, and at least one of the positive electrode, the negative electrode, the non-aqueous electrolyte and a separator is NaF, KF or CsF. , MgF
A lithium secondary battery containing at least one metal fluoride selected from the group consisting of 2 , CaF 2 , SrF 2 and BaF 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7150842A JPH08321326A (en) | 1995-05-24 | 1995-05-24 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7150842A JPH08321326A (en) | 1995-05-24 | 1995-05-24 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08321326A true JPH08321326A (en) | 1996-12-03 |
Family
ID=15505574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7150842A Pending JPH08321326A (en) | 1995-05-24 | 1995-05-24 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08321326A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998026469A1 (en) * | 1996-12-09 | 1998-06-18 | Valence Technology, Inc. | Stabilized electrochemical cell |
| WO1999034471A1 (en) * | 1997-12-26 | 1999-07-08 | Tonen Corporation | Electrolyte for lithium cells and method of producing the same |
| JPH11204145A (en) * | 1998-01-20 | 1999-07-30 | Yuasa Corp | Lithium secondary battery |
| US6183718B1 (en) | 1996-12-09 | 2001-02-06 | Valence Technology, Inc. | Method of making stabilized electrochemical cell active material of lithium manganese oxide |
| US6322744B1 (en) | 1999-02-17 | 2001-11-27 | Valence Technology, Inc. | Lithium manganese oxide-based active material |
| US6468695B1 (en) | 1999-08-18 | 2002-10-22 | Valence Technology Inc. | Active material having extended cycle life |
| JP2002313339A (en) * | 2001-04-16 | 2002-10-25 | Matsushita Battery Industrial Co Ltd | Nonaqueous electrolyte secondary battery |
| US6489055B1 (en) * | 1999-06-25 | 2002-12-03 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
| WO2003067688A1 (en) * | 2002-02-04 | 2003-08-14 | Sony Corporation | Nonaqueous electrolyte secondary cell |
| US6869547B2 (en) | 1996-12-09 | 2005-03-22 | Valence Technology, Inc. | Stabilized electrochemical cell active material |
| JP2008078199A (en) * | 2006-09-19 | 2008-04-03 | Daihatsu Motor Co Ltd | Power storage device |
| KR100946006B1 (en) * | 2001-03-30 | 2010-03-09 | 산요덴키가부시키가이샤 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
| US8159815B2 (en) | 2006-09-19 | 2012-04-17 | Daihatsu Motor Co., Ltd. | Electrochemical capacitor |
| WO2013146115A1 (en) * | 2012-03-28 | 2013-10-03 | 三洋電機株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using said positive electrode active material |
| KR101384429B1 (en) * | 2006-03-20 | 2014-04-10 | 소니 주식회사 | Anode and battery |
| WO2014156024A1 (en) * | 2013-03-27 | 2014-10-02 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
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| US10096830B2 (en) | 2014-12-26 | 2018-10-09 | Sanyo Electric Co., Ltd. | Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
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|---|---|---|---|---|
| JPH07220758A (en) * | 1994-02-03 | 1995-08-18 | Japan Storage Battery Co Ltd | Lithium battery |
| JPH08255610A (en) * | 1995-03-17 | 1996-10-01 | Canon Inc | Lithium secondary battery |
-
1995
- 1995-05-24 JP JP7150842A patent/JPH08321326A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07220758A (en) * | 1994-02-03 | 1995-08-18 | Japan Storage Battery Co Ltd | Lithium battery |
| JPH08255610A (en) * | 1995-03-17 | 1996-10-01 | Canon Inc | Lithium secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6869547B2 (en) | 1996-12-09 | 2005-03-22 | Valence Technology, Inc. | Stabilized electrochemical cell active material |
| US5869207A (en) * | 1996-12-09 | 1999-02-09 | Valence Technology, Inc. | Stabilized electrochemical cell |
| US6183718B1 (en) | 1996-12-09 | 2001-02-06 | Valence Technology, Inc. | Method of making stabilized electrochemical cell active material of lithium manganese oxide |
| WO1998026469A1 (en) * | 1996-12-09 | 1998-06-18 | Valence Technology, Inc. | Stabilized electrochemical cell |
| US6555026B1 (en) | 1996-12-09 | 2003-04-29 | Valence Technology, Inc. | Stabilized electrochemical cell active material |
| WO1999034471A1 (en) * | 1997-12-26 | 1999-07-08 | Tonen Corporation | Electrolyte for lithium cells and method of producing the same |
| JP4646399B2 (en) * | 1997-12-26 | 2011-03-09 | 三和油化工業株式会社 | Electrolytic solution for lithium battery and method for producing the same |
| JPH11204145A (en) * | 1998-01-20 | 1999-07-30 | Yuasa Corp | Lithium secondary battery |
| US6322744B1 (en) | 1999-02-17 | 2001-11-27 | Valence Technology, Inc. | Lithium manganese oxide-based active material |
| US6596435B2 (en) | 1999-02-17 | 2003-07-22 | Valence Technology, Inc. | Lithium manganese oxide-based active material |
| US6489055B1 (en) * | 1999-06-25 | 2002-12-03 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
| US6468695B1 (en) | 1999-08-18 | 2002-10-22 | Valence Technology Inc. | Active material having extended cycle life |
| KR100946006B1 (en) * | 2001-03-30 | 2010-03-09 | 산요덴키가부시키가이샤 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
| US7799458B2 (en) | 2001-03-30 | 2010-09-21 | Sanyo Electric Co., Ltd. | Nonaqueous electrolytic secondary battery and method of manufacturing the same |
| JP2002313339A (en) * | 2001-04-16 | 2002-10-25 | Matsushita Battery Industrial Co Ltd | Nonaqueous electrolyte secondary battery |
| WO2003067688A1 (en) * | 2002-02-04 | 2003-08-14 | Sony Corporation | Nonaqueous electrolyte secondary cell |
| US7311996B2 (en) | 2002-02-04 | 2007-12-25 | Sony Corporation | Non-aqueous electrolyte secondary battery |
| KR101384429B1 (en) * | 2006-03-20 | 2014-04-10 | 소니 주식회사 | Anode and battery |
| US8159815B2 (en) | 2006-09-19 | 2012-04-17 | Daihatsu Motor Co., Ltd. | Electrochemical capacitor |
| JP2008078199A (en) * | 2006-09-19 | 2008-04-03 | Daihatsu Motor Co Ltd | Power storage device |
| WO2013146115A1 (en) * | 2012-03-28 | 2013-10-03 | 三洋電機株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using said positive electrode active material |
| CN104221191A (en) * | 2012-03-28 | 2014-12-17 | 三洋电机株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using said positive electrode active material |
| JPWO2013146115A1 (en) * | 2012-03-28 | 2015-12-10 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material and non-aqueous electrolyte secondary battery using the positive electrode active material |
| US9570751B2 (en) | 2013-02-26 | 2017-02-14 | Samsung Sdi Co., Ltd. | Binder composition for secondary battery, anode including the binder composition, and lithium battery including the anode |
| WO2014156024A1 (en) * | 2013-03-27 | 2014-10-02 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| US10096830B2 (en) | 2014-12-26 | 2018-10-09 | Sanyo Electric Co., Ltd. | Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
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