JP4995424B2 - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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JP4995424B2
JP4995424B2 JP2005031640A JP2005031640A JP4995424B2 JP 4995424 B2 JP4995424 B2 JP 4995424B2 JP 2005031640 A JP2005031640 A JP 2005031640A JP 2005031640 A JP2005031640 A JP 2005031640A JP 4995424 B2 JP4995424 B2 JP 4995424B2
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secondary battery
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lithium secondary
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JP2006221847A (en
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茂博 猪股
共彦 木田
英晴 小野寺
俊二 渡邊
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Seiko Instruments Inc
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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
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Description

本発明は、リチウム二次電池に関するものである。   The present invention relates to a lithium secondary battery.

コイン型（ボタン型）リチウム二次電池は、高エネルギー密度、軽量であるといった特徴により、機器のバックアップ用の電源としての用途が増加している。従来のメモリーやクロックのバックアップ用リチウム二次電池は、公称電圧３V以上のものが主流であった。   Coin-type (button-type) lithium secondary batteries are increasingly used as backup power sources for devices due to their high energy density and light weight. Conventional lithium secondary batteries for memory and clock backups are mainly used with a nominal voltage of 3V or more.

しかし、省電力化のため携帯電話などの小型電子機器の動作電圧が低電圧化しており、メモリーやクロックのバックアップ用二次電池も低電圧領域で高容量のものが必要とされている。   However, in order to save power, the operating voltage of small electronic devices such as mobile phones has been lowered, and secondary batteries for memory and clock backup are also required to have a high capacity in a low voltage region.

低電圧領域（３V未満の領域）において、優れた充放電特性を示すチタン酸リチウムを正極活物質、ケイ素酸化物を負極活物質として用いたリチウム二次電池（例えば特許文献1参照）が知られている。
特開平10-162828号公報（第２項〜第3項、第２図） In a low voltage region (region less than 3 V), a lithium secondary battery using lithium titanate that exhibits excellent charge / discharge characteristics as a positive electrode active material and silicon oxide as a negative electrode active material is known (see, for example, Patent Document 1). ing.
Japanese Patent Laid-Open No. 10-162828 (Items 2 to 3 and FIG. 2)

正極活物質がチタン酸リチウムでバインダーに架橋型アクリル樹脂あるいはフッ素樹脂を用いたリチウム電池は、放電電圧が１．５Ｖ付近で大きな容量をもち、容量が大きく優れている。しかし、製造時に2.2Vであった電池電圧は、放置しておくと次第に2.8Ｖまで上昇する。このように、従来のリチウム電池は、経時的に電圧が上昇する課題があった。   A lithium battery in which the positive electrode active material is lithium titanate and a cross-linked acrylic resin or fluororesin is used as a binder has a large capacity when the discharge voltage is around 1.5 V, and has a large capacity. However, the battery voltage, which was 2.2 V at the time of manufacture, gradually increases to 2.8 V if left unattended. Thus, the conventional lithium battery has a problem that the voltage increases with time.

本発明者らは、正極活物質にチタン酸リチウムを用いたリチウム二次電池において前記正極ペレットのバインダーがカルボキシメチルセルロース（CMC)、ポリヴィニルアルコール（PVA)、デンプン等を用いると、電池を放置しておいても、電圧が2Ｖ未満になることを見出した。   In the lithium secondary battery using lithium titanate as the positive electrode active material, the present inventors left the battery when the binder of the positive electrode pellet used was carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), starch or the like. However, it has been found that the voltage is less than 2V.

本発明のリチウム二次電池は、チタン酸リチウムからなる正極ペレットを有し、前記正極ペレットのバインダーとしてカルボキシメチルセルロース（CMC)，ポリヴィニルアルコール（PVA)，デンプンのいずれかを用いる。   The lithium secondary battery of the present invention has a positive electrode pellet made of lithium titanate, and uses any of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and starch as a binder for the positive electrode pellet.

正極ペレットのバインダーとして、カルボキシメチルセルロース（CMC)，ポリヴィニルアルコール（PVA)，デンプンのいずれかを用いることにより経時的な電圧上昇を防止し電池電圧2Ｖ以下の、充放電特性に優れたリチウム二次電池の提供を可能とする。   By using one of carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), and starch as a binder for the positive electrode pellet, the voltage rise with time can be prevented, and the lithium secondary battery with a battery voltage of 2 V or less and excellent charge / discharge characteristics can be obtained. The secondary battery can be provided.

本発明はチタン酸リチウムが正極活物質で、そのペレットの結着剤としてのバインダーにカルボキシメチルセルロース（CMC)，ポリヴィニルアルコール（PVA)，デンプンを用いることを特徴とする。ポリアクリル酸をバインダーに用いた場合は、カルボキシルキの電荷のため大きな電気二重層が形成される。   The present invention is characterized in that lithium titanate is a positive electrode active material, and carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and starch are used as a binder as a binder for the pellets. When polyacrylic acid is used as the binder, a large electric double layer is formed due to the charge of carboxyl.

一方、カルボキシル基が少なく水酸基を持つＣＭＣ、ＰＶＡ、デンプンをバインダーとして用いると、バインダーの電荷が小さく形成される電気二重層は小さいため、リチウム二次電池の電位上昇を低く抑えられる。 On the other hand, when CMC , PVA , or starch having a small number of carboxyl groups and a hydroxyl group is used as a binder, the electric double layer formed with a small charge of the binder is small, so that the potential increase of the lithium secondary battery can be kept low.

チタン酸リチウムの組成はLiｘTiｙOｚ（0≦ｘ≦4、1≦ｙ≦5、2≦ｚ≦12）で表され、Li2TiO3、Li4Ti5O12、アナターゼ形TiO2、ルチル形TiO2など、１種または複数の混合物であっても良い。負極活物質は特に限定されず、従来から知られているグラファイト、ケイ素、ケイ素酸化物、リチウム−アルミ合金などを用いることができる。 The composition of lithium titanate is represented by LixTiyOz (0 ≦ x ≦ 4, 1 ≦ y ≦ 5, 2 ≦ z ≦ 12), Li 2 TiO 3 , Li 4 Ti 5 O 12 , anatase TiO 2 , rutile TiO such as 2, it may be one or more of the mixtures. The negative electrode active material is not particularly limited, and conventionally known graphite, silicon, silicon oxide, lithium-aluminum alloy, and the like can be used.

電解液は、縺|ブチロラクトン、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルフォーメイト、１，２−ジメトキシエタン、テトラヒドロフラン、ジオキソラン、ジメチルフォルムアミド等の有機溶媒の単独又は混合溶媒に、電解質としてＬｉＣｌＯ4，ＬｉＰＦ6，ＬｉＢＦ4，ＬｉＣＦ3ＳＯ3，Ｌｉ（ＣＦ3ＳＯ2）2Ｎ等のリチウムイオン解離性塩を溶解した非水（有機）電解液、ポリエチレンオキシドやポリフォスファゼン架橋体等の高分子に前記リチウム塩、有機溶媒を固溶させた高分子固体電解質を含んだものなど、リチウムイオン導電性の非水電解質であれば良い。特に、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート等の環状アルキルカーボネートとジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等の鎖状アルキルカーボネートの混合溶媒にＬｉＰＦ6，ＬｉＣｌＯ4，ＬｉＢＦ4又はＬｉＣＦ3ＳＯ3等の塩を溶解した有機電解液を用いた場合に、電池作成後2ヶ月経過後も電池電圧が2Ｖ以下に保たれ、充放電特性が優れ、サイクル寿命の長い電池が得られる。 The electrolyte is an organic solvent such as 縺 | butyrolactone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, 1,2-dimethoxyethane, tetrahydrofuran, dioxolane, dimethylformamide, etc. A non-aqueous (organic) electrolytic solution in which a lithium ion dissociable salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N or the like is dissolved in a single or mixed solvent as an electrolyte Any lithium ion conductive non-aqueous electrolyte may be used, such as a polymer solid electrolyte in which a lithium salt or an organic solvent is dissolved in a polymer such as ethylene oxide or a crosslinked polyphosphazene. In particular, a mixed solvent of a cyclic alkyl carbonate such as propylene carbonate, ethylene carbonate or butylene carbonate and a chain alkyl carbonate such as dimethyl carbonate, diethyl carbonate or ethyl methyl carbonate, such as LiPF 6 , LiClO 4 , LiBF 4 or LiCF 3 SO 3 In the case of using an organic electrolytic solution in which a salt is dissolved, the battery voltage is kept at 2 V or less even after two months have elapsed since the battery was made, and a battery having excellent charge / discharge characteristics and a long cycle life can be obtained.

本発明に係わるリチウム二次電池の断面図を図１に示す。正極活物質からなる正極ペレット１０１、正極ケース１０２、負極活物質からなる負極ペレット１０３、負極ケース１０４、金属リチウム１０５、正極と負極を分離するセパレータ１０６、ガスケット１０７、電解液１０８である。まず、正極ペレット１０１を正極ケース１０２に、負極ペレット１０３を負極ケース１０４に、それぞれ導電性接着剤で貼り付ける。次に、正極上にセパレータ１０６を載置し、電解液１０８を注入する。金属リチウム１０５を負極ペレット１０３に貼り付け、負極ケース１０４と正極ケース１０２をガスケット１０７を介して組み立て、正極ケースをかしめ封止を行う。電池の大きさは外径6.8mm、厚さ2.1mmである。   A cross-sectional view of a lithium secondary battery according to the present invention is shown in FIG. A positive electrode pellet 101 made of a positive electrode active material, a positive electrode case 102, a negative electrode pellet 103 made of a negative electrode active material, a negative electrode case 104, metallic lithium 105, a separator 106 separating a positive electrode and a negative electrode, a gasket 107, and an electrolyte solution 108. First, the positive electrode pellet 101 is attached to the positive electrode case 102 and the negative electrode pellet 103 is attached to the negative electrode case 104 with a conductive adhesive. Next, the separator 106 is mounted on the positive electrode, and the electrolytic solution 108 is injected. Metal lithium 105 is attached to the negative electrode pellet 103, the negative electrode case 104 and the positive electrode case 102 are assembled via the gasket 107, and the positive electrode case is caulked and sealed. The battery has an outer diameter of 6.8 mm and a thickness of 2.1 mm.

正極活物質としてチタン酸リチウム（Li4Ti5O12、）、負極活物質としてSiOを用いた場合を記す。正極活物質であるチタン酸リチウムに導電剤としてグラファイトを、バインダーとしてカルボキシメチルセルロース（CMC)を重量比 チタン酸リチウム：グラファイト：カルボキシメチルセルロース（C MC)＝85：10：5の割合で混合して正極合剤とした。次にこの正極合剤37.3mgを2ton/cm2で直径6.3mm厚さ0.57mmのペレット状に加圧成形し、正極とした。このようにして得られた正極を導電性接着剤を用いて正極ケースに接着し一体化した。その後真空乾燥機で真空、120℃で8時間乾燥した。 A case where lithium titanate (Li 4 Ti 5 O 12 ) is used as the positive electrode active material and SiO is used as the negative electrode active material will be described. Lithium titanate, which is a positive electrode active material, is mixed with graphite as a conductive agent and carboxymethyl cellulose (CMC) as a binder. A mixture was prepared. Next, 37.3 mg of this positive electrode mixture was pressure-molded into a pellet shape having a diameter of 6.3 mm and a thickness of 0.57 mm at 2 ton / cm 2 to obtain a positive electrode. The positive electrode obtained in this manner was bonded and integrated with the positive electrode case using a conductive adhesive. Thereafter, it was dried in a vacuum dryer at 120 ° C. for 8 hours.

負極は、次のようにして作製した。市販のSiOを粉砕したものを負極活物質として用いた。これに導電剤としてグラファイトを、バインダーとしてカルボキシメチルセルロース（CMC)をそれぞれ重量比45：40：15の割合で混合して負極合剤とした。負極合剤9.3mgを2ton/cm2で直径4mm、厚さ0.33mmのペレットに加圧成形したものを負極ペレットとした。この様にして得られた負極ペレットを、導電性樹脂接着剤を用いて負極ケースに接着し一体化した。真空乾燥機で真空120℃8時間乾燥した。乾燥した負極上に金属リチウムを直径4.0mm、厚さ0.48mmに打ち抜いたものを圧着し、リチウムと負極ペレットを積層し、負極とした。厚さ0.25mmのガラス繊維からなる不織布を乾燥後φ4.8mmに打ち抜きセパレータとした。ガスケットはPP製のものを用いた。電解液は、プロピレンカーボネイト（PC）：エチレンカーボネイト（EC）：1，２−ジメトキシエタン（DME）混合溶媒に、過塩素酸リチウムを1ｍｏｌ/Ｌ溶解したものを電池缶内に入れリチウム二次電池を作製した。 The negative electrode was produced as follows. A commercially available SiO powder was used as the negative electrode active material. This was mixed with graphite as a conductive agent and carboxymethyl cellulose (CMC) as a binder in a weight ratio of 45:40:15 to prepare a negative electrode mixture. A negative electrode pellet was obtained by press-forming 9.3 mg of the negative electrode mixture into a pellet having a diameter of 4 mm and a thickness of 0.33 mm at 2 ton / cm 2 . The negative electrode pellet obtained in this way was bonded and integrated with the negative electrode case using a conductive resin adhesive. It dried in vacuum 120 degreeC 8 hours with the vacuum dryer. A metal lithium punched out to a diameter of 4.0 mm and a thickness of 0.48 mm was pressed onto the dried negative electrode, and lithium and a negative electrode pellet were laminated to form a negative electrode. A non-woven fabric made of glass fibers having a thickness of 0.25 mm was dried and punched out to a diameter of 4.8 mm to form a separator. A gasket made of PP was used. The electrolyte is a lithium secondary battery in which 1 mol / L of lithium perchlorate is dissolved in a mixed solvent of propylene carbonate (PC): ethylene carbonate (EC): 1,2-dimethoxyethane (DME) in a battery can. Was made.

図２に実施例１の経時的な電池電圧変化のグラフを示す。図からも解る様に70日放置後も電池電圧が2Ｖ以下であった。   FIG. 2 shows a graph of battery voltage change over time in Example 1. As can be seen from the figure, the battery voltage was 2 V or less even after being left for 70 days.

正極ペレットのバインダーとしてポリヴィニルアルコール（PVA)を用い、実施例1と同様にして電池を作製した。図３に実施例2の経時的な電池電圧変化のグラフを示す。図からも解る様に70日放置後も電池電圧が2Ｖ以下であった。   A battery was fabricated in the same manner as in Example 1 using polyvinyl alcohol (PVA) as the binder for the positive electrode pellet. FIG. 3 shows a graph of changes in battery voltage over time in Example 2. As can be seen from the figure, the battery voltage was 2 V or less even after being left for 70 days.

正極ペレットのバインダーとしてデンプンを用い、実施例1と同様にして電池を作製した。図４に実施例3の経時的な電池電圧変化のグラフを示す。図からも解る様に70日放置後も電池電圧が2Ｖ以下であった。
[比較例1]
正極ペレットのバインダーとしてポリアクリル酸を用い、実施例1と同様にして電池を作製した。図５に比較例1の経時的な電池電圧変化のグラフを示す。図から解るように製造直後より電池電圧は2.2Ｖ以上であり、20日以降電池電圧は2.7Ｖ以上になった。 A battery was prepared in the same manner as in Example 1 using starch as a binder for the positive electrode pellet. FIG. 4 shows a graph of battery voltage change over time in Example 3. As can be seen from the figure, the battery voltage was 2 V or less after 70 days of standing.
[Comparative Example 1]
A battery was produced in the same manner as in Example 1 using polyacrylic acid as the binder for the positive electrode pellet. FIG. 5 shows a graph of battery voltage change over time of Comparative Example 1. As can be seen from the figure, the battery voltage was 2.2 V or more immediately after production, and the battery voltage became 2.7 V or more after 20 days.

本発明の二次電池の断面図である。It is sectional drawing of the secondary battery of this invention. 実施例１の経時的な電池電圧変化のグラフである。3 is a graph of battery voltage change over time in Example 1. 実施例２の経時的な電池電圧変化のグラフである。It is a graph of the battery voltage change with time of Example 2. 実施例３の経時的な電池電圧変化のグラフである。10 is a graph of battery voltage change over time in Example 3. 比較例１の経時的な電池電圧変化のグラフである。6 is a graph of battery voltage change over time in Comparative Example 1.

符号の説明Explanation of symbols

１０１ 正極ペレット
１０２ 正極ケース
１０３ 負極ペレット
１０４ 負極ケース
１０５ 金属リチウム
１０６ セパレータ
１０７ ガスケット
１０８ 電解液 101 Positive electrode pellet 102 Positive electrode case 103 Negative electrode pellet 104 Negative electrode case 105 Metal lithium 106 Separator 107 Gasket 108 Electrolyte

Claims (4)

チタン酸リチウムからなる正極ペレットを有し、前記正極ペレットのバインダーとしてポリヴィニルアルコール（ＰＶＡ）、デンプンのいずれかを用いることを特徴とするリチウム二次電池。   A lithium secondary battery comprising a positive electrode pellet made of lithium titanate and using either polyvinyl alcohol (PVA) or starch as a binder for the positive electrode pellet. 前記正極ペレットのバインダーが正極合剤の１００重量部に対し５重量部としたことを特徴とする請求項１に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, wherein the binder of the positive electrode pellet is 5 parts by weight with respect to 100 parts by weight of the positive electrode mixture. ケイ素からなる負極ペレットを有することを特徴とする請求項１もしくは２に記載のリチウム二次電池。   The lithium secondary battery according to claim 1, comprising a negative electrode pellet made of silicon. ケイ素酸化物からなる負極ペレットを有することを特徴とする請求項１もしくは２に記載のリチウム二次電池。 The lithium secondary battery according to claim 1 or 2, characterized in that it has a negative electrode pellet made of silicon oxide.
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