JP2552393B2 - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JP2552393B2 JP2552393B2 JP2333742A JP33374290A JP2552393B2 JP 2552393 B2 JP2552393 B2 JP 2552393B2 JP 2333742 A JP2333742 A JP 2333742A JP 33374290 A JP33374290 A JP 33374290A JP 2552393 B2 JP2552393 B2 JP 2552393B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- battery
- lithium battery
- porous body
- 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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は充放電特性を向上させたリチウム電池に関す
るものである。The present invention relates to a lithium battery having improved charge / discharge characteristics.
（従来の技術） 一般に各種ポータブル機器等に用いられている電池の
電極は、ペースト式，粉末加圧式，クラッド式，焼結式
などがある。(Prior Art) Generally, electrodes of batteries used in various portable devices include a paste type, a powder pressure type, a clad type, and a sintering type.
ペースト式は鉛蓄電池の場合で良く知られており、主
に鉛粉と水と希硫酸とを練合してペースト状にし、鉛を
主体とする格子に充填する方法である。Ni−Cd電池にお
いても水酸化ニッケルや酸化カドミウムを結着剤でペー
スト状にして用いられている。The paste method is well known in the case of a lead storage battery, and is a method of mainly kneading lead powder, water and dilute sulfuric acid to form a paste, and filling a grid mainly containing lead. Also in Ni-Cd batteries, nickel hydroxide or cadmium oxide is used as a paste with a binder.
粉末加圧式は乾電池で知られている二酸化マンガン電
池、または酸化銀電池などに用いられている。The powder pressurization type is used for a manganese dioxide battery known as a dry battery, a silver oxide battery, or the like.
一方、高エネルギー密度，高電圧を有するリチウム電
池が最近注目されているが、この電池もバインダ，導電
助剤（アセチレンブラック等）などと混合し、加圧成形
により正極材を作っている。On the other hand, a lithium battery having a high energy density and a high voltage has recently attracted attention, and this battery is also mixed with a binder, a conductive auxiliary agent (acetylene black, etc.) and the like to form a positive electrode material by pressure molding.
（発明が解決しようとする課題） リチウム電池の正極材として、MnO2,LiMn2O4,MoS,TiS
2,Cr3O8,V2O5,活性炭など各種材料が用いられている。
この時も加圧成形して正極を作るが、二次電池の場合Li
イオンの挿入，脱離を繰り返すうちに、活物質の体積変
化により、バインダや導電助剤と剥離，脱離してしま
う。これにより電池サイクル寿命が短かくなるという課
題を有していた。(Problems to be Solved by the Invention) MnO 2 , LiMn 2 O 4 , MoS, TiS are used as positive electrode materials for lithium batteries.
Various materials such as 2 , Cr 3 O 8 , V 2 O 5 and activated carbon are used.
Also at this time, pressure molding is performed to make a positive electrode, but in the case of a secondary battery, Li
During repeated insertion and desorption of ions, the volume change of the active material causes the desorption and desorption from the binder and the conductive additive. This causes a problem that the battery cycle life becomes short.
またこのような粉末加圧法による正極作製は、粒状の
活物質と導電助剤を絶縁性のバインダーを用いて結着さ
せるため、導電助剤が活物質と集電体を100％接続する
ことは不可能である。そして、絶縁性のバインダーがこ
れら粒子の間に入って電導を妨げることも回避し得ない
問題である。Further, in the production of a positive electrode by such a powder pressing method, since the granular active material and the conductive auxiliary agent are bound together by using an insulating binder, the conductive auxiliary agent does not connect the active material and the current collector 100%. It is impossible. Further, it is an unavoidable problem that the insulating binder enters between these particles to hinder electric conduction.
さらに、固体電解質の場合、液体電解質のように加圧
成形した極材の粒子表面を100％濡らすことは非常に困
難であり、且つ不要な空間も残る。このため活物質の利
用率が悪く、容量密度も低くなる。Furthermore, in the case of a solid electrolyte, it is very difficult to wet 100% of the particle surface of a pressure-formed electrode material like a liquid electrolyte, and an unnecessary space remains. Therefore, the utilization rate of the active material is poor and the capacity density is low.
本発明はこれら課題を解決し、充放電サイクル寿命，
放電特性を向上させ、加圧形成をなしく、薄形の電池も
容易に作れる電極を備えたリチウム電池を提供するもの
である。The present invention solves these problems,
Provided is a lithium battery provided with an electrode that has improved discharge characteristics, does not undergo pressure formation, and can easily make a thin battery.
（課題を解決するための手段） 上記の課題を解決するため、本発明は、正極の多孔体
の表面が、V2O5・nH2Oを主体とする正極活物質で被覆さ
れている、ことを特徴とする。(Means for Solving the Problems) In order to solve the above problems, the present invention provides that the surface of the positive electrode porous body is coated with a positive electrode active material mainly composed of V 2 O 5 · nH 2 O, It is characterized by
また、負極の負極活物質はLiまたはLi合金にすると良
い。The negative electrode active material of the negative electrode may be Li or Li alloy.
（作用） 本発明に用いる正極活物質のV2O5・nH2Oは、結晶水の
ないV2O5とは構造、特性共に異なるもので、水溶液とす
ることができるため、多孔体内に含浸し乾燥させること
により、容易に多孔体の表面を被覆することができ、Li
イオンの挿入、脱離による活物質の体積変化で生じる応
力を緩和し、活物質の脱落を防止する。また、多孔体の
表面で非常に良好な導電性が得られることから、活物質
の利用率を向上させ容量密度を高めると共に、薄形など
形状の自由度が大きく量産性に適している。(Function) V 2 O 5 · nH 2 O of the positive electrode active material used in the present invention has a different structure and characteristics from V 2 O 5 without crystal water, and can be formed as an aqueous solution. By impregnating and drying, the surface of the porous material can be easily coated.
The stress caused by the volume change of the active material due to the insertion and desorption of ions is relieved, and the active material is prevented from falling off. Further, since very good conductivity can be obtained on the surface of the porous body, the utilization factor of the active material is improved and the capacity density is increased, and the flexibility of the shape such as thin shape is large, which is suitable for mass production.
（実施例） 本発明の一実施例を以下に示す。(Example) An example of the present invention will be described below.
（正極作製） 平均繊維径が１μｍ以下のガラス繊維を水中に分散さ
せ、ステンレスの網を用いて、不織布を抄造する。正極
活物質のV2O5・nH2O水溶液は、結晶V2O5を溶融してこれ
を水中に入れてHVO3を作り、これを重合させることによ
って得られる。(Production of Positive Electrode) Glass fibers having an average fiber diameter of 1 μm or less are dispersed in water, and a nonwoven fabric is made into paper by using a stainless net. The V 2 O 5 · nH 2 O aqueous solution of the positive electrode active material can be obtained by melting crystalline V 2 O 5 , putting it in water to form HVO 3 , and polymerizing it.
次に、第１図に示すように、抄造したガラス繊維１の
不織布を多孔体２として導電性接着剤３でステンレス箔
４に接着させる。そしてこのステンレス箔４を正極活物
質であるV2O5・nH2O水溶液中に入れ、多孔体２内にV2O5
・nH2O水溶液を含浸させる。そしてこれを60℃で3hの条
件で乾燥させて、多孔体２である不織布の内面にV2O5・
nH2O5の膜を形成させる。これからわかるようにV2O5・n
H2O5は絶縁体であるガラス繊維１に密着し、表面積が広
くなっている。また導電性接着剤３のところまでV2O5・
nH2O5の膜はとぎれることなく形成されて、導電性の非
常に良いV2O5・nH2O5の膜で導通が取られている。この
ような状態になっているステンレス箔を180℃3hの条件
で熱処理して正極を作った。Next, as shown in FIG. 1, the non-woven fabric of the glass fiber 1 made into a paper is bonded as a porous body 2 to a stainless steel foil 4 with a conductive adhesive 3. Then put this stainless steel foil 4 to V 2 O 5 · nH in 2 O aqueous solution as a positive electrode active material, V 2 O 5 in the porous body 2
-Impregnate with an aqueous solution of nH 2 O. Then, this is dried at 60 ° C. for 3 hours, and V 2 O 5 · is applied to the inner surface of the nonwoven fabric which is the porous body 2.
A film of nH 2 O 5 is formed. As you can see, V 2 O 5・ n
H 2 O 5 adheres to the glass fiber 1 which is an insulator, and has a large surface area. In addition, V 2 O 5
The nH 2 O 5 film is formed without interruption, and conduction is achieved by the V 2 O 5 .nH 2 O 5 film having excellent conductivity. The positive electrode was produced by heat-treating the stainless steel foil in such a state under the condition of 180 ° C. for 3 hours.
（負極作製） 負極も正極と同じようにして作っても良いが今回は、
Niからなる多孔質な焼結体をLi−Al合金から成る溶融浴
に入れて、多孔体の内面にLi−Al合金を形成させる。こ
れをステンレス箔に密着させて負極を作製した。(Fabrication of negative electrode) The negative electrode may be fabricated in the same manner as the positive electrode, but this time,
A porous sintered body made of Ni is put into a molten bath made of a Li-Al alloy to form a Li-Al alloy on the inner surface of the porous body. This was brought into close contact with a stainless steel foil to produce a negative electrode.
（電池作製） 電解液としてプロピレンカーボネートに過塩素酸リチ
ウムを1M溶解したものを用いる。第２図に示すように、
この電解液をポリプロピレンからなる不織布に含浸した
もの６を正極７と密着させる。次に負極８を合せてホッ
トメルト状の封口剤９でステンレス箔４周囲を封口す
る。これからわかるように薄形の電池が容易にでき厚さ
1mmになっている。(Battery preparation) As the electrolytic solution, 1M lithium perchlorate dissolved in propylene carbonate is used. As shown in FIG.
A non-woven fabric made of polypropylene impregnated with this electrolytic solution 6 is brought into close contact with the positive electrode 7. Next, the anode 8 is put together, and the periphery of the stainless steel foil 4 is sealed with a hot-melt sealing agent 9. As you can see, thin batteries can be easily made
It is 1 mm.
（電池特性） 上記本発明品のほかに従来品としてV2O5・nH2Oを粉末
にし導電助剤とバインダーとで混合加圧形成した正極と
Li−Al箔の負極とを用いて電池を作製し比較した。(Battery characteristics) In addition to the above-described product of the present invention, as a conventional product, a positive electrode formed by mixing V 2 O 5 · nH 2 O into powder and mixing and forming it with a conductive auxiliary agent and a binder is used.
A battery was prepared using the negative electrode of Li-Al foil and compared.
放電:0.3mA/cm2,終止電圧2.0V、充電:0.3mA/cm2,4.2V
定電圧充電14h（25℃）のサイクル条件で充放電試験を
行ったが、第３図に示すように、従来品に比べて本発明
品は120Ah/g（正極活物質重量当り）という高い容量で1
00サイクルでも安定に推移している。Discharge: 0.3mA / cm 2 , final voltage 2.0V, Charge: 0.3mA / cm 2 , 4.2V
A charge / discharge test was carried out under a cycle condition of constant voltage charging 14h (25 ° C). As shown in Fig. 3, the product of the present invention has a high capacity of 120Ah / g (per weight of the positive electrode active material) compared to the conventional product. In 1
It has remained stable even in the 00 cycle.
上記した実施例以外でも本発明は行うことができる。
例えば正極は炭素繊維などの導電性繊維を用いた織布，
不織布を使ったり、ガラス繊維の表面に金属をコーティ
ングしたり導電性樹脂を付けたりして用いても良い。ま
た金属の発泡体やポリエステルなどの樹脂を発泡させ、
その表面に導電性物をコーティングしたものを集電体と
しても良い。またNi粉末などの金属粒子を焼結させて多
孔体を作り、これを集電体としても良い。The present invention can be carried out in other than the above-mentioned embodiments.
For example, the positive electrode is a woven fabric using conductive fibers such as carbon fibers,
A non-woven fabric may be used, or the surface of glass fiber may be coated with a metal or attached with a conductive resin. Also, by foaming metal foam or resin such as polyester,
The current collector may have a surface coated with a conductive material. Alternatively, metal particles such as Ni powder may be sintered to form a porous body, which may be used as a current collector.
一方正極活物質もV2O5・nH2Oだけでなく、V2O5・nH2O
水溶液中に、MnO2,LiMn2O4,MoS2,TiS2,Cr3O8,V6O13,黒
鉛，活性炭などの物質の粉末を入れることは容量増加が
できるので好ましい。また水溶液中に入れて混合するた
め、分散が均一にでき、乾燥させて集電に付着させても
V2O5・nH2Oにより密着性が良い。On the other hand, the positive electrode active material is not only V 2 O 5 · nH 2 O, but also V 2 O 5 · nH 2 O.
It is preferable to add powders of substances such as MnO 2 , LiMn 2 O 4 , MoS 2 , TiS 2 , Cr 3 O 8 , V 6 O 13 , graphite and activated carbon to the aqueous solution because the capacity can be increased. Also, since it is put in an aqueous solution and mixed, the dispersion can be made uniform, and even if it is dried and attached to a current collector.
Good adhesion due to V 2 O 5 · nH 2 O.
また電解液もジメトキシエタンなど他の有機溶媒や混
合物を用いても良い。さらに高分子固体電解質（例：ポ
リエチレンオキシド系，ポリプロピレンオキシド系，ポ
リメタクリル酸系，ポリホスファゼン系）を用いると液
漏れの心配がないので好ましい。また無機の固体電解質
とゴム系のバインダーを混合した柔軟性のある電解質で
も良い。As the electrolytic solution, another organic solvent such as dimethoxyethane or a mixture thereof may be used. Furthermore, it is preferable to use a polymer solid electrolyte (eg, polyethylene oxide type, polypropylene oxide type, polymethacrylic acid type, polyphosphazene type) since there is no risk of liquid leakage. Further, a flexible electrolyte in which an inorganic solid electrolyte and a rubber binder are mixed may be used.
一方、電解液に溶かす溶質は特に制限しないが、LiBF
4,LiAsF6,LiAlCl,LiPF6,CF3SO3Li,LiClなどが挙げられ
る。On the other hand, the solute dissolved in the electrolytic solution is not particularly limited, but LiBF
4 , LiAsF 6 , LiAlCl, LiPF 6 , CF 3 SO 3 Li, LiCl and the like.
（発明の効果） 本発明は、正極の多孔体の表面が、V2O5・nH2Oを主体
とする正極活物質で被覆されているものであるため、充
放電サイクル寿命、放電特性が良く、加圧形成なしに正
極を作製でき、量産性にすぐれている。さらに正極活物
質であるV2O5・nH2Oは水溶液状態から乾燥させて付着さ
せるため密着が良いことなど工業的価値極めて大であ
る。(Effect of the invention) The present invention has a positive-electrode porous body whose surface is coated with a positive-electrode active material mainly composed of V 2 O 5 · nH 2 O, and therefore has a long charge-discharge cycle life and discharge characteristics. Good, the positive electrode can be produced without pressure formation, and the mass productivity is excellent. Furthermore, V 2 O 5 · nH 2 O, which is a positive electrode active material, has great industrial value such as good adhesion because it is dried and attached from an aqueous solution state.
第１図は、本発明の一実施例における正極の状態を示す
拡大断面図、第２図は、本発明品の一実施例を示すリチ
ウム電池の断面図、第３図は充放電サイクルの容量推移
を示す比較特性図である。 １はガラス繊維、２は多孔体、３は導電性接着剤、４は
ステンレス箔、５はV2O5・nH2O、６は電解液＋プロピレ
ン不織布、７は正極、８は負極、９は封口剤FIG. 1 is an enlarged cross-sectional view showing a state of a positive electrode in one embodiment of the present invention, FIG. 2 is a cross-sectional view of a lithium battery showing one embodiment of the product of the present invention, and FIG. It is a comparison characteristic view showing change. 1 is a glass fiber, 2 is a porous material, 3 is a conductive adhesive, 4 is a stainless steel foil, 5 is V 2 O 5 · nH 2 O, 6 is an electrolytic solution + propylene non-woven fabric, 7 is a positive electrode, 8 is a negative electrode, 9 Is a sealing agent
───────────────────────────────────────────────────── フロントページの続き (72)発明者 早川 他▲く▼美 東京都新宿区西新宿２丁目１番１号 新 神戸電機株式会社内 (72)発明者 小牧 昭夫 東京都新宿区西新宿２丁目１番１号 新 神戸電機株式会社内 (72)発明者 中長 偉文 徳島県徳島市川内町加賀須野463番地 大塚化学株式会社徳島研究所内 (72)発明者 谷口 正俊 徳島県徳島市川内町加賀須野463番地 大塚化学株式会社徳島研究所内 審査官 酒井 美知子 (56)参考文献 特開 昭61−74268（ＪＰ，Ａ) 特開 平２−148566（ＪＰ，Ａ) 特開 昭62−274555（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hayakawa and others ▲ Ku ▼ Beauty, 2-1-1, Nishishinjuku, Shinjuku-ku, Tokyo Shin-Kobe Electric Co., Ltd. (72) Inventor Akio Komaki 2 Nishishinjuku, Shinjuku-ku, Tokyo Chome 1-1 Shin-Kobe Electric Machinery Co., Ltd. (72) Inventor Weibun Nakabun 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd., Tokushima Laboratory (72) Inventor Masatoshi Taniguchi Kawauchi-cho, Tokushima City, Tokushima Prefecture 463 Kagasuno Otsuka Chemical Co., Ltd. Tokushima Laboratory Examiner Michiko Sakai (56) Reference JP 61-74268 (JP, A) JP 2-148566 (JP, A) JP 62-274555 (JP) , A)
Claims (2)
とする正極活物質で被覆されている、ことを特徴とする
リチウム電池。1. A lithium battery in which the surface of a porous body of a positive electrode is covered with a positive electrode active material mainly containing V 2 O 5 .nH 2 O.
ことを特徴とする請求項１記載のリチウム電池。2. The lithium battery according to claim 1, wherein the negative electrode active material of the negative electrode is Li or a Li alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333742A JP2552393B2 (en) | 1990-11-30 | 1990-11-30 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333742A JP2552393B2 (en) | 1990-11-30 | 1990-11-30 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04206343A JPH04206343A (en) | 1992-07-28 |
| JP2552393B2 true JP2552393B2 (en) | 1996-11-13 |
Family
ID=18269452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2333742A Expired - Fee Related JP2552393B2 (en) | 1990-11-30 | 1990-11-30 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2552393B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5289735B2 (en) * | 2007-08-08 | 2013-09-11 | トヨタ自動車株式会社 | Lithium secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6174268A (en) * | 1984-09-17 | 1986-04-16 | Hitachi Maxell Ltd | Lithium secondary cell |
| JPS62274555A (en) * | 1986-05-23 | 1987-11-28 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
| JPH02148566A (en) * | 1988-11-28 | 1990-06-07 | Komatsu Ltd | High polymer-coated foaming material electrode and manufacture thereof |
-
1990
- 1990-11-30 JP JP2333742A patent/JP2552393B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04206343A (en) | 1992-07-28 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |