JP2001319687A - Lithium-ion secondary battery - Google Patents
Lithium-ion secondary batteryInfo
- Publication number
- JP2001319687A JP2001319687A JP2000137002A JP2000137002A JP2001319687A JP 2001319687 A JP2001319687 A JP 2001319687A JP 2000137002 A JP2000137002 A JP 2000137002A JP 2000137002 A JP2000137002 A JP 2000137002A JP 2001319687 A JP2001319687 A JP 2001319687A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- silver
- electrode
- secondary battery
- ion secondary
- 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.)
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カーボン負極の特性劣
化を抑え、充放電容量を向上させたリチウムイオン二次
電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion secondary battery in which the deterioration of the characteristics of a carbon negative electrode is suppressed and the charge / discharge capacity is improved.
【０００２】[0002]
【従来の技術】充電により再使用可能な二次電池として
使用されているリチウムイオン二次電池は、負極にカー
ボンを、正極にコバルト酸リチウムＬｉＣｏＯ2を使用
し、有機電解液を収容している。金属の中で最も卑なリ
チウムを使用することから高い電池電圧が可能で、しか
も電気化学当量が最も小さいためエネルギー密度が高
い。このような長所を活用して、携帯用電子・通信機器
にリチウムイオン二次電池が多用されている。リチウム
イオン二次電池は、たとえば図１に示す円筒形電池で
は、帯状の正極板１と負極板２とをセパレータ３を介し
て渦巻き状に巻き、円筒形の金属容器４に収容してい
る。金属容器４に絶縁板５，ガスケット６を介して正極
端子７が取り付けられ、正極リード８で正極板１を正極
端子７に導通させている。負極板２は、負極リード９を
介して負極端子１０に導通している。また、異常発熱を
防止するＰＴＣ素子１１や非復帰式の安全弁１２によ
り、安全性を確保している。2. Description of the Related Art A lithium ion secondary battery used as a secondary battery that can be reused by charging uses carbon as a negative electrode, lithium cobalt oxide LiCoO 2 as a positive electrode, and contains an organic electrolyte. . High battery voltage is possible due to the use of the lowest lithium among metals, and the energy density is high due to the smallest electrochemical equivalent. Utilizing such advantages, lithium ion secondary batteries are widely used in portable electronic and communication devices. In the lithium ion secondary battery, for example, in the cylindrical battery shown in FIG. 1, a strip-shaped positive electrode plate 1 and a negative electrode plate 2 are spirally wound via a separator 3 and housed in a cylindrical metal container 4. A positive electrode terminal 7 is attached to the metal container 4 via an insulating plate 5 and a gasket 6, and the positive electrode lead 8 connects the positive electrode plate 1 to the positive electrode terminal 7. The negative electrode plate 2 is electrically connected to a negative electrode terminal 10 via a negative electrode lead 9. Further, safety is ensured by the PTC element 11 for preventing abnormal heat generation and the non-return type safety valve 12.
【０００３】リチウムイオン二次電池の性能を向上する
ため、従来から種々の改良が提案されているが、大半は
カーボン負極の特性改善を目的としている。たとえば、
フッ酸，炭酸等を添加してカーボン負極の表面にリチウ
ムイオン伝導性の安定皮膜を形成すると、負極の特性が
改善される。また、Ａｇ微粒子を負極表面に担持させる
湿式法（特開平８−２７３７０２号公報），Ａｇ，Ａ
ｕ，Ｚｎ，Ｐｄ，Ｓｎ等でカーボン負極の表面を覆う蒸
着等の乾式法〔J. Power Sorces, 81-82, 368 (1999),
J. Electroanal. Chem., 462 (1999)〕等によっても、
負極特性が改善される。[0003] In order to improve the performance of lithium ion secondary batteries, various improvements have been conventionally proposed, but most of them are aimed at improving the characteristics of carbon anodes. For example,
When a stable film having lithium ion conductivity is formed on the surface of the carbon negative electrode by adding hydrofluoric acid, carbonic acid, or the like, the characteristics of the negative electrode are improved. Further, a wet method of supporting Ag fine particles on the surface of the negative electrode (JP-A-8-273702), Ag, A
Dry method such as vapor deposition covering the surface of the carbon negative electrode with u, Zn, Pd, Sn, etc. [J. Power Sources, 81-82, 368 (1999),
J. Electroanal. Chem., 462 (1999)]
The negative electrode characteristics are improved.
【０００４】[0004]
【発明が解決しようとする課題】従来のコバルト酸リチ
ウムＬｉＣｏＯ2に代え、原料コスト，環境保全性，低
毒性等の点で有利なＬｉＭｎ2Ｏ4が正極物質として使用
され始めている。しかし、ＬｉＭｎ2Ｏ4正極を組み込ん
だリチウムイオン二次電池では、高温作動時に正極から
Ｍｎ成分が主にＭｎ2+となって溶出し、還元反応によっ
て負極表面に析出する。負極へのＭｎ析出は、容量低
下，抵抗増大等により電池全体の特性を劣化させる原因
となる。そこで、負極特性を改善するために、溶出した
Ｍｎ成分が負極の特性に及ぼす悪影響を抑制することが
要求される。Instead of the conventional lithium cobaltate LiCoO 2 , LiMn 2 O 4 which is advantageous in terms of raw material cost, environmental preservation, low toxicity and the like has begun to be used as a cathode material. However, in a lithium ion secondary battery incorporating a LiMn 2 O 4 positive electrode, the Mn component mainly elutes as Mn 2+ from the positive electrode during high-temperature operation and precipitates on the negative electrode surface by a reduction reaction. Mn deposition on the negative electrode causes deterioration of the characteristics of the entire battery due to a decrease in capacity, an increase in resistance, and the like. Therefore, in order to improve the negative electrode characteristics, it is required to suppress the adverse effect of the eluted Mn component on the characteristics of the negative electrode.
【０００５】[0005]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、Ｍｎよりも標準
酸化還元電位の高い金属種をイオンとして電解液，電極
等の反応場に添加し、Ｍｎ析出に優先して当該金属種を
析出させることにより、ＬｉＭｎ2Ｏ4正極から溶出する
Ｍｎ成分の悪影響を抑え、良好な負極特性を維持し、充
放電容量の劣化が少ないリチウムイオン二次電池を提供
することを目的とする。本発明のリチウムイオン二次電
池は、その目的を達成するため、ＬｉＭｎ2Ｏ4を正極物
質とし、電解液又は電極にＭｎよりも標準酸化還元電位
が高い金属種をイオンとして添加していることを特徴と
する。Ｍｎよりも標準酸化還元電位が高い金属種として
は、Ａｇ，，Ｚｎ，Ｓｎ，Ｃｕ，Ｐｔ等がある。たとえ
ば、Ａｇイオン供給源として過塩素酸銀，６フッ化リン
酸銀，４フッ化ホウ酸銀，６フッ化ヒ酸銀，硫酸銀，硝
酸銀等を電極や電解液に添加するとき、Ｍｎ析出に優先
して電解液からＡｇが負極表面に析出する。DISCLOSURE OF THE INVENTION The present invention has been devised to solve such a problem, and uses a metal species having a higher standard oxidation-reduction potential than Mn as an ion to react an electrolyte, an electrode, or the like. By adding the metal species in preference to Mn precipitation, thereby suppressing the adverse effect of the Mn component eluted from the LiMn 2 O 4 positive electrode, maintaining good negative electrode characteristics, and causing less deterioration in charge / discharge capacity. An object is to provide a lithium ion secondary battery. In order to achieve the object, the lithium ion secondary battery of the present invention uses LiMn 2 O 4 as a positive electrode material, and adds a metal species having a higher standard oxidation-reduction potential than Mn to the electrolyte or electrode as an ion. It is characterized by. Metal species having a higher standard oxidation-reduction potential than Mn include Ag, Zn, Sn, Cu, Pt, and the like. For example, when silver perchlorate, silver hexafluorophosphate, silver tetrafluoroborate, silver hexafluoroarsenate, silver sulfate, silver nitrate, or the like is added as an Ag ion supply source to an electrode or an electrolytic solution, Mn precipitates. Ag is precipitated from the electrolytic solution on the surface of the negative electrode.
【０００６】[0006]
【作用】本発明者等は、Ｍｎ2+が溶存した電解液を含む
リチウムイオン二次電池においてカーボン負極の特性が
劣化する状況を種々調査検討した。負極へのＭｎ析出
は、次の不可逆的還元反応によって生成した金属Ｍｎや
追随する副反応生成物が負極表面に堆積する現象であ
る。 Ｍｎ2+＋２ｅ-→ＭｎThe present inventors have conducted various investigations and studies on the situation where the characteristics of the carbon negative electrode deteriorate in a lithium ion secondary battery containing an electrolyte solution in which Mn 2+ is dissolved. Mn deposition on the negative electrode is a phenomenon in which metal Mn generated by the next irreversible reduction reaction and following by-products are deposited on the negative electrode surface. Mn 2+ + 2e − → Mn
【０００７】したがって、Ｍｎの不可逆的反応を抑制す
る成分を電解液，電極等の反応場に存在させると、負極
へのＭｎ析出が抑制されることが判る。このような前提
で、反応場に種々の成分を添加することにより、負極へ
のＭｎ析出に及ぼす影響を調査した。その結果、金属イ
オン添加物としてＭｎよりも標準酸化還元電位が高い、
すなわち負極で反応しやすい金属種を反応場に存在させ
ると、Ｍｎ成分の還元に先行して当該金属種が負極に析
出し、電解液に接する負極材の表面に析出物皮膜が形成
されることが判った。なかでも、電気伝導性の良好なＡ
ｇを金属種として使用すると、生成したＡｇ系皮膜によ
り電解液中のＭｎ成分から負極が保護され、しかもＡｇ
系皮膜の優れた電気伝導性によって負極内部の抵抗も低
減する。[0007] Therefore, it can be seen that when a component that suppresses the irreversible reaction of Mn is present in a reaction field such as an electrolytic solution or an electrode, Mn deposition on the negative electrode is suppressed. Under such a premise, the effect of adding various components to the reaction field on the precipitation of Mn on the negative electrode was investigated. As a result, the standard oxidation-reduction potential is higher than Mn as a metal ion additive,
That is, when a metal species that is easily reacted at the negative electrode is present in the reaction field, the metal species is deposited on the negative electrode prior to the reduction of the Mn component, and a deposit film is formed on the surface of the negative electrode material that is in contact with the electrolytic solution. I understood. Above all, A with good electric conductivity
When g is used as the metal species, the negative electrode is protected from the Mn component in the electrolytic solution by the formed Ag-based film,
The resistance inside the negative electrode is also reduced due to the excellent electrical conductivity of the system coating.
【０００８】Ａｇは、過塩素酸銀，６フッ化リン酸銀，
４フッ化ホウ酸銀，６フッ化ヒ酸銀，硫酸銀，硝酸銀等
のＡｇイオン供給源として電解液に添加される。或い
は、これら銀塩を含む正極又は負極を使用することによ
っても、反応場にＡｇイオンを存在させることができ
る。正極に含まれる銀塩は、電解液に溶出し、負極では
銀塩が共存することによりＭｎ成分の析出に先行して負
極表面にＡｇ系皮膜となって析出する。この点，従来の
Ａｇ担持負極は湿式又は乾式の前処理によって作成され
ているが、本発明ではこのような前処理を不要とし、Ａ
ｇイオンを電池内に共存させる簡便な方法を採用し、電
気化学的析出反応を利用して均一なＡｇ系皮膜を負極表
面に生成させているため、少量の添加で十分な効果が発
現される。負極表面がＡｇ系皮膜で覆われるため、Ｍｎ
成分による充放電容量の劣化がないことは勿論、Ａｇ無
添加の系に比較して充放電容量自体も向上する。これ
は、負極に皮膜として析出したＡｇが負極物質のグラフ
ァイトと層間化合物を生成することにより、電極内部の
抵抗が低減し、グラファイト材の構造が安定化すること
によるものと推察される。Ag is silver perchlorate, silver hexafluorophosphate,
Silver tetrafluoroborate, silver hexafluoroarsenate, silver sulfate, silver nitrate and the like are added to the electrolyte as a source of Ag ions. Alternatively, Ag ions can be made to exist in the reaction field by using a positive electrode or a negative electrode containing these silver salts. The silver salt contained in the positive electrode is eluted into the electrolytic solution, and in the negative electrode, due to the coexistence of the silver salt, is deposited as an Ag-based film on the negative electrode surface prior to the precipitation of the Mn component. In this regard, the conventional Ag-carrying negative electrode is prepared by wet or dry pretreatment, but the present invention does not require such pretreatment, and
A simple method of coexisting g ions in the battery is used, and a uniform Ag-based film is formed on the negative electrode surface by using an electrochemical deposition reaction. . Since the surface of the negative electrode is covered with the Ag-based coating, Mn
Not only does the charge / discharge capacity not deteriorate due to the components, but also the charge / discharge capacity itself is improved as compared with the system without the addition of Ag. This is presumed to be due to the fact that Ag deposited as a film on the negative electrode forms graphite and an intercalation compound as a negative electrode material, thereby reducing the resistance inside the electrode and stabilizing the structure of the graphite material.
【０００９】[0009]
【実施例】電解液１３に作用極１４及び対極１５を浸漬
した電池構成（図２）で、電解質が充放電特性に及ぼす
影響を調査した。プロピレンカーボネート＋エチレンカ
ーボネート（体積比１：２）混合溶媒に電解質塩として
１モル／ｄｍ3のＬｉＣｌＯ4を添加することにより電解
液１３を調製した。作用極１４は、次のように作製され
た電極を使用した。ポリビニリデンジフルオライド（結
着剤）をＮ−メチルピロリジンに溶解してグラファイト
に混合し、得られた混合物をＮｉ網の片面に塗布し、１
００℃で乾燥させた。次いで、乾燥した塗膜をプレス
し、更に８０℃で乾燥することにより板状の電極とし
た。EXAMPLE In a battery configuration (FIG. 2) in which the working electrode 14 and the counter electrode 15 were immersed in the electrolytic solution 13, the effect of the electrolyte on the charge / discharge characteristics was investigated. An electrolytic solution 13 was prepared by adding 1 mol / dm 3 LiClO 4 as an electrolyte salt to a mixed solvent of propylene carbonate and ethylene carbonate (volume ratio 1: 2). The working electrode 14 used was an electrode manufactured as follows. Polyvinylidene difluoride (binder) is dissolved in N-methylpyrrolidine and mixed with graphite, and the resulting mixture is applied to one surface of a Ni net.
Dried at 00 ° C. Next, the dried coating film was pressed and further dried at 80 ° C. to obtain a plate-like electrode.
【００１０】対極１５は、塊状リチウムから適当量取り
出した金属リチウム片をＮｉ網集電体に圧着し、エタノ
ールで表面を活性化・清浄化した後、円盤状に成形する
ことにより用意した。また、対極１５の影響を抑制しな
がら電位を測定するため、塊状リチウムから適当量取り
出した金属リチウム片をＮｉ網集電体に圧着した参照極
１６を使用した。ガラスセル１７に収容した電解液１３
を室温に保持し、作用極１４，対極１５及び参照極１６
を電解液１３に浸漬した。そして、電流密度０．１０ｍ
Ａ／ｃｍ 2，電位範囲０．０２〜１．５Ｖ vs. Ｌｉ／Ｌ
ｉ+の条件で充放電を繰り返し、一定電流密度で放電終
止電位０．０２Ｖ，充電終止電位１．５Ｖとして評価す
ることにより、サイクル数に応じた充放電特性の変化を
調査した。[0010] The counter electrode 15 is prepared by taking an appropriate amount of bulk lithium.
The metal lithium piece that was taken out was pressed against a Ni net current collector,
After activating and cleaning the surface with a tool, it is shaped into a disk
We prepared by doing. Also, do not suppress the influence of the counter electrode 15.
To measure the potential, take an appropriate amount from the bulk lithium.
Reference electrode obtained by pressing the extracted metal lithium piece to the Ni mesh current collector
16 were used. Electrolyte 13 contained in glass cell 17
Is maintained at room temperature, and the working electrode 14, the counter electrode 15 and the reference electrode 16
Was immersed in the electrolyte 13. And the current density is 0.10 m
A / cm Two, Potential range 0.02-1.5V vs. Li / L
i+The charge and discharge are repeated under the conditions
Evaluation is made with a stop potential of 0.02 V and a charge termination potential of 1.5 V.
Change the charge / discharge characteristics according to the number of cycles.
investigated.
【００１１】図３の測定結果にみられるように、Ａｇ無
添加でＭｎイオンが電解液に溶存していない系では、サ
イクル数が１０回に達した段階で放電容量が低下した。
これに対し、過塩素酸銀を電解液に添加した系では、サ
イクル数が１０回に達した段階でも放電容量の降下が相
当に小さく、放電容量自体もＡｇ無添加の場合に比較し
て１０％以上改善されていた。他方、ＬｉＭｎ2Ｏ4を正
極物質としたリチウムイオン二次電池を想定して、過塩
素酸マンガンを添加した電解液では、サイクル数の増加
に伴って放電容量が大きく低下した。ところが、過塩素
酸マンガン及び過塩素酸銀が共存する電解液では、サイ
クル数が１０回に達した段階でも放電初期に比較して放
電容量の減少度が小さく、放電容量の減少が抑制され
た。以上の結果から、電解液にＡｇイオンを存在させる
ことによって、サイクル数に伴った充放電特性の劣化が
防止されることは勿論、充放電特性自体も改善されるこ
とが確認された。As can be seen from the measurement results in FIG. 3, in the system in which Ag was not added and Mn ions were not dissolved in the electrolytic solution, the discharge capacity was reduced when the number of cycles reached 10 times.
On the other hand, in the system in which silver perchlorate was added to the electrolyte, the drop in the discharge capacity was considerably small even at the stage when the number of cycles reached 10, and the discharge capacity itself was 10 times smaller than when Ag was not added. % Was improved. On the other hand, assuming a lithium ion secondary battery using LiMn 2 O 4 as a cathode material, in an electrolyte solution to which manganese perchlorate was added, the discharge capacity was significantly reduced with an increase in the number of cycles. However, in the electrolyte in which manganese perchlorate and silver perchlorate coexist, the degree of decrease in the discharge capacity was small compared to the initial stage of the discharge even when the number of cycles reached 10, and the decrease in the discharge capacity was suppressed. . From the above results, it was confirmed that the presence of Ag ions in the electrolytic solution not only prevented the deterioration of the charge / discharge characteristics with the number of cycles, but also improved the charge / discharge characteristics themselves.
【００１２】[0012]
【発明の効果】以上に説明したように、本発明のリチウ
ムイオン二次電池は、Ａｇ等のＭｎに比較して標準酸化
還元電位の高い金属種をイオンとして電極，電解液等の
反応場に存在させることにより、ＬｉＭｎ2Ｏ4正極から
溶出するマンガン成分に起因した負極特性の劣化を抑制
している。添加したＡｇイオンは、負極表面に電気伝導
性に優れたＡｇ系皮膜を形成するため負極特性の改善も
図られる。このようにして、本発明によるとき、充放電
特性の劣化がなく、高い充放電特性を呈するリチウムイ
オン二次電池が得られる。As described above, in the lithium ion secondary battery of the present invention, a metal species having a higher standard oxidation-reduction potential as compared with Mn such as Ag is used as an ion in a reaction field of an electrode, an electrolyte or the like. The presence thereof suppresses the deterioration of the negative electrode characteristics due to the manganese component eluted from the LiMn 2 O 4 positive electrode. The added Ag ions form an Ag-based film having excellent electric conductivity on the surface of the negative electrode, so that the characteristics of the negative electrode can be improved. Thus, according to the present invention, a lithium ion secondary battery that exhibits high charge / discharge characteristics without deterioration of the charge / discharge characteristics can be obtained.
【図１】 リチウムイオン二次電池の分解斜視図FIG. 1 is an exploded perspective view of a lithium ion secondary battery.
【図２】 実施例で使用した模型電池FIG. 2 is a model battery used in Examples.
【図３】 電解液に含まれるＭｎイオン及びＡｇイオン
がグラファイト負極の充放電特性に及ぼす影響を示した
グラフFIG. 3 is a graph showing the influence of Mn ions and Ag ions contained in an electrolytic solution on charge and discharge characteristics of a graphite negative electrode.
１：正極板 ２：負極板 ３：セパレータ ４：
金属容器 １３：電解液 １４：作用極 １５：対極 １
６：参照極1: Positive electrode plate 2: Negative electrode plate 3: Separator 4:
Metal container 13: Electrolyte 14: Working electrode 15: Counter electrode 1
6: Reference electrode
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H029 AJ03 AJ05 AK03 AL06 AM03 AM05 AM07 BJ02 BJ14 DJ08 EJ03 HJ18 5H050 AA07 AA08 BA17 CA09 CB09 DA02 DA09 EA01 GA10 HA02 HA18 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H029 AJ03 AJ05 AK03 AL06 AM03 AM05 AM07 BJ02 BJ14 DJ08 EJ03 HJ18 5H050 AA07 AA08 BA17 CA09 CB09 DA02 DA09 EA01 GA10 HA02 HA18
Claims (3)
も標準酸化還元電位の高い金属種がイオンとして電解液
又は電極に添加されていることを特徴とするリチウムイ
オン二次電池。1. A lithium ion secondary battery in which LiMn 2 O 4 is used as a positive electrode material and a metal species having a higher standard oxidation-reduction potential than Mn is added to the electrolyte or the electrode as ions.
種がＡｇ，Ｚｎ，Ｓｎ，Ｃｕ，Ｐｔから選ばれた１種又
は２種以上である請求項１記載のリチウムイオン二次電
池。2. The lithium ion secondary battery according to claim 1, wherein the metal species having a higher standard oxidation-reduction potential than Mn is one or more selected from Ag, Zn, Sn, Cu, and Pt.
化ホウ酸銀，６フッ化ヒ酸銀，硫酸銀，硝酸銀から選ば
れた１種又は２種以上をＡｇイオン供給源とする請求項
２記載のリチウムイオン二次電池。3. An Ag ion source comprising one or more selected from silver perchlorate, silver hexafluorophosphate, silver tetrafluoroborate, silver hexafluoroarsenate, silver sulfate, and silver nitrate. The lithium ion secondary battery according to claim 2, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000137002A JP2001319687A (en) | 2000-05-10 | 2000-05-10 | Lithium-ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000137002A JP2001319687A (en) | 2000-05-10 | 2000-05-10 | Lithium-ion secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001319687A true JP2001319687A (en) | 2001-11-16 |
Family
ID=18644861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000137002A Pending JP2001319687A (en) | 2000-05-10 | 2000-05-10 | Lithium-ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001319687A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003217657A (en) * | 2002-01-21 | 2003-07-31 | Sony Corp | Nonaqueous electrolyte battery |
| JP2018018785A (en) * | 2016-07-29 | 2018-02-01 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| CN110429334A (en) * | 2019-07-16 | 2019-11-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte and preparation method thereof and battery |
-
2000
- 2000-05-10 JP JP2000137002A patent/JP2001319687A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003217657A (en) * | 2002-01-21 | 2003-07-31 | Sony Corp | Nonaqueous electrolyte battery |
| JP2018018785A (en) * | 2016-07-29 | 2018-02-01 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| CN110429334A (en) * | 2019-07-16 | 2019-11-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte and preparation method thereof and battery |
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