JP3373978B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3373978B2 JP3373978B2 JP15252495A JP15252495A JP3373978B2 JP 3373978 B2 JP3373978 B2 JP 3373978B2 JP 15252495 A JP15252495 A JP 15252495A JP 15252495 A JP15252495 A JP 15252495A JP 3373978 B2 JP3373978 B2 JP 3373978B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- battery
- positive electrode
- calcium
- 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.)
- Expired - Fee Related
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はカルシウムイオンをイオ
ン電導媒体とする非水電解質二次電池に係わり、詳しく
はその高容量化を図ることを目的とした、正極材料の改
良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery using calcium ions as an ion conductive medium, and more particularly to improvement of a positive electrode material for the purpose of increasing its capacity.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】黒鉛、
コークス等の炭素材料を負極材料とし、ＣａＣｏ
2 Ｏ4 、Ｃａ3 Ｃｏ4Ｏ9 、Ｃａ2 Ｃｏ2 Ｏ5 、Ｃａ3
Ｃｏ2 Ｏ6 、ＣａＦｅＯ3 、ＣａＦｅＯ2 等のカルシウ
ム含有金属酸化物を正極材料とする非水電解質二次電池
が、特開平６−１６３０８０号公報に開示されている。2. Description of the Related Art Graphite,
A carbon material such as coke is used as a negative electrode material, and CaCo
2 O 4 , Ca 3 Co 4 O 9 , Ca 2 Co 2 O 5 , Ca 3
A non-aqueous electrolyte secondary battery using a calcium-containing metal oxide such as Co 2 O 6 , CaFeO 3 and CaFeO 2 as a positive electrode material is disclosed in JP-A-6-163080.
【０００３】この電池は、イオン価２価のカルシウムイ
オン（Ｃａ2+）をイオン電導媒体とするので、イオン価
１価のリチウムイオン（Ｌｉ+ ）をイオン電導媒体とす
るリチウム二次電池に比べて遙かに大きな容量を有す
る。This battery uses calcium ions (Ca 2+ ) having an ionic valence of 2 as an ion conductive medium, and therefore, compared with a lithium secondary battery using lithium ions (Li + ) having an ionic valence of 1 as an ion conductive medium. It has a much larger capacity.
【０００４】しかしながら、これらのカルシウム含有金
属酸化物は、分子量が大きいことから、単位質量当たり
の容量はさほど大きくない。してみれば、単位質量当た
りの容量がこれらのカルシウム含有金属酸化物よりも大
きいカルシウム化合物を正極材料として使用すれば、さ
らに高容量の電池が得られる可能性がある。However, since these calcium-containing metal oxides have large molecular weights, their capacity per unit mass is not so large. Therefore, if a calcium compound having a larger capacity per unit mass than these calcium-containing metal oxides is used as the positive electrode material, a battery having a higher capacity may be obtained.
【０００５】本発明は、かかる知見に基づきなされたも
のであって、その目的とするところは、特開平６−１６
３０８０号公報に開示の電池に比べて格段大きな電池容
量を有する、カルシウムイオンをイオン電導媒体とする
非水電解質二次電池を提供するにある。The present invention has been made on the basis of such findings, and the object of the present invention is described in JP-A-6-16.
Another object of the present invention is to provide a non-aqueous electrolyte secondary battery that uses calcium ions as an ion conductive medium and has a battery capacity significantly larger than that of the battery disclosed in Japanese Patent No. 3080.
【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
の本発明に係る非水電解質二次電池（本発明電池）は、
ＣａＳｉ2 及び／又はＣａＧｅ2 を正極活物質とする正
極と、炭素材料をカルシウムイオン吸蔵材とする負極
と、カルシウム塩を含有する非水電解質とを備える。The non-aqueous electrolyte secondary battery (the battery of the present invention) according to the present invention for achieving the above object comprises:
A positive electrode using CaSi 2 and / or CaGe 2 as a positive electrode active material, a negative electrode using a carbon material as a calcium ion storage material, and a non-aqueous electrolyte containing a calcium salt.
【０００７】炭素材料としては、コークス、有機物焼成
体、黒鉛が例示される。なかでも、黒鉛が、カルシウム
イオンの吸蔵放出量が多い点で好ましい。これらの炭素
材料は一種単独を使用してもよく、必要に応じて二種以
上を混合して使用してもよい。Examples of the carbon material include coke, a fired organic material and graphite. Of these, graphite is preferable because it has a large amount of storage and release of calcium ions. These carbon materials may be used alone or in combination of two or more as needed.
【０００８】カルシウム塩としては、過塩素酸カルシウ
ム〔Ｃａ（ＣｌＯ4 ）2 〕、ホウフッ化カルシウム〔Ｃ
ａ（ＢＦ4 ）2 〕、トリフルオロメチルスルホン酸カル
シウム〔Ｃａ（ＣＦ3 ＳＯ3 ）2 〕、ヘキサフルオロ燐
酸カルシウム〔Ｃａ（ＰＦ6）2 〕が例示される。過塩
素酸カルシウムが特に好ましい。Calcium salts include calcium perchlorate [Ca (ClO 4 ) 2 ] and calcium borofluoride [C
a (BF 4 ) 2 ], calcium trifluoromethyl sulfonate [Ca (CF 3 SO 3 ) 2 ], and calcium hexafluorophosphate [Ca (PF 6 ) 2 ]. Calcium perchlorate is particularly preferred.
【０００９】カルシウム塩を溶かすための溶媒として
は、エチレンカーボネート、ビニレンカーボネート、プ
ロピレンカーボネートなどの高誘電率溶媒や、これらと
ジエチルカーボネート、ジメチルカーボネート、１，２
−ジメトキシエタン、１，２−ジエトキシエタン、エト
キシメトキシエタンなどの低沸点溶媒との混合溶媒が好
適なものとして例示される。As a solvent for dissolving the calcium salt, a solvent having a high dielectric constant such as ethylene carbonate, vinylene carbonate or propylene carbonate, or diethyl carbonate, dimethyl carbonate, 1, 2
A mixed solvent with a low boiling point solvent such as -dimethoxyethane, 1,2-diethoxyethane or ethoxymethoxyethane is exemplified as a preferable example.
【００１０】本発明の特徴は、単位質量当たりの容量が
大きい特定のカルシウム化合物を正極材料として使用し
た点にある。それゆえ、電池を構成する他の部材につい
ては、非水電解質二次電池用として従来提案され、或い
は実用されている種々の材料を特に制限なく用いること
が可能である。A feature of the present invention is that a specific calcium compound having a large capacity per unit mass is used as a positive electrode material. Therefore, as other members constituting the battery, various materials conventionally proposed or put into practical use for the non-aqueous electrolyte secondary battery can be used without particular limitation.
【００１１】[0011]
【作用】従来のカルシウム含有金属酸化物と比較して単
位質量当たりの容量が大きいＣａＳｉ2 及び／又はＣａ
Ｇｅ2 が正極材料として使用されているので、電池容量
が大きい。[Function] CaSi 2 and / or Ca having a larger capacity per unit mass than the conventional calcium-containing metal oxide.
Since Ge 2 is used as the positive electrode material, the battery capacity is large.
【００１２】[0012]
【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.
【００１３】（実施例１）
〔正極〕正極材料としてのＣａＳｉ2 粉末（真密度：
２．５ｇ／ｃｍ3 ）９５重量部と導電剤としての黒鉛粉
末５重量部とを、結着剤としてのポリイミド樹脂２重量
部の１重量％ＮＭＰ（Ｎ−メチル−２−ピロリドン）溶
液と混合してスラリーを調製した。次いで、このスラリ
ーを正極集電体としてのアルミニウム箔の両面にドクタ
ーブレード法により塗布し、真空下において６０°Ｃで
乾燥してＮＭＰを蒸散させた後、３５０°Ｃで２時間熱
処理して、アルミニウム箔の両面に正極活物質層が形成
された正極を作製した。(Example 1) [Positive electrode] CaSi 2 powder (true density:
2.5 g / cm 3 ) 95 parts by weight and 5 parts by weight of graphite powder as a conductive agent are mixed with 2 parts by weight of a polyimide resin as a binder and a 1% by weight NMP (N-methyl-2-pyrrolidone) solution. To prepare a slurry. Then, this slurry was applied to both sides of an aluminum foil as a positive electrode current collector by a doctor blade method, dried under vacuum at 60 ° C to evaporate NMP, and then heat-treated at 350 ° C for 2 hours, A positive electrode having a positive electrode active material layer formed on both sides of an aluminum foil was produced.
【００１４】〔負極〕負極材料としての天然黒鉛粉末１
００重量部を、結着剤としてのポリイミド樹脂０．５重
量部の１重量％ＮＭＰ溶液と混合してスラリーを調製し
た。次いで、このスラリーを負極集電体としての銅箔の
両面に塗布し、真空下において６０°Ｃで乾燥してＮＭ
Ｐを蒸散させた後、３５０°Ｃで２時間熱処理して、銅
箔の両面に天然黒鉛層が形成された負極を作製した。[Negative Electrode] Natural graphite powder 1 as negative electrode material
00 parts by weight was mixed with 0.5 parts by weight of a 1% by weight NMP solution of a polyimide resin as a binder to prepare a slurry. Next, this slurry is applied to both sides of a copper foil as a negative electrode current collector, dried at 60 ° C. under vacuum, and NM
After P was evaporated, it was heat-treated at 350 ° C. for 2 hours to prepare a negative electrode in which a natural graphite layer was formed on both surfaces of the copper foil.
【００１５】〔非水電解液〕エチレンカーボネートとジ
エチルカーボネートとの体積比１：１の混合溶媒に、溶
質としてのＣａ（ＣｌＯ4 ）2 を１モル／リットルの割
合で溶かして、非水電解液を調製した。[Nonaqueous Electrolyte] Ca (ClO 4 ) 2 as a solute was dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 at a ratio of 1 mol / liter to prepare a nonaqueous electrolyte. Was prepared.
【００１６】以上の正極、負極及び非水電解液を使用し
て、円筒型（ＡＡサイズ）の非水電解質二次電池（本発
明電池Ａ１）を組み立てた。なお、セパレータとして
は、カルシウムイオン透過性を有するポリプロピレン製
の微多孔膜を使用した。A cylindrical (AA size) non-aqueous electrolyte secondary battery (invention battery A1) was assembled using the above positive electrode, negative electrode and non-aqueous electrolyte solution. As the separator, a polypropylene microporous membrane having calcium ion permeability was used.
【００１７】（実施例２）正極材料として、ＣａＳｉ2
粉末に代えて、ＣａＧｅ2 粉末（真密度：２．５ｇ／ｃ
ｍ3 ）を同重量使用したこと以外は実施例１と同様にし
て正極を作製し、この正極を使用して、本発明電池Ａ２
を組み立てた。Example 2 As the positive electrode material, CaSi 2
Instead of powder, CaGe 2 powder (true density: 2.5 g / c
m 3 ) was used in the same manner as in Example 1 except that the same weight was used, and this positive electrode was used to prepare a battery A2 of the invention.
Assembled.
【００１８】（比較例１）正極材料として、ＣａＳｉ2
粉末に代えて、ＣａＣｏ2 Ｏ4 粉末（真密度：４．９ｇ
／ｃｍ3 ）を同重量使用したこと以外は実施例１と同様
にして正極を作製し、この正極を使用して、比較電池Ｂ
１を組み立てた。(Comparative Example 1) As a positive electrode material, CaSi 2
Instead of powder, CaCo 2 O 4 powder (true density: 4.9 g
/ Cm 3 ) was used in the same manner as in Example 1 except that the same weight was used.
Assembled 1.
【００１９】（比較例２）正極材料として、ＣａＳｉ2
粉末に代えて、ＬｉＣｏＯ2 粉末（真密度：４．８ｇ／
ｃｍ3 ）を同重量使用するとともに、非水電解液の溶質
として、Ｃａ（ＣｌＯ4 ）2 に代えて、ＬｉＣｌＯ4 を
同モル量使用したこと以外は実施例１と同様にして正極
を作製し、この正極を使用して、比較電池Ｂ２を組み立
てた。Comparative Example 2 CaSi 2 was used as the positive electrode material.
Instead of the powder, LiCoO 2 powder (true density: 4.8 g /
cm 3 ) was used in the same amount and a positive electrode was prepared in the same manner as in Example 1 except that LiClO 4 was used as the solute of the non-aqueous electrolytic solution in place of Ca (ClO 4 ) 2 in the same molar amount. A comparative battery B2 was assembled using this positive electrode.
【００２０】表１に、各電池の正極材料及び非水電解液
の溶質をまとめて示す。Table 1 collectively shows the positive electrode material of each battery and the solute of the non-aqueous electrolyte.
【００２１】[0021]
【表１】 [Table 1]
【００２２】〔充放電試験〕各電池について、５００ｍ
Ａで４．４Ｖまで充電した後、５００ｍＡで３．０Ｖま
で放電する充放電試験を行い、平均作動電圧（Ｖ）及び
充放電容量（ｍＡｈ）を求めた。平均作動電圧は、１０
点平均により求めた。結果を先の表１に示す。また、図
１は、各電池の充放電特性を、縦軸に電池電圧（Ｖ）
を、横軸に充放電容量（ｍＡｈ）をとって示したグラフ
である。[Charge / Discharge Test] 500 m for each battery
After charging to 4.4 V with A, a charging / discharging test of discharging to 3.0 V at 500 mA was performed to determine an average operating voltage (V) and a charging / discharging capacity (mAh). Average operating voltage is 10
It was calculated by the point average. The results are shown in Table 1 above. In addition, FIG. 1 shows the charging / discharging characteristics of each battery, with the vertical axis representing the battery voltage (V).
Is a graph in which the horizontal axis represents the charge / discharge capacity (mAh).
【００２３】表１及び図１より、本発明電池Ａ１，Ａ２
は、比較電池Ｂ１，Ｂ２に比べて、格段大きな電池容量
を有することが分かる。From Table 1 and FIG. 1, the batteries A1 and A2 of the present invention are shown.
It can be seen that has a much larger battery capacity than the comparative batteries B1 and B2.
【００２４】また、表１及び図１より、本発明電池Ａ
１，Ａ２は、比較電池Ｂ１，Ｂ２に比べて、平均作動電
圧が高いことが分かる。From Table 1 and FIG. 1, the battery A of the present invention was obtained.
It can be seen that the average operating voltages of the batteries 1 and A2 are higher than those of the comparative batteries B1 and B2.
【００２５】上記実施例では、本発明を円筒型の非水電
解質二次電池に適用する場合を例に挙げて説明したが、
本発明は電池形状に特に制限があるわけではなく、扁平
型、角型など、他の種々の形状の非水電解質二次電池に
適用し得るものである。In the above embodiment, the case where the present invention is applied to the cylindrical type non-aqueous electrolyte secondary battery has been described as an example.
The present invention is not particularly limited in battery shape, and can be applied to non-aqueous electrolyte secondary batteries of various other shapes such as flat type and prismatic type.
【００２６】また、上記実施例では、正極材料としてＣ
ａＳｉ2 又はＣａＧｅ2 を一種単独使用したが、これら
の混合物を使用することももとより可能である。Further, in the above embodiment, C is used as the positive electrode material.
Although aSi 2 or CaGe 2 is used alone, it is naturally possible to use a mixture thereof.
【００２７】[0027]
【発明の効果】単位質量当たりの容量が大きいＣａＳｉ
2 又はＣａＧｅ2 が正極材料として使用されているの
で、本発明電池は、リチウム二次電池に比べて格段大き
な電池容量を有することはもとより、従来のカルシウム
イオンをイオン電導媒体とする非水電解質二次電池に比
べても、大きな電池容量を有する。EFFECT OF THE INVENTION CaSi having a large capacity per unit mass
Since 2 or CaGe 2 is used as the positive electrode material, the battery of the present invention has a much larger battery capacity than a lithium secondary battery, and also has a non-aqueous electrolyte electrolyte using a conventional calcium ion as an ion conducting medium. It has a larger battery capacity than the next battery.
【図１】実施例で組み立てた本発明電池及び比較電池の
充放電特性を示すグラフである。FIG. 1 is a graph showing charge / discharge characteristics of a battery of the present invention and a comparative battery assembled in Examples.
フロントページの続き (56)参考文献 特開 平６−163080（ＪＰ，Ａ) 特開 平６−338325（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/00 - 4/04 H01M 4/36 - 4/62 H01M 6/00 - 6/22 H01M 10/36 - 10/40 Continuation of the front page (56) Reference JP-A-6-163080 (JP, A) JP-A-6-338325 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 4 / 00-4/04 H01M 4/36-4/62 H01M 6/00-6/22 H01M 10/36-10/40
Claims (2)
物質とする正極と、炭素材料をカルシウムイオン吸蔵材
とする負極と、カルシウム塩を含有する非水電解質とを
備える非水電解質二次電池。1. A non-aqueous electrolyte secondary battery comprising a positive electrode using CaSi 2 and / or CaGe 2 as a positive electrode active material, a negative electrode using a carbon material as a calcium ion storage material, and a non-aqueous electrolyte containing a calcium salt. .
ある請求項１記載の非水電解質二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the calcium salt is calcium perchlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15252495A JP3373978B2 (en) | 1995-05-26 | 1995-05-26 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15252495A JP3373978B2 (en) | 1995-05-26 | 1995-05-26 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08321305A JPH08321305A (en) | 1996-12-03 |
| JP3373978B2 true JP3373978B2 (en) | 2003-02-04 |
Family
ID=15542326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15252495A Expired - Fee Related JP3373978B2 (en) | 1995-05-26 | 1995-05-26 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3373978B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004200015A (en) | 2002-12-19 | 2004-07-15 | Sanyo Electric Co Ltd | Electrolyte for nonaqueous battery, its manufacturing method, and nonaqueous battery electrolytic solution |
| JP5534578B2 (en) * | 2009-11-19 | 2014-07-02 | 旭化成株式会社 | Active material for positive electrode |
| CN110615465B (en) * | 2018-06-20 | 2021-09-14 | 天津大学 | Preparation method of amorphous germanium-based nanowire |
| CN111326794B (en) * | 2018-12-17 | 2021-07-20 | 深圳先进技术研究院 | Electrolyte, calcium ion secondary battery and preparation method thereof |
-
1995
- 1995-05-26 JP JP15252495A patent/JP3373978B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08321305A (en) | 1996-12-03 |
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