JPH0644958A - Manufacture of negative electrode for lithium secondary battery - Google Patents
Manufacture of negative electrode for lithium secondary batteryInfo
- Publication number
- JPH0644958A JPH0644958A JP4199652A JP19965292A JPH0644958A JP H0644958 A JPH0644958 A JP H0644958A JP 4199652 A JP4199652 A JP 4199652A JP 19965292 A JP19965292 A JP 19965292A JP H0644958 A JPH0644958 A JP H0644958A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- carbonaceous material
- secondary battery
- lithium 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.)
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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】この発明は、正極と負極との間で
一方が放出したリチウムを他方が吸蔵するという可逆反
応によって充放電を行うリチウム二次電池に関し、特
に、炭素質材料を活物質とする負極の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery that charges and discharges between a positive electrode and a negative electrode by a reversible reaction in which the other one occludes lithium emitted by the other, and particularly, a carbonaceous material as an active material. And a method for manufacturing a negative electrode.
【０００２】[0002]
【従来の技術】この種のリチウム二次電池では、充電を
行うと正極からリチウムが放出されて負極に吸蔵され、
放電時には負極からリチウムが放出されて正極に吸蔵さ
れる。その際に正負極間で可逆に移動可能なリチウム量
によって電池容量が決まる。2. Description of the Related Art In this type of lithium secondary battery, when charged, lithium is released from the positive electrode and occluded in the negative electrode,
During discharge, lithium is released from the negative electrode and occluded in the positive electrode. At that time, the battery capacity is determined by the amount of lithium that can reversibly move between the positive and negative electrodes.
【０００３】この種のリチウム二次電池に使用されるリ
チウムの吸蔵・放出が可能な負極活物質については各種
有機高分子化合物を炭化した炭素質材料、モリブデン、
タングステンの酸化物などさまざまなものが研究されて
いる。現状では、リチウム・コバルト酸化物を正極とし
カーボンを負極とするものや、リチウム・マンガン酸化
物を正極としタングステン酸化物を負極とするものなど
が知られている。いずれも電解液としてはプロピレンカ
ーボネイトやジメトキシエタンに代表されるような非水
溶媒に過塩素酸リチウムや六フッ化リン酸リチウムに代
表されるような電解質を溶解した非水電解液を用いる。
また電池の形態としては、コイン形や円筒形などの各種
のケース構造を採用している。Regarding the negative electrode active material capable of inserting and extracting lithium used in this type of lithium secondary battery, carbonaceous materials obtained by carbonizing various organic polymer compounds, molybdenum,
Various materials such as tungsten oxide have been studied. At present, there are known ones that use lithium / cobalt oxide as a positive electrode and carbon as a negative electrode, and one that uses lithium / manganese oxide as a positive electrode and tungsten oxide as a negative electrode. In both cases, a nonaqueous electrolytic solution in which an electrolyte represented by lithium perchlorate or lithium hexafluorophosphate is dissolved in a nonaqueous solvent represented by propylene carbonate or dimethoxyethane is used as the electrolytic solution.
Further, as the form of the battery, various case structures such as coin type and cylindrical type are adopted.
【０００４】[0004]
【発明が解決しようとする課題】従来のリチウム二次電
池では、理論的な容積エネルギー密度および重量エネル
ギー密度を十分に生かせず、エネルギー密度が実用上満
足できないという問題があった。本発明者らはその原因
が次のような点にあることを究明した。The conventional lithium secondary battery has a problem that the theoretical volumetric energy density and weight energy density cannot be fully utilized and the energy density cannot be practically satisfied. The present inventors have determined that the cause is as follows.
【０００５】従来のリチウム二次電池の製造に際して
は、正極のリチウム吸蔵・放出が可能な容量と負極のリ
チウム吸蔵・放出が可能な容量とが等しくなるように両
極の活物質の量を決定していた。これは正極と負極との
間でそれぞれの吸蔵容量分のリチウムを充放電に伴って
可逆に移動させることができるという前提に基づいてい
る。しかし各種の電極材料について詳細な分析・測定を
行った結果、電極材料によっては一度吸蔵されたリチウ
ムの一部が吸蔵されたままで再放出されないことが解っ
た。しかも現用されている電極材料にも、吸蔵されたま
ま放出されないリチウムの割合が相当大きいものがある
ことが解った。特に負極活物質として用いるカーボンで
代表される炭素質材料の場合、その種類によって程度の
大小はあるもののリチウムの初期吸蔵量に対して５０％
程度しか放出されず、その３０％のリチウム量しか吸蔵
・放出を繰り返すことができない。残りの５０％のリチ
ウムはカーボンに吸蔵されたまま残留し、以後の充放電
には関与しなくなる。In the production of a conventional lithium secondary battery, the amounts of active materials of both electrodes are determined so that the capacity of the positive electrode capable of absorbing and releasing lithium and the capacity of the negative electrode capable of absorbing and releasing lithium are equal. Was there. This is based on the premise that lithium of the storage capacity between the positive electrode and the negative electrode can be reversibly moved with charge and discharge. However, as a result of detailed analysis and measurement of various electrode materials, it was found that, depending on the electrode material, part of the lithium that was once occluded is still occluded and is not released again. Moreover, it has been found that some of the currently used electrode materials have a considerably large proportion of lithium that is occluded and is not released. In particular, in the case of a carbonaceous material typified by carbon used as a negative electrode active material, the amount is 50% with respect to the initial storage amount of lithium, although the size varies depending on the type.
Only about 30% of the amount of lithium is released, and the occlusion / release of lithium can be repeated. The remaining 50% of lithium remains absorbed in the carbon and does not participate in subsequent charge and discharge.
【０００６】従って正極にＬｉＣｏＯ2 、負極にカーボ
ンを用い、両極のリチウム吸蔵容量（初期吸蔵量）が等
しくなるように設計した従来のリチウム二次電池では、
正極側が吸蔵容量のほぼ１００％のリチウムを吸蔵・放
出できるのに対し、負極は５０％のリチウムしか吸蔵・
放電することができず、この少ない方の容量が電池の容
量を決定し、そのため正極の多くの部分が負極の初期充
電に関与しただけでその後は無駄になる。以上のことか
ら容積エネルギー密度および重量エネルギー密度が期待
値より大幅に小さくなっていた。Therefore, in a conventional lithium secondary battery designed using LiCoO 2 for the positive electrode and carbon for the negative electrode and designed so that the lithium storage capacities (initial storage amounts) of both electrodes are equal,
The positive electrode can store and release almost 100% of its storage capacity, while the negative electrode stores and stores only 50% of lithium.
It cannot be discharged, and this smaller capacity determines the capacity of the battery, so that most of the positive electrode is only involved in the initial charging of the negative electrode and is wasted thereafter. From the above, volumetric energy density and weight energy density were significantly smaller than expected values.
【０００７】この発明は前述した従来の問題点に鑑みな
されたもので、その目的は、負極活物質として炭素質材
料を用いるリチウム二次電池において、吸蔵されたまま
再放出されないリチウムの量を少なくすることができる
ようにした負極の製造方法を提供することにあり、これ
によって容積エネルギー密度および重量エネルギー密度
の大きなリチウム二次電池を実現することにある。The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to reduce the amount of lithium that is occluded but not re-emitted in a lithium secondary battery using a carbonaceous material as a negative electrode active material. Another object of the present invention is to provide a method for producing a negative electrode that can achieve the above, and thereby to realize a lithium secondary battery having a large volume energy density and a large weight energy density.
【０００８】[0008]
【課題を解決するための手段】そこでこの発明では、正
極と負極との間で一方が放出したリチウムを他方が吸蔵
するという可逆反応によって充放電を行うリチウム二次
電池において、負極活物質としての炭素質材料にリチウ
ムを充分に吸蔵させた状態でこれを水洗処理し、その後
乾燥処理するようにした。Therefore, in the present invention, as a negative electrode active material, a lithium secondary battery is charged and discharged by a reversible reaction in which one of the positive and negative electrodes absorbs lithium emitted by the other and the other occludes lithium. The carbonaceous material was washed with water in a state where lithium was sufficiently absorbed therein, and then dried.
【０００９】[0009]
【作用】前述のように炭素質材料では吸蔵されたまま再
放出されないリチウムの量（不可逆容量）が非常に大き
いが、その理由と、この発明により不可逆容量が小さく
なる理由の詳細については今のところ不明である。現状
では次のように考えられる。As described above, in the carbonaceous material, the amount of lithium that is occluded but not re-released (irreversible capacity) is very large. The reason for this and the reason why the present invention reduces the irreversible capacity are as follows. However, it is unknown. At present, it can be considered as follows.
【００１０】前記不可逆容量分のリチウムは炭素質材料
の内部へ吸蔵されるというよりは、炭素質材料の表面に
おいてリチウムイオンの還元が起こると同時に、有機電
解液と何らかの反応を起こして安定な化合物を生成する
かまたは炭素質材料表面の表面官能基と反応し、電気化
学的操作ではリチウムイオンとして再び取り出すことが
できない状態になっていると考えられる。そして、この
発明を採用してリチウム吸蔵後の炭素質材料を水洗処理
することにより前記の化合物が水と反応し、その表面に
リチウムの吸蔵・放出が可能な膜が生成されるか、ある
いはリチウムイオンが移動可能な膜が生成され、その結
果前述の不可逆容量が少なくなると考えられる。The irreversible capacity of lithium is not occluded in the carbonaceous material, but rather, lithium ions are reduced on the surface of the carbonaceous material, and at the same time, some reaction occurs with the organic electrolytic solution to provide a stable compound. It is considered that the compound is generated or reacts with the surface functional group on the surface of the carbonaceous material, and cannot be extracted again as lithium ion by an electrochemical operation. Then, by adopting the present invention and washing the carbonaceous material after lithium absorption with water, the above compound reacts with water to form a film capable of absorbing and desorbing lithium on the surface thereof, or It is considered that a film in which ions can move is generated, and as a result, the above-mentioned irreversible capacity decreases.
【００１１】[0011]
【実施例】炭素材料にリチウムを吸蔵する方法としては
主として（１）ＴＷＯ−ＢＵＬＢ法、（２）混合法、
（３）加圧法、（４）溶媒法、（５）電気化学的方法の
５つがある。以下にその概略を示す。Examples As a method of occluding lithium in a carbon material, (1) TWO-BULB method, (2) mixing method,
There are five methods: (3) pressurizing method, (4) solvent method, and (5) electrochemical method. The outline is shown below.
【００１２】（１）ＴＷＯ−ＢＵＬＢ法 図１のように反応容器のガラス管３の一端を封じ、炭素
質材料４の試料および金属リチウム片５をある距離だけ
隔てて別の場所に設置して真空排気後封管する。２組の
別々の電気炉１、２を用いて、Ｔ1 ＞Ｔ2 （Ｔ1 は炭素
質材料４の温度、Ｔ2 は金属リチウム片５の温度）とな
るように温度を操作し、炭素質材料４に気相のリチウム
を接触、反応させる方法。(1) TWO-BULB Method As shown in FIG. 1, one end of a glass tube 3 of a reaction vessel is sealed, and a sample of carbonaceous material 4 and a piece of metallic lithium 5 are placed at a different distance from each other. After vacuum evacuation, seal the tube. Using two sets of separate electric furnaces 1 and 2, the temperature is controlled so that T1> T2 (T1 is the temperature of the carbonaceous material 4, T2 is the temperature of the metallic lithium piece 5), and the carbonaceous material 4 is A method of contacting and reacting with vapor phase lithium.
【００１３】（２）混合法 不活性ガス雰囲気、または除湿空気雰囲気において、炭
素質材料と粉末状の金属リチウムを混合し加熱する方
法。(2) Mixing method A method in which a carbonaceous material and powdered metallic lithium are mixed and heated in an inert gas atmosphere or a dehumidified air atmosphere.
【００１４】（３）加圧法 不活性ガス雰囲気、または除湿空気雰囲気において、炭
素質材料と粉末状の金属リチウムを混合し加圧する方
法。(3) Pressurizing method A method of mixing and pressurizing a carbonaceous material and powdery metallic lithium in an inert gas atmosphere or a dehumidified air atmosphere.
【００１５】（４）溶媒法 不活性ガス雰囲気、または除湿空気雰囲気において、適
当な条件下で金属リチウムを有機溶媒に溶解させ、この
溶液中に炭素質材料を浸漬させた後ガラスフィルタ等に
よって濾過した後同じ有機溶媒で洗浄する方法。(4) Solvent Method In an inert gas atmosphere or a dehumidified air atmosphere, metallic lithium is dissolved in an organic solvent under appropriate conditions, a carbonaceous material is immersed in this solution, and then filtered with a glass filter or the like. Then, wash with the same organic solvent.
【００１６】（５）電気化学的方法 不活性ガス雰囲気、または除湿空気雰囲気において、リ
チウム塩を含む有機溶媒にリチウム金属またはリチウム
化合物を対極として電解または短絡させる方法。またこ
の時、粉末状金属リチウムと炭素質材料を混ぜ合わせ、
リチウム塩を含む有機溶媒中に浸漬させても同様の効果
が得られる。(5) Electrochemical method A method of electrolyzing or short-circuiting an organic solvent containing a lithium salt with a lithium metal or a lithium compound as a counter electrode in an inert gas atmosphere or a dehumidified air atmosphere. At this time, the powdery metallic lithium and carbonaceous material are mixed,
Similar effects can be obtained by immersing in an organic solvent containing a lithium salt.
【００１７】これら５つの何れの方法を用いても炭素質
材料にリチウムを吸蔵することは可能であることが知ら
れているが、ここでは最も簡単に行える電気化学的方法
を用いた場合の実施例の詳細を示す。なおこの時炭素質
材料に導電剤としてアセチレンブラック、結着剤として
ＰＴＦＥを重量比で１０：０．１：１にして混合、混練
し造粒して負極合剤とした。It is known that it is possible to occlude lithium in the carbonaceous material by using any of these five methods. Here, the electrochemical method, which is the simplest, can be used. Details of the example are shown below. At this time, acetylene black as a conductive agent and PTFE as a binder were mixed and kneaded at a weight ratio of 10: 0.1: 1 to form a negative electrode mixture.
【００１８】《比較例》石炭ピッチを窒素気流中６００
℃，３時間、１２００℃，３時間の熱処理を行い、ピッ
チコークスを得た。これらのピッチコークスを用いて、
図２に示すＣＲ２０１６偏平型電池タイプテストセルを
作製した。まずピッチコークス９６重量部に対して、結
着剤としてのポリテトラフルオロエチレン樹脂４重量部
を加えて混練、造粒後、２０mgを秤量した。この合剤を
内径１１mmの成形型に入れ、３t/cm2 の圧力で成形し、
円板状の電極１６とした。これを負極端子板１２の内底
部に設けた直径１１．２mmのステンレス（ＳＵＳ３０
４）ネット１４に圧着し、この上にポリプロピレン製不
織布１７、マイクロポーラスフィルム１８を順に重ね合
わせ、封口ガスケット１９で固定した。一方、正極活物
質のＬｉＣｏＯ2 は、酸化コバルト（ＣｏＯ）と炭酸リ
チウム（Ｌｉ2 ＣＯ3 ）をモル比で２：１に混合し、空
気中で９００℃，９時間加熱したものを使用した。この
ＬｉＣｏＯ2 ８０重量部に対して、結着剤としてのポリ
テトラフルオロエチレン樹脂１０重量部、導電剤として
のアセチレンブラック１０重量部を加えて混練、造粒
後、１００mgを秤量した。この合剤を、内径１５．４mm
の成形型に入れ、３t/cm2 の圧力で成形し、円板状の電
極１５とした。これを正極缶１１の内底部に設けた直径
１５mmのチタンネット１３に圧着した。両者を非水電解
液中で重ね合わせ、正極缶１１に負極端子板１２をカシ
メ付け密封し、ＣＲ２０１６偏平型電池タイプテストセ
ルを作製した。非水電解液として、プロピレンカーボネ
ート−ジメトキシエタン混合溶媒（体積比で１：１）に
１mol ／l のＬｉＣｌＯ4 を溶解させたものを使用し
た。なおこのテストセルの活物質量は、電気化学当量と
し正極＞＞負極となるようにし、電池容量が負極規制と
なるように設定した。<< Comparative Example >> Coal pitch is 600 in a nitrogen stream.
Heat treatment was performed at 1,300 ° C. for 3 hours at 1,200 ° C. to obtain pitch coke. With these pitch cokes,
A CR2016 flat battery type test cell shown in FIG. 2 was produced. First, 4 parts by weight of a polytetrafluoroethylene resin as a binder was added to 96 parts by weight of pitch coke, kneaded and granulated, and then 20 mg was weighed. Put this mixture in a mold with an inner diameter of 11 mm and mold at a pressure of 3 t / cm 2 ,
The disc-shaped electrode 16 was used. This is provided on the inner bottom of the negative electrode terminal plate 12 with stainless steel having a diameter of 11.2 mm (SUS30
4) It was pressure-bonded to the net 14, a polypropylene non-woven fabric 17 and a microporous film 18 were superposed in this order, and fixed with a sealing gasket 19. On the other hand, as LiCoO 2 as the positive electrode active material, cobalt oxide (CoO) and lithium carbonate (Li 2 CO 3 ) were mixed at a molar ratio of 2: 1 and heated in air at 900 ° C. for 9 hours. To 80 parts by weight of this LiCoO 2, 10 parts by weight of polytetrafluoroethylene resin as a binder and 10 parts by weight of acetylene black as a conductive agent were added, kneaded and granulated, and then 100 mg was weighed. This mixture has an inner diameter of 15.4 mm
It was placed in the molding die of No. 3 and was molded at a pressure of 3 t / cm 2 to obtain a disk-shaped electrode 15. This was pressed onto a titanium net 13 having a diameter of 15 mm provided on the inner bottom of the positive electrode can 11. Both of them were superposed in a non-aqueous electrolyte solution, and the negative electrode terminal plate 12 was caulked and sealed to the positive electrode can 11 to produce a CR2016 flat battery type test cell. As the non-aqueous electrolyte, a solution prepared by dissolving 1 mol / l LiClO 4 in a propylene carbonate-dimethoxyethane mixed solvent (volume ratio 1: 1) was used. The amount of active material in this test cell was set to electrochemical equivalent such that positive electrode >> negative electrode, and battery capacity was regulated to negative electrode.
【００１９】このテストセルを組み立てた後、電流密度
０．５mA／cm2 の定電流で４．２Vまで充電後、２．８V
まで放電した。この結果得られた充電、及び放電カー
ブを図３に比較例（図３中の一点鎖線）として示す。After assembling this test cell, it was charged to 4.2V with a constant current having a current density of 0.5mA / cm 2 and then 2.8V.
Discharged up to. The charging and discharging curves obtained as a result are shown in FIG. 3 as a comparative example (dotted line in FIG. 3).
【００２０】《実施例》負極合剤３０mgを秤量し、比較
例の場合と同様にこの合剤を内径１１mmの成形型に入
れ、３t ／cm2 の圧力で成形し、円板状の電極２１とし
た。一方、直径１５mmのステンレスネット２２にニッケ
ルリード板２５をスポット溶接した電極担持体にこの円
板状電極２１を圧着し、炭素質材料極を作製した。この
炭素質材料極を、２００℃，５時間、真空状態で乾燥し
た。その後、除湿空気雰囲気で、プロピレンカーボネー
ト−ジメトキシエタン混合溶媒（体積比で１：１）に１
mol／l のＬｉＣｌＯ4 を溶解させ、ガラス製のフタ２
０ａと同じくガラス製の容器本体２０ｂとからなる容器
２０に貯留された非水電解液２３中に、この炭素質材料
極とニッケルリード板２５の付いたリチウム金属２４と
を、図４に示すように配置し、両ニッケルリード板２
５，２５間を導線２６で接続して外部短絡を５時間行っ
た。以上の操作後、炭素質材料極を蒸留水５００ml中に
浸漬し、２４時間放置した後、炭素質材料極のステンレ
スネット２２からカーボンを脱落させ、このカーボンを
２００℃，５時間、真空状態で乾燥した。このカーボン
２０mgを秤量し、内径１１mmの成形型に入れ、３t ／cm
2 の圧力で成形し、円板状の電極１６とした。以後比較
例の場合と同様にしてＣＲ２０１６偏平型電池タイプテ
ストセルを作製した。<Example> 30 mg of the negative electrode mixture was weighed, and this mixture was put into a molding die having an inner diameter of 11 mm and molded under a pressure of 3 t / cm 2 in the same manner as in the comparative example. And On the other hand, the disc-shaped electrode 21 was pressure-bonded to an electrode carrier in which a nickel lead plate 25 was spot-welded to a stainless net 22 having a diameter of 15 mm to produce a carbonaceous material electrode. This carbonaceous material electrode was dried in vacuum at 200 ° C. for 5 hours. Then, in a dehumidified air atmosphere, add 1 to a propylene carbonate-dimethoxyethane mixed solvent (volume ratio 1: 1).
Dissolve mol / l LiClO 4 and add a glass lid 2
As shown in FIG. 4, the carbonaceous material electrode and the lithium metal 24 with the nickel lead plate 25 are placed in the non-aqueous electrolytic solution 23 stored in the container 20 made of the glass container body 20b similar to that of 0a. Placed on both nickel lead plates 2
An external short circuit was carried out for 5 hours by connecting the wires 5 and 25 with a lead wire 26. After the above operation, the carbonaceous material electrode is immersed in 500 ml of distilled water and left for 24 hours, then the carbon is dropped from the stainless steel net 22 of the carbonaceous material electrode, and the carbon is kept in a vacuum state at 200 ° C. for 5 hours. Dried. 20 mg of this carbon is weighed and put into a mold having an inner diameter of 11 mm, 3 t / cm
It was molded under a pressure of 2 to obtain a disk-shaped electrode 16. Thereafter, a CR2016 flat battery type test cell was prepared in the same manner as in the comparative example.
【００２１】このテストセルを組み立てた後、電流密度
０．５mA／cm2 の定電流で４．２Vまで充電後、２．８V
まで放電した。この結果得られた充電、及び放電カー
ブを図３に実施例（図３中の実線）として示す。After assembling this test cell, it was charged to 4.2V with a constant current having a current density of 0.5mA / cm 2 and then 2.8V.
Discharged up to. The charging and discharging curves obtained as a result are shown in FIG. 3 as an example (solid line in FIG. 3).
【００２２】[0022]
【発明の効果】以上詳細に説明したように、リチウムを
吸蔵させた炭素質材料を水洗し乾燥して負極を製造する
ようにした本発明によれば、その理由は明らかではない
が、本発明を適用しない場合には初期吸蔵されたままで
再利用不可能なリチウムの量（不可逆容量）が非常に大
きかったのに対し、大幅に不可逆容量を減らすことがで
きる。そのため本発明の方法により製造した負極を用い
てリチウム二次電池を構成すれば、容積エネルギー密度
および重量エネルギー密度の大きな電池を実現すること
ができる。As described in detail above, according to the present invention in which a carbonaceous material in which lithium is occluded is washed with water and dried to produce a negative electrode, the reason is not clear, but the present invention In the case where is not applied, the amount of lithium that was initially occluded and cannot be reused (irreversible capacity) was very large, whereas the irreversible capacity can be significantly reduced. Therefore, if a lithium secondary battery is constructed using the negative electrode manufactured by the method of the present invention, a battery having a large volume energy density and a large weight energy density can be realized.
【図１】炭素質材料にリチウムを吸蔵させる方法の１つ
であるＴＷＯ−ＢＵＬＢ法の説明図である。FIG. 1 is an explanatory diagram of a TWO-BULB method, which is one of the methods for occluding lithium in a carbonaceous material.
【図２】ＣＲ２０１６偏平型電池タイプテストセルの側
断面図である。FIG. 2 is a side sectional view of a CR2016 flat battery type test cell.
【図３】この発明の一実施例の効果を示す放充電特性図
である。FIG. 3 is a discharge-charging characteristic diagram showing effects of one embodiment of the present invention.
【図４】この発明の一実施例に係る炭素質材料にリチウ
ムを吸蔵させるための装置を示す説明図である。FIG. 4 is an explanatory view showing an apparatus for occluding lithium in a carbonaceous material according to an embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 吉郎 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 (72)発明者 名倉 秀哲 東京都港区新橋５丁目36番11号 富士電気 化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiro Harada 5-311, Shimbashi, Minato-ku, Tokyo Fuji Electric Chemical Co., Ltd. (72) Hidenori Nagura 5-36-11 Shinbashi, Minato-ku, Tokyo Fuji Electrochemical Co., Ltd.
Claims (1)
ウムを他方が吸蔵するという可逆反応によって充放電を
行うリチウム二次電池において、負極活物質としての炭
素質材料にリチウムを充分に吸蔵させた状態でこれを水
洗処理し、その後乾燥処理することを特徴とするリチウ
ム二次電池の負極の製造方法。1. In a lithium secondary battery that is charged and discharged by a reversible reaction in which one of the positive electrodes and the negative electrode absorbs lithium released by the other, the carbonaceous material as the negative electrode active material sufficiently absorbs lithium. A method for producing a negative electrode for a lithium secondary battery, which comprises subjecting this to a water-washing treatment and then a drying treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4199652A JPH0644958A (en) | 1992-07-27 | 1992-07-27 | Manufacture of negative electrode for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4199652A JPH0644958A (en) | 1992-07-27 | 1992-07-27 | Manufacture of negative electrode for lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0644958A true JPH0644958A (en) | 1994-02-18 |
Family
ID=16411401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4199652A Pending JPH0644958A (en) | 1992-07-27 | 1992-07-27 | Manufacture of negative electrode for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0644958A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08102324A (en) * | 1994-09-30 | 1996-04-16 | Mitsubishi Chem Corp | Nonaqueous secondary battery |
| JP2007500922A (en) * | 2003-07-29 | 2007-01-18 | エフエムシー・コーポレイション | Dispersion of lithium metal at the electrode. |
| JP2020080294A (en) * | 2018-11-12 | 2020-05-28 | 国立研究開発法人物質・材料研究機構 | Battery evaluation sample accommodation device |
-
1992
- 1992-07-27 JP JP4199652A patent/JPH0644958A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08102324A (en) * | 1994-09-30 | 1996-04-16 | Mitsubishi Chem Corp | Nonaqueous secondary battery |
| JP2007500922A (en) * | 2003-07-29 | 2007-01-18 | エフエムシー・コーポレイション | Dispersion of lithium metal at the electrode. |
| JP2020080294A (en) * | 2018-11-12 | 2020-05-28 | 国立研究開発法人物質・材料研究機構 | Battery evaluation sample accommodation device |
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