JP3188033B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary batteryInfo
- Publication number
- JP3188033B2 JP3188033B2 JP10052293A JP10052293A JP3188033B2 JP 3188033 B2 JP3188033 B2 JP 3188033B2 JP 10052293 A JP10052293 A JP 10052293A JP 10052293 A JP10052293 A JP 10052293A JP 3188033 B2 JP3188033 B2 JP 3188033B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- powder
- particle size
- present
- negative 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.)
- Expired - Lifetime
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
【０００１】[0001]
【産業上の利用分野】本発明は、非水系二次電池に係わ
り、詳しくは負極材料として黒鉛粉末を使用した非水系
二次電池の当該黒鉛粉末の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery, and more particularly to an improvement of a non-aqueous secondary battery using graphite powder as a negative electrode material.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
黒鉛粉末が、可撓性に優れること、樹枝状の電析リチウ
ムの成長に因る内部短絡の虞れが無いことなどの理由か
ら、従前の金属リチウムに代わる非水系二次電池用負極
材料として提案されている。2. Description of the Related Art In recent years,
Graphite powder is excellent in flexibility, because there is no risk of internal short-circuit due to the growth of dendritic lithium, as a negative electrode material for non-aqueous secondary batteries to replace conventional metallic lithium Proposed.
【０００３】而して、従来、平均粒径１０〜３０μｍ程
度に粉砕された黒鉛粉末が使用されているが、この黒鉛
粉末には、粒径１０μｍ以下のかなり小さな粉末や、粒
径３０μｍ以上のかなり大きな粉末が多量に含まれてい
る。[0003] Conventionally, graphite powder pulverized to an average particle size of about 10 to 30 µm has been used. This graphite powder includes a considerably small powder having a particle size of 10 µm or less and a powder having a particle size of 30 µm or more. It contains a large amount of fairly large powder.
【０００４】しかしながら、このような黒鉛粉末を使用
した従来電池には、初期充放電効率、保存特性、急速充
電特性及び高率放電特性などの電池特性があまり良くな
いという問題があった。However, conventional batteries using such graphite powder have a problem that battery characteristics such as initial charge / discharge efficiency, storage characteristics, rapid charge characteristics and high rate discharge characteristics are not very good.
【０００５】これらの問題を解決するべく鋭意研究した
結果、本発明者らは、粒径の小さい粉末を多量に含む黒
鉛粉末を使用した場合は初期充放電効率及び保存特性が
悪くなり、一方粒径の大きい粉末を多量に含む黒鉛粉末
を使用した場合は急速充電特性及び高率放電特性が悪く
なるという、黒鉛粉末の粒径と電池特性との間に密接な
関連があることを見出した。As a result of intensive studies to solve these problems, the present inventors have found that when graphite powder containing a large amount of powder having a small particle size is used, the initial charge / discharge efficiency and storage characteristics are deteriorated. It has been found that when a graphite powder containing a large amount of a powder having a large diameter is used, the rapid charge characteristics and the high rate discharge characteristics are deteriorated, that is, there is a close relationship between the particle size of the graphite powder and the battery characteristics.
【０００６】本発明は、かかる知見に基づきなされたも
のであって、その目的とするところは、従来電池に比し
電池特性に優れた非水系二次電池を提供するにある。The present invention has been made based on such findings, and an object of the present invention is to provide a non-aqueous secondary battery having excellent battery characteristics as compared with conventional batteries.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
の請求項１記載の発明に係る非水系二次電池（以下「第
１電池」と称する。）は、ＢＥＴ法による比表面積が１
〜１０ｍ 2 ／ｇであり、平均粒径が１０〜３０μｍであ
り、且つ、粒径３０μｍ以上の粉末の含有率が１０％以
下である黒鉛粉末が負極材料として使用されてなる。 According to a first aspect of the present invention, there is provided a non-aqueous secondary battery (hereinafter referred to as a "first battery") having a specific surface area of 1 according to a BET method .
10 to 10 m 2 / g, and the average particle size is 10 to 30 μm.
And the content of powder having a particle size of 30 μm or more is 10% or less.
The lower graphite powder is used as a negative electrode material.
【０００８】また、請求項２記載の発明に係る非水系二
次電池（以下「第２電池」と称する。）は、ＢＥＴ法に
よる比表面積が１〜１０ｍ 2 ／ｇであり、平均粒径が１
０〜３０μｍであり、且つ、粒径１０μｍ以下の粉末の
含有率及び粒径３０μｍ以上の粉末の含有率がいずれも
１０％以下である黒鉛粉末が負極材料として使用されて
なる。ここに、ＢＥＴ（Brunauer-Emmett-Teller）法と
は、吸着等温線上で単分子層吸着量を求め、吸着分子の
断面積から表面積を決定して比表面積を算出する方法で
ある。以下において、上記の第１電池及び第２電池を総
称して、本発明電池と称することがある。 [0008] The non-aqueous secondary battery (hereinafter referred to as "second battery") according to the second aspect of the invention is a BET method .
Has a specific surface area of 1 to 10 m 2 / g and an average particle size of 1
0-30 μm, and powder having a particle size of 10 μm or less.
Both the content and the content of powder with a particle size of 30 μm or more
10% or less of graphite powder is used as negative electrode material
Become. Here, BET (Brunauer-Emmett-Teller) method and
Calculates the adsorption amount of the monolayer on the adsorption isotherm,
By calculating the specific surface area by determining the surface area from the cross-sectional area
is there. Hereinafter, the first battery and the second battery are referred to as a total.
The battery of the present invention may be referred to as the battery of the present invention.
【０００９】[0009]
【００１０】本発明電池では、いずれもＢＥＴ法による
比表面積（以下、「ＢＥＴ比表面積」と称する。）が１
〜１０ｍ2 ／ｇであり、平均粒径が１０〜３０μｍであ
る黒鉛粉末が使用される。これは、ＢＥＴ比表面積が１
ｍ2 ／ｇ未満の場合は、電解液との接触面積が過小なた
め急速充電特性及び高率放電特性が低下し、一方ＢＥＴ
比表面積が１０ｍ2 ／ｇを越えた場合は、電解液との接
触面積が過大なため保存特性及び初期充放電効率が低下
するとともに、活物質と銅箔等の芯体（負極集電体）と
の密着性が低下して充放電容量が低下するからであり、
また平均粒径が１０μｍ未満の場合は、初期充放電効率
が著しく低下し、一方平均粒径が３０μｍを越えた場合
は、高率放電特性が著しく低下するからである。Each of the batteries of the present invention has a specific surface area (hereinafter, referred to as "BET specific surface area") of 1 according to the BET method.
~10m a 2 / g, the graphite powder having an average particle diameter of 10~30μm is used. This means that the BET specific surface area is 1
If it is less than m 2 / g, the contact area with the electrolytic solution is too small, so that the quick charge characteristics and the high rate discharge characteristics are reduced.
When the specific surface area exceeds 10 m 2 / g, the storage area and the initial charge / discharge efficiency are reduced due to an excessive contact area with the electrolyte, and the active material and a core such as a copper foil (negative electrode current collector) And the charge / discharge capacity is reduced,
Further, when the average particle size is less than 10 μm, the initial charge / discharge efficiency is significantly reduced, while when the average particle size is more than 30 μm, the high-rate discharge characteristics are significantly reduced.
【００１１】[0011]
【００１２】第１電池では、上記比表面積及び平均粒径
についての規制のほか、さらに粒径３０μｍ以上の粉末
の含有率が１０％以下に規制された黒鉛粉末が使用され
る。これは、粒径３０μｍ以上の大きな粉末の含有率が
１０％を越えると、充放電時の反応面積が小さくなると
ともに、充電時に大きな粉末の中心部までリチウムイオ
ン等の金属イオンを吸蔵したり放電時にその中心部から
金属イオンを放出したりするのに時間がかかるため、急
速充電特性及び高率放電特性が低下するからである。In the first battery , in addition to the regulation on the specific surface area and the average particle size, graphite powder whose content of powder having a particle size of 30 μm or more is regulated to 10% or less is used. This is because, when the content of a large powder having a particle diameter of 30 μm or more exceeds 10%, the reaction area during charging and discharging becomes small, and at the time of charging, metal ions such as lithium ions are occluded or discharged to the center of the large powder. This is because it sometimes takes time to release metal ions from the central portion, so that the rapid charge characteristics and the high-rate discharge characteristics deteriorate.
【００１３】第２電池では、上記比表面積及び平均粒径
についての規制のほか、さらに粒径１０μｍ以下の粉末
の含有率及び粒径３０μｍ以上の粉末の含有率がいずれ
も１０％以下に規制された黒鉛粉末が使用される。この
第２電池は、第１電池をさらに限定した電池であり、従
来電池と比較して、初期充放電効率、保存特性、急速充
電特性及び高率放電特性のいずれの点においても優れる
電池である。In the second battery , in addition to the regulation on the specific surface area and the average particle diameter, the content of powder having a particle diameter of 10 μm or less and the content of powder having a particle diameter of 30 μm or more are both regulated to 10% or less. Graphite powder is used. this
The second battery is a battery in which the first battery is further limited , and is superior in all of the initial charge / discharge efficiency, storage characteristics, rapid charge characteristics, and high-rate discharge characteristics as compared with conventional batteries.
【００１４】本発明における黒鉛粉末は、上記した比表
面積及び粒径に関する規制以外は特に限定されないが、
電池特性に優れた非水系二次電池を得る上で、格子面
（００２）面におけるｄ値（ｄ002 ）が３．３５０〜
３．３６５Å、就中３．３５５〜３．３６０Å、またｃ
軸方向の結晶子の大きさ（Ｌｃ）が２００Å以上、就中
５００Å以上の黒鉛粉末を使用することが好ましい。[0014] The graphite powder in the present invention is not particularly limited except for the regulation on the specific surface area and the particle size described above.
In order to obtain a non-aqueous secondary battery having excellent battery characteristics, the d value (d 002 ) on the lattice plane (002) plane should be 3.350 to 3.350.
3.365Å, especially 3.355 to 3.360Å, and c
It is preferable to use graphite powder having an axial crystallite size (Lc) of 200 ° or more, particularly 500 ° or more.
【００１５】上述したように、本発明電池は、粒度調整
された黒鉛粉末を負極材料として使用した点に最大の特
徴を有するものであり、正極材料、非水系電解質、セパ
レータ（液体電解質を使用する場合）などの電池を構成
する他の部材については、従来非水系二次電池用として
実用され、或いは提案されている種々の材料を使用する
ことが可能である。As described above, the battery of the present invention has the greatest feature in that the graphite powder whose particle size has been adjusted is used as a negative electrode material. The battery of the present invention has a positive electrode material, a non-aqueous electrolyte, and a separator (using a liquid electrolyte). For the other members constituting the battery such as (case), it is possible to use various materials which have been conventionally used or proposed for non-aqueous secondary batteries.
【００１６】例えば、正極材料（活物質）としては、Ｌ
ｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＦｅＯ
2 が好適なものとして挙げられる。For example, as the positive electrode material (active material), L
iCoO 2 , LiNiO 2 , LiMnO 2 , LiFeO
2 is preferred.
【００１７】また、非水系電解液としては、エチレンカ
ーボネート、ビニレンカーボネート、プロピレンカーボ
ネートなどの有機溶媒や、これらとジメチルカーボネー
ト、ジエチルカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、エトキシメトキシエタ
ンなどの低沸点溶媒との混合溶媒に、ＬｉＰＦ6 、Ｌｉ
ＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 などの電解液溶質を０．７
〜１．５Ｍ（モル／リットル）、就中１Ｍの割合で溶か
した溶液が例示される。液漏れの無いポジションフリー
の電池を得るために固体電解質を使用してもよい。Examples of the non-aqueous electrolyte include organic solvents such as ethylene carbonate, vinylene carbonate, and propylene carbonate, and organic solvents such as dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, and ethoxy. LiPF 6 , LiPF 6 and LiPF 6 are added to a mixed solvent with a low boiling point solvent such as methoxyethane.
Electrolyte solutes such as ClO 4 , LiCF 3 SO 3
For example, a solution dissolved at a rate of １．５1.5 M (mol / liter), particularly 1 M is exemplified. A solid electrolyte may be used to obtain a position-free battery without liquid leakage.
【００１８】[0018]
【作用】第１電池では、粒径３０μｍ以上の粉末の含有
率が１０％以下に規制された黒鉛粉末が使用されている
ので、反応面積が大きいとともに、充放電時の金属イオ
ンの吸蔵放出が速やかに行われる。 The first battery contains a powder having a particle diameter of 30 μm or more.
Graphite powder whose rate is regulated to 10% or less is used
Therefore, the reaction area is large and metal ions
Is quickly absorbed and released.
【００１９】[0019]
【００２０】第２電池では、粒径１０μｍ以下の粉末の
含有率及び粒径３０μｍ以上の粉末の含有率がいずれも
１０％以下に規制された黒鉛粉末が使用されているの
で、自己放電し難く、また充放電時の金属イオンの吸蔵
放出が速やかに行われる。In the second battery , graphite powder whose content of powder having a particle size of 10 μm or less and content of powder having a particle size of 30 μm or more are both regulated to 10% or less is used. In addition, the occlusion and release of metal ions at the time of charge and discharge are performed quickly.
【００２１】[0021]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００２２】（実施例１）単３型（ＡＡ）の非水系二次
電池（本発明電池）を作製した。(Example 1) AA type (AA) non-aqueous secondary batteries (batteries of the present invention) were prepared.
【００２３】〔正極〕正極活物質としてのＬｉＣｏＯ2
と導電剤としての人造黒鉛とを重量比９：１で混合して
得た混合物を、ポリフッ化ビニリデンの５重量％Ｎ−メ
チルピロリドン（ＮＭＰ）溶液に分散させてスラリーを
調製し、このスラリーをドクターブレード法にて正極集
電体としてのアルミニウム箔の両面に塗布した後、１５
０°Ｃで２時間真空乾燥して正極を作製した。[Positive electrode] LiCoO 2 as positive electrode active material
A mixture obtained by mixing the graphite and artificial graphite as a conductive agent at a weight ratio of 9: 1 was dispersed in a 5% by weight N-methylpyrrolidone (NMP) solution of polyvinylidene fluoride to prepare a slurry. After applying to both sides of aluminum foil as a positive electrode current collector by doctor blade method, 15
Vacuum drying was performed at 0 ° C. for 2 hours to produce a positive electrode.
【００２４】〔負極〕ＢＥＴ比表面積９．４ｍ 2 ／ｇ、平均粒径１０μｍ、粒
径１０μｍ以下の粉末の含有率２４％、粒径３０μｍ以
上の粉末の含有率４％の 黒鉛粉末を結着剤としてのポリ
フッ化ビニリデンの５重量％ＮＭＰ溶液に分散させてス
ラリーを調製し、このスラリーをドクターブレード法に
て負極集電体としての銅箔の両面に塗布した後、１５０
°Ｃで２時間真空乾燥して負極を作製した。[Negative electrode] BET specific surface area 9.4 m 2 / g, average particle size 10 μm, particle size
24% content of powder with a diameter of 10 μm or less, particle diameter of 30 μm or less
A graphite powder having a powder content of 4% is dispersed in a 5% by weight NMP solution of polyvinylidene fluoride as a binder to prepare a slurry, and this slurry is subjected to a doctor blade method to form a copper as a negative electrode current collector. After applying on both sides of the foil, 150
Vacuum drying was performed at 2 ° C. for 2 hours to produce a negative electrode.
【００２５】〔電解液〕エチレンカーボネートとジメチ
ルカーボネートとの等体積混合溶媒に、ＬｉＰＦ6 を１
Ｍの割合で溶かして電解液を調製した。[Electrolytic Solution] LiPF 6 is added to an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate.
M was dissolved at a ratio of M to prepare an electrolytic solution.
【００２６】〔電池の作製〕 以上の正負両極及び電解液を用いて単３型の本発明電池
ＢＡ２（第１電池）を作製した。なお、セパレータとし
ては、ポリプロピレン製の微多孔膜（セラニーズ社製、
商品名「セルガード」）を使用し、これに先の電解液を
含浸させた。[Preparation of Battery] AA type battery of the present invention using both the positive and negative electrodes and the electrolytic solution described above.
BA2 (first battery) was produced. In addition, as a separator, a polypropylene microporous membrane (manufactured by Celanese Corporation,
(Trade name "Celgard"), which was impregnated with the electrolytic solution.
【００２７】図１は作製した本発明電池ＢＡ２を模式的
に示す断面図であり、図示の電池ＢＡ２は、正極１、負
極２、これら両電極を離間するセパレータ３、正極リー
ド４、負極リード５、正極外部端子６、負極缶７などか
らなる。正極１及び負極２は、非水系電解液を注入され
たセパレータ３を介して渦巻き状に巻き取られた状態で
負極缶７内に収容されており、正極１は正極リード４を
介して正極外部端子６に、また負極２は負極リード５を
介して負極缶７に接続され、電池内部で生じた化学エネ
ルギーを電気エネルギーとして外部へ取り出し得るよう
になっている。[0027] Figure 1 is a sectional view schematically showing a present battery BA2 fabricated battery BA2 shown, positive electrode 1, negative electrode 2, a separator 3 for separating the both electrodes, a positive electrode lead 4, a negative electrode lead 5 , A positive electrode external terminal 6, a negative electrode can 7, and the like. The positive electrode 1 and the negative electrode 2 are housed in a negative electrode can 7 in a state of being spirally wound through a separator 3 into which a non-aqueous electrolyte is injected. The terminal 6 and the negative electrode 2 are connected to a negative electrode can 7 via a negative electrode lead 5, so that chemical energy generated inside the battery can be taken out as electric energy.
【００２８】[0028]
【００２９】（実施例２） 負極材料として、ＢＥＴ比表面積６．９ｍ2 ／ｇ、平均
粒径１２μｍ、粒径１０μｍ以下の粉末の含有率３％、
粒径３０μｍ以上の粉末の含有率５％の黒鉛粉末を使用
したこと以外は実施例１と同様にして、本発明電池ＢＡ
３（第２電池）を作製した。 Example 2 As a negative electrode material, a BET specific surface area of 6.9 m 2 / g, an average particle diameter of 12 μm, and a content of powder having a particle diameter of 10 μm or less 3%,
Battery BA of the present invention was prepared in the same manner as in Example 1 except that graphite powder having a content of 5% of powder having a particle size of 30 μm or more was used.
3 ( second battery ) was produced.
【００３０】（比較例）負極材料として、黒鉛塊に空気
流を噴射して粉砕した黒鉛粉末を粒度選別せずにそのま
ま使用したこと以外は実施例１と同様にして、比較電池
ＢＣ１を作製した。因みに、このとき使用した黒鉛粉末
は、ＢＥＴ比表面積７．５ｍ2 ／ｇ、平均粒径１２μ
ｍ、粒径１０μｍ以下の粉末の含有率２０％、粒径３０
μｍ以上の粉末の含有率１７％のものであった。(Comparative Example) A comparative battery BC1 was produced in the same manner as in Example 1 except that graphite powder pulverized by injecting an air stream into a graphite lump was used as it was without being subjected to particle size selection. . Incidentally, the graphite powder used at this time had a BET specific surface area of 7.5 m 2 / g and an average particle size of 12 μm.
m, content of powder having a particle size of 10 μm or less 20%, particle size 30
The content of the powder having a particle size of μm or more was 17%.
【００３１】〔初期充放電効率〕 本発明電池ＢＡ３及び比較電池ＢＣ１について、２００
ｍＡで充電終止電圧５Ｖまで充電した後、２００ｍＡで
放電終止電圧２Ｖまで放電して、各電池の初期充放電効
率を調べた。結果を図２に示す。[Initial Charge / Discharge Efficiency] For the battery BA3 of the present invention and the comparative battery BC1, a 200
After charging the battery to a charge end voltage of 5 V at mA, the battery was discharged to a discharge end voltage of 2 V at 200 mA, and the initial charge / discharge efficiency of each battery was examined. The results are shown in FIG.
【００３２】図２は、各電池の初期充放電効率を、縦軸
に電池電圧（Ｖ）を、また横軸に黒鉛粉末１ｇ当たりの
充電容量又は放電容量（ｍＡｈ／ｇ）をとって示したグ
ラフである。同図より、粒径の小さい粉末の含有量が少
ない本発明電池ＢＡ３は、微粉末を多く含む比較電池Ｂ
Ｃ１に比し、初期充放電効率が高いことが分かる。 FIG. 2 shows the initial charge / discharge efficiency of each battery, the vertical axis represents the battery voltage (V), and the horizontal axis represents the charge capacity or discharge capacity (mAh / g) per gram of graphite powder. It is a graph. As shown in the figure, the battery BA3 of the present invention having a small content of the powder having a small particle size is a comparative battery B containing a large amount of fine powder.
Compared to C1, is Ru divided high initial charge-discharge efficiency.
【００３３】〔保存特性〕 本発明電池ＢＡ３及び比較電池ＢＣ１について、２００
ｍＡで充電終止電圧５Ｖまで充電した後、室温（２５°
Ｃ）にて３日間保存し、次いで２００ｍＡで放電終止電
圧２Ｖまで放電して、各電池の保存特性を調べた。結果
を図３に示す。[Storage Characteristics] The battery BA3 of the present invention and the comparative battery BC1 have a storage capacity of 200
After charging the battery to a charge termination voltage of 5 V with mA, the room temperature (25 ° C.)
C) for 3 days, and then discharged at 200 mA to a discharge end voltage of 2 V, and the storage characteristics of each battery were examined. The results are shown in FIG.
【００３４】図３は、各電池の保存特性を、縦軸に電池
電圧（Ｖ）を、また横軸に黒鉛粉末１ｇ当たりの充電容
量又は放電容量（ｍＡｈ／ｇ）をとって示したグラフで
ある。同図より、粒径の小さい粉末の含有量が少ない本
発明電池ＢＡ３は、微粉末を多く含む比較電池ＢＣ１に
比し、保存後の放電容量の減少が小さく保存特性に優れ
ていることが分かる。 FIG. 3 is a graph showing the storage characteristics of each battery, the vertical axis representing battery voltage (V), and the horizontal axis representing charge capacity or discharge capacity (mAh / g) per gram of graphite powder. is there. The figure shows that Battery BA3 of the present invention, which has a small content of powder having a small particle size, has a small decrease in discharge capacity after storage and is excellent in storage characteristics as compared with Comparative Battery BC1, which contains a large amount of fine powder. that either.
【００３５】〔急速充電特性〕本発明電池ＢＡ２、ＢＡ
３及び比較電池ＢＣ１について、５００ｍＡで充電終止
電圧５Ｖまで充電して、各電池の急速充電特性を調べ
た。結果を図４に示す。[Quick Charging Characteristics] Batteries BA2 and BA of the present invention
3 and comparative battery BC1 were charged at 500 mA to a charge termination voltage of 5 V, and the rapid charging characteristics of each battery were examined. FIG. 4 shows the results.
【００３６】図４は、各電池の急速充電特性を、縦軸に
電池電圧（Ｖ）を、また横軸に黒鉛粉末１ｇ当たりの充
電容量（ｍＡｈ／ｇ）をとって示したグラフである。な
お、図中には、比較のために、２００ｍＡで充電したと
きの充電特性も示してある。図４より、粒径の大きい粉
末の含有量が少ない本発明電池ＢＡ２及びＢＡ３は、大
きな粉末を多く含む比較電池ＢＣ１に比し、２００ｍＡ
充電時の充電容量と５００ｍＡ充電時の充電容量との差
が小さく急速充電特性に優れていることが分かる。な
お、本発明電池ＢＡ２とＢＡ３とを比較した場合、本発
明電池ＢＡ３の方が急速充電特性に若干優れる傾向が認
められるが、これは本発明電池ＢＡ３の黒鉛粉末は充電
時に副反応を起こし易い粒径の小さい粒子の含有量が少
ないためリチウムイオンの吸蔵が速やかになされるため
と推察される。FIG. 4 is a graph showing the rapid charging characteristics of each battery, the battery voltage (V) on the vertical axis, and the charging capacity (mAh / g) per gram of graphite powder on the horizontal axis. In the figure, for comparison, the charging characteristics when charged at 200 mA are also shown. As shown in FIG. 4, the batteries BA2 and BA3 of the present invention having a small content of the powder having a large particle size had 200 mA compared to the comparative battery BC1 having a large amount of the large powder.
It can be seen that the difference between the charging capacity at the time of charging and the charging capacity at the time of 500 mA charging is small, and the rapid charging characteristics are excellent. When the batteries BA2 and BA3 of the present invention are compared with each other, the battery BA3 of the present invention tends to have slightly better quick charge characteristics. It is presumed that because the content of particles having a small particle size is small, lithium ions are quickly absorbed.
【００３７】〔高率放電特性〕本発明電池ＢＡ２、ＢＡ
３及び比較電池ＢＣ１について、５００ｍＡで放電終止
電圧２Ｖまで放電して、各電池の高率放電特性を調べ
た。結果を図５に示す。[High Rate Discharge Characteristics] Batteries BA2 and BA of the present invention
3 and the comparative battery BC1 were discharged at 500 mA to a discharge end voltage of 2 V, and the high rate discharge characteristics of each battery were examined. The results are shown in FIG.
【００３８】図５は、各電池の高率放電特性を、縦軸に
電池電圧（Ｖ）を、また横軸に黒鉛粉末１ｇ当たりの放
電容量（ｍＡｈ／ｇ）をとって示したグラフである。な
お、図中には、比較のために、２００ｍＡで放電したと
きの放電特性も示してある。図５より、本発明電池ＢＡ
２及びＢＡ３は、比較電池ＢＣ１に比し、２００ｍＡ放
電時の放電容量と５００ｍＡ放電時の放電容量との差が
小さく高率放電特性に優れていることが分かる。なお、
本発明電池ＢＡ２とＢＡ３とを比較した場合、高率放電
特性についても、本発明電池ＢＡ３の方が若干優れてい
ることが分かる。FIG. 5 is a graph showing the high rate discharge characteristics of each battery, the battery voltage (V) on the vertical axis, and the discharge capacity (mAh / g) per gram of graphite powder on the horizontal axis. . In the figure, for comparison, the discharge characteristics when discharging at 200 mA are also shown. FIG. 5 shows that the battery BA of the present invention
2 and BA3 show that the difference between the discharge capacity at the time of 200 mA discharge and the discharge capacity at the time of 500 mA discharge is smaller than that of the comparative battery BC1, and the battery is excellent in high-rate discharge characteristics. In addition,
When the batteries BA2 and BA3 of the present invention are compared, it is understood that the battery BA3 of the present invention is slightly superior in high-rate discharge characteristics.
【００３９】叙上の実施例では、本発明を単３型電池に
適用する場合について説明したが、本発明電池はその形
状に特に制限はなく、扁平型、角型など、他の種々の形
状の非水系二次電池に適用し得るものである。In the above embodiment, the case where the present invention is applied to an AA type battery is described. However, the shape of the battery of the present invention is not particularly limited, and various other shapes such as a flat type and a square type can be used. It can be applied to the non-aqueous secondary battery.
【００４０】また、実施例では液体電解質を使用した非
水系二次電池を例に挙げて説明したが、本発明は固体電
解質電池にも適用し得るものである。Further, in the embodiments, a non-aqueous secondary battery using a liquid electrolyte has been described as an example, but the present invention is also applicable to a solid electrolyte battery.
【００４１】[0041]
【発明の効果】以上詳述したように、いずれの本発明電
池においても、粒度調整された黒鉛粉末が負極材料とし
て使用されており、特に第１電池は、急速充電特性及び
高率放電特性に優れ、また第２電池は初期充放電効率、
保存特性、急速充電特性及び高率放電特性の全ての特性
に優れるなど、本発明は優れた特有の効果を奏する。As described in detail above, in any of the present battery, the graphite powders particle size control are used as a negative electrode material, particularly the first battery, rapid charge characteristics and
Excellent high rate discharge characteristics, and the second battery has initial charge and discharge efficiency,
All characteristics of storage characteristics, quick charge characteristics and high rate discharge characteristics
For example , the present invention has excellent unique effects.
【図１】単３型の本発明電池の断面図である。FIG. 1 is a cross-sectional view of an AA battery of the present invention.
【図２】実施例及び比較例で作製した各電池の初期充放
電効率を示すグラフである。FIG. 2 is a graph showing the initial charge / discharge efficiency of each battery produced in Examples and Comparative Examples.
【図３】実施例及び比較例で作製した各電池の保存特性
を示すグラフである。FIG. 3 is a graph showing storage characteristics of each battery manufactured in Examples and Comparative Examples.
【図４】実施例及び比較例で作製した各電池の急速充電
特性を示すグラフである。FIG. 4 is a graph showing the rapid charging characteristics of each battery produced in the examples and comparative examples.
【図５】実施例及び比較例で作製した各電池の高率放電
特性を示すグラフである。FIG. 5 is a graph showing high-rate discharge characteristics of each of the batteries manufactured in Examples and Comparative Examples.
【符号の説明】ＢＡ２ 本発明電池 １ 正極 ２ 負極 ３ セパレータ[Description of Signs ] BA2 battery of the present invention 1 Positive electrode 2 Negative electrode 3 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目18番地 三 洋電機株式会社内 (56)参考文献 特開 平２−284354（ＪＰ，Ａ) 特開 平５−74453（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/58 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Nishio, inventor 2--18 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshihiko Saito 2-18-18 Keihanhondori, Moriguchi-shi, Osaka (56) References JP-A-2-284354 (JP, A) JP-A-5-74453 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4 / 58
Claims (2)
ｇであり、平均粒径が１０〜３０μｍであり、且つ、粒
径３０μｍ以上の粉末の含有率が１０％以下である黒鉛
粉末が負極材料として使用されていることを特徴とする
非水系二次電池。 1. A specific surface area by a BET method of 1 to 10 m 2 /
g, the average particle size is 10 to 30 μm, and the
Graphite having a content of powder having a diameter of 30 μm or more of 10% or less
Characterized in that powder is used as negative electrode material
Non-aqueous secondary battery.
ｇであり、平均粒径が１０〜３０μｍであり、且つ、粒
径１０μｍ以下の粉末の含有率及び粒径３０μｍ以上の
粉末の含有率がいずれも１０％以下である黒鉛粉末が負
極材料として使用されていることを特徴とする非水系二
次電池。 2. A specific surface area by a BET method of 1 to 10 m 2 /
g, the average particle size is 10 to 30 μm, and the
Powder having a diameter of 10 μm or less and a particle diameter of 30 μm or more
Graphite powder having a powder content of 10% or less was negative.
Non-aqueous system characterized by being used as an electrode material
Next battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052293A JP3188033B2 (en) | 1993-04-02 | 1993-04-02 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052293A JP3188033B2 (en) | 1993-04-02 | 1993-04-02 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06295725A JPH06295725A (en) | 1994-10-21 |
| JP3188033B2 true JP3188033B2 (en) | 2001-07-16 |
Family
ID=14276295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10052293A Expired - Lifetime JP3188033B2 (en) | 1993-04-02 | 1993-04-02 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3188033B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5660948A (en) * | 1995-09-26 | 1997-08-26 | Valence Technology, Inc. | Lithium ion electrochemical cell |
| CN1275341C (en) | 1996-08-08 | 2006-09-13 | 日立化成工业株式会社 | Negative-pole producing method for lithium secondary cell |
| JP5534440B2 (en) * | 1996-12-04 | 2014-07-02 | 日立化成株式会社 | Negative electrode for lithium secondary battery and lithium secondary battery |
| EP1009056B1 (en) * | 1997-05-27 | 2007-04-04 | TDK Corporation | Non-aqueous electrolyte secondary battery |
| ID21573A (en) * | 1997-05-30 | 1999-06-24 | Matsushita Electric Ind Co Ltd | SECONDARY ELECTROLITE CELLS NOT WATER AND THE METHOD OF MAKING NEGATIVE ELECTRODES |
| CN1118880C (en) * | 1997-05-30 | 2003-08-20 | 松下电器产业株式会社 | Nonaqueous electrolyte secondary battery |
| CH693053A5 (en) | 1997-07-04 | 2003-01-31 | Hitachi Powdered Metals | graphitic material for a negative electrode of a battery cell to lithium ions and a method to manufacture it. |
| US6989137B1 (en) | 1998-10-09 | 2006-01-24 | Showa Denko K.K. | Carbonaceous material for cell and cell containing the carbonaceous material |
| CA2346752C (en) * | 1998-10-09 | 2010-08-17 | Kunio Nishimura | Carbon material for battery and battery containing the carbon material |
| JP2002029720A (en) * | 2000-07-04 | 2002-01-29 | Sumitomo Electric Ind Ltd | Reformed graphite particles and battery using the same |
| JP3579340B2 (en) * | 2000-09-29 | 2004-10-20 | 株式会社東芝 | Non-aqueous electrolyte secondary battery |
| JP4729716B2 (en) * | 2003-02-20 | 2011-07-20 | 三菱化学株式会社 | Lithium secondary battery negative electrode and lithium secondary battery |
| EP1596451A4 (en) * | 2003-02-20 | 2008-07-09 | Mitsubishi Chem Corp | Active substance for negative electrode of lithium secondary battery, negative electrode of lithium secondary battery and lithium secondary battery |
| HUE038917T2 (en) | 2004-01-16 | 2018-12-28 | Hitachi Chemical Co Ltd | Negative electrode for lithium secondary battery and lithium secondary battery |
| JP4379432B2 (en) * | 2006-05-10 | 2009-12-09 | トヨタ自動車株式会社 | Power output device, vehicle equipped with the same, and secondary battery setting method |
-
1993
- 1993-04-02 JP JP10052293A patent/JP3188033B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06295725A (en) | 1994-10-21 |
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