JPH0636803A - Charging of lithium secondary battery - Google Patents
Charging of lithium secondary batteryInfo
- Publication number
- JPH0636803A JPH0636803A JP4213796A JP21379692A JPH0636803A JP H0636803 A JPH0636803 A JP H0636803A JP 4213796 A JP4213796 A JP 4213796A JP 21379692 A JP21379692 A JP 21379692A JP H0636803 A JPH0636803 A JP H0636803A
- Authority
- JP
- Japan
- Prior art keywords
- charging
- secondary battery
- negative electrode
- electromotive force
- pulse current
- 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
-
- 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
【０００１】[0001]
【産業上の利用分野】本発明は、金属リチウムを負極と
する高起電力のＬi二次電池に対してパルス電流方式で
充電する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of charging a high-electromotive force Li secondary battery having metallic lithium as a negative electrode by a pulse current method.
【０００２】[0002]
【従来の技術】有機電解液を用いてなるＬi二次電池に
おいて、起電力の点よりは金属リチウムによる負極形成
が有利であることが知られているが、一定電流を連続通
電する従来の充電方法では充電不良を誘発して繰り返し
充電できないため実用には至っておらず、起電力の低下
を受容しつつ充電不良を生じないリチウム合金や層間化
合物、多孔質体を負極に用いたものが実用されている。2. Description of the Related Art In a Li secondary battery using an organic electrolyte, it is known that formation of a negative electrode using metallic lithium is advantageous from the viewpoint of electromotive force. In the method, it has not been put into practical use because it induces charging failure and cannot be repeatedly charged.Therefore, a lithium alloy or intercalation compound that does not cause charging failure while accepting a decrease in electromotive force, and one that uses a porous body as a negative electrode is practically used. ing.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、金属リチウ
ムを負極に用いた高起電力のＬi二次電池の実用化を目
的に、充電を繰り返しても充電不良を生じない充電方法
の開発を課題とする。SUMMARY OF THE INVENTION The present invention aims to develop a charging method that does not cause charging failure even if charging is repeated for the purpose of putting a Li secondary battery of high electromotive force using metallic lithium as a negative electrode into practical use. It is an issue.
【０００４】[0004]
【課題を解決するための手段】本発明は、金属リチウム
を負極とするＬi二次電池に対し、その正負極を介して
通電・停止を繰り返すパルス電流方式で充電することを
特徴とするＬi二次電池の充電方法を提供するものであ
る。The present invention is characterized in that a Li secondary battery having metallic lithium as a negative electrode is charged by a pulse current system in which energization / stopping is repeated through the positive and negative electrodes. A method of charging a secondary battery is provided.
【０００５】[0005]
【作用】本発明者らは、負極に金属リチウムを用いたＬ
i二次電池を実用化するために鋭意研究を重ねる中でデ
ンドライトの成長が充電不良の誘発原因であることを究
明し、さらに研究を重ねてパルス電流による充電方式に
より充電不良を克服できることを見出した。すなわち通
電・停止を繰り返すパルス電流方式で充電することによ
りデンドライトの成長を防止でき、充電不良を生じずに
繰り返し充電できて負極に金属リチウムを用いた高起電
力のＬi二次電池の実用化が可能になる。The present inventors have found that L using metallic lithium for the negative electrode.
i As a result of intensive research to put the secondary battery into practical use, it was clarified that the growth of dendrites was the cause of charging failure, and further research was conducted to find that charging failure by pulse current could overcome charging failure. It was That is, it is possible to prevent the growth of dendrites by charging with a pulse current method that repeats energizing / stopping, and it is possible to commercialize a Li secondary battery with high electromotive force that uses lithium metal as a negative electrode and that can be repeatedly charged without causing defective charging. It will be possible.
【０００６】前記においてパルス電流充電方式による充
電不良の解消機構の詳細は不明であるが、デンドライト
は充電時の通電で電池形成成分が結晶化して電析初期に
は針状結晶物として成長するものと考えられが、パルス
充電による通電の停止でデンドライトが成長する濃度に
低下する前に拡散層の成長が停止し、次の通電までに濃
度が均一化されて拡散層が消失し、これが充電のパルス
毎に繰り返されるためデンドライトが成長しないものと
考えられる。Although the details of the mechanism for eliminating the charging failure by the pulse current charging method are not clear, the dendrite grows as a needle-shaped crystalline substance at the initial stage of electrodeposition due to crystallization of the battery-forming component due to energization during charging. It is thought that the growth of the diffusion layer stops before the concentration of dendrite grows to a low level due to the stoppage of energization due to pulse charging, the concentration is made uniform by the next energization, and the diffusion layer disappears. It is considered that the dendrite does not grow because it is repeated every pulse.
【０００７】[0007]
【実施例】本発明は、電池の正負極を介して通電・停止
を繰り返すパルス電流方式により、負極に金属リチウム
を用いた高起電力のＬi二次電池に対し充電するもので
ある。充電対象のＬi二次電池としては、負極を金属リ
チウムで形成したものであるほかは特に限定はなく、有
機電解液を用いて従来に準じて形成したものであってよ
い。EXAMPLE The present invention is for charging a high-electromotive force Li secondary battery using metallic lithium for the negative electrode by a pulse current method in which energization / stopping is repeated via the positive and negative electrodes of the battery. The Li secondary battery to be charged is not particularly limited except that the negative electrode is made of metallic lithium, and may be formed conventionally using an organic electrolytic solution.
【０００８】充電は、適宜なパルス電源を用いて行うこ
とができ、充電の電圧や電流等については従来に準じる
ことができる。パルス電流の一般的な通電条件は、通電
時間０．１〜１０ｍＳ、停止時間０．５〜１００ｍＳで
ある。Charging can be performed using an appropriate pulse power source, and the charging voltage, current, etc. can be in accordance with the conventional one. General energization conditions of the pulse current are energization time of 0.1 to 10 mS and stop time of 0.5 to 100 mS.
【０００９】実施例１ セパレータにガラスフィルターを用いてＬiＣoＯ2／Ｐ
Ｃ＋ＬiＣlＯ4（１Ｍ）／Ｌiからなるセルを形成し、こ
のＬi二次電池に図１の如きパルス電流を供給して充電
する操作を繰り返してサイクル特性を調べた。測定は、
充放電測定装置（北斗電工社製）を用いて、通電時間１
ｍＳ、停止時間３ｍＳ、充電電流１ｍＡ、充電時間２０
０分間とした。なお電極面積は正負極共に２cm2とし
た。Example 1 LiCoO 2 / P using a glass filter as a separator
A cell composed of C + LiClO 4 (1M) / Li was formed, and the cycle characteristics were examined by repeating the operation of supplying a pulse current as shown in FIG. 1 to the Li secondary battery to charge it. The measurement is
Using a charge / discharge measuring device (manufactured by Hokuto Denko), energizing time 1
mS, stop time 3 mS, charging current 1 mA, charging time 20
It was set to 0 minutes. The electrode area was 2 cm 2 for both positive and negative electrodes.
【００１０】実施例２ 通電時間２ｍＳ、停止時間２ｍＳ、充電電流４ｍＡ、充
電時間１００分間としたほかは実施例１に準じてサイク
ル特性を調べた。Example 2 The cycle characteristics were examined according to Example 1 except that the energization time was 2 mS, the stop time was 2 mS, the charging current was 4 mA, and the charging time was 100 minutes.
【００１１】比較例１ 実施例１と同じ構成のＬi二次電池に充電電流１ｍＡで
５０分間連続して充電する操作（充電電気量は実施例１
と同じ）を繰り返して前記に準じサイクル特性を調べ
た。Comparative Example 1 An operation of continuously charging a Li secondary battery having the same structure as that of Example 1 at a charging current of 1 mA for 50 minutes (the amount of charged electricity was measured in Example 1).
The same as the above) was repeated and the cycle characteristics were examined according to the above.
【００１２】比較例２ 充電電流を４ｍＡとしたほかは比較例１に準じてサイク
ル特性を調べた。Comparative Example 2 The cycle characteristics were examined according to Comparative Example 1 except that the charging current was 4 mA.
【００１３】実施例、比較例でのサイクル特性評価にお
ける各回の充放電効率を表１に示した。Table 1 shows the charging / discharging efficiencies for each cycle in the cycle characteristic evaluation in Examples and Comparative Examples.
【表１】 [Table 1]
【００１４】表１より、比較例１の連続充電方式では２
１サイクル目から充放電効率が徐々に低下しはじめて２
５サイクル目で急激に低下するが、実施例のパルス電流
による充電方式では２５サイクル目でも８６％ないし８
４％の充放電効率を示し、充放電効率の低下の程度が非
常に緩やかで２５サイクルを超えても良好な充放電効率
を示した。なお比較例２では、１サイクルにてデンドラ
イトによる短絡トラブルが発生して充電不能となった。From Table 1, in the continuous charging method of Comparative Example 1, 2
Charging and discharging efficiency started to decrease gradually from the first cycle. 2
It sharply drops at the 5th cycle, but in the charging system by the pulse current of the embodiment, 86% to 8% even at the 25th cycle.
The charge and discharge efficiency was 4%, and the degree of decrease in the charge and discharge efficiency was extremely gentle, and the good charge and discharge efficiency was exhibited even after 25 cycles. In Comparative Example 2, short-circuit trouble due to dendrite occurred in one cycle and charging was impossible.
【００１５】[0015]
【発明の効果】本発明によれば、負極に金属リチウムを
用いた高起電力のＬi二次電池に対して充電不良を生じ
ることなく充電を多数回繰り返すことができる。According to the present invention, a high-electromotive force Li secondary battery using metallic lithium as a negative electrode can be charged many times without causing a charging failure.
【図１】実施例１におけるパルス電流による充電を示し
たグラフFIG. 1 is a graph showing charging by pulse current in Example 1.
Claims (1)
に対し、その正負極を介して通電・停止を繰り返すパル
ス電流方式で充電することを特徴とするＬi二次電池の
充電方法。1. A method for charging a Li secondary battery, which comprises charging a Li secondary battery using metal lithium as a negative electrode by a pulse current method in which energization / stopping is repeated via the positive and negative electrodes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4213796A JPH0636803A (en) | 1992-07-17 | 1992-07-17 | Charging of lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4213796A JPH0636803A (en) | 1992-07-17 | 1992-07-17 | Charging of lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0636803A true JPH0636803A (en) | 1994-02-10 |
Family
ID=16645196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4213796A Pending JPH0636803A (en) | 1992-07-17 | 1992-07-17 | Charging of lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0636803A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6377030B1 (en) | 1998-07-31 | 2002-04-23 | Canon Kabushiki Kaisha | Method of charging secondary battery by varying current or voltage at an inflection point in a storage region before full charge and device therefor |
| CN100369351C (en) * | 2005-07-01 | 2008-02-13 | 刘卫国 | Combined pulse charging method and apparatus |
| WO2009090913A1 (en) | 2008-01-14 | 2009-07-23 | Toyota Jidosha Kabushiki Kaisha | Lithium ion secondary cell charge method and hybrid vehicle |
| JP2009181907A (en) * | 2008-01-31 | 2009-08-13 | Toyota Motor Corp | Charging method and charging system for lithium-ion secondary battery |
| US7777452B2 (en) | 2002-11-19 | 2010-08-17 | Nec Corporation | Lithium ion secondary battery system, and method for operating lithium ion secondary battery |
| JP2017152356A (en) * | 2016-02-23 | 2017-08-31 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Charging method for lithium ion battery |
| CN107146918A (en) * | 2017-06-26 | 2017-09-08 | 浙江大学 | A kind of pulse charge method applied to lithium metal battery |
-
1992
- 1992-07-17 JP JP4213796A patent/JPH0636803A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6377030B1 (en) | 1998-07-31 | 2002-04-23 | Canon Kabushiki Kaisha | Method of charging secondary battery by varying current or voltage at an inflection point in a storage region before full charge and device therefor |
| US7777452B2 (en) | 2002-11-19 | 2010-08-17 | Nec Corporation | Lithium ion secondary battery system, and method for operating lithium ion secondary battery |
| US8022673B2 (en) | 2002-11-19 | 2011-09-20 | Nec Corporation | Lithium ion secondary battery system, and method for operating lithium ion secondary battery |
| CN100369351C (en) * | 2005-07-01 | 2008-02-13 | 刘卫国 | Combined pulse charging method and apparatus |
| WO2009090913A1 (en) | 2008-01-14 | 2009-07-23 | Toyota Jidosha Kabushiki Kaisha | Lithium ion secondary cell charge method and hybrid vehicle |
| US8310198B2 (en) | 2008-01-14 | 2012-11-13 | Toyota Jidosha Kabushiki Kaisha | Lithium ion secondary cell charge method and hybrid vehicle |
| JP2009181907A (en) * | 2008-01-31 | 2009-08-13 | Toyota Motor Corp | Charging method and charging system for lithium-ion secondary battery |
| JP2017152356A (en) * | 2016-02-23 | 2017-08-31 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Charging method for lithium ion battery |
| CN107146918A (en) * | 2017-06-26 | 2017-09-08 | 浙江大学 | A kind of pulse charge method applied to lithium metal battery |
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