JPS58206063A - Battery - Google Patents
BatteryInfo
- Publication number
- JPS58206063A JPS58206063A JP57090205A JP9020582A JPS58206063A JP S58206063 A JPS58206063 A JP S58206063A JP 57090205 A JP57090205 A JP 57090205A JP 9020582 A JP9020582 A JP 9020582A JP S58206063 A JPS58206063 A JP S58206063A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- active mass
- compound
- mixture
- positive electrode
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
【発明の詳細な説明】
本発明は小型にして放電容黄の大きい一次及び二次電池
に関し、更に詳細にはリチウムを負極活物質として用い
る電池に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to primary and secondary batteries that are small in size and have a large discharge capacity, and more particularly to a battery that uses lithium as a negative electrode active material.
従来からリチウムを負極活物質として用いる亮エネルギ
ー密蜜電池に関する提案は多くなされており、例えば、
正極活、物質として、Ｂｒｌ及びＩ。Many proposals have been made for high energy dense batteries that use lithium as the negative electrode active material, for example,
Brl and I as positive electrode active materials.
等のようなハロゲ７、ＣｕＦ、 、ＡｆＦｌ 、ＡｆＦ
。Halogens such as 7, CuF, , AfFl, AfF
.
Ｎ１ＲｌＣｕＣ１４、ＡｆＣ４ＮｉＣ４、ＣｏＦ＠、Ｃ
ｒＦｓ、ＭｎＦ１％ ５ｂＦｓ 、ＣｄＦｔ 、ＡＢＦ
ｓ％ ＨグＦ、、ＣｕＢｒ。N1RlCuC14, AfC4NiC4, CoF@, C
rFs, MnF1% 5bFs, CdFt, ABF
s% HgF,,CuBr.
Ｃｄ（４、Ｐｂ（、！を及びＣｏＣ４等のような金属ハ
ロゲン化物、ＡｆＳＣＮ、 ＣｕＳＣＮ 及びＮｉ
（ＳＣＮｅｔ 等のような金属ロダン化゛吻、Ｍｎ０
ｔ 、ＣｒｙＯ３、ｖ、 ０１％ ５ｎ０２、Ｐｂ０ｔ
、’ｒｔｏ、、Ｂｉｔ Ｏｎ、Ｃｒｙｓ 、Ｆｅｓ ０
４ 、ＮｉへＡｆｔ、Ｈｆ０１Ｃｕ！０１ＣｕＯ１Ａｒ
ｔ ＷＯ４等のような金属酸化物、ＮｉＳｘ、Ａ１Ｂｓ
、ＣｕＢ５． Ｐｂ鵞Ｂｔ Ｓｓ 及びＭｎＢ、Ｓ、
等のような金属硫化物、ＴｉＳ２ 、Ｎｂ５ｅｔ 及
び、ＷＳ、 等のような層状化合物、フッ化黒鉛、更
にはベンゾキノン類、５ＯＣ４及びｓｏ＊ｃ１４ 等の
ようなオキシバ２イド等を用いた電池が提案されている
。そして具体的には、例えば、正極活物質として黒鉛及
びフッ素のインターカレーション化合物、負錐活吻質と
してリチウム金属をそｉｔそれ使用したｔに池が知られ
ており（米国特許第３，５１４，３３７号明細書参照）
、父、フッ化黒鉛を正極活→勿實としたリチウム電池（
松下五器社製）及び二酸化マンガンを正極活物質とした
リチウム電池（三洋電機社型）が鼾に市販されている。Cd(4, Pb(,!) and metal halides such as CoC4, AfSCN, CuSCN and Ni
(Metal Rodanization like SCNet etc., Mn0
t, CryO3,v, 01% 5n02, Pb0t
,'rto,,Bit On,Crys,Fes 0
4, Aft to Ni, Hf01Cu! 01CuO1Ar
t Metal oxides such as WO4, NiSx, A1Bs
, CuB5. Pb, Bt, Ss and MnB,S,
Batteries using metal sulfides such as TiS2, Nb5et and WS, layered compounds such as fluorinated graphite, benzoquinones, oxybide such as 5OC4 and so*c14, etc. have been proposed. has been done. Specifically, for example, it is known that an intercalation compound of graphite and fluorine is used as a positive electrode active material, and lithium metal is used as a negative electrode active material (U.S. Pat. No. 3,514 (See specification No. 337)
, my father, a lithium battery with graphite fluoride as the active cathode (
Lithium batteries (manufactured by Matsushita Goki Co., Ltd.) and lithium batteries (manufactured by Sanyo Electric Co., Ltd.) using manganese dioxide as the positive electrode active material are commercially available.
しかしながら、これらの電池はその電池特性から必ずし
４十分であるとはいえなかった。又Ｖｔ Ｏｓを用いる
′べ池についてもすでに知られているが（Ｗ、Ｂ、Ｅｂ
ｎｅｒａｎｄ Ｗ、 Ｃ，Ｍｅｒｚ、 Ｒｏｅ ２８ｔ
ｈ Ｐｏｗｅｒ ＳｏｕｒｓｅｓＳｙｍｐｏ：＋ Ｊｕ
ｎｅ １９７８． Ｐ２１４）Ｖｌ！ ０！ｌは導電率
が低く充分なカノード特性を得るには至っていなかった
。However, these batteries could not necessarily be said to be 4-sufficient due to their battery characteristics. Also, it is already known about the 'base pond using VtOs (W, B, Eb
nerand W, C, Merz, Roe 28t
h Power SourcesSympo:+Ju
ne 1978. P214) Vl! 0! 1 had low conductivity and was not able to obtain sufficient cathode characteristics.
本発明は、このような現状Ｋｆｉみてなされた本のであ
り、その目的は小型にして優れた特性を有する二次電池
を提供することでおる。The present invention was developed in view of the current state of KFI, and its purpose is to provide a compact secondary battery with excellent characteristics.
本発明につき概説すれば、本発明の二次ｗ１池は正極活
物質は、ＷＯ，とＶｖ Ｏｓの同溶体である（ ＷｘＶ
ｌ−１） ｚ Ｏｓ （ただし、０ （ｘ （０，５
）化合物であり、負ｑｉ、活物質は該正′−活４７質及
びリチウムに対し化学的に安ポであシかっリチウムイオ
ンが該正極活・勿質と電気化学反応をする丸めの移動を
行なう物質であることを、′Ｖ！ｊ徴とするものである
。To summarize the present invention, in the secondary w1 pond of the present invention, the positive electrode active material is an isosolution of WO and VvOs (WxV
l-1) z Os (However, 0 (x (0,5
) compound, negative qi, the active material is chemically reactive with respect to the positive electrode active material and lithium, and the lithium ions undergo an electrochemical reaction with the positive electrode active material and lithium. 'V! It is a characteristic of J.
本発明による電池の正極活物質は前述のＷＯ５と′ｖ！
への固溶体である（ＷｘＶｌ−１）１０ｇ （ただし
、０＜Ｘ＜０．５）である。本発明によれば、従来、正
極活物質として知られていたＶ、 Ｏ，のＶを６価のＷ
で置換することにより、導電率を改良すると共に、よシ
イオン半径の大きいＷでＶを置換することにより構造に
歪みを与え、Ｌｉ とのトポケミカルな反応を容易にし
、これにより、充放電特性を改良したのである。The positive electrode active materials of the battery according to the present invention are the above-mentioned WO5 and 'v!
(WxVl-1) is a solid solution of 10g (0<X<0.5). According to the present invention, V, O, which has been conventionally known as a positive electrode active material, can be replaced with hexavalent W.
By replacing V with Li, the conductivity is improved, and by replacing V with W, which has a large ionic radius, it distorts the structure and facilitates the topochemical reaction with Li, thereby improving the charge-discharge characteristics. That's what I did.
上記の弐において、Ｘが固溶限界である０、５以−上と
なると、混合相となってしまい放電直圧が下がり、サイ
クル寿命が低下する。In the above 2, when X exceeds the solid solubility limit of 0.5, the mixture becomes a mixed phase, which lowers the direct discharge pressure and shortens the cycle life.
本発明における正極活物質としての上記（’ＷｘＶｓ−
１）冨Ｏ曝（０（ｘ（０，ｓ ）化合物を正極として使
用する場合、正極はこれらの化合物の粉末又はこれと結
合剤粉末との混合物をニッケル、＠等の支持体上に膜状
に圧着成形するか又はこれらの化合物粉末に導電性を付
与するための炭素粉末を混合し、この混合物を金属容器
に入れ、或いは前ｉ［、混合物を結合剤溶液と混合して
ニッケル、鋼等の支持体上に塗布、乾燥して膜状に成形
する等の手段により形成される。The above ('WxVs-
1) When using a 0(x(0,s) compound as a positive electrode, the positive electrode is prepared by coating a powder of these compounds or a mixture of this with a binder powder in the form of a film on a support such as nickel or @). or by mixing these compound powders with carbon powder for imparting conductivity, and placing this mixture in a metal container, or by mixing the mixture with a binder solution and molding it with nickel, steel, etc. It is formed by means such as coating it on a support, drying it, and forming it into a film.
負極活）物質であるリチウムは一般のリチウム電池のそ
れと同様にシート状として、又はそのシートまニッケル
又は鋼の網に圧着して負傷として形成される。Lithium, which is the negative electrode active material, is formed in the form of a sheet, similar to that of a general lithium battery, or as a wound by pressing the sheet onto a nickel or steel mesh.
電解質として（ｒま、グロピレンカーボネー÷、エチレ
ンカーボネート、ｒ−ブチロラクトン、ジメチルスルホ
キシド、アセトニトリル、ホルムアミド、ジメチルホル
ムアミド、ニトロメタン等の非プロトン性仔機溶媒とＬ
ｉ Ｃｔｅａ、ＬｉＡｔＣム、ＬｉＢＦいＬｉＣｔ
等のリチウム塩との組合せ又はＬｉ“ を伝導体とする
同体電解質吠いは溶融塩など、一般にリチウムを負極活
物質として用いた電池で使用される暁知の第解質を用い
ることが出来る。As an electrolyte (r, glopylene carbonate, ethylene carbonate, r-butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethylformamide, nitromethane, and other aprotic secondary solvents and L
i Ctea, LiAtCmu, LiBFi LiCt
It is possible to use a combination with a lithium salt such as a lithium salt, or a molten salt of an isoelectrolyte using Li as a conductor.
又電池構成上、必要ならば多孔質のポリプロピレン等よ
りなる隔膜を使用しても良い。Furthermore, if necessary due to the battery structure, a diaphragm made of porous polypropylene or the like may be used.
次に本発明を実施例により説明するが、本発明はこれら
によりなんら限定されるものではない。EXAMPLES Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way.
なお、１実施例において電池作製は全て乾燥アルゴンガ
ス雰囲気下で行った。In addition, in one example, all battery preparations were performed under a dry argon gas atmosphere.
実施例１
第１図は、本発明の一具体例であるボタン型電池の構成
を示した断面概略図であり、１はステンレズ製容器、２
はリチウム負極、３は多孔質ポリプロピレン製隔膜、４
はカーボン繊維よりなるフェルト、５は正極合剤、６は
ナイロン製パツキンを示す。図面に示した電池構成によ
り電池を作製した。電池セルの直径は２０ ｍｍ 、高
さは４ｍｍとした。電解液としては、蒸留脱水プロピレ
ンカーボネートに溶解した脱水Ｌ ｉ ＣＬＯａ の
１モル／を溶液を用い、隔膜３及びカーボン繊維よりな
るフェルト４に含浸させて使用した。Example 1 FIG. 1 is a schematic cross-sectional view showing the structure of a button-type battery that is a specific example of the present invention, in which 1 is a stainless steel container, 2 is a stainless steel container, and 2 is a stainless steel container.
is a lithium negative electrode, 3 is a porous polypropylene diaphragm, 4 is
5 indicates a felt made of carbon fiber, 5 indicates a positive electrode mixture, and 6 indicates a nylon packing. A battery was manufactured using the battery configuration shown in the drawings. The battery cell had a diameter of 20 mm and a height of 4 mm. As the electrolytic solution, 1 mol/mol of dehydrated Li CLOa dissolved in distilled dehydrated propylene carbonate was used by impregnating the diaphragm 3 and the felt 4 made of carbon fiber.
正極合剤５は、０．２２の（Ｗｏ、１Ｖｏ、＊ ） ｔ
Ｏｓ （ｘ＝ｏ、ｉ）粉末と０．１ｆのアセチレン
ブラックを上記電解液と混合して形成した。多孔質ポリ
プロピレン製隔膜３をはさんでリチウムシートをリチウ
ム負極２として用いた。この様にして作製した電池の開
路電圧は３．５ｖであった。０．３２ ｍＡ／ｃｓｆで
定電流放電を行った結果を第２図に示す。電圧が１■に
なるまでの平均起電力は２．６５Ｖ、同じく放電容員密
＃＃′ｉ２６０ Ａｂ／ＩＣｔ、 エネルギ密度は６
８０ Ｗｈ／に９であった。The positive electrode mixture 5 has a (Wo, 1Vo, *)t of 0.22.
It was formed by mixing Os (x=o, i) powder and 0.1f acetylene black with the above electrolyte. A lithium sheet was used as the lithium negative electrode 2 with a porous polypropylene diaphragm 3 in between. The open circuit voltage of the battery thus produced was 3.5V. Figure 2 shows the results of constant current discharge at 0.32 mA/csf. The average electromotive force until the voltage becomes 1■ is 2.65V, the discharge capacity density is ##'i260 Ab/ICt, and the energy density is 6.
It was 9 to 80 Wh/.
次に充放電特性の結果を第３図に示す。正極合剤は前述
の定電流放電の場合と同様（Ｗｎ、Ｉｖｏ、＊ ）＊Ｏ
５の粉末０．２ｆと０．１１のアセチレンブラックを混
合したものであり、他の電池構成も全て前と同じ条件で
作製した。第３図は０．３２ ｍＡ／ｃｄで３０時間放
電した後３時間休止し、０．３２ ｍＡ／ｃＩＩで３０
時間充電した後３時間休止し、その後放電を再び行うと
いう繰返しを行った結果を２０回目まで示したものであ
り（Ｗｏ、Ｉ ＶＯ，Ｉ ）ｚ Ｏｓ は充電可能な正
極活剤である。Next, the results of charge and discharge characteristics are shown in FIG. The positive electrode mixture is the same as in the case of constant current discharge described above (Wn, Ivo, *) *O
The battery was prepared by mixing 0.2f of powder No. 5 and acetylene black of 0.11, and all other battery configurations were made under the same conditions as before. Figure 3 shows that after 30 hours of discharge at 0.32 mA/cd, a 3-hour pause, and 30 hours of discharge at 0.32 mA/cII.
The results are shown for the 20th time after charging for 3 hours, stopping for 3 hours, and then discharging again. (Wo, I VO, I ) z Os is a rechargeable positive electrode active agent.
ｑ〜＋Ｏ，けＷＯｌとＶｔ Ｏｓをうけ定量秤歇した後
アセトン中で混合し、６５０℃で２４時間空気中で焼成
した本のを用いた。＠成した試料は粉末Ｘ線回折法によ
って単相であることを確認した。A book was used which had been subjected to quantitative weighing of q~+O,ke WOL and VtOs, mixed in acetone, and baked in air at 650°C for 24 hours. The prepared sample was confirmed to be single-phase by powder X-ray diffraction method.
実施例２
実施例１と同様の条件下で（ＷｘＶｔ−ｘ ）ｔ Ｏｓ
のＸを種々変えた正極合剤を用いて、第１図に示した電
池を作製した場合の放電曲線をｘ＝０．０１、ｘ−０，
３、ｘ ＝ ０．５ （参考）について第２図に示す。Example 2 Under the same conditions as Example 1 (WxVt-x)tOs
The discharge curves when the battery shown in FIG. 1 was prepared using positive electrode mixtures with various X values of
3, x = 0.5 (reference) is shown in Figure 2.
又下記の第１表にその放電容量、エネルギ密度及び充放
電回数を示す。Further, Table 1 below shows the discharge capacity, energy density, and number of charging/discharging cycles.
（以下余白）
参考であるＸ ＝ ０．５ を除いていずれの場合４
工ネルギ密度が高くしかもサイクルライフの長い二次電
池を得ることが出来る。(Left below) 4 in all cases except for X = 0.5 for reference
A secondary battery with high energy density and long cycle life can be obtained.
以上の説明から明らかなように、本発明の電池は起電力
及び放電容量の大きい小型、鳩エネルギ密度の電池とし
て種々の分野に使用出来るという利点を有するものであ
る。As is clear from the above description, the battery of the present invention has the advantage that it can be used in various fields as a compact battery with high electromotive force and discharge capacity, and a high energy density.
、第１図は本発明の一具体例であるボタ／型電池の構成
を示しだ断面機略図、第２図は本発明の各実施例におけ
る電池の放電時間と電圧との関係を示したグラフ、第３
図は（曳、１ ｖ、、、 ）ｔ Ｏｓ を正極活物質
として用いた電池の充放電サイクル特性を示したもので
ある。
１・・・ステンレス製容器、２・・・リチウム負極、３
・・・多孔質ポリプロピレン製隔膜、４・・・カーボン
繊維よシなるフェルト、５・・・正極合剤、６・・・ナ
イロン製パツキン。, FIG. 1 is a cross-sectional schematic diagram showing the structure of a button/type battery that is a specific example of the present invention, and FIG. 2 is a graph showing the relationship between battery discharge time and voltage in each embodiment of the present invention. , 3rd
The figure shows the charge/discharge cycle characteristics of a battery using tOs as the positive electrode active material. 1... Stainless steel container, 2... Lithium negative electrode, 3
... Porous polypropylene diaphragm, 4... Carbon fiber felt, 5... Positive electrode mixture, 6... Nylon packing.
Claims (1)
、 ｓ） という組成を有する化合物であり、負債活物
質はリチウムであり電解質物質は正極活物質及びリチウ
ムに対し化学的に安定でありかつリチウムイオンが正極
活物質と電気的反応をするための移動を行なう物質であ
ることを特徴とする充放電可能な電池。The positive electrode active material is (WxVt-7)t Os (0<X<o
, s), the debt active material is lithium, the electrolyte material is chemically stable with respect to the positive electrode active material and lithium, and the lithium ions are capable of moving for electrical reaction with the positive electrode active material. A chargeable and dischargeable battery characterized by being a substance that performs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57090205A JPS58206063A (en) | 1982-05-27 | 1982-05-27 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57090205A JPS58206063A (en) | 1982-05-27 | 1982-05-27 | Battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58206063A true JPS58206063A (en) | 1983-12-01 |
Family
ID=13991982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57090205A Pending JPS58206063A (en) | 1982-05-27 | 1982-05-27 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58206063A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61206168A (en) * | 1985-03-11 | 1986-09-12 | Nippon Telegr & Teleph Corp <Ntt> | Lithium secondary battery |
| JPS61206167A (en) * | 1985-03-11 | 1986-09-12 | Nippon Telegr & Teleph Corp <Ntt> | Lithium secondary battery |
| FR2615657A1 (en) * | 1987-05-19 | 1988-11-25 | Bridgestone Corp | NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512675A (en) * | 1978-07-12 | 1980-01-29 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
-
1982
- 1982-05-27 JP JP57090205A patent/JPS58206063A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512675A (en) * | 1978-07-12 | 1980-01-29 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61206168A (en) * | 1985-03-11 | 1986-09-12 | Nippon Telegr & Teleph Corp <Ntt> | Lithium secondary battery |
| JPS61206167A (en) * | 1985-03-11 | 1986-09-12 | Nippon Telegr & Teleph Corp <Ntt> | Lithium secondary battery |
| JPH0456428B2 (en) * | 1985-03-11 | 1992-09-08 | Nippon Telegraph & Telephone | |
| JPH0467751B2 (en) * | 1985-03-11 | 1992-10-29 | Nippon Telegraph & Telephone | |
| FR2615657A1 (en) * | 1987-05-19 | 1988-11-25 | Bridgestone Corp | NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
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