JPH1140156A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH1140156A JPH1140156A JP9208645A JP20864597A JPH1140156A JP H1140156 A JPH1140156 A JP H1140156A JP 9208645 A JP9208645 A JP 9208645A JP 20864597 A JP20864597 A JP 20864597A JP H1140156 A JPH1140156 A JP H1140156A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- sodium
- carbon material
- secondary battery
- 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
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
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、非水電解質二次電
池に関する。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】リチウ
ム二次電池の正極活物質としては、リチウムイオン（Ｌ
ｉ+ ）を電気化学的に脱離・挿入することが可能なＬｉ
ＣｏＯ2 及びＬｉＮｉＯ2 がよく知られているが（特公
昭６３−５９５０７号公報など参照）、高価で、比容量
がいずれも２７４ｍＡｈ／ｇ程度と小さい。2. Description of the Related Art As a positive electrode active material of a lithium secondary battery, lithium ion (L
Li capable of electrochemically desorbing and inserting i + )
CoO 2 and LiNiO 2 are well known (see Japanese Patent Publication No. 63-59507), but are expensive and have specific capacities as small as about 274 mAh / g.
【０００３】ナトリウム二次電池の正極活物質として
は、ナトリウムとマンガンとの複合酸化物（ＭｎＯ2 と
ＮａＯＨとの混合焼成品）が提案されているが（特開平
１−２６０７６７号公報参照）、比容量が小さい。ま
た、負極活物質として、ナトリウム単体、ナトリウム合
金などを用いていたため、充放電サイクル特性が良くな
い。As a positive electrode active material of a sodium secondary battery, a composite oxide of sodium and manganese (a mixed and baked product of MnO 2 and NaOH) has been proposed (see JP-A-1-260767). Small specific capacity. Further, since sodium alone or a sodium alloy is used as the negative electrode active material, the charge / discharge cycle characteristics are not good.
【０００４】そこで、最近、コバルト、ニッケル、マン
ガンに代わる遷移元素として安価な鉄を使用したリチウ
ムと鉄との複合酸化物及びナトリウムと鉄との複合酸化
物が、それぞれリチウム二次電池及びナトリウム二次電
池の正極活物質として、検討された。Therefore, recently, a composite oxide of lithium and iron and a composite oxide of sodium and iron using inexpensive iron as a transition element in place of cobalt, nickel and manganese have been used in lithium secondary batteries and sodium secondary batteries, respectively. It was studied as a positive electrode active material for secondary batteries.
【０００５】その結果、リチウムと鉄との複合酸化物
は、安価ではあるが、電気化学的にごく僅かな量しかリ
チウムイオンを脱離・挿入することができないので、リ
チウム二次電池の正極活物質としては実用できないが、
ナトリウムと鉄との複合酸化物は、安価で、電気化学的
にナトリウムイオン（Ｎａ+ ）を脱離・挿入することが
でき、しかも比容量が大きいので、ナトリウム二次電池
の正極活物質として有望であることが分かった。As a result, although the composite oxide of lithium and iron is inexpensive, only a very small amount of lithium ions can be electrochemically desorbed and inserted electrochemically. Although it cannot be used as a substance,
A complex oxide of sodium and iron is inexpensive, can electrochemically desorb and insert sodium ions (Na + ), and has a large specific capacity, making it a promising cathode active material for sodium secondary batteries. It turned out to be.
【０００６】しかしながら、正極活物質としてナトリウ
ムと鉄との複合酸化物を用いても、負極活物質としてナ
トリウム単体やナトリウム合金を用いたのでは、リチウ
ム二次電池においてリチウム単体やリチウム合金を用い
た場合と同様、充放電サイクル特性が良いナトリウム二
次電池は得られない。However, even if a composite oxide of sodium and iron is used as the positive electrode active material, if only sodium or a sodium alloy is used as the negative electrode active material, lithium alone or a lithium alloy is used in a lithium secondary battery. As in the case, a sodium secondary battery having good charge / discharge cycle characteristics cannot be obtained.
【０００７】そこで、正極活物質としてナトリウムと鉄
との複合酸化物を用いたナトリウム二次電池の充放電サ
イクル特性を改善するべく、ナトリウム単体やナトリウ
ム合金に代えて、炭素材料を用いることが検討されてき
た。リチウム単体やリチウム合金に代えて、黒鉛、コー
クス等の炭素材料を用いると、リチウム二次電池の充放
電サイクル特性が向上することが知られているが、それ
と同じことが、ナトリウム二次電池において、ナトリウ
ム単体やナトリウム合金に代えて、炭素材料を用いた場
合にも成立するか否かが検討されたのである。Therefore, in order to improve the charge / discharge cycle characteristics of a sodium secondary battery using a composite oxide of sodium and iron as a positive electrode active material, it has been studied to use a carbon material instead of sodium alone or a sodium alloy. It has been. It is known that when a carbon material such as graphite or coke is used instead of lithium alone or a lithium alloy, the charge / discharge cycle characteristics of the lithium secondary battery are improved. Therefore, it was examined whether or not the above-mentioned condition was satisfied when a carbon material was used instead of sodium alone or a sodium alloy.
【０００８】その結果、リチウムイオンは、炭素材料に
電気化学的に多量に吸蔵され得るけれども、ナトリウム
イオンは、炭素材料に電気化学的にごく僅かしか吸蔵さ
れないことが分かった。このため、炭素材料は、正極活
物質としてナトリウムと鉄との複合酸化物を用いた二次
電池の負極材料としては、実用し得ない材料であると考
えられてきた。As a result, it has been found that lithium ions can be electrochemically occluded in a carbon material in a large amount, but sodium ions are electrochemically absorbed very little in a carbon material. For this reason, the carbon material has been considered to be a material that cannot be used as a negative electrode material of a secondary battery using a composite oxide of sodium and iron as a positive electrode active material.
【０００９】しかしながら、鋭意研究した結果、本発明
者らは、ナトリウムイオンは、それ単独では炭素材料に
ごく僅かな量しか挿入できないけれども、それをリチウ
ムイオンとともに炭素材料に挿入するようにすれば、多
量のナトリウムイオンを挿入することができるとの驚く
べき知見を得た。However, as a result of diligent research, the present inventors have found that, although sodium ions alone can insert only a small amount into a carbon material, if they are inserted into the carbon material together with lithium ions, A surprising finding was that a large amount of sodium ions could be inserted.
【００１０】本発明は、かかる知見に基づきなされたも
のであって、放電容量が大きく、しかも充放電サイクル
特性が良い非水電解質二次電池を提供することを目的と
する。The present invention has been made based on such knowledge, and has as its object to provide a non-aqueous electrolyte secondary battery having a large discharge capacity and good charge-discharge cycle characteristics.
【００１１】[0011]
【課題を解決するための手段】本発明に係る非水電解質
二次電池（以下において、本発明電池と称することがあ
る。）は、ナトリウムと鉄を含む複合酸化物を正極活物
質として有する正極と、炭素材料をナトリウムイオン及
びリチウムイオンの吸蔵材として有する負極と、リチウ
ムイオンを含有する非水電解質とを備える。A non-aqueous electrolyte secondary battery according to the present invention (hereinafter sometimes referred to as the battery of the present invention) has a positive electrode having a composite oxide containing sodium and iron as a positive electrode active material. And a negative electrode having a carbon material as a storage material for sodium ions and lithium ions, and a non-aqueous electrolyte containing lithium ions.
【００１２】ナトリウムと鉄を含む複合酸化物として
は、ＮａＦｅ1-x Ｍx Ｏ2 （０≦ｘ≦０．９；ＭはＣ
ｏ、Ｎｉ及びＭｎよりなる群から選ばれた少なくとも一
種の遷移元素）が挙げられる。遷移元素ＭによるＦｅの
置換量ｘが、０．９を越えると、複合酸化物の結晶構造
の安定性が低下する。具体例としては、ＮａＦｅＯ2 、
ＮａＦｅ0.6 Ｃｏ0.4 Ｏ2 、ＮａＦｅ0.6 Ｎｉ
0.4 Ｏ2 、ＮａＦｅ0.6 Ｃｏ0.2 Ｎｉ0.2 Ｏ2 、ＮａＦ
ｅ0.6 Ｍｎ0.4 Ｏ2 、ＮａＦｅ0.6 Ｎｉ0.2 Ｍｎ0.2 Ｏ
2 が挙げられる。As a composite oxide containing sodium and iron, NaFe 1-x M x O 2 (0 ≦ x ≦ 0.9; M is C
o, at least one transition element selected from the group consisting of Ni and Mn). When the substitution amount x of Fe by the transition element M exceeds 0.9, the stability of the crystal structure of the composite oxide decreases. Specific examples include NaFeO 2 ,
NaFe 0.6 Co 0.4 O 2 , NaFe 0.6 Ni
0.4 O 2 , NaFe 0.6 Co 0.2 Ni 0.2 O 2 , NaF
e 0.6 Mn 0.4 O 2 , NaFe 0.6 Ni 0.2 Mn 0.2 O
2 is mentioned.
【００１３】炭素材料としては、黒鉛、コークス、有機
物焼成体などが挙げられるが、格子面（００２）面の面
間隔ｄ002 が３．３５〜３．３７Åであり、且つｃ軸方
向の結晶子の大きさＬｃが２５０Å以上である炭素材料
が、放電容量が大きいので、好ましい。Examples of the carbon material include graphite, coke, and a fired organic material. The lattice spacing (002) plane spacing d 002 is 3.35 to 3.37 °, and the crystallites in the c-axis direction. Is preferable because the discharge capacity is large.
【００１４】リチウムイオンを含有する非水電解質とし
ては、リチウム塩を電解質塩として使用した非水電解質
が例示される。この場合に使用するリチウム塩の具体例
としては、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＮ（Ｃ2 Ｆ5
ＳＯ2 ）2 、ＬｉＣｌＯ4 、Ｌｉ2 Ｂ10Ｃｌ10、Ｌｉ2
Ｂ12Ｃｌ12が挙げられる。リチウム塩は、一種単独を使
用してもよく、必要に応じて二種以上を併用してもよ
い。As the non-aqueous electrolyte containing lithium ions, a non-aqueous electrolyte using a lithium salt as an electrolyte salt is exemplified. Specific examples of the lithium salt used in this case include LiPF 6 , LiBF 4 , and LiN (C 2 F 5
SO 2 ) 2 , LiClO 4 , Li 2 B 10 Cl 10 , Li 2
B 12 Cl 12 is mentioned. As the lithium salt, one kind may be used alone, or two or more kinds may be used in combination as needed.
【００１５】本発明における非水電解質は、リチウムイ
オンとともにナトリウムイオンを含有するものであって
もよい。リチウムイオンとナトリウムイオンの両方のイ
オンを含有する非水電解質としては、リチウム塩とナト
リウム塩を電解質塩として使用した非水電解質が例示さ
れる。この場合に使用するリチウム塩の具体例として
は、先にリチウム塩の具体例として挙げたものと同じも
のが挙げられ、またナトリウム塩の具体例としては、Ｎ
ａＰＦ6 、ＮａＣｌＯ4 、ＮａＢＦ4 、ＮａＣＦ3 ＳＯ
3 、ＮａＮ（ＣＦ3 ＳＯ3 ）2 、ＮａＮ（Ｃ2 Ｆ5 ＳＯ
2 ）2 、ＮａＣ（ＣＦ3 ＳＯ3 ）3 が挙げられる。ナト
リウム塩は、一種単独を使用してもよく、必要に応じて
二種以上を併用してもよい。[0015] The non-aqueous electrolyte in the present invention may contain sodium ions together with lithium ions. Examples of the non-aqueous electrolyte containing both lithium ions and sodium ions include a non-aqueous electrolyte using a lithium salt and a sodium salt as electrolyte salts. Specific examples of the lithium salt used in this case include the same as those described above as the specific examples of the lithium salt, and specific examples of the sodium salt include N
aPF 6 , NaClO 4 , NaBF 4 , NaCF 3 SO
3 , NaN (CF 3 SO 3 ) 2 , NaN (C 2 F 5 SO
2 ) 2 and NaC (CF 3 SO 3 ) 3 . As the sodium salt, one kind may be used alone, or two or more kinds may be used in combination as needed.
【００１６】電解質塩を溶かす溶媒は、特に限定され
ず、従来公知の溶媒を使用することができる。エチレン
カーボネート、プロピレンカーボネート、ビニレンカー
ボネート、ブチレンカーボネート等の環状炭酸エステ
ル、及び、環状炭酸エステルとジメチルカーボネート、
ジエチルカーボネート、メチルエチルカーボネート、
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
媒が例示される。The solvent for dissolving the electrolyte salt is not particularly limited, and a conventionally known solvent can be used. Ethylene carbonate, propylene carbonate, vinylene carbonate, cyclic carbonate such as butylene carbonate, and cyclic carbonate and dimethyl carbonate,
Diethyl carbonate, methyl ethyl carbonate,
Examples thereof include a mixed solvent with a low boiling point solvent such as 1,2-dimethoxyethane, 1,2-diethoxyethane, and ethoxymethoxyethane.
【００１７】本発明電池を充電すると、ナトリウムイオ
ンが正極活物質から脱離して、負極の炭素材料に、非水
電解質中のリチウムイオンとともに挿入される。理論的
には、充電電位が低いリチウムイオンが先に挿入された
後に、充電電位が高いナトリウムイオンが挿入されるこ
とになるが、両イオンの充電電位は極めて近いので、実
際には、リチウムイオンとナトリウムイオンは、殆ど同
時に負極の炭素材料に挿入される。一方、本発明電池を
放電すると、ナトリウムイオンが炭素材料から脱離し
て、正極活物質に挿入されるとともに、リチウムイオン
が炭素材料から脱離して、非水電解質中に戻る。理論的
には、放電電位が低いナトリウムイオンが先に脱離した
後に、放電電位が高いリチウムイオンが脱離することに
なるが、両イオンの放電電位は極めて近いので、実際
は、リチウムイオンとナトリウムイオンは、殆ど同時に
炭素材料から脱離する。When the battery of the present invention is charged, sodium ions are desorbed from the positive electrode active material and inserted into the carbon material of the negative electrode together with lithium ions in the non-aqueous electrolyte. Theoretically, a lithium ion having a low charging potential is inserted first, and then a sodium ion having a high charging potential is inserted. However, since the charging potentials of both ions are extremely close, in practice, lithium ions are inserted. And sodium ions are almost simultaneously inserted into the carbon material of the negative electrode. On the other hand, when the battery of the present invention is discharged, sodium ions are desorbed from the carbon material and inserted into the positive electrode active material, and lithium ions are desorbed from the carbon material and return to the non-aqueous electrolyte. Theoretically, lithium ions with a high discharge potential are desorbed after sodium ions with a low discharge potential are desorbed first.However, since the discharge potentials of both ions are very close, in practice, lithium ions and sodium The ions desorb from the carbon material almost simultaneously.
【００１８】本発明電池は、負極に炭素材料を使用して
いるので、充放電サイクル特性が良い。また、本発明電
池は、充電時に、ナトリウムイオンが、非水電解質中の
リチウムイオンとともに、負極の炭素材料に挿入される
ようにしてあるので、多量のナトリウムイオンが負極の
炭素材料に挿入される。このため、本発明電池は放電容
量が大きい。なお、多量のナトリウムイオンが負極の炭
素材料に挿入される理由は、リチウムイオンの挿入によ
り格子面（００２）面の面間隔が拡幅されるためと推察
される。Since the battery of the present invention uses a carbon material for the negative electrode, it has good charge / discharge cycle characteristics. Further, in the battery of the present invention, at the time of charging, sodium ions are inserted into the carbon material of the negative electrode together with lithium ions in the non-aqueous electrolyte, so that a large amount of sodium ions are inserted into the carbon material of the negative electrode. . For this reason, the battery of the present invention has a large discharge capacity. The reason why a large amount of sodium ions are inserted into the carbon material of the negative electrode is presumed to be that the lattice spacing (002) plane is widened by the insertion of lithium ions.
【００１９】[0019]
【実施例】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で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 with reference to examples, but the present invention is not limited to the following examples and can be carried out by appropriately changing the scope of the invention without changing its gist. It is something.
【００２０】（本発明電池Ａ１〜Ａ１８の作製）下記の
如く正極、負極及び非水電解液を作製し、これらを用い
てＡＡサイズの非水電解質二次電池Ａ１〜Ａ１８を作製
した。正極と負極の容量比を１：１．１とした。セパレ
ータにはポリプロピレン製の微多孔膜を用いた。電池寸
法は、直径１８ｍｍ；高さ６５ｍｍである。(Preparation of Batteries A1 to A18 of the Present Invention) A positive electrode, a negative electrode and a nonaqueous electrolyte were prepared as described below, and AA size nonaqueous electrolyte secondary batteries A1 to A18 were prepared using these. The capacity ratio between the positive electrode and the negative electrode was 1: 1.1. A polypropylene microporous membrane was used as the separator. The battery dimensions are 18 mm in diameter; 65 mm in height.
【００２１】〔正極の作製〕ＮａＦｅＯ2 ９０重量部
と、アセチレンブラック（導電剤）６重量部と、ポリフ
ッ化ビニリデン４重量部とを混練して正極合剤を作製
し、この正極合剤とＮ−メチル−２−ピロリドン（ＮＭ
Ｐ）とを混合してスラリーを調製し、このスラリーをア
ルミニウム箔（集電体）の両面にドクターブレード法に
より塗布した後、１００°Ｃで２時間真空乾燥して、正
極を作製した。[Preparation of Positive Electrode] 90 parts by weight of NaFeO 2, 6 parts by weight of acetylene black (conductive agent) and 4 parts by weight of polyvinylidene fluoride were kneaded to prepare a positive electrode mixture. -Methyl-2-pyrrolidone (NM
And P) were mixed to prepare a slurry. The slurry was applied to both surfaces of an aluminum foil (current collector) by a doctor blade method, and then dried under vacuum at 100 ° C. for 2 hours to produce a positive electrode.
【００２２】〔負極の作製〕表１に示す炭素材料（天然
黒鉛、人造黒鉛又はピッチコークス）９５重量部と、ポ
リフッ化ビニリデン４重量部とを混練して負極合剤を作
製し、この負極合剤とＮ−メチル−２−ピロリドンとを
混合してスラリーを調製し、このスラリーを銅箔（集電
体）の両面にドクターブレード法により塗布した後、１
００°Ｃで２時間真空乾燥して、負極を作製した。天然
黒鉛としては関西熱化学社製の商品コード「ＮＧ１２」
（ｄ002 ＝３．３５Å；Ｌｃ＞１０００Å）を、人造黒
鉛としては中越黒鉛社製の商品コード「ＲＡ３０００」
（ｄ002 ＝３．３７Å；Ｌｃ＝２５０Å）を、ピッチコ
ークスとしては興亜石油社製の商品コード「ＳＪコー
ク」（ｄ002 ＝３．４５Å；Ｌｃ＝２０Å）を、それぞ
れ使用した。[Preparation of Negative Electrode] 95 parts by weight of a carbon material (natural graphite, artificial graphite or pitch coke) shown in Table 1 and 4 parts by weight of polyvinylidene fluoride were kneaded to prepare a negative electrode mixture. A slurry was prepared by mixing the agent and N-methyl-2-pyrrolidone, and the slurry was applied to both surfaces of a copper foil (current collector) by a doctor blade method.
Vacuum drying was performed at 00 ° C. for 2 hours to produce a negative electrode. Product code "NG12" manufactured by Kansai Thermal Chemical Co., Ltd. as natural graphite
(D 002 = 3.35 °; Lc> 1000 °) was used as the artificial graphite, product code “RA3000” manufactured by Chuetsu Graphite Co., Ltd.
(D 002 = 3.37 °; Lc = 250 °), and as pitch coke, a product code “SJ Coke” manufactured by Koa Oil Co., Ltd. (d 002 = 3.45 °; Lc = 20 °) was used.
【００２３】〔非水電解液の調製〕エチレンカーボネー
トとジメチルカーボネートとの体積比１：１の混合溶媒
に、表１に示すリチウム塩を１モル／リットル溶かして
非水電解液を調製した。但し、Ｌｉ2 Ｂ10Ｃｌ10及びＬ
ｉ2 Ｂ12Ｃｌ12については、それぞれを０．４モル／リ
ットル溶かして非水電解液を調製した。[Preparation of Nonaqueous Electrolyte] A nonaqueous electrolyte was prepared by dissolving 1 mol / l of a lithium salt shown in Table 1 in a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1. However, Li 2 B 10 Cl 10 and L
For i 2 B 12 Cl 12 , each was dissolved at 0.4 mol / l to prepare a non-aqueous electrolyte.
【００２４】（比較電池Ｂ１〜Ｂ１８の作製）正極活物
質としてＮａＦｅＯ2 ９０重量部に代えてＬｉＣｏＯ2
９０重量部を使用したこと以外は本発明電池Ａ１〜Ａ１
８の作製と同様にして、表２に示す比較電池Ｂ１〜Ｂ１
８を作製した。(Preparation of Comparative Batteries B1 to B18) LiCoO 2 was used instead of 90 parts by weight of NaFeO 2 as a positive electrode active material.
Except that 90 parts by weight were used, the batteries A1 to A1 of the present invention were used.
8 in the same manner as in the production of Comparative Battery B1 to B1 shown in Table 2.
No. 8 was produced.
【００２５】（比較電池Ｂ１９〜Ｂ３０の作製）下記の
如く正極、負極及び非水電解液を作製し、これらを用い
たこと以外は本発明電池Ａ１〜Ａ１８の作製と同様にし
て、比較電池Ｂ１９〜Ｂ３０を作製した。(Preparation of Comparative Batteries B19 to B30) A positive electrode, a negative electrode and a non-aqueous electrolyte were prepared as described below, and a comparative battery B19 was prepared in the same manner as the preparation of batteries A1 to A18 of the present invention except that these were used. To B30.
【００２６】〔正極の作製〕γ型二酸化マンガンと水酸
化ナトリウムとをモル比１：１で充分に混合した後、ア
ルゴン雰囲気中にて、３５０°Ｃで２時間焼成してＮａ
含有マンガン酸化物を得た。正極活物質としてＮａＦｅ
Ｏ2 ９０重量部に代えてこのＮａ含有マンガン酸化物９
０重量部を使用したこと以外は本発明電池Ａ１〜Ａ１８
の正極の作製と同様にして、正極を作製した。[Preparation of Positive Electrode] After sufficiently mixing γ-type manganese dioxide and sodium hydroxide at a molar ratio of 1: 1, the mixture was calcined at 350 ° C. for 2 hours in an argon atmosphere to obtain Na.
A manganese oxide was obtained. NaFe as a positive electrode active material
Instead of 90 parts by weight of O 2 , this Na-containing manganese oxide 9
Batteries A1 to A18 of the present invention except that 0 parts by weight were used.
A positive electrode was produced in the same manner as in the production of the positive electrode.
【００２７】〔負極の作製〕表３に示す炭素材料（天然
黒鉛、人造黒鉛又はピッチコークス）９５重量部と、ポ
リフッ化ビニリデン４重量部とを混練して負極合剤を作
製し、この負極合剤とＮ−メチル−２−ピロリドンとを
混合してスラリーを調製し、このスラリーを銅箔（集電
体）の両面にドクターブレード法により塗布した後、１
００°Ｃで２時間真空乾燥して、負極を作製した。天然
黒鉛、人造黒鉛及びピッチコークスとしては、本発明電
池Ａ１〜Ａ１８の負極の作製において使用したそれらと
同じものを使用した。[Preparation of Negative Electrode] A negative electrode mixture was prepared by kneading 95 parts by weight of a carbon material (natural graphite, artificial graphite or pitch coke) shown in Table 3 and 4 parts by weight of polyvinylidene fluoride. A slurry was prepared by mixing the agent and N-methyl-2-pyrrolidone, and the slurry was applied to both surfaces of a copper foil (current collector) by a doctor blade method.
Vacuum drying was performed at 00 ° C. for 2 hours to produce a negative electrode. The same natural graphite, artificial graphite and pitch coke as those used in the production of the negative electrodes of the batteries A1 to A18 of the present invention were used.
【００２８】また、ナトリウムと鉛とを鉄製るつぼにモ
ル比５：２で秤取し、アルゴン雰囲気中にて、３５０°
Ｃで１５時間加熱した後、室温まで徐冷して焼鈍し、ナ
トリウムと鉛との合金（ナトリウム合金）を得た。この
ナトリウム合金９５重量部とポリフッ化ビニリデン５重
量部とを混練して負極合剤を作製し、この負極合剤とＮ
−メチル−２−ピロリドンとを混合してスラリーを調製
し、このスラリーを銅箔（集電体）の両面にドクターブ
レード法により塗布した後、アルゴン雰囲気中にて１０
０°Ｃで２時間乾燥して、負極を作製した。Also, sodium and lead were weighed into an iron crucible at a molar ratio of 5: 2, and were placed at 350 ° C. in an argon atmosphere.
After heating at C for 15 hours, it was gradually cooled to room temperature and annealed to obtain an alloy of sodium and lead (sodium alloy). 95 parts by weight of this sodium alloy and 5 parts by weight of polyvinylidene fluoride were kneaded to prepare a negative electrode mixture.
-Methyl-2-pyrrolidone to prepare a slurry, and apply this slurry to both surfaces of a copper foil (current collector) by a doctor blade method.
It dried at 0 degreeC for 2 hours, and produced the negative electrode.
【００２９】〔非水電解液の調製〕エチレンカーボネー
トとジメチルカーボネートとの体積比１：１の混合溶媒
に、表３に示すナトリウム塩を１モル／リットル溶かし
て非水電解液を調製した。[Preparation of Non-Aqueous Electrolyte] A non-aqueous electrolyte was prepared by dissolving 1 mol / l of a sodium salt shown in Table 3 in a mixed solvent of ethylene carbonate and dimethyl carbonate at a volume ratio of 1: 1.
【００３０】〈各電池の放電容量及び電池寿命〉各電池
について、１０００ｍＡで４．２Ｖまで定電流充電した
後、１０００ｍＡで２．７５Ｖまで定電流放電する工程
を１サイクルとする充放電サイクル試験を行い、各電池
の１サイクル目の放電容量（ｍＡｈ）及び電池寿命を調
べた。電池寿命は、放電容量が１サイクル目の放電容量
の７５％以下になるまでの充放電サイクルで評価した。
結果を表１〜表３に示す。<Discharge Capacity and Battery Life of Each Battery> A charge / discharge cycle test was performed for each battery, in which a constant current charge was performed at 1000 mA to 4.2 V and then a constant current discharge was performed at 1000 mA to 2.75 V as one cycle. The first cycle discharge capacity (mAh) and battery life of each battery were examined. The battery life was evaluated in charge / discharge cycles until the discharge capacity became 75% or less of the discharge capacity in the first cycle.
The results are shown in Tables 1 to 3.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】表１及び表２より、正極活物質としてＮａ
ＦｅＯ2 を、また非水電解液の電解質塩としてリチウム
塩をそれぞれ使用することにより、充電時に、負極の炭
素材料にナトリウムイオンとリチウムイオンが挿入され
るようにした本発明電池Ａ１〜Ａ１８は、正極活物質と
してＬｉＣｏＯ2 を、また非水電解液の電解質塩として
リチウム塩を使用することにより、充電時に、負極の炭
素材料にリチウムイオンのみが挿入されるようにした比
較電池Ｂ１〜Ｂ１８に比べて、電池寿命が長く、充放電
サイクル特性が良いことが分かる。また、本発明電池Ａ
Ｘと比較電池ＢＸ（Ｘ＝１〜１８）の放電容量を比較す
ると、本発明電池ＡＸの方が、比較電池ＢＸに比べて、
放電容量が大きいことも分かる。また、表１より、炭素
材料としては、ｄ002 が３．３５〜３．３７Åであり、
且つｃ軸方向の結晶子の大きさＬｃが２５０Å以上であ
る天然黒鉛又は人造黒鉛を使用することが好ましいこと
が分かる。As shown in Tables 1 and 2, Na was used as the positive electrode active material.
By using FeO 2 and a lithium salt as an electrolyte salt of the non-aqueous electrolyte, the batteries A1 to A18 of the present invention, in which sodium ions and lithium ions are inserted into the carbon material of the negative electrode during charging, By using LiCoO 2 as the positive electrode active material and a lithium salt as the electrolyte salt of the non-aqueous electrolyte, compared to comparative batteries B1 to B18 in which only lithium ions are inserted into the carbon material of the negative electrode during charging. This shows that the battery life is long and the charge / discharge cycle characteristics are good. In addition, the battery A of the present invention
Comparing the discharge capacities of X and the comparative battery BX (X = 1 to 18), the battery AX of the present invention has a smaller capacity than the comparative battery BX.
It can also be seen that the discharge capacity is large. From Table 1, as the carbon material, d 002 is 3.35 to 3.37 °,
It can be seen that it is preferable to use natural graphite or artificial graphite having a crystallite size Lc of 250 ° or more in the c-axis direction.
【００３５】表３より、正極活物質としてナトリウム含
有マンガン酸化物を、また非水電解液の電解質塩として
ナトリウム塩をそれぞれ使用することにより、充電時
に、負極の炭素材料にナトリウムイオンのみが挿入され
るようにした比較電池（ナトリウム二次電池）Ｂ１９〜
Ｂ２１、Ｂ２３〜Ｂ２５、Ｂ２７〜Ｂ２９は、負極の炭
素材料にナトリウムイオンがわずかな量しか挿入されな
いために放電容量が小さいとともに、電池寿命が短いこ
とが分かる。また、負極活物質としてナトリウム合金を
使用した比較電池Ｂ２２、Ｂ２６、Ｂ３０は、ナトリウ
ム合金の充放電サイクル特性が良くないために、電池寿
命が短いことが分かる。As shown in Table 3, by using sodium-containing manganese oxide as the positive electrode active material and sodium salt as the electrolyte salt of the non-aqueous electrolyte, only sodium ions are inserted into the carbon material of the negative electrode during charging. Battery (sodium secondary battery) B19 ~
It can be seen that B21, B23 to B25, and B27 to B29 have a small discharge capacity and a short battery life because only a small amount of sodium ions are inserted into the carbon material of the negative electrode. In addition, it can be seen that the comparative batteries B22, B26, and B30 using the sodium alloy as the negative electrode active material have a short battery life due to poor charge / discharge cycle characteristics of the sodium alloy.
【００３６】[0036]
【発明の効果】放電容量が大きく、しかも充放電サイク
ル特性が良い非水電解質二次電池が提供される。The present invention provides a non-aqueous electrolyte secondary battery having a large discharge capacity and good charge-discharge cycle characteristics.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01M 10/40 H01M 10/40 Z A
Claims (8)
物質として有する正極と、炭素材料をナトリウムイオン
及びリチウムイオンの吸蔵材として有する負極と、リチ
ウムイオンを含有する非水電解質とを備えることを特徴
とする非水電解質二次電池。A positive electrode having a composite oxide containing sodium and iron as a positive electrode active material, a negative electrode having a carbon material as a storage material for sodium ions and lithium ions, and a non-aqueous electrolyte containing lithium ions Non-aqueous electrolyte secondary battery characterized by the following.
（０≦ｘ≦０．９；ＭはＣｏ、Ｎｉ及びＭｎよりなる群
から選ばれた少なくとも一種の遷移元素）である請求項
１記載の非水電解質二次電池。2. The method according to claim 2, wherein the composite oxide is NaFe 1-x M x O 2
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein (0 ≦ x ≦ 0.9; M is at least one transition element selected from the group consisting of Co, Ni and Mn).
間隔ｄ002 が３．３５〜３．３７Åであり、且つｃ軸方
向の結晶子の大きさＬｃが２５０Å以上である炭素材料
である請求項１記載の非水電解質二次電池。3. The carbon material having a lattice spacing (002) plane spacing d 002 of 3.35 to 3.37 ° and a crystallite size Lc in the c-axis direction of 250 ° or more. The non-aqueous electrolyte secondary battery according to claim 1, wherein
として使用した非水電解質である請求項１記載の非水電
解質二次電池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte is a non-aqueous electrolyte using a lithium salt as an electrolyte salt.
リウムイオンを含有する非水電解質である請求項１記載
の非水電解質二次電池。5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte is a non-aqueous electrolyte containing lithium ions and sodium ions.
含有する非水電解質が、リチウム塩とナトリウム塩を電
解質塩として使用した非水電解質である請求項５記載の
非水電解質二次電池。6. The non-aqueous electrolyte secondary battery according to claim 5, wherein the non-aqueous electrolyte containing lithium ions and sodium ions is a non-aqueous electrolyte using lithium salts and sodium salts as electrolyte salts.
4 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 、ＬｉＣｌＯ4 、Ｌｉ
2 Ｂ10Ｃｌ10及びＬｉ2 Ｂ12Ｃｌ12よりなる群から選ば
れた少なくとも一種のリチウム塩である請求項４又は６
記載の非水電解質二次電池。7. The method according to claim 7, wherein the lithium salt is LiPF 6 , LiBF
4 , LiN (C 2 F 5 SO 2 ) 2 , LiClO 4 , Li
A 2 B 10 Cl 10 and Li 2 B 12 at least one lithium salt selected from the group consisting of Cl 12 is claim 4 or 6
The non-aqueous electrolyte secondary battery according to the above.
ｌＯ4 、ＮａＢＦ4 、ＮａＣＦ3 ＳＯ3 、ＮａＮ（ＣＦ
3 ＳＯ3 ）2 、ＮａＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 及びＮａＣ
（ＣＦ3 ＳＯ3 ）3 よりなる群から選ばれた少なくとも
一種のナトリウム塩である請求項６記載の非水電解質二
次電池。8. The method according to claim 8, wherein the sodium salt is NaPF 6 , NaC
10 O 4 , NaBF 4 , NaCF 3 SO 3 , NaN (CF
3 SO 3 ) 2 , NaN (C 2 F 5 SO 2 ) 2 and NaC
The non-aqueous electrolyte secondary battery according to claim 6, which is at least one sodium salt selected from the group consisting of (CF 3 SO 3 ) 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20864597A JP3439082B2 (en) | 1997-07-16 | 1997-07-16 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20864597A JP3439082B2 (en) | 1997-07-16 | 1997-07-16 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1140156A true JPH1140156A (en) | 1999-02-12 |
| JP3439082B2 JP3439082B2 (en) | 2003-08-25 |
Family
ID=16559682
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|---|---|---|---|
| JP20864597A Expired - Fee Related JP3439082B2 (en) | 1997-07-16 | 1997-07-16 | Non-aqueous electrolyte secondary battery |
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| Country | Link |
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