JP6635283B2 - Negative electrode for non-aqueous electrolyte storage element and non-aqueous electrolyte storage element - Google Patents
Negative electrode for non-aqueous electrolyte storage element and non-aqueous electrolyte storage element Download PDFInfo
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- JP6635283B2 JP6635283B2 JP2015066838A JP2015066838A JP6635283B2 JP 6635283 B2 JP6635283 B2 JP 6635283B2 JP 2015066838 A JP2015066838 A JP 2015066838A JP 2015066838 A JP2015066838 A JP 2015066838A JP 6635283 B2 JP6635283 B2 JP 6635283B2
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- negative electrode
- aqueous electrolyte
- binder
- active material
- storage element
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Images
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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、非水電解質蓄電素子用負極、及びこの負極を備えた非水電解質蓄電素子に関する。 The present invention relates to a negative electrode for a non-aqueous electrolyte storage element and a non-aqueous electrolyte storage element including the negative electrode.
リチウム二次電池、リチウムイオンキャパシタ等の非水電解質蓄電素子は、携帯用端末、電気自動車、ハイブリッド自動車等に広く用いられており、今後もエネルギー密度の向上が期待されている。 Non-aqueous electrolyte storage elements such as lithium secondary batteries and lithium ion capacitors are widely used in portable terminals, electric vehicles, hybrid vehicles, and the like, and are expected to have improved energy density in the future.
従来、非水電解質蓄電素子の負極には、充放電サイクル性能が良好で、コスト面で有利な炭素材料が用いられてきた。しかし、炭素材料は、リチウムイオンの黒鉛結晶中への吸蔵・放出により充放電がなされるため、最大リチウム導入化合物であるＬｉＣ６から計算される理論容量３７２ｍＡｈ／ｇを超える充放電容量が得られない。 Conventionally, a carbon material that has good charge / discharge cycle performance and is advantageous in cost has been used for the negative electrode of the nonaqueous electrolyte storage element. However, since the carbon material is charged and discharged by occlusion and release of lithium ions into the graphite crystal, a charge and discharge capacity exceeding 372 mAh / g, which is the theoretical capacity calculated from LiC 6 as the maximum lithium-introducing compound, is obtained. Absent.
これに対して、ＳｉやＳｎの金属単体や、これらの元素を含む合金又は化合物は、炭素材料と比較して大きな理論容量を有するため、これらを負極活物質に用いる検討がなされている。 In contrast, simple metals such as Si and Sn, and alloys or compounds containing these elements have larger theoretical capacities than carbon materials. Therefore, studies have been made on using these as a negative electrode active material.
非水電解質蓄電素子の電極は、一般に、集電体と、該集電体に形成された活物質を含む合剤層からなっている。前記合剤層は、一般に、活物質に、バインダーと、必要に応じて導電剤、増粘剤、フィラー等の他の材料とを混練したものに溶媒を加えてスラリーとし、これを集電体に塗布又は圧着した後、熱処理により溶媒を乾燥除去し、プレス成型して形成される。 An electrode of a nonaqueous electrolyte storage element generally includes a current collector and a mixture layer containing an active material formed on the current collector. In general, the mixture layer is formed by adding a solvent to a material obtained by kneading an active material, a binder, and other materials such as a conductive agent, a thickener, and a filler, if necessary, to obtain a slurry. After applying or press-bonding, the solvent is dried and removed by heat treatment, and press-molding is performed.
特許文献１には、「可逆的にリチウムの吸蔵および放出が可能な活物質粉末と、結着剤と、を含む負極合剤を含み、前記活物質が、ＳｉおよびＳｎよりなる群から選ばれる少なくとも１種の元素を含み、前記結着剤が、エチレン−アクリル酸共重合体およびエチレン−メタクリル酸共重合体よりなる群から選ばれる少なくとも１種を含み、前記エチレン−アクリル酸共重合体に含まれるアクリル酸単位の含有量が、１０ｍｏｌ％〜６０ｍｏｌ％であり、前記エチレン−メタクリル酸共重合体に含まれるメタクリル酸単位の含有量が、１０ｍｏｌ％〜６０ｍｏｌ％である、リチウムイオン二次電池用負極。」（補正書の請求の範囲［１］）の発明が記載されている。
そして、この共重合体よりなる結着剤について、「それぞれアクリル酸単位およびメタクリル酸単位の影響により、共重合体の結晶化度は低くなる。よって、これらの共重合体は、柔軟性が高くなる。また、これらの共重合体は、それぞれアクリル酸単位およびメタクリル酸単位を含有するため、高い接着性も有する。」（００２２）という作用により、「特に低温でのサイクル特性に優れたリチウムイオン二次電池を提供することが可能となる。」（００１７）という効果を奏すると記載されている。
Regarding the binder made of this copolymer, "The crystallinity of the copolymer is reduced due to the influence of acrylic acid units and methacrylic acid units, respectively. Therefore, these copolymers have high flexibility. In addition, since these copolymers each contain an acrylic acid unit and a methacrylic acid unit, they also have high adhesiveness. "(0022) It is possible to provide a secondary battery. "(0017).
特許文献２には、「電極活物質と導電助材と有機バインダーからなる正極および負極、非水溶媒と支持塩からなる耐熱電解液、耐熱セパレータ、耐熱ガスケット等の部材からなる非水電解質電池において、正極、負極の両方又は一方を２００℃〜４５０℃で熱処理して用いたことを特徴とする非水電解質二次電池。」（請求項１）の発明が記載されている。
また、この非水電解質二次電池について、「前記負極が負極活物質として、リチウムイオンを吸蔵放出可能なケイ素の酸化物または錫の酸化物を用いた」（請求項２）、「有機バインダーがポリアクリル酸からなり、」（請求項５）、「電極活物質と導電助材と有機バインダーからなる電極を２００℃〜４５０℃で熱処理して用いた。」（００１３）と記載されている。
そして、この熱処理の効果について、「活物質、有機バインダー、導電助材の熱的に活性な部分（微粉、合成時の未反応部分等）が加熱により変化し、リフロー温度でも安定になったことにあると推測できる。また、２００℃以上の加熱は有機物に大きな変化を与える。有機バインダーは、熱処理により大きく電解液との濡れ性が向上する。これは、２００℃付近で分解が始まるため、有機バインダーの表面の官能基等が改質されたか、有機バインダーの一部が分解し多孔質になったためと考えられる。」（００２４）と記載されている。
Regarding this non-aqueous electrolyte secondary battery, “the negative electrode used as the negative electrode active material was an oxide of silicon or an oxide of tin capable of inserting and extracting lithium ions” (Claim 2); (Claim 5), and "An electrode made of an electrode active material, a conductive additive, and an organic binder was heat-treated at 200 ° C. to 450 ° C. and used” (0013).
Regarding the effect of this heat treatment, "The thermally active parts (fine powder, unreacted parts at the time of synthesis, etc.) of the active material, organic binder, and conductive additive changed by heating and became stable even at the reflow temperature. In addition, heating at 200 ° C. or more gives a large change to organic substances.The heat treatment of the organic binder greatly increases the wettability with the electrolytic solution. It is considered that the functional group or the like on the surface of the organic binder has been modified, or a part of the organic binder has been decomposed to become porous. "
特許文献３には、「負極活物質、バインダーおよび導電材を含むリチウム二次電池用負極材料組成物において、前記バインダーは、アクリロニトリルに対しアクリル酸のモル比が０.０１〜２のポリアクリロニトリル-アクリル酸共重合体であることを特徴とするリチウム二次電池用負極材料組成物。」（請求項１）の発明が記載されている。
前記負極活物質として挙げられた「シリコン系負極活物質および錫系負極活物質」について、「充放電時、リチウムとの反応による体積変化が２００〜３００％であって非常に大きい。」（００１０）、「負極活物質は、充放電サイクルが行われるにつれ体積が変化し、これにより、電池のサイクル寿命が短縮されるなど電池性能の劣化現象が発生することになる。」（００１２）と記載されている。
そして、「負極材料組成物に含まれるバインダーの種類と量は、負極活物質の充放電サイクルによる体積変化に影響を与える。」（００１２）、「負極用バインダーとして、分子量が大きいポリアクリロニトリル-アクリル酸共重合体を用いることにより、集電体および電極混合物間の密着性が向上すると共に、有機系電解液に対する溶解、又は膨潤を減少させて、充放電を繰り返しても活物質の剥離及び脱落を防止することができ、これにより、前記負極用バインダーを用いて製造されたリチウム二次電池の容量や出力維持率の低下を抑制できる効果を得ることができる。」（００２７）、「上記のような負極混合物を集電体上に塗布、乾燥および圧延して製作される。この際、乾燥温度は２００℃以下にし、望ましくは１５０℃以下が要求される。２００℃よりも高い温度ではポリアクリロニトリルが速く分解されて目的とする効果を得ることができない。」（００３９）と記載されている。また、実施例に記載されている乾燥温度は１３０℃のみである（００５２）、（００５８）。
Regarding the “silicon-based negative electrode active material and the tin-based negative electrode active material” listed as the negative electrode active material, “the volume change due to the reaction with lithium during charging and discharging is 200 to 300%, which is very large” (0010). ), "The negative electrode active material changes in volume as the charge / discharge cycle is performed, thereby causing a deterioration in battery performance such as a reduction in the cycle life of the battery" (0012). Have been.
Then, "The type and amount of the binder contained in the negative electrode material composition affects the volume change of the negative electrode active material due to charge / discharge cycles." (0012), "Polyacrylonitrile-acryl having a large molecular weight as a negative electrode binder By using the acid copolymer, the adhesion between the current collector and the electrode mixture is improved, and the dissolution or swelling in the organic electrolyte solution is reduced, so that the active material is separated and dropped even after repeated charging and discharging. , And the effect of suppressing a decrease in the capacity and output retention of the lithium secondary battery manufactured using the negative electrode binder can be obtained. "(0027)," The negative electrode mixture is coated on a current collector, dried and rolled, and the drying temperature is set to 200 ° C. or lower, preferably 150 ° C. or lower. If the temperature is higher than 200 ° C., polyacrylonitrile is rapidly decomposed and the desired effect cannot be obtained. ”(0039). The drying temperatures described in the examples are only 130 ° C. (0052) and (0058).
特許文献４には、「リチウムを電気化学的に吸蔵・放出できる金属粒子Ａと、前記金属粒子Ａよりも導電性が高く、且つ前記金属粒子Ａよりもリチウムの吸蔵・放出能力が低い金属粒子Ｂと、を用いて得られ‥る複合粒子。」（請求項１）、であって、「前記金属粒子Ａが、シリコン及びスズから選ばれる少なくとも１種である」発明（請求項３）が記載されている。
また、集電体と、この複合粒子を有し、さらに炭素質物質及びバインダを含むリチウムイオン二次電池用負極（請求項８，９）の発明、及び、これの製造方法として、前記複合粒子、炭素質物質、及び主骨格がポリアクリロニトリルであるバインダを含む混合物を得る工程、前記混合物を１００℃〜１６０℃の範囲内で熱処理する工程、を含むリチウムイオン二次電池用負極の製造方法（請求項１５，１６）の発明も記載されている。
そして、上記の各発明について、「高容量で、優れた充放電サイクル性を示す複合粒子‥を用いたリチウムイオン二次電池用負極、リチウムイオン二次電池用負極の製造方法、及びリチウムイオン二次電池を提供することができる。」（００２８）と記載され、前記製造方法における熱処理の作用効果として、「溶媒の除去、バインダの高強度化が進み、複合粒子間及び複合粒子と集電体間の密着性を向上することができる。」（００８１）と記載されている。
Patent Literature 4 discloses “metal particles A capable of electrochemically occluding and releasing lithium, and metal particles having higher conductivity than the metal particles A and lower ability of occluding and releasing lithium than the metal particles A. B. A composite particle obtained by using B. ”(Claim 1), wherein the“ the metal particle A is at least one selected from silicon and tin ”(Claim 3). Has been described.
The invention of a negative electrode for a lithium ion secondary battery (Claims 8 and 9) comprising a current collector and the composite particles, and further comprising a carbonaceous substance and a binder, and a method for producing the same, wherein the composite particles Obtaining a mixture including a binder, a carbonaceous substance, and a binder whose main skeleton is polyacrylonitrile; and heat-treating the mixture at a temperature in the range of 100 ° C to 160 ° C. Claims 15 and 16) are also described.
Then, regarding each of the above-mentioned inventions, “a negative electrode for a lithium ion secondary battery, a method for producing a negative electrode for a lithium ion secondary battery using a composite particle 高 having a high capacity and excellent charge / discharge cycle properties, and a lithium ion secondary battery” (0028), and as the effect of the heat treatment in the above-described manufacturing method, "the removal of the solvent and the increase in the strength of the binder proceed, and the inter-composite particles and the composite particles and the current collector are produced. Adhesion between the two can be improved. "(0081).
非特許文献１には、ポリアクリロニトリルを２００〜３００℃で加熱すると、ポリアクリロニトリルの隣接したニトリル基の環化反応と同時に不均化反応（脱水素反応）とが起こり、アクリドン環やナフチリジン環の生成を含む構造変化が生じることが記載されている。
According to
負極活物質にＳｉ及びＳｎから選ばれる少なくとも一つの元素を含む金属単体、合金又は化合物を用いた非水電解質蓄電素子は、特許文献３（００１０）に記載されるように、充放電時の負極での膨張収縮が大きいことが知られている。例えば、炭素材料である黒鉛がＬｉイオンを吸蔵した場合の体積膨張は、約１．２倍であるのに対し、Ｓｉ材料ではＳｉとＬｉが合金化する際、約４倍の体積変化を起こす。そのため、負極合剤層内のバインダーに大きな応力が印加されるから、活物質粒子間及び負極合剤層と集電体間の密着性が低下し、充放電サイクル性能が低下するという問題がある。
上記の課題に対し、密着性や柔軟性の優れたバインダーについて、ポリアクリル酸又はポリメタクリル酸とエチレンとの共重合体（特許文献１）や、ポリアクリル酸を２００℃以上で熱変性したもの（特許文献２）、ポリアクリロニトリル構造を含む樹脂材料（特許文献３，４）等が検討されている。
しかし、充放電サイクル性能の向上は未だ十分でない。また、ポリアクリロニトリル構造を含む樹脂材料をバインダーに用いる場合、熱処理温度として２００℃を超えるものについての検討はされていない。
As described in Patent Document 3 (0010), a non-aqueous electrolyte storage element using a metal simple substance, an alloy or a compound containing at least one element selected from Si and Sn as a negative electrode active material has a negative electrode during charge and discharge. Is known to have a large expansion and contraction. For example, the volume expansion when graphite as a carbon material occludes Li ions is about 1.2 times, while the Si material causes about 4 times volume change when Si and Li are alloyed. . For this reason, since a large stress is applied to the binder in the negative electrode mixture layer, there is a problem that the adhesion between the active material particles and between the negative electrode mixture layer and the current collector is reduced, and the charge / discharge cycle performance is reduced. .
In order to solve the above problems, a binder having excellent adhesion and flexibility is obtained by copolymerizing polyacrylic acid or polymethacrylic acid with ethylene (Patent Document 1) or polyacrylic acid thermally modified at 200 ° C. or higher. (Patent Document 2), resin materials having a polyacrylonitrile structure (
However, the improvement in charge / discharge cycle performance is not yet sufficient. Further, when a resin material having a polyacrylonitrile structure is used as a binder, no study has been made on a heat treatment temperature exceeding 200 ° C.
本発明は、Ｓｉ及びＳｎから選ばれる少なくとも一つの元素を含む金属単体、合金又は化合物を負極に用いた非水電解質蓄電素子において、充放電サイクル性能を向上させることを目的とする。 An object of the present invention is to improve charge / discharge cycle performance in a nonaqueous electrolyte energy storage device using a single metal, alloy, or compound containing at least one element selected from Si and Sn for a negative electrode.
上記の目的を達成するために、本発明は以下の手段を有する。
（１）Ｓｉ及びＳｎから選ばれる少なくとも一つの元素を含む金属単体、合金又は化合物を含む負極活物質と、バインダーと、を含む合剤層を有する非水電解質蓄電素子用負極の製造方法であって、
上記負極活物質と、ポリアクリロニトリル構造を有し、さらにポリアクリル酸構造又はポリメタクリル酸構造の少なくとも一方を有する樹脂材料と、を混合すること、
及び、減圧下又は不活性雰囲気下で上記混合物を３００℃以上で熱処理して、前記樹脂材料を、ナフチリジン環構造を有し、さらにポリアクリル酸構造又はポリメタクリル酸構造の少なくとも一方を有する樹脂にすること、
を備える、非水電解質蓄電素子用負極の製造方法。
In order to achieve the above object, the present invention has the following means.
(1) A method for producing a negative electrode for a non-aqueous electrolyte energy storage device having a mixture layer containing a negative electrode active material containing a metal simple substance, an alloy or a compound containing at least one element selected from Si and Sn, and a binder. hand,
The negative electrode active material, having a polyacrylonitrile structure, and further mixed with a resin material having at least one of a polyacrylic acid structure or a polymethacrylic acid structure,
And, the mixture is heat-treated at 300 ° C. or more under reduced pressure or an inert atmosphere to convert the resin material into a resin having a naphthyridine ring structure and further having at least one of a polyacrylic acid structure or a polymethacrylic acid structure. To do,
A method for producing a negative electrode for a non-aqueous electrolyte energy storage device, comprising:
本発明によれば、高容量であるＳｉやＳｎを含む負極を用いて、充放電サイクル性能の優れたリチウム二次電池、キャパシタ等の非水電解質蓄電素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte electrical storage element, such as a lithium secondary battery and a capacitor excellent in charge / discharge cycle performance, can be provided using the high capacity negative electrode containing Si and Sn.
Ｓｉ及びＳｎから選ばれる少なくとも一つの元素を含む負極活物質と、バインダーとしてポリアクリロニトリル構造を含む樹脂材料を用いて負極合剤層を形成する場合、推奨される加熱温度は、従来は１６０℃以下であり（特許文献４参照）、２００℃を超える温度が用いられることはなかった（特許文献３参照）。
本発明者らは、上記の負極合剤層の形成に当たり、分散用の溶媒を含むスラリーを塗布した後の加熱温度を変化させて、加熱温度が蓄電素子の電極特性に与える影響について検討した。すると、驚くべきことに、２５０℃以上、好ましくは３００℃以上の温度を採用することによって、充放電サイクル性能が顕著に向上することを見出した。
When forming a negative electrode mixture layer using a negative electrode active material containing at least one element selected from Si and Sn, and a resin material having a polyacrylonitrile structure as a binder, the recommended heating temperature is conventionally 160 ° C. or less. (See Patent Document 4), and a temperature exceeding 200 ° C. was never used (see Patent Document 3).
The present inventors examined the influence of the heating temperature on the electrode characteristics of the energy storage device by changing the heating temperature after applying the slurry containing the dispersing solvent when forming the negative electrode mixture layer. Then, surprisingly, it has been found that by employing a temperature of 250 ° C. or higher, preferably 300 ° C. or higher, the charge / discharge cycle performance is significantly improved.
この現象の機序を解明すべく、ポリアクリロニトリル構造を有する樹脂材料の熱処理温度による構造変化を、ＩＲ吸収スペクトルにより分析した。その結果、図１に示すように、１５０℃、２００℃の熱処理ではＣＮ三重結合に対応する吸収ピークが明白に現れているのに対して、３００℃以上の熱処理では消失していることがわかった。 In order to elucidate the mechanism of this phenomenon, the structural change of the resin material having a polyacrylonitrile structure due to the heat treatment temperature was analyzed by an IR absorption spectrum. As a result, as shown in FIG. 1, it was found that the absorption peak corresponding to the CN triple bond clearly appeared in the heat treatment at 150 ° C. and 200 ° C., but disappeared in the heat treatment at 300 ° C. or more. Was.
ポリアクリロニトリルを２００〜３００℃で熱処理すると、ニトリル基の環化反応と同時に不均化反応（脱水素反応）が起こることが知られている。
図２は、非特許文献１に記載の耐炎化工程によるポリアクリロニトリルの構造変化を示している。
図２（ａ）に記載の構造を有するポリアクリロニトリルを２００〜３００℃で熱処理すると、図２（ｂ）に記載の隣接したニトリル基の環化反応と同時に不均化反応（脱水素反応）が起こることによって、図２（ｃ）の、一番左の括弧内の構造として表されるアクリドン環、左から２番目の括弧内の構造として表されるナフチリジン環、及び左から３番目の括弧内の構造として表される水素化ナフチリジン環が生成される。
本発明者らが行った３００℃以上での熱処理では、ニトリル基の殆どが環化したため、未反応ニトリルのＣＮ三重結合が消失したと考えられる。また、負極作成時の熱処理は、集電体の酸化防止や、バインダーの変性防止のため、減圧下又は不活性雰囲気下で行うから、酸素を含むアクリドン環の生成は起こり難いと考えられる。したがって、上記のＩＲ吸収スペクトルは、アクリロニトリル構造の少なくとも一部がナフチリジン環構造に変化したことを示すものである。
It is known that when polyacrylonitrile is heat-treated at 200 to 300 ° C., a disproportionation reaction (dehydrogenation reaction) occurs simultaneously with a cyclization reaction of a nitrile group.
FIG. 2 shows a structural change of polyacrylonitrile due to the flameproofing process described in
When polyacrylonitrile having the structure shown in FIG. 2A is heat-treated at 200 to 300 ° C., the disproportionation reaction (dehydrogenation reaction) occurs simultaneously with the cyclization reaction of adjacent nitrile groups shown in FIG. 2B. By happening, the acridone ring represented as the structure in the leftmost parenthesis, the naphthyridine ring represented as the structure in the second parenthesis from the left, and the third parenthesis from the left in FIG. A hydrogenated naphthyridine ring represented by the structure of
In the heat treatment at 300 ° C. or higher performed by the present inventors, it is considered that the CN triple bond of the unreacted nitrile disappeared because most of the nitrile groups were cyclized. In addition, since the heat treatment at the time of forming the negative electrode is performed under reduced pressure or in an inert atmosphere in order to prevent the current collector from being oxidized and to prevent the binder from being denatured, it is considered that the generation of an acridone ring containing oxygen hardly occurs. Therefore, the above IR absorption spectrum indicates that at least a part of the acrylonitrile structure has been changed to a naphthyridine ring structure.
本発明では、ポリアクリロニトリル構造の少なくとも一部がナフチリジン環を含む環状構造に変化し、バインダーの弾性率が高まったと考えられる。そのため、活物質の膨張収縮による応力がナフチリジン環を有するバインダーで効果的に吸収されることにより、負極合剤層の体積変化を抑制できるから、活物質の脱落や合剤層と集電体箔の密着性低下が防止され、充放電サイクル性能が飛躍的に向上したものと推察される。
なお、バインダーがナフチリジン環構造を有することは、熱分解ＧＣ／ＭＳ分析（Pyrolysis Gas Chromatography Mass Spectrometry）によって確認することができる。
In the present invention, it is considered that at least a part of the polyacrylonitrile structure was changed to a cyclic structure containing a naphthyridine ring, and the elastic modulus of the binder was increased. Therefore, since the stress caused by the expansion and contraction of the active material is effectively absorbed by the binder having a naphthyridine ring, the change in volume of the negative electrode mixture layer can be suppressed. It is presumed that the decrease in adhesion was prevented, and the charge / discharge cycle performance was dramatically improved.
The fact that the binder has a naphthyridine ring structure can be confirmed by pyrolysis GC / MS analysis (Pyrolysis Gas Chromatography Mass Spectrometry).
以下、本発明を非水電解質電池やレドックスキャパシタに適用した場合の実施形態について述べる。
なお、本発明を電気二重層キャパシタに適用する場合、電極材料には、活性炭、カーボンナノチューブ、フラーレン等の静電容量の大きい炭素材料等を用いることができる。電極材料以外の部材については、リチウム二次電池と同様の形態で実施することができる。
Hereinafter, an embodiment in which the present invention is applied to a non-aqueous electrolyte battery or a redox capacitor will be described.
When the present invention is applied to an electric double layer capacitor, a carbon material having a large capacitance such as activated carbon, carbon nanotube, fullerene or the like can be used as an electrode material. About members other than an electrode material, it can implement in the same form as a lithium secondary battery.
（負極活物質）
負極活物質としては、Ｓｉ又はＳｎの金属単体、Ｓｉ又はＳｎと遷移金属（Ｔｉ、Ｃｒ、Ｃｕ、Ｎｉ、Ｃｏ等）との合金、若しくはＳｉ又はＳｎの酸化物又は窒化物等の化合物の中から１種以上を選択することができる。Ｓｉを含む物質を用いることにより、放電容量の大きい、高エネルギー密度の非水電解液蓄電素子を得ることができる。Ｓｉ又はＳｎを含む物質は、Ｌｉイオンと固溶体や金属間化合物を形成することにより、Ｌｉイオンを多量に貯蔵することができる。Ｓｉ又はＳｎを含む物質としては、ＳｉとＯとを構成元素に含む一般式ＳｉＯｘ（ｘ＜２）で表される物質が好ましい。
(Negative electrode active material)
As the negative electrode active material, a metal such as Si or Sn alone, an alloy of Si or Sn and a transition metal (Ti, Cr, Cu, Ni, Co, or the like), or a compound such as an oxide or nitride of Si or Sn is used. One or more types can be selected from. By using a substance containing Si, a non-aqueous electrolyte storage element having a large discharge capacity and a high energy density can be obtained. A substance containing Si or Sn can store a large amount of Li ions by forming a solid solution or an intermetallic compound with Li ions. As the substance containing Si or Sn, a substance represented by the general formula SiO x (x <2) containing Si and O as constituent elements is preferable.
ＳｉＯｘ等の導電性が低い活物質を用いる場合、導電性物質で被覆して用いることが好ましい。この場合、負極活物質粒子の表面の少なくとも一部が導電性物質によって被覆されていれば良い。ＳｉＯｘを導電性物質で被覆することにより、表面の導電性物質により導電経路が維持され、充放電サイクル特性が向上するものと推定される。 When an active material having low conductivity such as SiO x is used, it is preferable to use the active material after coating with a conductive material. In this case, it is sufficient that at least a part of the surface of the negative electrode active material particles is covered with the conductive material. It is presumed that by coating SiO x with a conductive substance, the conductive path on the surface is maintained by the conductive substance and the charge / discharge cycle characteristics are improved.
ＳｉＯｘを被覆する導電性物質としては、Ｃｕ、Ｎｉ、Ｔｉ、Ｓｎ、Ａｌ、Ｃｏ、Ｆｅ、Ｚｎ、Ａｇ若しくはこれらの二種以上の合金又は炭素材料が挙げられるが、これらの中では炭素材料を用いることが好ましい。 Examples of the conductive substance that coats SiO x include Cu, Ni, Ti, Sn, Al, Co, Fe, Zn, Ag, and alloys of two or more of these, and carbon materials. It is preferable to use
ＳｉＯｘを、炭素材料で被覆する方法としては、ベンゼン、トルエン、キシレン、メタンなどを炭素源として気相中で分解し、粒子の表面に化学的に蒸着させるＣＶＤ方法、ピッチ、タールあるいはフルフリルアルコールなどの炭素源を粒子の表面に塗布した後に焼成する方法、あるいは粒子と炭素材料との間に機械的エネルギーを作用させて複合体を形成するメカノケミカル反応を用いた方法を用いることができる。中でも、均一に炭素材料を被覆できることからＣＶＤ法を用いることが好ましい。 As a method for coating SiO x with a carbon material, a CVD method of decomposing in the gas phase using benzene, toluene, xylene, methane or the like as a carbon source and chemically depositing it on the surface of particles, pitch, tar or furfuryl A method in which a carbon source such as alcohol is applied to the surface of the particles and then fired, or a method using a mechanochemical reaction in which mechanical energy acts between the particles and the carbon material to form a complex can be used. . Among them, it is preferable to use the CVD method because the carbon material can be uniformly coated.
また、ＳｉＯｘに対する導電性物質の割合は、２〜２０質量％であることが好ましい。導電性物質の被覆量は、導電性を充分に確保し、充放電サイクル性能を向上させるためには、２質量%以上であることが好ましく、また、大きな放電容量を得るためには、２０％以下であることが好ましい。 Further, the ratio of the conductive substance to SiO x is preferably 2 to 20% by mass. The coating amount of the conductive substance is preferably 2% by mass or more in order to secure sufficient conductivity and improve the charge / discharge cycle performance, and 20% in order to obtain a large discharge capacity. The following is preferred.
Ｓｉ又はＳｎを含む活物質は、さらに炭素材料と混合することが好ましい。炭素材料としては、天然黒鉛、人造黒鉛、アセチレンブラック、ケッチェンブラック、気相成長炭素繊維などが挙げられる。中でも、導電性を充分に確保できることから、平均粒径（Ｄ５０）が１〜１５μｍの鱗片状黒鉛を含有することが好ましい。Ｓｉ又はＳｎを含む活物質：炭素材料の比は、１：９〜１０：０とすることが好ましい。 It is preferable that the active material containing Si or Sn is further mixed with a carbon material. Examples of the carbon material include natural graphite, artificial graphite, acetylene black, Ketjen black, and vapor grown carbon fiber. Above all, it is preferable to contain flaky graphite having an average particle size (D50) of 1 to 15 μm because conductivity can be sufficiently ensured. The ratio of the active material containing Si or Sn to the carbon material is preferably 1: 9 to 10: 0.
（負極バインダー）
負極のバインダーには、ポリアクリロニトリル構造を有する樹脂材料に２５０℃以上の熱処理を加えたものを使用する。当該熱処理により、前記樹脂材料の隣り合うニトリル基の少なくとも一部がナフチジン環に構造変化し、弾性率の高いバインダーを得ることができる。
ポリアクリロニトリル構造を有する樹脂材料は、アクリロニトリルのホモ重合体、又はアクリロニトリルとメタクリロニトリルの共重合体を主骨格とするものである。この主骨格に、接着性を高めるアクリル酸エステルモノマー及び／又はメタクリル酸エステルモノマーを付加重合したアクリロニトリル−アクリル酸（メタクリル酸）エステル共重合体であること、すなわち、ポリアクリロニトリル構造を有し、さらにポリアクリル酸構造又はポリメタクリル酸構造の少なくとも一方を有する樹脂材料が好ましい。この樹脂材料には、さらに柔軟性を付与するために、直鎖エーテル等を適宜付加することができる。
前記の共重合体中、アクリル酸（メタクリル酸）構造の含有割合は、主骨格１００質量部に対して、１〜５０質量部であることが好ましく、２〜４０質量部がより好ましく、５〜３０質量部が特に好ましい。５０質量部以下とすることにより、耐電解液性を良好にし、１質量％以上とすることにより、可撓性を付与することができる。
なお、アクリル酸エステルモノマー及び／又はメタクリル酸エステルモノマーの付加重合は、後述の負極活物質と樹脂材料を混合したスラリーを集電体に塗布した後の熱処理と同時に行ってもよい。
(Negative electrode binder)
As the binder of the negative electrode, a resin material having a polyacrylonitrile structure and subjected to a heat treatment at 250 ° C. or higher is used. By the heat treatment, at least a part of the adjacent nitrile group of the resin material changes into a naphthidine ring, and a binder having a high elastic modulus can be obtained.
The resin material having a polyacrylonitrile structure has a main skeleton of a homopolymer of acrylonitrile or a copolymer of acrylonitrile and methacrylonitrile. This main backbone, acrylonitrile by addition polymerization of acrylic acid ester monomer and / or methacrylic acid ester monomer enhance adhesion - it is acrylic acid (methacrylic acid) ester copolymer, i.e., a polyacrylonitrile structure, further A resin material having at least one of a polyacrylic acid structure and a polymethacrylic acid structure is preferable. A linear ether or the like can be appropriately added to the resin material in order to further impart flexibility.
In the copolymer, the content ratio of the acrylic acid (methacrylic acid) structure is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and preferably 5 to 40 parts by mass, based on 100 parts by mass of the main skeleton. 30 parts by weight are particularly preferred. When the content is 50 parts by mass or less, the resistance to the electrolytic solution is improved, and when the content is 1% by mass or more, flexibility can be imparted.
Incidentally, the addition polymerization of acrylic acid ester monomer and / or methacrylic acid ester monomer may be carried out simultaneously with the heat treatment after coating the slurry prepared by mixing a negative electrode active material and the resin material described later to the current collector.
アクリル酸エステルモノマーとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸ｎ−ペンチル、アクリル酸ｎ−ヘキシル、アクリル酸シクロヘキシル、アクリル酸２−エチルヘキシル、アクリル酸ｎ−ヘプチル、アクリル酸ｎ−オクチル、アクリル酸イソオクチル、アクリル酸イソデシル、アクリル酸ラウリル、アクリル酸イソミリスチル、アクリル酸トリデシル、アクリル酸ドデシル、アクリル酸ステアリル、アクリル酸イソボルニル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸ナフチル、アクリル酸グリシジル、アクリル酸２−ヒドロキシエチル、アクリル酸トリフルオロエチル等のフッ素含有アクリル酸系モノマー等が挙げられる。 Acrylic ester monomers such as methyl acrylate, ethyl acrylate, n- propyl, acrylate i- propyl, n- butyl acrylate, i- butyl acrylate, t- butyl acrylate, n -Pentyl, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, isomiristyl acrylate, acrylic acid Tridecyl, dodecyl acrylate, stearyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, naphthyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, trifluoroethyl acrylate Fluorine-containing acrylic monomers such like.
メタクリル酸エステルモノマーとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸ｎ−ペンチル、メタクリル酸ｎ−ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸ｎ−ヘプチル、メタクリル酸ｎ−オクチル、メタクリル酸イソオクチル、メタクリル酸イソデシル、メタクリル酸ラウリル、メタクリル酸イソミリスチル、メタクリル酸トリデシル、メタクリル酸ドデシル、メタクリル酸ステアリル、メタクリル酸イソボルニル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸ナフチル、メタクリル酸グリシジル、メタクリル酸２−ヒドロキシエチル、メタクリル酸トリフルオロエチル等のフッ素含有メタクリル酸系モノマー等が挙げられる。 As the methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, n- propyl methacrylate i- propyl, n- butyl methacrylate, i- butyl methacrylate, t- butyl methacrylate, n -Pentyl, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, isomyristyl methacrylate, methacrylic acid Tridecyl, dodecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, glycidyl methacrylate, methac Le 2-hydroxyethyl methacrylate, and a fluorine-containing methacrylic acid-based monomers such as trifluoroethyl methacrylate.
直鎖エーテルとしては、エーテル構造の繰り返し部分が、例えば、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ヘキサエチレングリコール、ヘプタエチレングリコール、オクタエチレングリコール、ノナエチレングリコール、デカエチレングリコール、ウンデカエチレングリコール、ドデカエチレングリコール、トリデカエチレングリコール、テトラデカエチレングリコール、ペンタデカエチレングリコール、ヘキサデカエチレングリコール、ヘプタデカエチレングリコール、オクタデカエチレングリコール、ノナデカエチレングリコール、メタンジオール、１，３―プロパンジオール、１，４―ブタンジオール、１，５―ペンタンジオール、１，６―ヘキサンジオール、１，７―ヘプタンジオール、ジアクリル酸１，８―オクタンジオール、１，９―ノナンジオール、１，１０―デカンジオール等であるものが挙げられる。
As the linear ether, a repeating portion of the ether structure is, for example, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, Undecaethylene glycol, dodecaethylene glycol, tridecaethylene glycol, tetradecaethylene glycol, pentadecaethylene glycol, hexadecaethylene glycol, heptadecaethylene glycol, octadecaethylene glycol, nonadecaethylene glycol, methanediol, 1,3 -Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7
（負極）
上記のＳｉ又はＳｎを含む負極活物質に、上記のポリアクリロニトリル構造を有する樹脂材料を、負極の総質量に対して１〜５０質量％、好ましくは２〜３０質量％添加し、必要に応じて導電剤、増粘剤、フィラー等の他の構成成分を混練し、Ｎ−メチルピロリドン、トルエン等の有機溶媒又は水に混合させた後、得られた混合液（スラリー）を銅箔等の集電体の上に塗布し又は圧着し、減圧下又は不活性雰囲気下、２５０℃以上の温度で、２〜５０時間熱処理した後、プレスすることにより、集電体上に負極合剤層が形成された負極を作製する。熱処理を減圧下又は不活性雰囲気下で行う理由は、負極集電体に用いる銅箔の酸化防止、及びバインダー樹脂材料の酸化分解の防止のためである。
前記塗布方法については、例えば、アプリケーターロールなどのローラーコーティング、スクリーンコーティング、ドクターブレード方式、スピンコーティング、バーコータ等の手段を用いて任意の厚さ及び任意の形状に塗布することが好ましいが、これらに限定されるものではない。
(Negative electrode)
The above-mentioned resin material having a polyacrylonitrile structure is added to the above-mentioned negative electrode active material containing Si or Sn in an amount of 1 to 50% by mass, preferably 2 to 30% by mass based on the total mass of the negative electrode. Other components such as a conductive agent, a thickener, and a filler are kneaded, mixed with an organic solvent such as N-methylpyrrolidone, toluene, or water, and then the resulting mixture (slurry) is collected into a copper foil or the like. Apply or press on the current collector, heat-treat under reduced pressure or inert atmosphere at a temperature of 250 ° C. or more for 2 to 50 hours, and then press to form a negative electrode mixture layer on the current collector The prepared negative electrode is manufactured. The reason for performing the heat treatment under reduced pressure or in an inert atmosphere is to prevent oxidation of the copper foil used for the negative electrode current collector and to prevent oxidative decomposition of the binder resin material.
Regarding the application method, for example, it is preferable to apply to an arbitrary thickness and an arbitrary shape using a roller coating such as an applicator roll, a screen coating, a doctor blade method, a spin coating, a bar coater, or the like. It is not limited.
（正極）
リチウム二次電池に適用する場合の正極活物質としては、二酸化マンガン、五酸化バナジウムのような遷移金属化合物や、硫化鉄、硫化チタンのような遷移金属カルコゲン化合物、Ｌｉ１＋ｘＭｅＯ２（１≦ｘ、ＭｅはＣｏ、Ｎｉ及びＭｎから選択される一種以上の遷移金属）で表されるα−ＮａＦｅＯ２型、又はＬｉＭｎ２Ｏ４等のスピネル型のリチウム遷移金属複合酸化物、これらの複合酸化物の遷移金属サイト又はリチウムサイトをＡｌ、Ｖ、Ｆｅ、Ｃｒ、Ｔｉ、Ｚｎ、Ｓｒ、Ｍｏ、Ｗ、Ｍｇなどの金属元素、若しくはＰ、Ｂなどの非金属元素で置換した化合物、ＬｉＦｅＰＯ４等のオリビン型のリン酸化合物を用いることができる。
この中では、Ｌｉ１＋αＭｅ１−αＯ２（０＜α、Ｍｅは遷移金属）で表されるリチウム過剰型α−ＮａＦｅＯ２型の正極活物質が、負極活物質の高容量性を活かす組み合わせとして好ましい。
正極のバインダーには、ポリテトラフルオロエチレン（ＰＴＦＥ），ポリフッ化ビニリデン（ＰＶＤＦ），ポリエチレン，ポリプロピレン等の熱可塑性樹脂、エチレン−プロピレン−ジエンターポリマー（ＥＰＤＭ），スルホン化ＥＰＤＭ，スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のゴム弾性を有するポリマーを１種または２種以上の混合物として用いることができる。負極と同じ樹脂材料を用いてもよい。また、バインダーの添加量は、正極の総質量に対して１〜５０質量％が好ましく、特に２〜３０質量％が好ましい。
正極活物質及びバインダーに、必要に応じて導電剤、増粘剤、フィラー等の他の構成成分を混練し、溶媒と混合した後、負極と同様の手段を用いてアルミニウム箔等の集電体の上に塗布又は圧着し、８０〜１２０℃の温度で乾燥して正極を作製することができる。
(Positive electrode)
As a positive electrode active material when applied to a lithium secondary battery, a transition metal compound such as manganese dioxide or vanadium pentoxide, a transition metal chalcogen compound such as iron sulfide or titanium sulfide, Li 1 + x MeO 2 (1 ≦ x , Me is one or more transition metals selected from Co, Ni and Mn), a spinel-type lithium transition metal composite oxide such as α-NaFeO 2 type or LiMn 2 O 4 , or a composite oxide thereof. A compound in which a transition metal site or a lithium site is replaced with a metal element such as Al, V, Fe, Cr, Ti, Zn, Sr, Mo, W, or Mg, or a nonmetal element such as P or B, LiFePO 4 or the like. An olivine-type phosphate compound can be used.
Among them, a lithium-rich α-NaFeO 2 type positive electrode active material represented by Li 1 + α Me 1−α O 2 (0 <α, Me is a transition metal) is a combination utilizing the high capacity of the negative electrode active material. Is preferred.
For the binder of the positive electrode, thermoplastic resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene and polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, and styrene-butadiene rubber (SBR) ) And polymers having rubber elasticity such as fluororubber can be used alone or as a mixture of two or more. The same resin material as the negative electrode may be used. Further, the addition amount of the binder is preferably from 1 to 50% by mass, and particularly preferably from 2 to 30% by mass, based on the total mass of the positive electrode.
After kneading other components such as a conductive agent, a thickener, and a filler as necessary with the positive electrode active material and the binder, and mixing with a solvent, a current collector such as an aluminum foil is formed using the same means as the negative electrode. On the substrate and dried at a temperature of 80 to 120 ° C. to produce a positive electrode.
（非水電解質）
本発明に係る非水電解質蓄電素子に用いる非水電解質は、限定されるものではなく、一般に非水電解質二次電池等への使用が提案されているものが使用可能である。非水電解質に用いる非水溶媒としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、クロロエチレンカーボネート、ビニレンカーボネート等の環状炭酸エステル類；γ−ブチロラクトン、γ−バレロラクトン等の環状エステル類；ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等の鎖状カーボネート類；ギ酸メチル、酢酸メチル、酪酸メチル等の鎖状エステル類；テトラヒドロフランまたはその誘導体；１，３−ジオキサン、１，４−ジオキサン、１，２−ジメトキシエタン、１，４−ジブトキシエタン、メチルジグライム等のエーテル類；アセトニトリル、ベンゾニトリル等のニトリル類；ジオキソランまたはその誘導体；エチレンスルフィド、スルホラン、スルトンまたはその誘導体等の単独またはそれら２種以上の混合物等を挙げることができるが、これらに限定されるものではない。
(Non-aqueous electrolyte)
The non-aqueous electrolyte used in the non-aqueous electrolyte storage element according to the present invention is not limited, and those generally proposed for use in non-aqueous electrolyte secondary batteries and the like can be used. Examples of the non-aqueous solvent used for the non-aqueous electrolyte include propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, cyclic carbonates such as vinylene carbonate; γ-butyrolactone, cyclic esters such as γ-valerolactone; dimethyl carbonate; Chain carbonates such as diethyl carbonate and ethyl methyl carbonate; chain esters such as methyl formate, methyl acetate and methyl butyrate; tetrahydrofuran or derivatives thereof; 1,3-dioxane, 1,4-dioxane, 1,2-dimethoxy Ethers such as ethane, 1,4-dibutoxyethane and methyldiglyme; nitriles such as acetonitrile and benzonitrile; dioxolane or derivatives thereof; ethylene sulfide, sulfolane, sultone or derivatives thereof. Examples of the conductor include a single conductor or a mixture of two or more conductors, but are not limited thereto.
非水電解質に用いる電解質塩としては、限定されない。例えば、リチウム二次電池の場合、ＬｉＣｌＯ４，ＬｉＢＦ４，ＬｉＡｓＦ６，ＬｉＰＦ６，ＬｉＳＣＮ，ＬｉＢｒ，ＬｉＩ，Ｌｉ２ＳＯ４，Ｌｉ２Ｂ１０Ｃｌ１０，ＮａＣｌＯ４，ＮａＩ，ＮａＳＣＮ，ＮａＢｒ，ＫＣｌＯ４，ＫＳＣＮ等のリチウム（Ｌｉ）、ナトリウム（Ｎａ）またはカリウム（Ｋ）の１種を含む無機イオン塩、ＬｉＣＦ３ＳＯ３，ＬｉＮ（ＣＦ３ＳＯ２）２，ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２，ＬｉＮ（ＣＦ３ＳＯ２）（Ｃ４Ｆ９ＳＯ２），ＬｉＣ（ＣＦ３ＳＯ２）３，ＬｉＣ（Ｃ２Ｆ５ＳＯ２）３，（ＣＨ３）４ＮＢＦ４，（ＣＨ３）４ＮＢｒ，（Ｃ２Ｈ５）４ＮＣｌＯ４，（Ｃ２Ｈ５）４ＮＩ，（Ｃ３Ｈ７）４ＮＢｒ，（ｎ−Ｃ４Ｈ９）４ＮＣｌＯ４，（ｎ−Ｃ４Ｈ９）４ＮＩ，（Ｃ２Ｈ５）４Ｎ−ｍａｌｅａｔｅ，（Ｃ２Ｈ５）４Ｎ−ｂｅｎｚｏａｔｅ，（Ｃ２Ｈ５）４Ｎ−ｐｈｔｈａｌａｔｅ、ステアリルスルホン酸リチウム、オクチルスルホン酸リチウム、ドデシルベンゼンスルホン酸リチウム等の有機イオン塩等が挙げられ、これらのイオン性化合物を単独、あるいは２種類以上混合して用いることが可能である。 The electrolyte salt used for the non-aqueous electrolyte is not limited. For example, in the case of a lithium secondary battery, LiClO 4 , LiBF 4 , LiAsF 6, LiPF 6 , LiSCN, LiBr, LiI, Li 2 SO 4 , Li 2 B 10 Cl 10 , NaClO 4 , NaI, NaSCN, NaBr, KClO 4 , An inorganic ion salt containing one kind of lithium (Li), sodium (Na) or potassium (K), LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , (CH 3 ) 4 NBF 4 , (CH 3 ) 4NBr, (C 2 H 5) 4 NClO 4, (C 2 H 5) 4 NI, (C 3 H 7) 4 NBr, (n-C 4 H 9) 4 NC O 4, (n-C 4 H 9) 4 NI, (C 2 H 5) 4 N-maleate, (C 2 H 5) 4 N-benzoate, (C 2 H 5) 4N-phthalate, lithium stearyl sulfonate And organic ion salts such as lithium octylsulfonate and lithium dodecylbenzenesulfonate. These ionic compounds can be used alone or in combination of two or more.
リチウム二次電池の場合、ＬｉＰＦ６又はＬｉＢＦ４と、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２のようなパーフルオロアルキル基を有するリチウム塩とを混合して用いることにより、さらに電解質の粘度を下げることができるので、低温特性をさらに高めることができ、また、自己放電を抑制することができる。 In the case of a lithium secondary battery, the viscosity of the electrolyte is further reduced by using a mixture of LiPF 6 or LiBF 4 and a lithium salt having a perfluoroalkyl group such as LiN (C 2 F 5 SO 2 ) 2. Therefore, the low-temperature characteristics can be further improved, and the self-discharge can be suppressed.
また、非水電解質として常温溶融塩やイオン液体を用いてもよい。 Further, a room temperature molten salt or an ionic liquid may be used as the non-aqueous electrolyte.
非水電解質における電解質塩の濃度としては、高い電池特性を有するリチウム二次電池を確実に得るために、０．１ｍｏｌ／ｌ〜５ｍｏｌ／Ｌが好ましく、さらに好ましくは、０．５ｍｏｌ／ｌ〜２．５ｍｏｌ／Ｌである。 The concentration of the electrolyte salt in the non-aqueous electrolyte is preferably from 0.1 mol / l to 5 mol / L, more preferably from 0.5 mol / l to 2 mol / L in order to reliably obtain a lithium secondary battery having high battery characteristics. 0.5 mol / L.
（セパレータ）
セパレータとしては、織布、不織布、合成樹脂微多孔膜等を用いることができ、特に、合成樹脂微多孔膜が好適に用いることができる。その材質としては、ナイロン、セルロースアセテート、ニトロセルロース、ポリスルホン、ポリアクリロニトリル、ポリフッ化ビニリデン、およびポリプロピレン、ポリエチレン、ポリブテン等のポリオレフィンが例示される。なかでもポリエチレンおよびポリプロピレン製微多孔膜、またはこれらを複合した微多孔膜などのポリオレフィン系微多孔膜が、厚さ、膜強度、膜抵抗等の面で好適に用いられる。
(Separator)
As the separator, a woven fabric, a nonwoven fabric, a synthetic resin microporous membrane, or the like can be used. In particular, a synthetic resin microporous membrane can be preferably used. Examples of the material include nylon, cellulose acetate, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, and polyolefins such as polypropylene, polyethylene, and polybutene. Above all, a polyolefin-based microporous membrane such as a polyethylene and polypropylene microporous membrane or a composite microporous membrane thereof is suitably used in terms of thickness, film strength, film resistance and the like.
（非水電解質蓄電素子の構成）
蓄電素子の形状は特に限定されるものではなく、本発明は、角形、楕円形、コイン形、ボタン形、シート形蓄電素子等の様々な形状の非水電解液蓄電素子に適用可能である。
図３に角型素子の一例を示す。セパレータを挟んで巻回された正極及び負極よりなる電極群２が角形の容器３に収納され、正極リード４’を介して正極端子４が、負極リード５’を介して負極端子５が容器外に導出されている。
(Configuration of non-aqueous electrolyte storage element)
The shape of the storage element is not particularly limited, and the present invention can be applied to various shapes of nonaqueous electrolyte storage elements such as a square, an ellipse, a coin, a button, and a sheet storage element.
FIG. 3 shows an example of a square element. An
（非水電解質蓄電素子装置の構成）
本発明に係る非水電解質蓄電素子は、特に電気自動車（ＥＶ）、ハイブリッド自動車（ＨＥＶ）、プラグインハイブリッド自動車（ＰＨＥＶ）などの自動車用電源として用いる場合に、複数の蓄電素子を集合して構成した蓄電装置として搭載することができる。
図４に、蓄電素子１が集合した蓄電ユニット２０をさらに集合した蓄電装置３０の一例を示す。
(Configuration of non-aqueous electrolyte storage element device)
The non-aqueous electrolyte energy storage device according to the present invention is configured by assembling a plurality of energy storage devices, particularly when used as a power source for vehicles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV). As a power storage device.
FIG. 4 shows an example of
＜実施例１＞
（負極の作製）
活物質として、カーボンで被覆されたＳｉＯｘ（ｘは約１、カーボン含有率６質量％、Ｄ５０＝５μｍ、以下、単に「ＳｉＯ」という。）、炭素材料として、流動法窒素ガス吸着法により測定されたＢＥＴ比表面積が７．７ｍ２／ｇであり、粒径（Ｄ５０）が１０μｍの鱗片状黒鉛（ＴＩＭＣＡＬ Ｌｔｄ製、ＳＦＧ−１５）を使用した。
バインダーに用いる樹脂材料として、ポリアクリロニトリルを主骨格としポリアクリル酸構造を含む樹脂を用いた。前記樹脂は、アクリロニトリルとアクリル酸ブチルとの共重合体である。
前記ＳｉＯと前記炭素材料とを４：６の質量比で混合した。前記樹脂材料を固形分として９３質量％含有するＮ−メリルピロリドン溶液を加え、さらに、分散用の溶媒としてＮ−メチルピロリドンを適量追加して混練分散し、スラリーを調製した。前記スラリーは、固形分換算で、前記ＳｉＯ、前記炭素材料、及び前記樹脂を５４：３６：１０の質量比で含有する。このスラリーを厚さ２０μｍの銅箔集電体の片面に塗布した後、ロールプレスを行った。次に、密閉容器中に載置し、トラップを経由した真空ポンプに接続し、該容器をマントルヒーターで加熱することにより、２５０℃で５時間、１０−１Ｐａ以下の減圧下で熱処理して、非水電解液蓄電素子用負極を作製した。このようにして、銅箔集電体上に合剤層を形成した。スラリーの塗布量は、熱処理後の塗布質量が３．２ｍｇ／ｃｍ２となるように調整した。前記プレス条件は、前記合剤層の多孔度が３４%となるように調節した。
<Example 1>
(Preparation of negative electrode)
As an active material, carbon-coated SiO x (x is about 1, carbon content 6% by mass, D50 = 5 μm, hereinafter simply referred to as “SiO”), and as a carbon material, measured by a flow method nitrogen gas adsorption method. A flake graphite (manufactured by TIMCAL Ltd, SFG-15) having a determined BET specific surface area of 7.7 m 2 / g and a particle size (D50) of 10 μm was used.
As a resin material used for the binder, a resin containing polyacrylonitrile as a main skeleton and having a polyacrylic acid structure was used. The resin is a copolymer of acrylonitrile and butyl acrylate.
The SiO and the carbon material were mixed at a mass ratio of 4: 6. An N-merylpyrrolidone solution containing 93% by mass of the resin material as a solid content was added, and an appropriate amount of N-methylpyrrolidone was further added and kneaded and dispersed as a dispersion solvent to prepare a slurry. The slurry contains the SiO, the carbon material, and the resin in a mass ratio of 54:36:10 in terms of solid content. This slurry was applied on one side of a copper foil current collector having a thickness of 20 μm, and then roll-pressed. Next, it is placed in a closed container, connected to a vacuum pump via a trap, and heated by a mantle heater to heat the container at 250 ° C. for 5 hours under a reduced pressure of 10 −1 Pa or less. Then, a negative electrode for a non-aqueous electrolyte storage element was produced. Thus, the mixture layer was formed on the copper foil current collector. The application amount of the slurry was adjusted so that the application mass after the heat treatment was 3.2 mg / cm 2 . The pressing conditions were adjusted so that the porosity of the mixture layer became 34%.
（非水電解質蓄電素子の作製）
上記の負極を作用極とし、対極及び参照極をＬｉ金属とし、非水電解質として、１ＭのＬｉＣｌＯ４をエチレンカーボネートとジエチルカーボネート（体積比１：１）の混合溶媒に溶解した非水電解液を用い、非水電解質蓄電素子を作製した。
(Preparation of non-aqueous electrolyte storage element)
A non-aqueous electrolyte obtained by dissolving 1 M LiClO 4 in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 1) as a non-aqueous electrolyte was prepared by using the negative electrode as a working electrode, the counter electrode and the reference electrode as Li metal, and a non-aqueous electrolyte. A non-aqueous electrolyte energy storage device was manufactured using this.
（容量確認試験）
前記非水電解質蓄電素子に対して、１サイクルの初期充放電を行った。充電は、充電電流０．１ＣｍＡ、充電下限電圧０．０２Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）、充電時間１６ｈの定電流定電圧充電とし、１サイクル目の放電は、放電電流０．２ＣｍＡ、放電終止電位２．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）の定電流放電とした。
次に、初回容量確認試験を行った。充電は、充電電流０．２ＣｍＡ、充電下限電圧０．０２Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）、充電時間８ｈの定電流定電圧充電とし、放電は、放電電流０．２ＣｍＡ、放電終止電位２．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）の定電流放電とし、この充放電を２サイクル繰り返した。この容量確認試験における１サイクル目の放電容量を「初回放電容量（ｍＡｈ／ｇ）」とし、１サイクル目の充電容量に対する放電容量の百分率を「初回クーロン効率（％）」として求めた。
(Capacity confirmation test)
One cycle of initial charge and discharge was performed on the nonaqueous electrolyte storage element. The charging was performed at a constant current and constant voltage for a charging current of 0.1 CmA, a charging lower limit voltage of 0.02 V (vs. Li / Li + ), and a charging time of 16 h. A constant current discharge at a potential of 2.0 V (vs. Li / Li + ) was performed.
Next, an initial capacity confirmation test was performed. The charging was performed at a constant current of 0.2 CmA, a charging lower limit voltage of 0.02 V (vs. Li / Li + ), and a constant current and constant voltage of 8 h. The discharging was performed at a discharging current of 0.2 CmA and a discharging end potential of 2.0 V. (Vs. Li / Li + ) constant current discharge, and this charge / discharge was repeated for two cycles. The discharge capacity in the first cycle in this capacity confirmation test was determined as “initial discharge capacity (mAh / g)”, and the percentage of the discharge capacity relative to the charge capacity in the first cycle was determined as “initial coulomb efficiency (%)”.
（充放電サイクル試験）
続いて、３０サイクルの充放電サイクル試験を行った。充電は、充電電流１．０ＣｍＡ、充電終止電圧０．０２Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）、充電時間３ｈの定電流定電圧充電とし、放電は、放電電流１．０ＣｍＡ、放電終止電圧２．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）の定電流放電とし、この充放電を３０サイクル繰り返した。
その後、充放電サイクル試験後の容量確認試験を行った。条件は、上記初回容量確認試験と同一である。０．２ＣｍＡ、０．０２Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）の定電流定電圧充電を８時間、０．２ＣｍＡ、２．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）の定電流放電を２サイクル行い、放電容量を測定した。
この容量確認試験における１サイクル目の放電容量の、上記「初回放電容量」に対する百分率を「容量維持率（％）」として求めた。
(Charge / discharge cycle test)
Subsequently, a 30-cycle charge / discharge cycle test was performed. The charging was performed at a constant current of 1.0 CmA, a charging end voltage of 0.02 V (vs. Li / Li + ), and a constant current and constant voltage of 3 h. The discharging was performed at a discharging current of 1.0 CmA and a discharging end voltage of 2.0 V. (Vs. Li / Li + ) constant current discharge, and this charge / discharge was repeated for 30 cycles.
Thereafter, a capacity confirmation test after the charge / discharge cycle test was performed. The conditions are the same as the above-mentioned initial capacity confirmation test. 0.2CmA, 0.02V (vs.Li/Li +) of the constant-current constant-voltage charging for 8 hours, 0.2 CmA, 2.0 V is performed two cycles of constant current discharge (vs.Li/Li +), the discharge The capacity was measured.
The percentage of the first cycle discharge capacity in the capacity confirmation test with respect to the above-mentioned "initial discharge capacity" was determined as "capacity maintenance rate (%)".
＜実施例２〜４＞
熱処理温度を、それぞれ３００℃、３５０℃、４００℃とした以外は、実施例１と同様にして、実施例２〜４の負極を作製した。
<Examples 2 to 4>
Negative electrodes of Examples 2 to 4 were produced in the same manner as in Example 1 except that the heat treatment temperatures were set to 300 ° C., 350 ° C., and 400 ° C., respectively.
＜比較例１〜２＞
熱処理温度を、それぞれ１５０℃、２００℃とした以外は、実施例１と同様にして、比較例１，２の負極を作製した。
<Comparative Examples 1-2>
Negative electrodes of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the heat treatment temperatures were set to 150 ° C. and 200 ° C., respectively.
＜比較例３〜８＞
バインダーに用いる樹脂材料をアクリロニトリル−アクリル酸共重合体からポリフッ化ビニリデンに変更し、熱処理温度をそれぞれ１５０℃、２００℃、２５０℃、３００℃、３５０℃、４００℃とした以外は、実施例１と同様にして、比較例３〜８の負極を作製した。
<Comparative Examples 3 to 8>
Example 1 Example 1 was repeated except that the resin material used for the binder was changed from acrylonitrile-acrylic acid copolymer to polyvinylidene fluoride, and the heat treatment temperatures were changed to 150 ° C, 200 ° C, 250 ° C, 300 ° C, 350 ° C, and 400 ° C, respectively. In the same manner as in the above, negative electrodes of Comparative Examples 3 to 8 were produced.
各実施例、比較例の負極を作用極とした非水電解質蓄電素子の初回放電容量、初回クーロン効率、及び容量保持率を、以下の表１に示す。 Table 1 below shows the initial discharge capacity, the initial coulomb efficiency, and the capacity retention of the nonaqueous electrolyte energy storage devices using the negative electrode of each example and comparative example as a working electrode.
実施例１〜４、及び比較例１，２はポリアクリロニトリルを主骨格とする樹脂材料に対して、熱処理温度を異ならせた結果を示す。
比較例１，２は、従来の推奨温度である１５０℃や、２００℃で熱処理を行った結果であり、容量維持率は４０％台以下である。
これに対して、２５０℃で熱処理を行った実施例１は、６７．７％の容量維持率を示し、３００℃〜４００℃で熱処理を行った実施例２〜４は、９６．７％以上と、さらに高い容量維持率を示している。また、３００℃〜４００℃で熱処理を行った実施例２〜４は、初回クーロン効率についても優れている。
これは、２００℃以下の熱処理では、樹脂材料のニトリル基の環状構造への変化が起こらず、弾性率が低いままであるが、２５０℃以上の熱処理で、環状構造の生成がある程度進行し、さらに、３００℃以上の熱処理で、大部分のニトリル基が環状構造に変化し、弾性率が飛躍的に高まったためと推察される。
Examples 1 to 4 and Comparative Examples 1 and 2 show the results obtained by changing the heat treatment temperature for a resin material having polyacrylonitrile as a main skeleton.
Comparative Examples 1 and 2 are the results of heat treatment at 150 ° C. or 200 ° C., which is the conventional recommended temperature, and the capacity retention ratio is on the order of 40% or less.
On the other hand, Example 1 in which heat treatment was performed at 250 ° C. showed a capacity retention of 67.7%, and Examples 2 to 4 in which heat treatment was performed at 300 ° C. to 400 ° C. had 96.7% or more. This indicates a higher capacity retention rate. Examples 2 to 4 in which the heat treatment was performed at 300 ° C to 400 ° C also have an excellent initial coulomb efficiency.
This is because the heat treatment at 200 ° C. or less does not cause the nitrile group of the resin material to change to a cyclic structure and the elastic modulus remains low, but the heat treatment at 250 ° C. or more promotes the formation of the cyclic structure to some extent, Further, it is presumed that most of the nitrile groups were changed to a cyclic structure by the heat treatment at 300 ° C. or higher, and the elastic modulus was dramatically increased.
また、実施例１〜４と比較例１，２とでは、熱処理温度が高いほど、初回放電容量が大きくなっている。
実施例１〜４と比較例１，２の各負極において、ＳＥＭ−ＥＤＸ分析を行ったところ、２５０℃までの熱処理では、ＣがＳｉ及びＯの分布と重なるように不均一に分布していたことから、バインダーがＳｉＯ粒子の近傍に凝集していることが認められた。これに対して、３００℃以上の熱処理では、Ｃの分布はＳｉ及びＯの分布に依存せず、合剤層全体に比較的均一に分布していた。したがって、負極を３００℃以上で熱処理したことにより、一度融解したバインダーが合剤全体の活物質と均一に分布し、且つ、ナフチリジン環構造が形成されたことにより、ＳｉＯ粒子の膨張収縮に伴う合剤層の体積変化を顕著に抑制する作用が備えられたため、優れた結着性が発現し、高い初回放電容量と良好な充放電サイクル性能を示したものと推察される。
In Examples 1 to 4 and Comparative Examples 1 and 2, the higher the heat treatment temperature, the larger the initial discharge capacity.
When SEM-EDX analysis was performed on each of the negative electrodes of Examples 1 to 4 and Comparative Examples 1 and 2, in the heat treatment up to 250 ° C., C was unevenly distributed so as to overlap with the distributions of Si and O. From this, it was recognized that the binder was aggregated in the vicinity of the SiO particles. On the other hand, in the heat treatment at 300 ° C. or higher, the distribution of C did not depend on the distribution of Si and O, and was relatively uniformly distributed over the entire mixture layer. Therefore, by heat-treating the negative electrode at a temperature of 300 ° C. or higher, the binder once melted is uniformly distributed with the active material of the entire mixture, and the naphthyridine ring structure is formed. It is presumed that, because of the action of remarkably suppressing the change in volume of the agent layer, excellent binding properties were exhibited, and high initial discharge capacity and good charge / discharge cycle performance were exhibited.
比較例１〜８はポリフッ化ビニリデンをバインダーに用いた負極の試験結果であり、１５０〜４００℃のいずれの温度で熱処理を施しても、容量維持率は実施例１〜４に及ばない。これは、ポリフッ化ビニリデンは環状化する基を有さないから、弾性率が変化する要素がないことによると推察される。 Comparative Examples 1 to 8 are test results of the negative electrode using polyvinylidene fluoride as a binder, and the capacity retention ratio is lower than that of Examples 1 to 4 even when heat treatment is performed at any temperature of 150 to 400 ° C. This is presumed to be due to the fact that polyvinylidene fluoride does not have a cyclizing group, and therefore has no element that changes the elastic modulus.
以上のとおり、本発明は、黒鉛に比べて高い理論容量を有する負極材料を備え、良好な充放電サイクル性能を有する非水電解質蓄電素子を提供することができるから、車載用の電源素子としての利用が可能である。 As described above, the present invention includes a negative electrode material having a higher theoretical capacity than graphite, and can provide a nonaqueous electrolyte storage element having good charge / discharge cycle performance. Available.
１ 蓄電素子
２ 電極群
３ 容器
４ 正極端子
４’正極リード
５ 負極端子
５’負極リード
２０ 蓄電ユニット
３０ 蓄電装置
DESCRIPTION OF
Claims (1)
上記負極活物質と、ポリアクリロニトリル構造を有し、さらにポリアクリル酸構造又はポリメタクリル酸構造の少なくとも一方を有する樹脂材料と、を混合すること、
及び、減圧下又は不活性雰囲気下で上記混合物を３００℃以上で熱処理して、前記樹脂材料を、ナフチリジン環構造を有し、さらにポリアクリル酸構造又はポリメタクリル酸構造の少なくとも一方を有する樹脂にすること、
を備える、非水電解質蓄電素子用負極の製造方法。 A method for producing a negative electrode for a non-aqueous electrolyte energy storage device having a mixture layer including a simple substance of a metal containing at least one element selected from Si and Sn, an alloy or a compound, and a binder,
The negative electrode active material, having a polyacrylonitrile structure, and further mixed with a resin material having at least one of a polyacrylic acid structure or a polymethacrylic acid structure,
And, the mixture is heat-treated at 300 ° C. or more under reduced pressure or an inert atmosphere to convert the resin material into a resin having a naphthyridine ring structure and further having at least one of a polyacrylic acid structure or a polymethacrylic acid structure. To do,
A method for producing a negative electrode for a non-aqueous electrolyte energy storage device, comprising:
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