JP2002252028A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2002252028A JP2002252028A JP2001050128A JP2001050128A JP2002252028A JP 2002252028 A JP2002252028 A JP 2002252028A JP 2001050128 A JP2001050128 A JP 2001050128A JP 2001050128 A JP2001050128 A JP 2001050128A JP 2002252028 A JP2002252028 A JP 2002252028A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- lithium secondary
- lithium
- negative electrode
- positive 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.)
- Granted
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]
【発明の属する技術分野】この発明は、正極と、負極
と、非水電解液とを備えたリチウム二次電池に係り、特
に、家庭用の電力貯蔵用電源等のように長期にわたって
使用されるリチウム二次電池において、十分なサイクル
寿命が得られるようにした点に特徴を有するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery provided with a positive electrode, a negative electrode, and a non-aqueous electrolyte, and is particularly used for a long period of time, such as a power supply for home use. It is characterized in that a sufficient cycle life is obtained in a lithium secondary battery.
【０００２】[0002]
【従来の技術】近年、高出力，高エネルギー密度の新型
二次電池の１つとして、非水電解液を用い、リチウムイ
オンを正極と負極との間で移動させて充放電を行うよう
にしたリチウム二次電池が利用されるようになった。2. Description of the Related Art In recent years, a non-aqueous electrolyte has been used as one of new high-power, high-energy-density secondary batteries, in which lithium ions are moved between a positive electrode and a negative electrode to perform charging and discharging. Lithium secondary batteries have been used.
【０００３】そして、このようなリチウム二次電池は、
携帯用機器の電源等の様々な分野に利用されており、近
年においては、電力貯蔵用電源や動力用電源として利用
されるようになっている[0003] Such a lithium secondary battery is
It is used in various fields such as the power supply of portable devices, and in recent years, has been used as a power storage power supply or a motive power supply.
【０００４】ここで、リチウム二次電池を電力貯蔵用電
源として利用する場合、高容量及び高出力であると共に
サイクル寿命に優れていることが要求される。Here, when a lithium secondary battery is used as a power source for power storage, it is required that the lithium secondary battery has a high capacity, a high output, and an excellent cycle life.
【０００５】このため、最近においては、正極における
正極材料として、リチウム含有ニッケル・コバルト複合
酸化物を用いると共に、負極における負極材料として、
高結晶性炭素材料である天然黒鉛と、低結晶性炭素材料
であるコークス又は難黒鉛化炭素とを混合した炭素材料
を用いるようにしたリチウム二次電池が提案されている
［Extended Abstracts of the 10th IMLB, Abstract N
o.337 (2000) 及び第４１回電池討論会予稿集、p558 (2
000) ］。[0005] For this reason, recently, a lithium-containing nickel-cobalt composite oxide has been used as a positive electrode material in a positive electrode, and a negative electrode material in a negative electrode has recently been used.
There has been proposed a lithium secondary battery using a carbon material obtained by mixing natural graphite, which is a highly crystalline carbon material, and coke, which is a low crystalline carbon material, or non-graphitizable carbon [Extended Abstracts of the 10th. IMLB, Abstract N
o.337 (2000) and Proceedings of the 41st Battery Symposium, p558 (2
000)].
【０００６】しかし、このようなリチウム二次電池を家
庭用の電力貯蔵用電源として使用するにあたり、１０年
の使用を想定すると、約３５００サイクルという極めて
長いサイクル寿命が要求されることになり、上記のよう
な正極や負極を用いたリチウム二次電池においても、こ
れに対応するような十分なサイクル寿命が得られないと
いう問題があった。However, when such a lithium secondary battery is used as a power supply for home power storage, assuming use for 10 years, an extremely long cycle life of about 3500 cycles is required. Such a lithium secondary battery using a positive electrode or a negative electrode has a problem that a sufficient cycle life corresponding to this cannot be obtained.
【０００７】[0007]
【発明が解決しようとする課題】この発明は、正極と、
負極と、非水電解液とを備えたリチウム二次電池におけ
る上記のような問題を解決することを課題とするもので
あり、家庭用の電力貯蔵用電源等のように長期にわたっ
て使用される場合において、リチウム二次電池が十分な
サイクル寿命をもつようにすることを課題とするもので
ある。SUMMARY OF THE INVENTION The present invention provides a positive electrode,
An object of the present invention is to solve the above-described problems in a lithium secondary battery including a negative electrode and a non-aqueous electrolyte, and is used for a long period of time such as a power storage power supply for home use. It is an object of the present invention to make a lithium secondary battery have a sufficient cycle life.
【０００８】[0008]
【課題を解決するための手段】この発明におけるリチウ
ム二次電池においては、上記のような課題を解決するた
め、正極と、負極と、非水電解液とを備えたリチウム二
次電池において、上記の正極に、一般式ＬｉＮｉ1-x Ｃ
ｏx Ｏ2 （但し、０．１≦ｘ≦０．６の条件を満た
す。）で表されるリチウム含有ニッケル・コバルト複合
酸化物を用いると共に、上記の負極に、天然黒鉛が６０
〜９０重量％の範囲で含まれると共に難黒鉛化炭素が４
０〜１０重量％の範囲で含まれる炭素材料を用い、さら
に上記の非水電解液として、パルス磁場勾配ＮＭＲ法に
よって算出される7Ｌｉ核の自己拡散係数が１．５×１
０-6ｃｍ2 ／ｓ以上になった非水電解液を用いるように
したのである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, a lithium secondary battery according to the present invention includes a lithium secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte. Of the general formula LiNi 1-x C
o x O 2 (where, 0.1 ≦ x ≦ 0.6 satisfies the condition.) with a lithium-containing nickel cobalt complex oxide represented by the negative pole of the natural graphite is 60
-90% by weight, and 4% of non-graphitizable carbon.
Using a carbon material contained in the range of 0 wt%, still as a non-aqueous electrolyte described above, pulsed field gradient NMR method self-diffusion coefficient of 7 Li nucleus is calculated by the 1.5 × 1
A non-aqueous electrolyte solution of 0 -6 cm 2 / s or more was used.
【０００９】そして、この発明におけるリチウム二次電
池のように、正極に、一般式ＬｉＮｉ1-x Ｃｏx Ｏ
2 （但し、０．１≦ｘ≦０．６の条件を満たす。）で表
されるリチウム含有ニッケル・コバルト複合酸化物を用
いると、他の材料を用いる場合に比べて正極の容量が大
きくなって、サイクル特性が向上する。Then, as in the lithium secondary battery of the present invention, the general formula LiNi 1-x Co x O
2 (However, the lithium-containing nickel-cobalt composite oxide represented by 0.1 ≦ x ≦ 0.6 is satisfied.) The capacity of the positive electrode becomes larger than when other materials are used. Thus, the cycle characteristics are improved.
【００１０】ここで、このようなリチウム含有ニッケル
・コバルト複合酸化物としては、例えば、ＬｉＮｉ0.7
Ｃｏ0.3 Ｏ2 を用いることが好ましい。また、このよう
なリチウム含有ニッケル・コバルト複合酸化物を得るに
あたっては、ＬｉＯＨ等のリチウム化合物と、Ｎｉ（Ｏ
Ｈ）2 等のニッケル化合物と、Ｃｏ（ＯＨ）2 等のコバ
ルト化合物とを適当なモル比で混合させ、乾燥空気中に
おいて７００〜９００℃の温度で２０時間程度加熱処理
することによって製造することができる。Here, as such a lithium-containing nickel-cobalt composite oxide, for example, LiNi 0.7
It is preferable to use Co 0.3 O 2 . In order to obtain such a lithium-containing nickel-cobalt composite oxide, a lithium compound such as LiOH and Ni (O
And nickel compounds such as H) 2, Co (OH) was mixed with a cobalt compound of 2 such as in appropriate molar ratios, be prepared by about 20 hours of heat treatment at a temperature of 700 to 900 ° C. in a dry air Can be.
【００１１】また、この発明におけるリチウム二次電池
のように、負極に天然黒鉛が６０〜９０重量％の範囲で
含まれると共に難黒鉛化炭素が４０〜１０重量％の範囲
で含まれる炭素材料を用いると、天然黒鉛のみを用いる
場合等に比べて、サイクル特性が向上し、好ましくは、
天然黒鉛と難黒鉛化炭素との重量比率が８０：２０にな
るようにする。Further, as in the lithium secondary battery of the present invention, a carbon material containing natural graphite in the range of 60 to 90% by weight and hardly graphitizable carbon in the range of 40 to 10% by weight in the negative electrode is used. When used, cycle characteristics are improved as compared with the case where only natural graphite is used, and preferably,
The weight ratio between natural graphite and non-graphitizable carbon is set to 80:20.
【００１２】ここで、上記の天然黒鉛としては、Ｘ線回
析法によって求められる（００２）面の面間隔ｄ002 が
０．３３５ｎｍ〜０．３３７ｎｍであり、結晶子の大き
さＬｃが８０ｎｍ以上であり、またその平均粒径が１５
μｍ〜２０μｍの範囲のものを用いることが好ましい。The natural graphite has a (002) plane spacing d 002 of 0.335 nm to 0.337 nm, determined by X-ray diffraction, and a crystallite size Lc of 80 nm or more. And its average particle size is 15
It is preferable to use one having a range of μm to 20 μm.
【００１３】また、上記の難黒鉛化炭素としては、Ｘ線
回析法によって求められる（００２）面の面間隔ｄ002
が０．３８ｎｍ〜０．４１ｎｍであり、結晶子の大きさ
Ｌｃが０．５ｎｍ〜１０ｎｍの範囲であり、またその平
均粒径が３μｍ〜７μｍの範囲のものを用いることが好
ましい。[0013] As the non-graphitizable carbon described above, determined by X-ray diffraction method (002) plane of the plane spacing d 002
Is 0.38 nm to 0.41 nm, the crystallite size Lc is in the range of 0.5 nm to 10 nm, and the average particle size is preferably 3 μm to 7 μm.
【００１４】また、この発明におけるリチウム二次電池
のように、パルス磁場勾配ＮＭＲ法によって算出される
7Ｌｉ核の自己拡散係数が１．５×１０-6ｃｍ2 ／ｓ以
上になった非水電解液を用いると、この非水電解液中に
おいてリチウムイオンがスムーズに移動するようになっ
て、電池反応がより均一に行われるようになり、サイク
ル特性が向上する。Further, as in the lithium secondary battery according to the present invention, it is calculated by a pulse magnetic field gradient NMR method.
When a non-aqueous electrolyte having a self-diffusion coefficient of 7 Li nucleus of 1.5 × 10 −6 cm 2 / s or more is used, lithium ions move smoothly in this non-aqueous electrolyte, The battery reaction is performed more uniformly, and the cycle characteristics are improved.
【００１５】ここで、パルス磁場勾配ＮＭＲ法によって
算出される7Ｌｉ核の自己拡散係数が大きくなるほど、
非水電解液中においてリチウムイオンがスムーズに移動
するようになるが、7Ｌｉ核の自己拡散係数が大きくな
り過ぎると、非水電解液の粘性が低下して、この非水電
解液が分解する副反応等が生じやすくなり、電池のサイ
クル特性が低下するため、上記の7Ｌｉ核の自己拡散係
数が２．４×１０-6ｃｍ2 ／ｓ以下の非水電解液を用い
ることが好ましい。[0015] Here, the self-diffusion coefficient of 7 Li nucleus calculated by pulsed field gradient NMR method increases,
Lithium ions are to move smoothly in the nonaqueous electrolytic solution, 7 the self-diffusion coefficient of Li nucleus becomes too large, the viscosity of the non-aqueous electrolyte is reduced, decompose the nonaqueous electrolyte solution side reaction or the like tends to occur, to lower the cycle characteristics of the battery, it is preferable to use a self-diffusion coefficient of the above 7 Li nucleus 2.4 × 10 -6 cm 2 / s or less for non-aqueous electrolyte.
【００１６】なお、上記のパルス磁場勾配ＮＭＲ法は、
核磁気核を含む物質の自己拡散係数を直接に測定できる
方法であり、従来用いられてきたイオン導電率等の評価
手法に比べて、リチウムイオンが非水電解液中における
溶媒と結合した溶媒和の状態で、非水電解液中を移動す
る情報がより正確に得られるようになる。The above-mentioned pulsed magnetic field gradient NMR method comprises:
This method can directly measure the self-diffusion coefficient of a substance containing nuclear magnetic nuclei. Compared with the conventionally used evaluation methods such as ionic conductivity, solvation in which lithium ions are combined with the solvent in In this state, the information that moves in the non-aqueous electrolyte can be obtained more accurately.
【００１７】ここで、上記のパルス磁場勾配ＮＭＲ法に
おいて、バルス磁場勾配を照射していない場合のシグナ
ル強度Ｅｏに対するバルス磁場勾配を照射した場合のシ
グナル強度Ｅの比（＝Ｅ／Ｅｏ）は、下記のＳｔｅｊｓ
ｋａｌの式で表すことができる。Here, in the above-mentioned pulse magnetic field gradient NMR method, the ratio (= E / Eo) of the signal intensity E when the pulse magnetic field gradient is irradiated to the signal intensity Eo when the pulse magnetic field gradient is not irradiated is: The following Stejs
It can be represented by the following equation:
【００１８】 Ｅ／Ｅｏ＝ｅｘｐ［−Ｄ（γｇδ）2 （Δ―δ／３）］E / Eo = exp [−D (γgδ) 2 (Δ−δ / 3)]
【００１９】なお、上記の式中、Ｄは自己拡散係数、γ
は磁気回転比（原子核固有の定数）、ｇはパルス磁場勾
配強度、δはパルス磁場勾配の照射時間、Δはパルス磁
場勾配の間隔である。In the above equation, D is a self-diffusion coefficient, γ
Is the gyromagnetic ratio (constant inherent to the nucleus), g is the pulse magnetic field gradient strength, δ is the irradiation time of the pulse magnetic field gradient, and Δ is the interval of the pulse magnetic field gradient.
【００２０】そして、この発明においては、パルス磁場
勾配の照射時間δを２ｍｓ、パルス磁場勾配の間隔Δを
２０ｍｓに設定し、パルス磁場勾配強度ｇを０〜５Ｔ／
ｍの間で変化させて、上記のシグナル強度の比（＝Ｅ／
Ｅｏ）を求め、これに基づいて、非水電解液における7
Ｌｉ核の自己拡散係数Ｄを求めた。In the present invention, the irradiation time δ of the pulse magnetic field gradient is set to 2 ms, the interval Δ of the pulse magnetic field gradient is set to 20 ms, and the pulse magnetic field gradient intensity g is set to 0 to 5 T /
m, the ratio of the above signal intensities (= E /
Eo), and based on this, 7
The self-diffusion coefficient D of the Li nucleus was determined.
【００２１】ここで、上記のような非水電解液において
は、その非水系溶媒として、高誘電率溶媒と低粘度溶媒
との混合溶媒を用いるようにすることが好ましい。Here, in the non-aqueous electrolyte described above, it is preferable to use a mixed solvent of a high dielectric constant solvent and a low viscosity solvent as the non-aqueous solvent.
【００２２】そして、上記の高誘電率溶媒としては、例
えば、エチレンカーボネート、プロピレンカーボネー
ト、ブチレンカーボネート等の環状カーボネート類を１
種以上用いるようにし、また上記の低粘度溶媒として
は、例えば、ジメチルカーボネート、エチルメチルカー
ボネート、ジエチルカーボネート等の鎖状カーボネート
類や、テトラヒドロフラン、２−メチルテトラヒドロフ
ラン、１，４−ジオキサン、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン等のエーテル類や、アセ
トニトリル等のニトリル類や、プロピオン酸メチル等の
エステル類や、ジメチルホルムアミド等のアミド類を１
種以上用いるようにする。Examples of the high dielectric constant solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate.
The low-viscosity solvents include, for example, chain carbonates such as dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2 -Ethers such as dimethoxyethane and 1,2-diethoxyethane, nitriles such as acetonitrile, esters such as methyl propionate, and amides such as dimethylformamide.
Use more than seeds.
【００２３】また、非水系溶媒として、上記のような高
誘電率溶媒と低粘度溶媒との混合溶媒を用いるにあたっ
ては、高誘電率溶媒と低粘度溶媒との体積比率が１０：
９０〜８０：２０の範囲になるようにし、好ましくは、
２０：８０〜６０：４０の範囲になるようにする。When a mixed solvent of a high dielectric constant solvent and a low viscosity solvent as described above is used as the non-aqueous solvent, the volume ratio of the high dielectric constant solvent to the low viscosity solvent is 10:
In the range of 90 to 80:20, preferably
The range is from 20:80 to 60:40.
【００２４】また、上記の非水電解液においては、その
電解質として、例えば、ＬｉＰＦ6、ＬｉＡｓＦ6 、Ｌ
ｉＢＦ4 、ＬｉＣＦ3 ＳＯ3 、ＬｉＮ（Ｃl Ｆ2l+1ＳＯ
2 ）（Ｃm Ｆ2m+1ＳＯ2 ）（なお、ｌ、ｍは１以上の整
数である。）、ＬｉＣ（ＣpＦ2p+1ＳＯ2 ）（Ｃq Ｆ
2q+1ＳＯ2 ）（Ｃr Ｆ2r+1ＳＯ2 ）（なお、ｐ、ｑ、ｒ
は１以上の整数である。）等を用いることができる。な
お、このような電解質を前記の非水系溶媒に溶解させて
非水電解液を得るにあたっては、非水電解液中における
この電解質のモル濃度が、０．１〜１．５ｍｏｌ／ｌ、
好ましくは０．５〜１．５ｍｏｌ／ｌの濃度になるよう
にする。In the above non-aqueous electrolyte, the electrolyte may be, for example, LiPF 6 , LiAsF 6 , L
iBF 4, LiCF 3 SO 3, LiN (C l F 2l + 1 SO
2) (C m F 2m + 1 SO 2) ( Note, l, m is an integer of 1 or more.), LiC (C p F 2p + 1 SO 2) (C q F
2q + 1 SO 2) (C r F 2r + 1 SO 2) ( Note, p, q, r
Is an integer of 1 or more. ) Etc. can be used. When dissolving such an electrolyte in the non-aqueous solvent to obtain a non-aqueous electrolyte, the molar concentration of the electrolyte in the non-aqueous electrolyte is 0.1 to 1.5 mol / l.
Preferably, the concentration is 0.5 to 1.5 mol / l.
【００２５】[0025]
【実施例】以下、この発明のリチウム二次電池につい
て、実施例を挙げて具体的に説明すると共に、この実施
例におけるリチウム二次電池においてはサイクル特性が
改善されることを、比較例を挙げて明らかにする。な
お、この発明におけるリチウム二次電池は、下記の実施
例に示したものに限定されず、その要旨を変更しない範
囲において適宜変更して実施できるものである。EXAMPLES Hereinafter, the lithium secondary battery of the present invention will be specifically described with reference to examples, and it will be described with reference to comparative examples that the lithium secondary battery in this example has improved cycle characteristics. To reveal. The lithium secondary battery according to the present invention is not limited to those shown in the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.
【００２６】（実施例１）実施例１においては、下記の
ようにして作製した正極と負極と非水電解液とを用い
て、直径が３０ｍｍ，高さが６５ｍｍになった図１に示
すような円筒型のリチウム二次電池を作製した。Example 1 In Example 1, a positive electrode, a negative electrode and a non-aqueous electrolyte prepared as described below were used, and the diameter was 30 mm and the height was 65 mm as shown in FIG. A cylindrical rechargeable lithium battery was fabricated.
【００２７】［正極の作製］正極を作製するにあたって
は、正極材料としてリチウム含有ニッケル・コバルト複
合酸化物であるＬｉＮｉ0.7 Ｃｏ0.3 Ｏ2 の粉末を用
い、このＬｉＮｉ0.7Ｃｏ0.3 Ｏ2 粉末と、導電剤であ
る炭素粉末と、結着剤であるポリフッ化ビニリデンとを
９０：５：５の重量比で混合し、この混合物にＮ−メチ
ル−２−ピロリドンを加えてスラリー化させ、このスラ
リーを正極集電体であるアルミニウム箔の両面にドクタ
ーブレード法により塗布し、乾燥させた後、これを圧延
し、所定の幅に切断して正極を作製した。[0027] In preparing the Preparation of positive electrode] The positive electrode using the powder of LiNi 0.7 Co 0.3 O 2 is a lithium-containing nickel cobalt complex oxide as a positive electrode material, and the LiNi 0.7 Co 0.3 O 2 powder, conductive Carbon powder as a binder and polyvinylidene fluoride as a binder are mixed at a weight ratio of 90: 5: 5, and N-methyl-2-pyrrolidone is added to the mixture to form a slurry. After being applied to both sides of an aluminum foil as a current collector by a doctor blade method and dried, the obtained was rolled and cut into a predetermined width to produce a positive electrode.
【００２８】［負極の作製］負極を作製するにあたって
は、負極材料として、平均粒径が１８μｍ，（００２）
面の面間隔ｄ002 が０．３３５６ｎｍ，結晶子の大きさ
Ｌｃが１００ｎｍ以上の天然黒鉛の粉末と、平均粒径が
３．６μｍ，（００２）面の面間隔ｄ002 が０．３９０
ｎｍ，結晶子の大きさＬｃが１ｎｍの難黒鉛化炭素の粉
末とを８０：２０の重量比率で混合させたものを用いる
ようにした。[Preparation of Negative Electrode] In preparing the negative electrode, the average particle diameter was 18 μm, (002)
A natural graphite powder having a plane spacing d 002 of 0.3356 nm and a crystallite size Lc of 100 nm or more, a mean particle size of 3.6 μm, and a (002) plane spacing d 002 of 0.390
A mixture of a powder of non-graphitizable carbon having a diameter of 1 nm and a crystallite size Lc of 1 nm was used in a weight ratio of 80:20.
【００２９】そして、上記の負極材料と結着剤であるポ
リフッ化ビニリデンとを９７：３の重量比で混合し、こ
の混合物にＮ−メチル−２−ピロリドンを加えてスラリ
ー化させ、このスラリーを負極集電体である銅箔の両面
にドクターブレード法により塗布し、乾燥させた後、こ
れを圧延し、所定の幅に切断して負極を作製した。Then, the above-mentioned negative electrode material and polyvinylidene fluoride as a binder are mixed at a weight ratio of 97: 3, and N-methyl-2-pyrrolidone is added to this mixture to form a slurry. The negative electrode current collector was coated on both sides of a copper foil by a doctor blade method, dried, and then rolled and cut into a predetermined width to prepare a negative electrode.
【００３０】［非水電解液の作製］非水電解液を作製す
るにあたっては、溶媒としてエチレンカーボネートとエ
チルメチルカーボネートとを３０：７０の体積比率で混
合させた混合溶媒を用い、この混合溶媒に、電解質とし
てヘキサフルオロリン酸リチウムＬｉＰＦ6 を１ｍｏｌ
／ｌの濃度になるように溶解させて非水電解液を作製し
た。なお、この非水電解液においては、パルス磁場勾配
ＮＭＲ法によって算出される7Ｌｉ核の自己拡散係数
が、下記の表１に示すように、２．０５×１０-6ｃｍ2
／ｓになっていた。[Preparation of Non-Aqueous Electrolyte] In preparing a non-aqueous electrolyte, a mixed solvent of ethylene carbonate and ethyl methyl carbonate mixed at a volume ratio of 30:70 was used as a solvent. 1 mol of lithium hexafluorophosphate LiPF 6 as electrolyte
/ L to obtain a non-aqueous electrolyte solution. In this non-aqueous electrolyte, the self-diffusion coefficient of the 7 Li nucleus calculated by the pulsed magnetic field gradient NMR method was 2.05 × 10 −6 cm 2 as shown in Table 1 below.
/ S.
【００３１】［電池の作製］電池を作製するにあたって
は、図１に示すように、上記のようにして作製した正極
１と負極２との間に、セパレータ３としてリチウムイオ
ン透過性のポリエチレン製の微多孔膜を介在させ、これ
らをスパイラル状に巻いて電池缶４内に収容させた後、
この電池缶４内に上記のようにして作製した非水電解液
を注液して封口し、正極１を正極リード５を介して正極
外部端子６に接続させると共に負極２を負極リード７を
介して電池缶４に接続させ、正極外部端子６と電池缶４
とを絶縁パッキン８により電気的に分離させた。[Preparation of Battery] In preparing a battery, as shown in FIG. 1, a lithium ion-permeable polyethylene made of polyethylene was used as a separator 3 between the positive electrode 1 and the negative electrode 2 prepared as described above. After interposing a microporous membrane and winding them in a spiral shape and storing them in the battery can 4,
The non-aqueous electrolyte solution prepared as described above is injected into the battery can 4 and sealed, and the positive electrode 1 is connected to the positive external terminal 6 via the positive electrode lead 5 and the negative electrode 2 is connected to the negative electrode lead 7 via the negative electrode lead 7. To the battery can 4, and the positive electrode external terminal 6 and the battery can 4
Are electrically separated by an insulating packing 8.
【００３２】（実施例２）実施例２においては、非水電
解液を作製するにあたり、エチレンカーボネートとジエ
チルカーボネートとを３０：７０の体積比率で混合させ
た混合溶媒を用い、この混合溶媒に、電解質としてヘキ
サフルオロリン酸リチウムＬｉＰＦ6 を１ｍｏｌ／ｌの
濃度になるように溶解させて非水電解液を作製した。な
お、この非水電解液においては、パルス磁場勾配ＮＭＲ
法によって算出される7Ｌｉ核の自己拡散係数が、下記
の表１に示すように、１．５９×１０-6ｃｍ2 ／ｓにな
っていた。Example 2 In Example 2, a non-aqueous electrolytic solution was prepared by using a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 30:70. Lithium hexafluorophosphate LiPF 6 was dissolved as an electrolyte to a concentration of 1 mol / l to prepare a non-aqueous electrolyte. In this non-aqueous electrolyte, a pulsed magnetic field gradient NMR
The self-diffusion coefficient of 7 Li nucleus calculated by law, as shown in Table 1 below, had become 1.59 × 10 -6 cm 2 / s .
【００３３】そして、上記のようにして作製した非水電
解液を用いる以外は、上記の実施例１の場合と同様にし
て、実施例２のリチウム二次電池を作製した。Then, a lithium secondary battery of Example 2 was fabricated in the same manner as in Example 1 except that the nonaqueous electrolyte solution fabricated as described above was used.
【００３４】（比較例１）比較例１においては、非水電
解液を作製するにあたり、エチレンカーボネートとジエ
チルカーボネートとを５０：５０の体積比率で混合させ
た混合溶媒を用い、この混合溶媒に、電解質としてヘキ
サフルオロリン酸リチウムＬｉＰＦ6 を１ｍｏｌ／ｌの
濃度になるように溶解させて非水電解液を作製した。な
お、この非水電解液においては、パルス磁場勾配ＮＭＲ
法によって算出される7Ｌｉ核の自己拡散係数が、下記
の表１に示すように、１．３８×１０-6ｃｍ2 ／ｓにな
っていた。Comparative Example 1 In Comparative Example 1, a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 50:50 was used for preparing a non-aqueous electrolyte. Lithium hexafluorophosphate LiPF 6 was dissolved as an electrolyte to a concentration of 1 mol / l to prepare a non-aqueous electrolyte. In this non-aqueous electrolyte, a pulsed magnetic field gradient NMR
The self-diffusion coefficient of 7 Li nucleus calculated by law, as shown in Table 1 below, had become 1.38 × 10 -6 cm 2 / s .
【００３５】そして、上記のようにして作製した非水電
解液を用いる以外は、上記の実施例１の場合と同様にし
て、比較例１のリチウム二次電池を作製した。Then, a lithium secondary battery of Comparative Example 1 was produced in the same manner as in Example 1 except that the nonaqueous electrolytic solution produced as described above was used.
【００３６】次に、上記のようにして作製した実施例１
〜２及び比較例１の各リチウム二次電池における充放電
サイクル特性を調べた。Next, Example 1 manufactured as described above was used.
2 and Comparative Example 1 were examined for charge / discharge cycle characteristics.
【００３７】ここで、充放電サイクル特性を調べるにあ
たっては、上記の各リチウム二次電池を、１６８０ｍＡ
の定電流で２６９５ｍＡｈの容量まで充電を行い、１サ
イクル目の充電終止電圧Ｐ1 （ｍＶ）を測定した後、１
６８０ｍＡの定電流で２．７Ｖになるまで放電し、これ
を１サイクルとして２５０サイクルの充放電を繰り返し
て行った後、各リチウム二次電池を１６８０ｍＡ定電流
で２６９５ｍＡｈの容量まで充電を行い、２５１サイク
ル目の充電終止電圧Ｐ251 （ｍＶ）を測定し、下記の式
により、１サイクルあたりの充電終止電圧の上昇率（ｍ
Ｖ／サイクル）を算出し、その結果を、下記の表１に示
した。なお、このように一定容量まで充電させるように
して、充放電を繰り返して行った場合、充電終止電圧の
上昇率が小さいほど、充放電サイクル特性が優れること
になる。Here, when examining the charge / discharge cycle characteristics, each of the above lithium secondary batteries was used at 1680 mA.
After charging at a constant current of 2695 mAh to measure the charge end voltage P 1 (mV) in the first cycle,
Discharging was performed at a constant current of 680 mA until the voltage reached 2.7 V, and charging and discharging were repeated for 250 cycles. The charge end voltage P 251 (mV) at the cycle was measured, and the rate of increase of the charge end voltage per cycle (m
V / cycle), and the results are shown in Table 1 below. In addition, when charging and discharging are repeatedly performed while charging to a certain capacity in this manner, the smaller the rate of increase of the end-of-charge voltage, the better the charge-discharge cycle characteristics.
【００３８】充電終止電圧の上昇率（ｍＶ／サイクル）
＝（Ｐ251 −Ｐ1 ）／２５０Rate of rise of charge end voltage (mV / cycle)
= (P 251 -P 1 ) / 250
【００３９】[0039]
【表１】 [Table 1]
【００４０】この結果から明らかなように、正極にリチ
ウム含有ニッケル・コバルト複合酸化物であるＬｉＮｉ
0.7 Ｃｏ0.3 Ｏ2 の粉末を用いると共に、負極に天然黒
鉛の粉末と難黒鉛化炭素の粉末とを８０：２０の重量比
率で混合させたものを用いたリチウム二次電池におい
て、パルス磁場勾配ＮＭＲ法により算出される7Ｌｉ核
自己拡散係数が１．５×１０-6ｃｍ2 ／ｓ以上になった
非水電解液を用いた実施例１，２の各リチウム二次電池
は、パルス磁場勾配ＮＭＲ法により算出される7Ｌｉ核
自己拡散係数が１．５×１０-6ｃｍ2 ／ｓ未満の１．３
８×１０-6ｃｍ2／ｓになった非水電解液を用いた比較
例１のリチウム二次電池に比べて、充電終止電圧の上昇
率が大きく低下しており、充放電サイクル特性が著しく
向上していた。As is apparent from the results, the positive electrode was made of LiNi, a nickel-cobalt composite oxide containing lithium.
In a lithium secondary battery using a powder of 0.7 Co 0.3 O 2 mixed with a powder of natural graphite and a powder of non-graphitizable carbon at a weight ratio of 80:20, a pulsed magnetic field gradient NMR was used. Each of the lithium secondary batteries of Examples 1 and 2 using a non-aqueous electrolyte having a self-diffusion coefficient of 7 Li of 1.5 × 10 −6 cm 2 / s or more calculated by a pulse magnetic field gradient was used. 1.3 in which the 7 Li nucleus self-diffusion coefficient calculated by the NMR method is less than 1.5 × 10 −6 cm 2 / s.
Compared with the lithium secondary battery of Comparative Example 1 using the non-aqueous electrolyte of 8 × 10 −6 cm 2 / s, the rate of increase in the end-of-charge voltage was greatly reduced, and the charge / discharge cycle characteristics were remarkably large. Had improved.
【００４１】なお、上記の実施例においては、直径が３
０ｍｍ，高さが６５ｍｍになった円筒型のリチウム二次
電池について説明したが、リチウム二次電池の形状や大
きさ等については特に限定されず、扁平なコイン形や、
角形状等の種々の形状のリチウム二次電池についても同
様の効果が得られる。In the above embodiment, the diameter is 3
Although a cylindrical lithium secondary battery having a height of 0 mm and a height of 65 mm has been described, the shape and size of the lithium secondary battery are not particularly limited.
Similar effects can be obtained for lithium secondary batteries having various shapes such as a rectangular shape.
【００４２】[0042]
【発明の効果】以上詳述したように、この発明における
リチウム二次電池においては、正極に一般式ＬｉＮｉ
1-x Ｃｏx Ｏ2 （但し、０．１≦ｘ≦０．６の条件を満
たす。）で表されるリチウム含有ニッケル・コバルト複
合酸化物を用いると共に、負極に天然黒鉛が６０〜９０
重量％の範囲で含まれると共に難黒鉛化炭素が４０〜１
０重量％の範囲で含まれる炭素材料を用い、さらに非水
電解液として、パルス磁場勾配ＮＭＲ法によって算出さ
れる7Ｌｉ核の自己拡散係数が１．５×１０-6ｃｍ2 ／ｓ
以上になった非水電解液を使用するようにしたため、正
極及び負極の容量が大きくなると共に、この非水電解液
中においてリチウムイオンがスムーズに移動するように
なり、電池反応がより均一に行われるようになった。As described in detail above, the present invention
In a lithium secondary battery, the general formula LiNi
1-xCoxOTwo(However, the condition of 0.1 ≦ x ≦ 0.6 is satisfied.
Add ) Nickel-cobalt complex containing lithium
A composite oxide is used, and the natural graphite contains 60 to 90
% Of the non-graphitizable carbon in the range of 40 to 1% by weight.
Use a carbon material contained in the range of 0% by weight, and
Calculated by pulsed magnetic field gradient NMR method as electrolyte
Be7Li nucleus self-diffusion coefficient is 1.5 × 10-6cmTwo / S
Since the non-aqueous electrolyte solution described above was used,
As the capacity of the electrode and the anode increases, this non-aqueous electrolyte
Lithium ions move smoothly inside
As a result, the battery reaction was performed more uniformly.
【００４３】この結果、この発明におけるリチウム二次
電池においては、充放電サイクル特性が著しく向上し
た。As a result, in the lithium secondary battery of the present invention, the charge / discharge cycle characteristics were significantly improved.
【図１】この発明の実施例及び比較例において作製した
リチウム二次電池の内部構造を示した断面説明図であ
る。FIG. 1 is an explanatory cross-sectional view showing an internal structure of a lithium secondary battery produced in an example of the present invention and a comparative example.
１ 正極 ２ 負極 1 Positive electrode 2 Negative electrode
【手続補正書】[Procedure amendment]
【提出日】平成１３年４月１７日（２００１．４．１
７）[Submission date] April 17, 2001 (2001.4.1
7)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１７】ここで、上記のパルス磁場勾配ＮＭＲ法に
おいて、パルス磁場勾配を照射していない場合のシグナ
ル強度Ｅｏに対するパルス磁場勾配を照射した場合のシ
グナル強度Ｅの比（＝Ｅ／Ｅｏ）は、下記のＳｔｅｊｓ
ｋａｌの式で表すことができる。[0017] Here, in the above-mentioned pulsed field gradient NMR method, the ratio of signal intensity E when irradiated with pulse magnetic field gradient for the signal intensity Eo when not irradiated with the pulse field gradient (= E / Eo) Is the Stejs below
It can be represented by the following equation:
───────────────────────────────────────────────────── フロントページの続き (72)発明者 喜田 佳典 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 米津 育郎 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 Ｆターム(参考） 5H029 AJ05 AK03 AL06 AL07 AL19 AM02 AM03 AM04 AM05 AM07 CJ08 DJ16 HJ00 HJ01 HJ02 HJ05 5H050 AA07 BA17 CA08 CB07 CB08 FA17 HA01 HA05 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshinori Kida 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshiyuki Noma 2-chome Keihanhondori, Moriguchi-shi, Osaka 5-5 Sanyo Electric Co., Ltd. (72) Inventor Ikuro Yonezu 2-5-5 Keihanhondori, Moriguchi-shi, Osaka F-term in Sanyo Electric Co., Ltd. 5H029 AJ05 AK03 AL06 AL07 AL19 AM02 AM03 AM04 AM05 AM07 CJ08 DJ16 HJ00 HJ01 HJ02 HJ05 5H050 AA07 BA17 CA08 CB07 CB08 FA17 HA01 HA05
Claims (5)
リチウム二次電池において、上記の正極に、一般式Ｌｉ
Ｎｉ1-x Ｃｏx Ｏ2 （但し、０．１≦ｘ≦０．６の条件
を満たす。）で表されるリチウム含有ニッケル・コバル
ト複合酸化物を用いると共に、上記の負極に、天然黒鉛
が６０〜９０重量％の範囲で含まれると共に難黒鉛化炭
素が４０〜１０重量％の範囲で含まれる炭素材料を用
い、さらに上記の非水電解液として、パルス磁場勾配Ｎ
ＭＲ法によって算出される7Ｌｉ核の自己拡散係数が
１．５×１０-6ｃｍ2 ／ｓ以上になった非水電解液を用
いたことを特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode has a general formula Li
A lithium-containing nickel-cobalt composite oxide represented by Ni 1-x Co x O 2 (provided that 0.1 ≦ x ≦ 0.6 is satisfied) is used, and natural graphite is added to the negative electrode. A carbon material which is contained in the range of 60 to 90% by weight and which contains the non-graphitizable carbon in the range of 40 to 10% by weight is used.
A lithium secondary battery using a non-aqueous electrolyte having a self-diffusion coefficient of 7 Li nuclei calculated by an MR method of 1.5 × 10 −6 cm 2 / s or more.
おいて、上記の正極に用いるリチウム含有ニッケル・コ
バルト複合酸化物が、ＬｉＮｉ0.7 Ｃｏ0.3Ｏ2 である
ことを特徴とするリチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the lithium-containing nickel-cobalt composite oxide used for the positive electrode is LiNi 0.7 Co 0.3 O 2 .
電池において、上記の負極に用いる炭素材料における天
然黒鉛と難黒鉛化炭素との混合比率が８０重量％：２０
重量％であることを特徴とするリチウム二次電池。3. The lithium secondary battery according to claim 1, wherein a mixing ratio of natural graphite and non-graphitizable carbon in the carbon material used for the negative electrode is 80% by weight: 20.
% By weight.
チウム二次電池において、上記の炭素材料における上記
の天然黒鉛の平均粒径が１５μｍ〜２０μｍの範囲であ
ると共に、上記の難黒鉛化炭素の平均粒径が３μｍ〜７
μｍの範囲であることを特徴とするリチウム二次電池。4. The lithium secondary battery according to claim 1, wherein the average particle size of the natural graphite in the carbon material is in a range of 15 μm to 20 μm, and Average particle size of graphitized carbon is 3 μm to 7
A lithium secondary battery having a range of μm.
チウム二次電池において、上記の非水電解液における非
水系溶媒に高誘電率溶媒と低粘度溶媒とを含む混合溶媒
を用いたことを特徴とするリチウム二次電池。5. The lithium secondary battery according to claim 1, wherein a mixed solvent containing a high dielectric constant solvent and a low viscosity solvent is used as the non-aqueous solvent in the non-aqueous electrolyte. A rechargeable lithium battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011081995A (en) * | 2009-10-06 | 2011-04-21 | Asahi Kasei E-Materials Corp | Separator for oven resistant property storage device |
| JP2011081994A (en) * | 2009-10-06 | 2011-04-21 | Asahi Kasei E-Materials Corp | Separator for high-temperature preservation characteristics storage device |
| WO2016174862A1 (en) * | 2015-04-28 | 2016-11-03 | 株式会社Ｇｓユアサ | Negative electrode for nonaqueous-electrolyte power storage element |
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