JP2000123867A5 - - Google Patents
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- JP2000123867A5 JP2000123867A5 JP1998297465A JP29746598A JP2000123867A5 JP 2000123867 A5 JP2000123867 A5 JP 2000123867A5 JP 1998297465 A JP1998297465 A JP 1998297465A JP 29746598 A JP29746598 A JP 29746598A JP 2000123867 A5 JP2000123867 A5 JP 2000123867A5
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- Prior art keywords
- positive electrode
- negative electrode
- secondary battery
- aqueous secondary
- electrolyte
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- 239000000203 mixture Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- -1 cyclic ester Chemical class 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
Description
【０００３】
しかしながら、この非水二次電池について、本発明者らは、さらなる高性能化を目指して検討を進めていくうちに、電池の容量が増加するのに伴い、負極の負極合剤層の密度を高くする必要があり、負極合剤層の密度が１．４５ｇ／ｃｍ3 になると、所望のサイクル特性が得られにくくなることが判明した。[0003]
However, as for the non-aqueous secondary battery, the present inventors proceeded with studies for further performance enhancement, and as the battery capacity increased, the density of the negative electrode mixture layer of the negative electrode increased. It has been found that it is necessary to increase the density, and when the density of the negative electrode mixture layer becomes 1.45 g / cm 3 , it becomes difficult to obtain desired cycle characteristics.
【０００４】
【発明が解決しようとする課題】
本発明は、上記のような従来の非水二次電池の問題点を解決し、負極合剤層の密度が１．４５ｇ／ｃｍ3 以上の高容量の非水二次電池において、サイクル特性が優れた非水二次電池を提供することを目的とする。[0004]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of the conventional non-aqueous secondary battery, and provides a high-capacity non-aqueous secondary battery in which the density of the negative electrode mixture layer is 1.45 g / cm 3 or more. An object is to provide an excellent non-aqueous secondary battery.
【０００５】
【課題を解決するための手段】
本発明は、正極、負極および電解質を有し、正極に４Ｖ級の活物質を用い、負極に炭素材料を用い、その負極の負極合剤層の密度が１．４５ｇ／ｃｍ3 である非水二次電池において、電解質中に環状で環内にＣ＝Ｃ不飽和結合を有するエステルまたはその誘導体を含有させることによって、上記課題を解決したものである。[0005]
[Means for Solving the Problems]
The present invention relates to a non-aqueous electrolyte having a positive electrode, a negative electrode, and an electrolyte, using a 4 V-class active material for the positive electrode, using a carbon material for the negative electrode, and having a negative electrode mixture layer of the negative electrode with a density of 1.45 g / cm 3. In a secondary battery, the above problem has been solved by incorporating an ester having a cyclic C—C unsaturated bond or a derivative thereof in a ring in an electrolyte.
【０００６】
【発明の実施の形態】
また、本発明においては、電極積層体の単位面積当たりの放電容量が１３０ｍＡｈ／ｃｍ3 以上で、上記炭素材料の（００２）面の面間距離ｄ002 が３．５Å以下で、かつｃ軸方向の結晶子の大きさＬｃが３０Å以上である場合や、環状で環内にＣ＝Ｃ不飽和結合を有するエステルまたはその誘導体の含有量が電解質の溶媒成分中０．０５〜８重量％であることを好ましい形態とする。[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Further, in the present invention, the electrode laminate has a discharge capacity per unit area of 130 mAh / cm 3 or more, an inter-plane distance d 002 of the (002) plane of the carbon material of 3.5 ° or less, and a c-axis direction. The crystallite size Lc is 30 ° or more, or the content of a cyclic ester having a C ＝ C unsaturated bond in the ring or a derivative thereof is 0.05 to 8% by weight in the solvent component of the electrolyte. This is a preferred mode.
【００１９】
正極に用いる正極集電材は、アルミニウムを主成分とする金属箔が好ましく、そのアルミニウムの純度は９８重量％以上９９．９重量％未満が好ましい。通常のリチウムイオン二次電池では純度が９９．９重量％以上のアルミニウム箔が正極集電材として用いられているが、本発明においては高容量化やサイクル特性の向上を図るため厚さが１５μｍ以下の薄い金属箔を用いるのが好ましい。そのため、薄くても使用に耐え得る強度にしておくことが好ましく、そのような強度を確保するためには純度が９９．９重量％未満であることが好ましい。アルミニウムに添加する金属として特に好ましいのは、鉄とシリコンである。鉄は０．５重量％以上が好ましく、さらに好ましくは０．７重量％以上であり、また、２重量％以下が好ましく、より好ましくは１．３重量％以下である。シリコンは０．１重量％以上が好ましく、より好ましくは０．２重量％以上であり、また１．０重量％以下が好ましく、より好ましくは０．３重量％以下である。これらの鉄やシリコンはアルミニウムと合金化していることが必要であり、アルミニウム中に不純物として存在するものではない。[0019]
The positive electrode current collector used for the positive electrode is preferably a metal foil containing aluminum as a main component, and the purity of aluminum is preferably 98% by weight or more and less than 99.9% by weight. In a normal lithium ion secondary battery, an aluminum foil having a purity of 99.9% by weight or more is used as a positive electrode current collector. However, in the present invention, the thickness is 15 μm or less in order to increase capacity and improve cycle characteristics. It is preferable to use a thin metal foil. Therefore, it is preferable to have a strength that can be used even if it is thin, and in order to secure such strength, the purity is preferably less than 99.9% by weight. Particularly preferred metals to be added to aluminum are iron and silicon. Iron is preferably 0.5% by weight or more, more preferably 0.7% by weight or more, and preferably 2% by weight or less, more preferably 1.3% by weight or less. Silicon is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and preferably 1.0% by weight or less, more preferably 0.3% by weight or less. These iron and silicon need to be alloyed with aluminum, and do not exist as impurities in aluminum.
【００２４】
負極に用いる材料は、リチウムイオンをドープ、脱ドープできるものであればよく、本発明においては、それを負極活物質と呼んでいるが、そのような負極活物質として、例えば、黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭などの炭素材料を用いる。特に２５００℃以上で焼成したメソカーボンマイクロビーズは、負極合剤層を高密度に作製してもサイクル特性が良好であることから好ましい。[0024]
The material used for the negative electrode may be any material capable of doping and undoping lithium ions, and in the present invention, it is referred to as a negative electrode active material. As such a negative electrode active material, for example, graphite, pyrolysis Carbon materials such as carbons, cokes, glassy carbons, fired bodies of organic polymer compounds, mesocarbon microbeads, carbon fibers, and activated carbon are used. In particular, mesocarbon microbeads fired at 2500 ° C. or more are preferable because the cycle characteristics are good even when the negative electrode mixture layer is formed at a high density.
【００２５】
負極活物質として負極に用いる炭素材料は下記の特性を持つものが好ましい。すなわち、その（００２）面の面間距離ｄ002 に関しては、３．５Å以下が好ましく、より好ましくは３．４５Å以下、さらに好ましくは３．４Å以下である。またｃ軸方向の結晶子の大きさＬｃは３０Å以上が好ましく、より好ましくは８０Å以上、さらに好ましくは２５０Å以上である。そして、上記炭素材料の平均粒径は８〜２０μｍ、特に１０〜１５μｍが好ましく、純度は９９．９重量％以上が好ましい。[0025]
The carbon material used for the negative electrode as the negative electrode active material preferably has the following characteristics. That is, the inter-plane distance d 002 of the (002) plane is preferably 3.5 ° or less, more preferably 3.45 ° or less, and even more preferably 3.4 ° or less. The crystallite size Lc in the c-axis direction is preferably 30 ° or more, more preferably 80 ° or more, and further preferably 250 ° or more. The average particle size of the carbon material is preferably 8 to 20 μm, particularly preferably 10 to 15 μm, and the purity is preferably 99.9% by weight or more.
【００２６】
負極は、例えば、上記負極活物質としての炭素材料に、必要に応じ、正極の場合と同様の導電助剤やバインダなどを加え、混合して負極合剤を調製し、それを溶剤に分散させてペーストにし（バインダはあらかじめ溶剤に溶解させておいてから負極活物質などと混合してもよい）、その負極合剤ペーストを銅箔などからなる負極集電材に塗布し、乾燥して、負極集電材の少なくとも一部に負極合剤層を形成することによって作製される。ただし、負極の作製方法は上記例示の方法に限られることなく、他の方法によってもよい。[0026]
The negative electrode, for example, to the carbon material as the negative electrode active material, if necessary, the same conductive aids and binders as in the case of the positive electrode are added, mixed to prepare a negative electrode mixture, and dispersed in a solvent. Paste (the binder may be dissolved in a solvent in advance and then mixed with the negative electrode active material, etc.), the negative electrode mixture paste is applied to a negative electrode current collector made of copper foil or the like, dried, and dried. It is produced by forming a negative electrode mixture layer on at least a part of the current collector. However, the method for manufacturing the negative electrode is not limited to the above-described method, but may be another method.
【００２８】
負極に炭素材料を用いるに際して、高容量化を図るために、その負極の負極合剤層の密度を１．４５ｇ／ｃｍ3 以上にするが、特に負極合剤層の密度を１．５ｇ／ｃｍ3 以上にすることが好ましい。通常、負極合剤層を高密度にすると、高容量は得られやすくなるが、電解液の浸透が遅くなり、また活物質の利用度も不均一になりやすいため、サイクル特性が低下しやすくなるが、本発明によれば、そのような場合にも、優れたサイクル特性が得られる。すなわち、本発明において用いる環状で環内にＣ＝Ｃ不飽和結合を有するエステルまたはその誘導体は、上記のように負極合剤層を高密度にした場合にも、その効果を顕著に発現する。[0028]
When a carbon material is used for the negative electrode, the density of the negative electrode mixture layer of the negative electrode is set to 1.45 g / cm 3 or more in order to increase the capacity. In particular, the density of the negative electrode mixture layer is 1.5 g / cm 3. It is preferred to be 3 or more. Normally, when the density of the negative electrode mixture layer is increased, a high capacity is easily obtained, but the permeation of the electrolytic solution is slow, and the utilization of the active material is also likely to be uneven, so that the cycle characteristics are likely to be deteriorated. However, according to the present invention, even in such a case, excellent cycle characteristics can be obtained. That is, the cyclic ester having a C ＝ C unsaturated bond in the ring or a derivative thereof used in the present invention remarkably exerts its effect even when the negative electrode mixture layer has a high density as described above.
【００３０】
本発明は、電極積層体の単位体積当たりの放電容量が１３０ｍＡｈ／ｃｍ3 以上の非水二次電池を対象とすることを好ましいとしているが、これは高容量化を図るという理由に基づいている。本発明において、電極積層体の体積とは、正極、負極およびセパレータを積層したものまたは正極、負極およびセパレータを巻回したものの電池内における嵩体積であって、後者のように巻回したものにあっては、巻回に際して使用した巻き軸に基づく巻回体中心部の透孔などは体積として含まない。要は正極、負極、セパレータが占める嵩体積を合計したものである。これら正極、負極、セパレータの３つの体積は電池の容量を決定する重要な因子であり、電池の大きさにかかわらず、電極積層体の単位体積当たりの放電容量（放電容量／電極積層体の体積）を計算することによって、電池の容量密度を比較することができる。また、ここでいう放電容量とは、電池を前記の標準使用条件で充放電させた場合の放電容量である。そして、より高容量化を図るという観点からは、電極積層体の単位体積当たりの放電容量は１４０ｍＡｈ／ｃｍ3 以上がより好ましく、１５０ｍＡｈ／ｃｍ3 以上がさらに好ましい。[0030]
The present invention is preferably directed to a non-aqueous secondary battery having a discharge capacity per unit volume of the electrode laminate of 130 mAh / cm 3 or more, but this is based on the reason of achieving high capacity. . In the present invention, the volume of the electrode laminate is the volume of the positive electrode, the negative electrode and the separator laminated or the positive electrode, the negative electrode and the separator wound, and the bulk volume in the battery, which is the same as the latter. In this case, the volume at the center of the wound body based on the winding shaft used for winding is not included. In short, it is the sum of the bulk volumes occupied by the positive electrode, the negative electrode, and the separator. The three volumes of the positive electrode, the negative electrode, and the separator are important factors that determine the capacity of the battery. Regardless of the size of the battery, the discharge capacity per unit volume of the electrode stack (discharge capacity / volume of the electrode stack) ), The capacity densities of the batteries can be compared. The term “discharge capacity” as used herein refers to a discharge capacity when a battery is charged and discharged under the standard use conditions described above. And more from the viewpoint of achieving Koyo capacity, discharge capacity per unit volume of the electrode stack is more preferably 140 mAh / cm 3 or more, more preferably 150 mAh / cm 3 or more.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29746598A JP3957415B2 (en) | 1998-10-20 | 1998-10-20 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29746598A JP3957415B2 (en) | 1998-10-20 | 1998-10-20 | Non-aqueous secondary battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000123867A JP2000123867A (en) | 2000-04-28 |
| JP2000123867A5 true JP2000123867A5 (en) | 2004-09-30 |
| JP3957415B2 JP3957415B2 (en) | 2007-08-15 |
Family
ID=17846854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29746598A Expired - Lifetime JP3957415B2 (en) | 1998-10-20 | 1998-10-20 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3957415B2 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9929698D0 (en) * | 1999-12-15 | 2000-02-09 | Danionics As | Non-aqueous electrochemical cell |
| TW531924B (en) * | 2000-05-26 | 2003-05-11 | Sony Corp | Nonaqueous electrolyte secondary battery |
| BRPI0607367A2 (en) | 2005-02-15 | 2009-09-01 | Lg Chemical Ltd | lithium secondary battery of ammonium composite content electrolyte |
| JP5017800B2 (en) * | 2005-05-12 | 2012-09-05 | ソニー株式会社 | Secondary battery electrolyte and secondary battery |
| KR101082152B1 (en) | 2006-06-20 | 2011-11-09 | 주식회사 엘지화학 | Electrolyte for improving life characteristics at a high temperature and lithium secondary battery comprising the same |
| JP5277550B2 (en) | 2007-03-12 | 2013-08-28 | セントラル硝子株式会社 | Method for producing lithium difluorophosphate and non-aqueous electrolyte battery using the same |
| EP2212965B1 (en) | 2007-11-09 | 2015-06-10 | LG Chem, Ltd. | Lithium secondary battery containing additives for improved high-temperature characteristics |
| JP5544748B2 (en) * | 2009-04-22 | 2014-07-09 | セントラル硝子株式会社 | Electrolytes for electrochemical devices, electrolytes using the same, and nonaqueous electrolyte batteries |
| JP5573313B2 (en) | 2010-04-06 | 2014-08-20 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery using the same |
| JP5796417B2 (en) | 2011-08-31 | 2015-10-21 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery |
| US10938066B2 (en) | 2014-02-14 | 2021-03-02 | Stella Chemifa Corporation | Nonaqueous electrolyte solution for secondary batteries and secondary battery provided with same |
| JP6361486B2 (en) | 2014-12-01 | 2018-07-25 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery using the same |
| JP6767117B2 (en) | 2015-02-04 | 2020-10-14 | ステラケミファ株式会社 | Non-aqueous electrolyte for secondary batteries and secondary batteries equipped with it |
| JP6665396B2 (en) | 2015-02-19 | 2020-03-13 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
| JP6601094B2 (en) | 2015-09-25 | 2019-11-06 | 日清紡ホールディングス株式会社 | Additive for electrolyte |
| CN105336987A (en) * | 2015-11-17 | 2016-02-17 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN113782817B (en) | 2015-12-22 | 2024-04-12 | 中央硝子株式会社 | Electrolyte for nonaqueous electrolyte battery and nonaqueous electrolyte battery using same |
| CN109326823B (en) | 2017-07-31 | 2020-04-21 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN109428120B (en) | 2017-08-30 | 2021-09-17 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery |
| JP7223221B2 (en) | 2017-09-12 | 2023-02-16 | セントラル硝子株式会社 | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and non-aqueous electrolyte battery |
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| CN109950621B (en) | 2017-12-21 | 2022-05-03 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN111403807B (en) | 2019-01-02 | 2022-12-06 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| JPWO2020170833A1 (en) | 2019-02-19 | 2021-12-23 | 株式会社Adeka | Electrolyte compositions, non-aqueous electrolytes and non-aqueous electrolyte secondary batteries |
| CN114447432B (en) | 2020-11-03 | 2023-12-15 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
-
1998
- 1998-10-20 JP JP29746598A patent/JP3957415B2/en not_active Expired - Lifetime
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