JP2000173663A - Lithium secondary battery - Google Patents

Lithium secondary battery

Info

Publication number
JP2000173663A
JP2000173663A JP10345896A JP34589698A JP2000173663A JP 2000173663 A JP2000173663 A JP 2000173663A JP 10345896 A JP10345896 A JP 10345896A JP 34589698 A JP34589698 A JP 34589698A JP 2000173663 A JP2000173663 A JP 2000173663A
Authority
JP
Japan
Prior art keywords
positive electrode
secondary battery
lithium secondary
active material
lithium
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
Application number
JP10345896A
Other languages
Japanese (ja)
Other versions
JP4356127B2 (en
Inventor
Akinori Kita
昭憲 北
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP34589698A priority Critical patent/JP4356127B2/en
Publication of JP2000173663A publication Critical patent/JP2000173663A/en
Application granted granted Critical
Publication of JP4356127B2 publication Critical patent/JP4356127B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a lithium secondary battery superior in a charging and discharging cycle characteristics, enabling solving of a problem of battery capacity reduction in a relatively short charge/discharge cycle caused by decomposition of an organic solvent in a nonaqueous electrolytic solution on a positive electrode side due to repetition of charge and discharge. SOLUTION: This lithium secondary battery comprises a positive electrode, a negative electrode and a nonaqueous electrolytic solution, including an organic solvent. In this battery, metal fluoride is added into a positive electrode active material. As the metal fluoride, one kind from among LiF, TiF4, VF5, MnF2, NiF2 and CoF2 is used. In the case of LiF, a content of the metal fluoride in the active material is set at 0.5-20 wt.%. LixNi1-yCoyOz (wherein 0<x<1.3, 0<=y<=1, 1.8<z<2.2) is used as the active material.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はリチウム二次電池に
関し、さらに詳しくは正極活物質の改良により充放電サ
イクル特性に優れたリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly, to a lithium secondary battery having improved charge / discharge cycle characteristics by improving a positive electrode active material.

【０００２】[0002]

【従来の技術】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、リチウムと水とが反応しやすいことから、電解質と
して有機溶媒を含有する非水電解液が使用される。2. Description of the Related Art In recent years, lithium secondary batteries have attracted attention as batteries having a high energy density. In this battery, a non-aqueous electrolyte containing an organic solvent is used as an electrolyte because lithium and water easily react with each other.

【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、ＣｒＯ5 、Ｖ2 Ｏ等の金属酸化物、ＬｉＭｎ
2 Ｏ4 、ＬｉＮｉＯ2 、ＬｉＣｏＯ2 、Ｌｉ2 ＮｉＣｏ
Ｏ4 等のリチウム−遷移金属複合酸化物等がよく知られ
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 CrO 5 and V 2 O, LiMn
2 O 4 , LiNiO 2 , LiCoO 2 , Li 2 NiCo
Lithium-transition metal composite oxides such as O 4 are well known.

【０００４】[0004]

【発明が解決しようとする課題】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
水電解液中の有機溶媒が分解することに起因した、電池
容量が比較的短い充放電サイクルのうちに減少するとい
う問題があった。従って本発明の課題は、この問題を解
決して、充放電サイクル特性に優れたリチウム二次電池
を提供することにある。However, the conventional lithium secondary battery has a relatively short battery capacity due to the decomposition of the organic solvent in the non-aqueous electrolyte on the positive electrode side when charging and discharging are repeated. There is a problem that the number of charges decreases during a charge / discharge cycle. Accordingly, an object of the present invention is to solve this problem and to provide a lithium secondary battery having excellent charge / discharge cycle characteristics.

【０００５】[0005]

【課題を解決するための手段】本発明は上記課題に鑑み
なされたものであって、請求項１に記載の発明は、正極
と、負極と、有機溶媒を含有する非水電解液とを有して
なるリチウム二次電池において、前記正極の活物質中
に、金属フッ化物が含まれているリチウム二次電池を構
成する。Means for Solving the Problems The present invention has been made in view of the above problems, and the present invention according to claim 1 has a positive electrode, a negative electrode, and a nonaqueous electrolyte containing an organic solvent. A lithium secondary battery in which a metal fluoride is contained in the positive electrode active material.

【０００６】また、請求項２に記載の発明は、請求項１
に記載の発明において、金属フッ化物としてＴｉＦ4 、
ＶＦ5 、ＭｎＦ2 、ＮｉＦ2 、ＣｏＦ2 からなる群の中
のいずれか１種を用いてリチウム二次電池を構成する。[0006] The invention described in claim 2 is the invention according to claim 1.
In the invention described in 1, the metal fluoride is TiF 4 ,
A lithium secondary battery is formed using any one of the group consisting of VF 5 , MnF 2 , NiF 2 , and CoF 2 .

【０００７】また、請求項３に記載の発明は、請求項１
に記載の発明において、金属フッ化物としてＬｉＦを用
いてリチウム二次電池を構成する。[0007] The invention according to claim 3 provides the invention according to claim 1.
In the invention described in (1), a lithium secondary battery is configured using LiF as the metal fluoride.

【０００８】また、請求項４に記載の発明は、請求項３
に記載の発明において、金属フッ化物として用いたＬｉ
Ｆの正極活物質中の含有量を０．５重量％以上、２０重
量％以下としてリチウム二次電池を構成する。[0008] The invention described in claim 4 is the invention according to claim 3.
In the invention described in the above, Li used as the metal fluoride
The content of F in the positive electrode active material is 0.5% by weight or more and 20% by weight or less to configure a lithium secondary battery.

【０００９】さらに、請求項５および請求項６に記載の
発明は、請求項３および請求項４に記載の発明におい
て、正極の活物質としてＬｉx Ｎｉ1-y Ｃｏy Ｏz （但
し、０＜ｘ＜１．３、０≦ｙ≦１、１．８＜ｚ＜２．
２）を用いてリチウム二次電池を構成する。Further, according to the invention described in claims 5 and 6, in the invention described in claims 3 and 4, Lix Ni1-y Coy Oz (where 0 <x <1) is used as the active material of the positive electrode. 0.3, 0 ≦ y ≦ 1, 1.8 <z <2.
A lithium secondary battery is constructed using 2).

【００１０】金属フッ化物を含有する正極活物質を使用
することによって、正極近傍における非水電解液中に存
在する微量の酸性不純物の酸解離平衡が変化した結果、
正極側での有機溶媒の分解を起こりにくくする被膜が生
成して、充放電サイクル特性が改善されるものと考えら
れる。As a result of using the positive electrode active material containing metal fluoride, the acid dissociation equilibrium of a small amount of acidic impurities present in the non-aqueous electrolyte near the positive electrode is changed.
It is considered that a film that hardly causes decomposition of the organic solvent on the positive electrode side is formed, and the charge / discharge cycle characteristics are improved.

【００１１】[0011]

【発明の実施の形態】本発明はリチウム二次電池におい
て、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、金属フッ化物を含有する正極活物質を使用した
ことを特徴とするものである。従って、正極材料、負極
材料、有機溶媒、溶質等、従来からリチウム二次電池用
として提案され、或いは実用に供されている種々の材料
を用いてリチウム二次電池を形成することが可能であ
り、その充放電サイクル特性が改善される。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is characterized in that a lithium secondary battery uses a positive electrode active material containing a metal fluoride in order to suppress a decrease in battery capacity when charging and discharging are repeated. Things. Therefore, it is possible to form a lithium secondary battery using various materials that have been conventionally proposed or practically used for a lithium secondary battery, such as a positive electrode material, a negative electrode material, an organic solvent, and a solute. And its charge / discharge cycle characteristics are improved.

【００１２】まず、正極材料として、ＴｉＳ2 、ＭｏＳ
2 、ＮｂＳｅ3 等の金属カルコゲン化物、ＣｒＯ5 、Ｖ
2 Ｏ等の金属酸化物、ＬｉＭｎ2 Ｏ4 、Ｌｉx Ｎｉ1-y
（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等を用いる
ことができる。First, TiS 2 , MoS
2 , metal chalcogenides such as NbSe 3 , CrO 5 , V
Metal oxides such as 2 O, LiMn 2 O 4, Lix Ni1-y
(However, 0 <x <1.3, 0 ≦ y ≦ 1, 1.8 <z <
2.2) and the like can be used.

【００１３】また、負極材料として、リチウムイオンを
電気化学的に吸蔵および放出することができる物質、例
えば金属リチウム等を使用することが可能である。その
外にリチウムイオンを電気化学的に吸蔵および放出する
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
金等）、炭素材料（黒鉛、コークス、有機物焼成体
等）、金属酸化物（ＬｉＮｂ2 Ｏ5 等）が例示される。As the negative electrode material, it is possible to use a substance capable of electrochemically storing and releasing lithium ions, for example, metallic lithium. In addition, as a substance capable of electrochemically storing and releasing lithium ions, a lithium alloy (lithium-
Examples thereof include an aluminum alloy, a lithium-lead alloy, a lithium-tin alloy, a carbon material (such as graphite, coke, and a fired organic substance), and a metal oxide (such as LiNb 2 O 5 ).

【００１４】また、非水電解液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
ンカーボネート等の高誘電率溶媒や、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
キシエタン等の低沸点溶媒との混合溶媒がある。The organic solvent of the non-aqueous electrolyte may be a high dielectric constant solvent such as ethylene carbonate, vinylene carbonate, propylene carbonate or the like, or a mixture thereof with diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-dimethoxyethane. There is a mixed solvent with a low boiling point solvent such as diethoxyethane and ethoxymethoxyethane.

【００１５】さらに溶質としては、ＬｉＰＦ6 、ＬｉＣ
ｌＯ4 、ＬｉＣＦ3 ＳＯ3 、ＬｉＮ（ＣＦ3 Ｓ
Ｏ2 ）2 、ＬｉＢＦ4 、ＬｉＡｓＦ6 が例示される。
尚、本発明における有機溶媒を含有する非水電解液に
は、ゲル状固体電解質（疑似固体電解質）も含まれるも
のである。Further, as the solute, LiPF 6 , LiC
10 4 , LiCF 3 SO 3 , LiN (CF 3 S
O 2 ) 2 , LiBF 4 and LiAsF 6 are exemplified.
The non-aqueous electrolyte containing an organic solvent in the present invention also includes a gel solid electrolyte (pseudo solid electrolyte).

【００１６】さて、本発明の特徴を成す正極材料中に添
加する金属フッ化物としては、ＬｉＦ、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、充放電サイクルに
優れたリチウム二次電池を得る上で、ＬｉＦがより好ま
しい。また、金属フッ化物の正極材料に対する好適な添
加量は、金属フッ化物の種類によって若干異なるが、Ｌ
ｉＦの場合、正極材料に対して０．５〜２０重量％であ
ることが好ましい。The metal fluoride to be added to the positive electrode material, which is a feature of the present invention, includes alkali metal fluorides such as LiF and NaF; alkaline earth metal fluorides such as MgF 2 and CaF 2 ; 2 , and fluorides of transition metals such as FeF 3 . Among them, LiF is more preferable for obtaining a lithium secondary battery having excellent charge / discharge cycles. Further, the preferable addition amount of the metal fluoride to the positive electrode material is slightly different depending on the type of the metal fluoride.
In the case of iF, the content is preferably 0.5 to 20% by weight based on the positive electrode material.

【００１７】以下に本発明の実施例について説明する
が、本発明はこれらの実施例に限定されるものではな
く、その技術的思想を変更しない範囲において実施する
ことが可能である。尚、以下に示す実施例１〜４、比較
例１はコバルト酸リチウム（ＬｉＣｏＯ2）を正極に含
み、金属フッ化物としてＬｉＦを使用した場合の効果を
示すための例である。Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to these embodiments, and can be implemented within the scope of changing the technical idea. In addition, Examples 1 to 4 and Comparative Example 1 described below are examples for showing the effect when lithium cobalt oxide (LiCoO 2 ) is contained in the positive electrode and LiF is used as the metal fluoride.

【００１８】＜実施例１＞炭酸コバルト（ＣｏＣＯ3 ）
粉末と炭酸リチウム（Ｌｉ2 ＣＯ3 ）粉末とを、メノウ
乳鉢を用いて混合した。この際の混合比は、Ｌｉ／Ｃｏ
＝１／２となるようにした。この混合粉末を電気炉を用
いて常圧の空気中で９００℃で加熱することで正極活物
質であるコバルト酸リチウム（ＬｉＣｏＯ2 ）を得た。Example 1 Cobalt carbonate (CoCO 3 )
The powder and lithium carbonate (Li 2 CO 3 ) powder were mixed using an agate mortar. The mixing ratio at this time is Li / Co
= 1/2. The mixed powder was heated at 900 ° C. in air at normal pressure using an electric furnace to obtain lithium cobalt oxide (LiCoO 2 ) as a positive electrode active material.

【００１９】正極活物質粉末に、フッ化リチウム（Ｌｉ
Ｆ）粉末と、導電材としてグラファイトと、バインダー
としてポリフッ化ビニリデンとを混合し、さらにジメチ
ルホルムアルデヒドを適宜滴下して十分に混練した。こ
の混練物を乾燥させ、乾燥物を粉砕することにより正極
合剤粉末を得た。このとき、乾燥状態の正極合剤中の炭
酸リチウムの含有量は０．５重量％であった。Lithium fluoride (Li)
F) Powder, graphite as a conductive material, and polyvinylidene fluoride as a binder were mixed, and dimethylformaldehyde was appropriately dropped and kneaded sufficiently. The kneaded product was dried, and the dried product was pulverized to obtain a positive electrode mixture powder. At this time, the content of lithium carbonate in the dried positive electrode mixture was 0.5% by weight.

【００２０】得られた正極合剤粉末をアルミニウムメッ
シュと共に加圧成型してこの成型体を正極とし、一方、
リチウムを負極とし、さらに６フッ化リン酸リチウムの
プロピレンカーボネート溶液（１ｍｏｌ／ｌ）を電解液
として、直径２０ｍｍ、高さ２．５ｍｍのコイン型電池
を作成した。The obtained positive electrode mixture powder is press-molded together with an aluminum mesh, and this molded body is used as a positive electrode.
Using lithium as a negative electrode and a propylene carbonate solution of lithium hexafluorophosphate (1 mol / l) as an electrolytic solution, a coin-type battery having a diameter of 20 mm and a height of 2.5 mm was prepared.

【００２１】＜実施例２＞乾燥状態の正極合剤中の炭酸
リチウムの含有量を５重量％とする以外は、実施例１と
同様にして正極合剤粉末を調整し、同型のコイン型電池
を作成した。<Example 2> A positive electrode mixture powder was prepared in the same manner as in Example 1 except that the content of lithium carbonate in the dried positive electrode mixture was 5% by weight. It was created.

【００２２】＜実施例３＞乾燥状態の正極合剤中の炭酸
リチウムの含有量を１０重量％とする以外は、実施例１
と同様にして正極合剤粉末を調整し、同型のコイン型電
池を作成した。Example 3 Example 1 was repeated except that the content of lithium carbonate in the dried positive electrode mixture was 10% by weight.
Positive electrode mixture powder was prepared in the same manner as in Example 1 to prepare a coin-type battery of the same type.

【００２３】＜実施例４＞乾燥状態の正極合剤中の炭酸
リチウムの含有量を２０重量％とする以外は、実施例１
と同様にして正極合剤粉末を調整し、同型のコイン型電
池を作成した。Example 4 Example 1 was repeated except that the content of lithium carbonate in the dried positive electrode mixture was 20% by weight.
Positive electrode mixture powder was prepared in the same manner as in Example 1 to prepare a coin-type battery of the same type.

【００２４】＜比較例１＞正極合剤中にフッ化リチウム
を含有させない以外は、実施例１と同様にして正極合剤
粉末を調整し、同型のコイン型電池を作成した。Comparative Example 1 A positive electrode mixture powder was prepared in the same manner as in Example 1 except that lithium fluoride was not contained in the positive electrode mixture, to produce a coin-type battery of the same type.

【００２５】実施例１〜４、比較例１で作成したコイン
型電池において、電池温度６０℃の加速試験条件下で充
放電サイクル試験を行なった。この際、電流密度０．２
７ｍＡ／ｃｍ2 で４．２Ｖまで充電した後、引き続き満
充電まで４．２Ｖ定電圧充電を行ない、その後、放電電
圧が３．７Ｖになるまで放電を行なった。この充放電を
繰り返すサイクル試験において、サイクル毎の容量維持
率（容量維持率＝サイクル毎の放電容量／初回サイクル
の放電容量×１００％）を求め、その結果を図１に示
す。A charge / discharge cycle test was performed on the coin-type batteries prepared in Examples 1 to 4 and Comparative Example 1 under an acceleration test condition at a battery temperature of 60 ° C. At this time, the current density was 0.2
After charging to 4.2 V at 7 mA / cm 2 , constant voltage charging at 4.2 V was continued until full charge, and then discharging was performed until the discharge voltage reached 3.7 V. In the cycle test in which charge and discharge are repeated, the capacity retention rate for each cycle (capacity retention rate = discharge capacity for each cycle / discharge capacity for the first cycle x 100%) was obtained, and the results are shown in Fig. 1.

【００２６】図１から、実施例１〜４で作成したリチウ
ム二次電池は、比較例１で作製した電池に比べて、充放
電サイクルに伴う放電容量の劣化が抑制されていること
が分かる。From FIG. 1, it can be seen that the lithium secondary batteries prepared in Examples 1 to 4 suppress the deterioration of the discharge capacity accompanying the charge / discharge cycle as compared with the battery prepared in Comparative Example 1.

【００２７】また、図１の実施例３と実施例４との結果
から、フッ化リチウムを乾燥状態にある正極合剤の２０
重量％を越える量で含有させても大きな添加効果が見込
めないことが予測できる。一方、フッ化リチウムの含有
量を増加させると正極活物質の含有量が相対的に減少し
て電池容量が低下するため、炭酸リチウムの配合量を、
乾燥状態の正極合剤の２０重量％以下とすることが好ま
しいことが分かる。Further, from the results of Example 3 and Example 4 shown in FIG. 1, lithium fluoride was used as the positive electrode mixture in a dry state.
It can be expected that a large addition effect cannot be expected even if it is contained in an amount exceeding the weight%. On the other hand, when the content of lithium fluoride is increased, the content of the positive electrode active material is relatively reduced and the battery capacity is reduced.
It can be seen that the content is preferably 20% by weight or less of the positive electrode mixture in a dry state.

【００２８】一方、実施例１と比較例１との結果から、
炭酸リチウムを乾燥状態の正極合剤の０．５重量％以
上、添加しないと十分な効果が得られないことがわか
る。On the other hand, from the results of Example 1 and Comparative Example 1,
It can be seen that a sufficient effect cannot be obtained unless lithium carbonate is added in an amount of 0.5% by weight or more of the positive electrode mixture in a dry state.

【００２９】以上のことから、乾燥状態の正極合剤に
０．５重量％〜２０重量％の炭酸リチウムを添加するこ
とが、充放電サイクルにおける電池容量の維持に好適で
ある。From the above, it is preferable to add 0.5% by weight to 20% by weight of lithium carbonate to the dried positive electrode mixture to maintain the battery capacity in the charge / discharge cycle.

【００３０】[0030]

【発明の効果】本発明によると、乾燥状態の正極合剤に
０．５〜２０重量％の炭酸リチウムを添加することで、
充放電サイクルにおける電池の容量維持に優れたリチウ
ム二次電池を提供することが可能となる。According to the present invention, by adding 0.5 to 20% by weight of lithium carbonate to a dry cathode mixture,
It is possible to provide a lithium secondary battery excellent in maintaining the capacity of the battery in the charge / discharge cycle.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明にかかわるリチウム二次電池の充放電
サイクル毎の容量維持率を示す図である。FIG. 1 is a diagram showing a capacity retention ratio for each charge / discharge cycle of a lithium secondary battery according to the present invention.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 正極と、負極と、有機溶媒を含有する非
水電解液とを有してなるリチウム二次電池において、 前記正極の活物質中に、金属フッ化物が含まれているこ
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 a metal fluoride is contained in an active material of the positive electrode. Characteristic lithium secondary battery. 【請求項２】 前記金属フッ化物がＴｉＦ4 、ＶＦ5 、
ＭｎＦ2 、ＮｉＦ2 、ＣｏＦ2 からなる群の中のいずれ
か１種であることを特徴とする、請求項１に記載のリチ
ウム二次電池。2. The method according to claim 1, wherein the metal fluoride is TiF 4 , VF 5 ,
MnF 2, NiF 2, characterized in that it is any one of the group consisting of CoF 2, the lithium secondary battery according to claim 1. 【請求項３】 前記金属フッ化物がＬｉＦであることを
特徴とする、請求項１に記載のリチウム二次電池。3. The lithium secondary battery according to claim 1, wherein the metal fluoride is LiF. 【請求項４】 前記ＬｉＦの、正極活物質中の含有量が
０．５重量％以上、２０重量％以下であることを特徴と
する、請求項３に記載のリチウム二次電池。4. The lithium secondary battery according to claim 3, wherein the content of LiF in the positive electrode active material is 0.5% by weight or more and 20% by weight or less. 【請求項５】 正極の活物質がＬｉx Ｎｉ1-y Ｃｏy Ｏ
z であって、０＜ｘ＜１．３、０≦ｙ≦１、１．８＜ｚ
＜２．２であることを特徴とする、請求項３に記載のリ
チウム二次電池。5. The active material of the positive electrode is Lix Ni1-y Coy O
z, 0 <x <1.3, 0 ≦ y ≦ 1, 1.8 <z
The lithium secondary battery according to claim 3, wherein <2.2 is satisfied. 【請求項６】 正極の活物質がＬｉx Ｎｉ1-y Ｃｏy Ｏ
z であって、０＜ｘ＜１．３、０≦ｙ≦１、１．８＜ｚ
＜２．２であることを特徴とする、請求項４に記載のリ
チウム二次電池。6. The active material of the positive electrode is Lix Ni1-y Coy O
z, 0 <x <1.3, 0 ≦ y ≦ 1, 1.8 <z
The lithium secondary battery according to claim 4, wherein <2.2 is satisfied.
JP34589698A 1998-12-04 1998-12-04 Lithium secondary battery Expired - Fee Related JP4356127B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP34589698A JP4356127B2 (en) 1998-12-04 1998-12-04 Lithium secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP34589698A JP4356127B2 (en) 1998-12-04 1998-12-04 Lithium secondary battery

Publications (2)

Publication Number Publication Date
JP2000173663A true JP2000173663A (en) 2000-06-23
JP4356127B2 JP4356127B2 (en) 2009-11-04

Family

ID=18379735

Family Applications (1)

Application Number Title Priority Date Filing Date
JP34589698A Expired - Fee Related JP4356127B2 (en) 1998-12-04 1998-12-04 Lithium secondary battery

Country Status (1)

Country Link
JP (1) JP4356127B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016058316A (en) * 2014-09-11 2016-04-21 トヨタ自動車株式会社 Lithium ion secondary battery and method for manufacturing the same
JPWO2016147856A1 (en) * 2015-03-13 2017-12-07 ヤマハ発動機株式会社 Non-aqueous electrolyte secondary battery positive electrode active material and method for producing the same, battery including the positive electrode active material, and battery charge / discharge method
US10355269B2 (en) * 2015-01-14 2019-07-16 Toyota Jidosha Kabushiki Kaisha Lithium ion secondary battery having positive electrode active material particle with fluorine and phosphorous containing film, and method of manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016058316A (en) * 2014-09-11 2016-04-21 トヨタ自動車株式会社 Lithium ion secondary battery and method for manufacturing the same
US10355269B2 (en) * 2015-01-14 2019-07-16 Toyota Jidosha Kabushiki Kaisha Lithium ion secondary battery having positive electrode active material particle with fluorine and phosphorous containing film, and method of manufacturing the same
JPWO2016147856A1 (en) * 2015-03-13 2017-12-07 ヤマハ発動機株式会社 Non-aqueous electrolyte secondary battery positive electrode active material and method for producing the same, battery including the positive electrode active material, and battery charge / discharge method

Also Published As

Publication number Publication date
JP4356127B2 (en) 2009-11-04

Similar Documents

Publication Publication Date Title
JP3269396B2 (en) Non-aqueous electrolyte lithium secondary battery
JPH08264183A (en) Lithium secondary battery
JP2006216509A (en) Positive electrode and nonaqueous electrolyte secondary battery using the same
JP2002134112A (en) Nonaqueous electrolyte secondary battery
KR100593772B1 (en) Nonaqueous Electrolyte Secondary Battery
JPH1027626A (en) Lithium secondary battery
JP3258841B2 (en) Lithium secondary battery
JPH07335261A (en) Lithium secondary battery
JP2008235150A (en) Non-aqueous electrolyte secondary battery
JP2004327444A (en) Electrolyte for lithium secondary battery, and lithium secondary battery including this
JP2008071702A (en) Nonaqueous electrolyte secondary battery, and its manufacturing method
JP2000012090A (en) Lithium secondary battery
JPH1027609A (en) Secondary battery with nonaqueous electrolyte
JP4707430B2 (en) Positive electrode and non-aqueous electrolyte secondary battery
JP2002270181A (en) Non-aqueous electrolyte battery
JP2000048820A (en) Lithium secondary battery
JP2006164695A (en) Nonaqueous electrolyte secondary battery
JP2003331922A (en) Cell
JP4356127B2 (en) Lithium secondary battery
JPH1027627A (en) Lithium secondary battery
JP2000277111A (en) Lithium secondary battery
JP2004095325A (en) Lithium secondary battery
JP2000277112A (en) Lithium secondary battery
JPH1125973A (en) Negative electrode mateal for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery having negative electrode using the same
JP3452488B2 (en) Non-aqueous electrolyte lithium secondary battery

Legal Events

Date Code Title Description
RD03 Notification of appointment of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7423

Effective date: 20050404

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20050804

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080826

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20081007

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20081208

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20090407

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20090604

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20090714

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20090727

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120814

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120814

Year of fee payment: 3

LAPS Cancellation because of no payment of annual fees