JPS62226576A - Cylindrical liquid oxyhalogen compound-lithium battery - Google Patents
Cylindrical liquid oxyhalogen compound-lithium batteryInfo
- Publication number
- JPS62226576A JPS62226576A JP6933186A JP6933186A JPS62226576A JP S62226576 A JPS62226576 A JP S62226576A JP 6933186 A JP6933186 A JP 6933186A JP 6933186 A JP6933186 A JP 6933186A JP S62226576 A JPS62226576 A JP S62226576A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- metal
- current collector
- electrode
- nickel powder
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000006230 acetylene black Substances 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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
- H01M4/06—Electrodes for primary cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は渦巻状極板群を備えた円筒形液状オキシハロゲ
ン化物−リチウム電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a cylindrical liquid oxyhalide-lithium battery with a spiral plate group.
従来の技術
塩化チオニル−リチウム電池あるいは塩化スルフリル−
リチウム電池等の正極活物質兼電解液に液状オキシハロ
ゲン化物を用いる電池系は高エネルギー密度および高出
力電池として知られており、特に大きな作用面積を有す
る渦巻状極板群を用いた電池は、他の構成より成る電池
と比較すると大電流を取出すことができるという利点が
ある。Conventional technology Thionyl chloride - lithium battery or sulfuryl chloride -
Battery systems such as lithium batteries that use liquid oxyhalide as the positive electrode active material and electrolyte are known as high energy density and high output batteries, and batteries that use a spiral plate group with a particularly large active area are Compared to batteries of other configurations, it has the advantage of being able to draw a large amount of current.
かかる電池の正極は一般に金網あるいはエキスバンドメ
タルより成る金属集電体上にカーボンブラック、活性炭
等の多孔質炭素とポリテトラフルオロエチレン等の結着
剤との混合物を塗布することにより成っている。The positive electrode of such a battery is generally made by applying a mixture of porous carbon such as carbon black or activated carbon and a binder such as polytetrafluoroethylene onto a metal current collector made of wire mesh or expanded metal.
このような液状オキシハロゲン化物−リチウム電池の一
般的な構造は第１図に示す如くである。The general structure of such a liquid oxyhalide-lithium battery is as shown in FIG.
即ち、金属リチウムを金属集電体に３着させた負極２と
、金網あるいはエキスバンドメタルよりなる金属集電体
上にカーボンブラック、活性炭等の多孔質炭素とポリテ
トラフルオロエチレン等の結着剤との混合物を塗布して
なる正極３とをセパレータ４を介して巻回した渦巻状極
数群を円筒状金属缶１内に装填し、該金属缶１の上面開
口部を金属蓋体８により封口し、電解質（例えば、塩化
アルミニウム・・・・・・ＡｌＣｌ３．塩化リチウム・
・・・・・ＬＩ Ｃ１等）が溶解された液状オキシハロ
ゲン化物からなる電解液５を前記金属蓋体８に安全弁を
兼ねるガラスシール７を介して貫通させたパイプ状正極
端子６より注入した後、該パイプ状正極端子の上端を封
着した構造を備えている。That is, a negative electrode 2 has three metallic lithium particles deposited on a metal current collector, and a metal current collector made of wire mesh or expanded metal is coated with porous carbon such as carbon black or activated carbon and a binder such as polytetrafluoroethylene. A spiral pole group in which a positive electrode 3 coated with a mixture of Seal the cap and add an electrolyte (e.g. aluminum chloride...AlCl3. Lithium chloride...
After injecting an electrolytic solution 5 made of a liquid oxyhalide in which LI C1 etc.) is dissolved into the metal lid 8 through the pipe-shaped positive terminal 6 penetrated through the glass seal 7 which also serves as a safety valve. , has a structure in which the upper end of the pipe-shaped positive electrode terminal is sealed.
従来技術の問題点
上記渦巻状極板群構造を備えた従来の電池は以下に挙げ
る問題点を持っていた。Problems with the Prior Art The conventional batteries having the above-mentioned spiral plate group structure had the following problems.
即ち、金属集電体上に塗布された多孔質炭素と結着剤で
あるポリテトラフルオロエチレンのみの混合物からなる
正極では、多孔質炭素同士の結合力は結着剤の混合比の
みに依存していた。正極の加工性を向上させるため、可
撓性をもたせるにはポリテトラフルオロエチレンの含有
率を増加させれば良いが、多孔質炭素の含有率が減少し
、それに比例して有効反応表面積も減少するため、良好
な電池性能を（ｑることができない。逆に有効反応表面
積を増加させるために多孔質炭素の含有率を増加させれ
ば、それに反比例してポリテトラフルオロエチレンの含
有率が減少し、可撓性が欠けると同時に多孔質炭素間の
結着力が減少し、正極板からの多孔性炭素の脱落が生じ
、電池内部短絡の原因となった。また、極板巻回時に正
極が滑らかな曲面を示さず、第３図に示す如く、部分的
に屈曲し、正・負極間距離の不均一化をもたらし、その
結果、放電性能の劣化を引起こしていた。さらに、正極
板からの多孔質炭素の脱落や極板の屈曲部分発生により
セパレータが部分的に強く圧迫される結果、貯蔵中ある
いは使用時に内部短絡を起こすという欠点があった。こ
のような内部短絡は経時的変化によって生じるため、電
池製造時での検出が極めて困難であった。In other words, in a positive electrode made of a mixture of only porous carbon coated on a metal current collector and polytetrafluoroethylene as a binder, the bonding force between the porous carbons depends only on the mixing ratio of the binder. was. In order to improve the workability of the positive electrode and make it flexible, the content of polytetrafluoroethylene can be increased, but the content of porous carbon decreases, and the effective reaction surface area decreases proportionally. Therefore, good battery performance cannot be achieved. Conversely, if the content of porous carbon is increased to increase the effective reaction surface area, the content of polytetrafluoroethylene decreases inversely. However, at the same time as the flexibility was lost, the binding force between the porous carbons decreased, causing the porous carbon to fall off from the positive electrode plate, causing an internal short circuit in the battery. As shown in Figure 3, the curved surface was not smooth and was partially bent, resulting in uneven distance between the positive and negative electrodes, resulting in deterioration of discharge performance. As a result of strong local pressure on the separator due to the porous carbon falling off or the bending of the electrode plates, internal short circuits may occur during storage or use.Such internal short circuits can occur over time. This makes detection during battery manufacturing extremely difficult.
問題点を解決するための手段
本発明は負極活物質である金属リチウムから成る負極と
、主成分として多孔質炭素から成る正極とをセパレータ
を介して巻回した渦巻状極板群を備え、液状オキシハロ
ゲン化物を正極活物質兼電解液に用いる円筒形液状オキ
シハロゲン化物−リチウム電池において、前記正極中に
ニッケル粉を添加したことを特徴とするものである。Means for Solving the Problems The present invention comprises a spiral electrode plate group in which a negative electrode made of metallic lithium as a negative electrode active material and a positive electrode made of porous carbon as a main component are wound with a separator interposed therebetween. A cylindrical liquid oxyhalide-lithium battery using an oxyhalide as a positive electrode active material and electrolyte, characterized in that nickel powder is added to the positive electrode.
添加するニッケル粉と多孔性炭素との混合割合は重量比
で１＝１〜１：１０が好ましい。これ以上のｆｆ１ｆｆ
ｔ比でニッケル粉を添加すると正極中の多孔性炭素含有
層が減少し、有効反応表面積がそれに比例して減少する
ので望ましくなく、またこれ以下であると得られた正極
板が良好な可撓性を示さない。またニッケル粉の形状の
差、例えば塊状、球状、フレーク状等による正極の可撓
性への影響はない。ニッケル粉の粒径については１５０
μｍ以下が良好で、望ましくは５〜５０ｔ１１１である
。１５０μｍ以上では添加重量比をかなり大きくしない
と良好な可撓性が得られない。The mixing ratio of the nickel powder and porous carbon to be added is preferably 1=1 to 1:10 by weight. No more ff1ff
Adding nickel powder at a ratio of t is undesirable because it reduces the porous carbon-containing layer in the positive electrode, and the effective reaction surface area decreases proportionally, and below this ratio, the resulting positive electrode plate has good flexibility. Does not show gender. Furthermore, the flexibility of the positive electrode is not affected by differences in the shape of the nickel powder, such as lumps, spheres, flakes, etc. 150 for the particle size of nickel powder
The thickness is preferably 5 to 50 t111, preferably 5 to 50 t111. If the thickness is 150 μm or more, good flexibility cannot be obtained unless the addition weight ratio is considerably increased.
実 施 例 以下、本発明を実施例により説明する。Example The present invention will be explained below using examples.
先ず、アセチレンブラック７５ｉ １１％、ポリテトラ
フルオロエチレン１０重量％と、平均粒度２０μｍの形
状が球形であるニッケル粉１５重Ｍ％の混合物をニッケ
ルエキスバンドメタルの金属集電体に塗布し、良さ３５
０＋ｎｍ 、幅５０ｍｍ、厚み０．７ｍ１ｌｌの本発明
による正極３を１ｑた。負極２にはニッケル薄板（厚み
０．Ｏ５ｌｌ１ｍ ）よりなる金属集電体に金属リチウ
ムを貼り付けたものを用い、セパレータを介して前記正
極とともに巻回し、第１図に示す如き渦巻状極板群を得
た。この極板群を負極端子兼用の金属缶１に装填し、金
属缶の内部側面に負極の金属ｇＡ電体から取出したり一
ド１０を、パイプ状正極端子６の下部側面に正極の金属
集電体から取出したり一ド１１を各々溶接した。金属缶
１の上端と安全弁を兼ねるガラスシール７を有する金属
蓋体８の周縁部とをレーザ溶接した後、パイプ状正極端
子６から塩化チオニルに塩化アルミニウムと塩化リチウ
ムとを溶解した正極活物質を兼ねる電解液５を注入し、
次いでパイプ状正極端子６の最上部をレーザ溶接により
密封して電池とした。First, a mixture of 11% of acetylene black 75i, 10% by weight of polytetrafluoroethylene, and 15% by weight of nickel powder having a spherical shape with an average particle size of 20 μm was applied to a metal current collector made of nickel expanded band metal.
1 q of positive electrodes 3 according to the present invention having a width of 0+nm, a width of 50 mm, and a thickness of 0.7 ml were prepared. For the negative electrode 2, a metal current collector made of a thin nickel plate (thickness: 0.05 mm) and lithium metal pasted thereon is used, which is wound together with the positive electrode through a separator to form a spiral electrode plate group as shown in FIG. I got it. This electrode plate group is loaded into a metal can 1 which also serves as a negative electrode terminal, and a negative electrode metal gA current collector is placed on the inner side of the metal can, and one electrode 10 is placed on the lower side of the pipe-shaped positive electrode terminal 6 as a positive electrode metal current collector. The parts 11 were removed from the body and welded together. After laser welding the upper end of the metal can 1 and the peripheral edge of the metal lid 8 having the glass seal 7 which also serves as a safety valve, a positive electrode active material in which aluminum chloride and lithium chloride are dissolved in thionyl chloride is poured from the pipe-shaped positive electrode terminal 6. Inject electrolyte 5 which also serves as
Next, the uppermost part of the pipe-shaped positive electrode terminal 6 was sealed by laser welding to form a battery.
なお、１２．１３は渦巻状極板群の正型３と金属缶１と
を隔離するため、極板群の上下に配置した絶縁板である
。Incidentally, reference numerals 12 and 13 are insulating plates arranged above and below the electrode plate group in order to isolate the regular mold 3 of the spiral electrode plate group and the metal can 1.
発明の効果
本発明による正極は、従来品に比べ、機械的強度に鳴れ
、多孔質炭素の脱落が見られず、さらに良好な可撓性を
示す。この正穫板を使用し、巻回された渦巻状極板群は
第２図に示した如く滑らかな曲面を有し、極板間距離が
均一に保たれ、かつ良好な電池性能を発運する。また、
滑らかな均一曲面で渦巻状に極板が巻回されるため、正
極中の金属集電体に応力が集中することがなく、セパレ
ークを局部的に圧迫しないので、経時的に電池内部短絡
を引起こす恐れがない。Effects of the Invention The positive electrode according to the present invention has higher mechanical strength than conventional products, no shedding of porous carbon is observed, and exhibits better flexibility. Using this Seishi plate, the wound spiral electrode plate group has a smooth curved surface as shown in Figure 2, and the distance between the electrode plates is kept uniform, and good battery performance is achieved. do. Also,
Since the electrode plate is spirally wound with a smooth, uniform curved surface, stress does not concentrate on the metal current collector in the positive electrode, and the separator plate is not locally compressed, which prevents short circuits inside the battery over time. There is no risk of it happening.
上記実施例に基づき製造した本発明電池と従来の電池と
の内部短絡の有無について比較した結果を第１表に示す
。Table 1 shows the results of a comparison of the presence or absence of internal short circuits between the battery of the present invention manufactured based on the above example and a conventional battery.
第１表
次いで、試作した電池を２ケ月間室温で貯蔵し、開路電
圧の変化を経時的に調べた。塩化チオニル−リチウム電
池は室温で開路電圧３，６５ Ｖを示すが、内部短絡が
起ると、その程度に比例して開路電圧が減少するため、
この開路電圧でもって内部短絡の有無を確認した。その
結果を第２表に示す。Table 1 Next, the prototype batteries were stored at room temperature for two months, and changes in open circuit voltage were examined over time. A thionyl chloride-lithium battery exhibits an open circuit voltage of 3.65 V at room temperature, but when an internal short circuit occurs, the open circuit voltage decreases in proportion to the extent of the short circuit.
This open circuit voltage was used to check whether there was an internal short circuit. The results are shown in Table 2.
第２表
また、本発明による電池と従来の電池それぞれ５個につ
いて６Ω定抵抗負荷によって放電し、容量試験を行なっ
た結果を第４図に示す。本発明電池の容量は均一であり
、従来例と比較して、そのバラつきが小さい。本発明に
おけるニッケル粉と多孔質炭素との重量比および粒径に
ついては前述した範囲内で実施例による結果とほぼ同じ
で良好な電池性能を得た。Table 2 In addition, FIG. 4 shows the results of a capacity test performed by discharging five batteries according to the present invention and five conventional batteries under a 6Ω constant resistance load. The capacity of the battery of the present invention is uniform, and its variation is smaller than that of the conventional example. The weight ratio and particle size of nickel powder and porous carbon in the present invention were within the above-mentioned ranges, and good battery performance was obtained, which was almost the same as the results in Examples.
さらに、上記実施例では正極活物質を兼りた電解液に塩
化チオニルを使用したが、その他、塩化スルフリル、塩
化ホスフオリル等の液状′、Ａ＝１ジハロゲン化物が使
用でき、さらには二酸化イオウなどの液状のものについ
ても同様な効果を発揮する。Furthermore, although thionyl chloride was used as the electrolyte that also served as the positive electrode active material in the above example, other liquids such as sulfuryl chloride and phosphoryl chloride, A=1 dihalides, and even sulfur dioxide, etc. can be used. Similar effects can be achieved with liquids.
第１図は円筒形液状オキシハロゲン化物−リチウム電池
の断面図、第２図は本発明電池における渦巻状極板群の
断面図、第３図は従来のこの種電池における渦巻状［１
群の断面図、第４図は比較放電曲線である。
１・・・・・・今風缶体 ２・・・・・・負極３・
・・・・・正極 ４・・・・・・セパレータ５
・・・・・・電解液 ６・・・・・・正極端子片
１ 因
１人 宅 Ｗ 圏FIG. 1 is a cross-sectional view of a cylindrical liquid oxyhalide-lithium battery, FIG. 2 is a cross-sectional view of a spiral electrode group in a battery of the present invention, and FIG. 3 is a cross-sectional view of a spiral electrode group in a conventional battery of this type.
A cross-sectional view of the group, FIG. 4, is a comparative discharge curve. 1...Modern can body 2...Negative electrode 3.
...Positive electrode 4 ...Separator 5
・・・・・・Electrolyte 6・・・Positive terminal piece 1 Cause 1 person Home W Area
Claims (1)
から成る正極とをセパレータを介して巻回させた渦巻状
極板群を備え、液状オキシハロゲン化物を正極活物質兼
電解液に用いるものにおいて、前記正極中にニッケル粉
を添加たことを特徴とする円筒形液状オキシハロゲン化
物−リチウム電池。A device comprising a spiral electrode group in which a negative electrode made of metallic lithium and a positive electrode mainly made of porous carbon are wound through a separator, and a liquid oxyhalide is used as the positive electrode active material and electrolyte, A cylindrical liquid oxyhalide-lithium battery, characterized in that nickel powder is added to the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6933186A JPS62226576A (en) | 1986-03-26 | 1986-03-26 | Cylindrical liquid oxyhalogen compound-lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6933186A JPS62226576A (en) | 1986-03-26 | 1986-03-26 | Cylindrical liquid oxyhalogen compound-lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62226576A true JPS62226576A (en) | 1987-10-05 |
Family
ID=13399458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6933186A Pending JPS62226576A (en) | 1986-03-26 | 1986-03-26 | Cylindrical liquid oxyhalogen compound-lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62226576A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006012840A (en) * | 2004-06-25 | 2006-01-12 | Saft (Soc Accumulateurs Fixes Traction) Sa | Battery having cathode of carbon aerogel |
| CN105552397A (en) * | 2016-02-01 | 2016-05-04 | 宁波超霸能源有限公司 | Disposable wound product of lithium metal battery |
| CN106229527A (en) * | 2016-09-30 | 2016-12-14 | 宁波超霸能源有限公司 | Battery winding product and disposable lithium metal battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5652878A (en) * | 1979-09-24 | 1981-05-12 | Duracell Int | Chemical battery for error resistance |
-
1986
- 1986-03-26 JP JP6933186A patent/JPS62226576A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5652878A (en) * | 1979-09-24 | 1981-05-12 | Duracell Int | Chemical battery for error resistance |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006012840A (en) * | 2004-06-25 | 2006-01-12 | Saft (Soc Accumulateurs Fixes Traction) Sa | Battery having cathode of carbon aerogel |
| CN105552397A (en) * | 2016-02-01 | 2016-05-04 | 宁波超霸能源有限公司 | Disposable wound product of lithium metal battery |
| CN106229527A (en) * | 2016-09-30 | 2016-12-14 | 宁波超霸能源有限公司 | Battery winding product and disposable lithium metal battery |
| CN106229527B (en) * | 2016-09-30 | 2018-08-17 | 宁波超霸能源有限公司 | Battery winding product and disposable lithium metal battery |
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