JP6072595B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary battery Download PDFInfo
- Publication number
- JP6072595B2 JP6072595B2 JP2013087029A JP2013087029A JP6072595B2 JP 6072595 B2 JP6072595 B2 JP 6072595B2 JP 2013087029 A JP2013087029 A JP 2013087029A JP 2013087029 A JP2013087029 A JP 2013087029A JP 6072595 B2 JP6072595 B2 JP 6072595B2
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- JP
- Japan
- Prior art keywords
- layer
- negative electrode
- secondary battery
- positive electrode
- aqueous secondary
- Prior art date
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、安全性に優れた非水二次電池に関するものである。 The present invention relates to a non-aqueous secondary battery excellent in safety.
リチウムイオン二次電池をはじめとする非水二次電池は、エネルギー密度が高いといった特徴から、携帯電話やノート型パーソナルコンピューターなどの携帯機器の電源として広く用いられている。そして、携帯機器の高性能化に伴って非水二次電池の高容量化が更に進む傾向にあり、それと共に、使用寿命の延長、安全性や信頼性の向上といった各種研究開発に対して継続的な努力が要求される。 Non-aqueous secondary batteries such as lithium ion secondary batteries are widely used as power sources for portable devices such as mobile phones and notebook personal computers because of their high energy density. And with higher performance of mobile devices, the capacity of non-aqueous secondary batteries tends to increase further, and at the same time, it continues to various research and development such as extending the service life and improving safety and reliability. Effort is required.
従来から、非水二次電池のセパレータとしては、厚みが２０〜３０μｍ程度のポリオレフィン系の多孔質フィルム（微多孔膜）が使用されており、そのポリオレフィンには、特に、電池の熱暴走温度以下で空孔が閉塞することによって電池の内部抵抗を上昇させ、短絡の際などに電池の安全性を向上させるシャットダウン機能を確保するために、ポリエチレンが使用されている。 Conventionally, as a separator for a non-aqueous secondary battery, a polyolefin-based porous film (microporous film) having a thickness of about 20 to 30 μm has been used. In particular, the polyolefin has a thermal runaway temperature or less. In order to secure a shutdown function that increases the internal resistance of the battery by closing the pores and improves the safety of the battery in the event of a short circuit, polyethylene is used.
しかしながら、ポリオレフィン系の多孔質フィルムでは多孔質化や強度向上などを目的として、一軸延伸や二軸延伸を施したものが用いられている。そのため、こうした多孔質フィルム製のセパレータには延伸による歪が生じていることから、高温時に残留応力によって収縮するといった問題がある。 However, a polyolefin-based porous film that has been uniaxially stretched or biaxially stretched is used for the purpose of making it porous or improving its strength. For this reason, such a separator made of a porous film has a problem of shrinkage due to residual stress at a high temperature because strain is caused by stretching.
ポリエチレン製の多孔質フィルムセパレータの場合、その収縮温度は、ポリエチレンの融点、すなわちシャットダウン温度と非常に近いところに存在する。このため、ポリエチレン製の多孔質フィルムセパレータを使用するときには、充電異常時などに電池の温度がシャットダウン温度に達したときに、電流を直ちに減少させて電池の温度上昇を防止しなければならない。セパレータの空孔が十分に閉塞せず電流を直ちに減少できなかった場合には、電池の温度は容易にセパレータの収縮温度にまで上昇するため、内部短絡による発火の危険性があるからである。 In the case of a polyethylene porous film separator, the shrinkage temperature is very close to the melting point of polyethylene, that is, the shutdown temperature. For this reason, when using a polyethylene porous film separator, when the battery temperature reaches the shutdown temperature in the event of abnormal charging, the current must be immediately reduced to prevent the battery temperature from rising. This is because when the pores of the separator are not sufficiently closed and the current cannot be reduced immediately, the battery temperature easily rises to the contraction temperature of the separator, and there is a risk of ignition due to an internal short circuit.
こうした事情を受けて、セパレータの耐熱収縮性の向上を図り、これを用いた非水二次電池などの電気化学素子の信頼性や安全性を高める検討もなされている。例えば、特許文献１には、シャットダウン機能を確保するための樹脂を主体として含む第１セパレータ層と、耐熱温度が１５０℃以上のフィラーを主体として含む第２セパレータ層とを有する多孔質のセパレータが提案されている。特許文献１に記載の技術によれば、異常高温となった際の安全性に優れた非水二次電池を提供することができる。 In view of such circumstances, studies have been made to improve the heat shrinkage resistance of the separator and increase the reliability and safety of electrochemical elements such as non-aqueous secondary batteries using the separator. For example, Patent Document 1 discloses a porous separator having a first separator layer mainly including a resin for ensuring a shutdown function and a second separator layer mainly including a filler having a heat resistant temperature of 150 ° C. or higher. Proposed. According to the technique described in Patent Document 1, it is possible to provide a non-aqueous secondary battery that is excellent in safety when the temperature becomes abnormally high.
その一方で、非水二次電池には、シャットダウン機能の更なる向上の要請もある。 On the other hand, non-aqueous secondary batteries are also requested to further improve the shutdown function.
本発明は、前記事情に鑑みてなされたものであり、その目的は、安全性に優れた非水二次電池を提供することにある。 This invention is made | formed in view of the said situation, The objective is to provide the non-aqueous secondary battery excellent in safety | security.
前記目的を達成し得た本発明の非水二次電池は、正極、負極、セパレータおよび非水電解質を構成要素とする非水二次電池であって、前記正極と前記負極との間に、架橋剤と、熱によって前記架橋剤で架橋でき、かつ架橋開始温度が９０〜１３０℃の多糖類とを含む層（Ａ）を有することを特徴とするものである。 The non-aqueous secondary battery of the present invention that has achieved the above object is a non-aqueous secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte as a component, and between the positive electrode and the negative electrode, It has a layer (A) that includes a crosslinking agent and a polysaccharide that can be crosslinked with the crosslinking agent by heat and has a crosslinking initiation temperature of 90 to 130 ° C.
本発明によれば、安全性に優れた非水二次電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the non-aqueous secondary battery excellent in safety can be provided.
本発明の非水二次電池は、架橋剤と、熱によって前記架橋剤で架橋でき、かつ架橋開始温度が９０〜１３０℃の多糖類とを含む層（Ａ）を、正極と負極との間に有しており、内部温度が異常に上昇した際には、その熱の作用によって架橋剤と多糖類とで強固な架橋ネットワークが層（Ａ）内に形成される。これにより、例えば、セパレータの熱収縮が生じても、熱変形し難い層（Ａ）によって正極と負極との接触による短絡が抑制できると共に、セパレータの構成樹脂の溶融によって生じる通常のシャットダウンと同様に、正極−負極間の絶縁性が高まり、電気抵抗が上昇するために電気化学反応の進行が抑えられる（本発明の非水二次電池における電気抵抗上昇現象も「シャットダウン」と記載する）。本発明の非水二次電池では、層（Ａ）における前記の作用によって、優れた安全性を確保できる。 The nonaqueous secondary battery of the present invention comprises a layer (A) containing a crosslinking agent and a polysaccharide that can be crosslinked with the crosslinking agent by heat and has a crosslinking initiation temperature of 90 to 130 ° C., between the positive electrode and the negative electrode. When the internal temperature rises abnormally, a strong cross-linking network is formed in the layer (A) with the cross-linking agent and the polysaccharide by the action of the heat. As a result, for example, even when the thermal contraction of the separator occurs, a short circuit due to contact between the positive electrode and the negative electrode can be suppressed by the layer (A) which is not easily thermally deformed, and similarly to a normal shutdown caused by melting of the constituent resin of the separator. Further, since the insulation between the positive electrode and the negative electrode is increased and the electrical resistance is increased, the progress of the electrochemical reaction is suppressed (the electrical resistance increase phenomenon in the nonaqueous secondary battery of the present invention is also described as “shutdown”). In the nonaqueous secondary battery of the present invention, excellent safety can be ensured by the above-described action in the layer (A).
層（Ａ）において、架橋剤と多糖類とでの架橋開始温度（架橋構造の形成が開始する温度）は、９０〜１３０℃である。このような温度で架橋構造を形成できる場合には、例えば、ポリエチレン製の微多孔膜で構成されたセパレータを有する非水二次電池でシャットダウンが開始する温度よりも、少し低い温度でシャットダウンを開始させ得るため、より安全性に優れた非水二次電池とすることができる。後述する架橋剤と多糖類との組み合わせであれば、架橋開始温度を前記のような温度とすることができる。 In the layer (A), the crosslinking initiation temperature (the temperature at which the formation of the crosslinked structure starts) between the crosslinking agent and the polysaccharide is 90 to 130 ° C. When a crosslinked structure can be formed at such a temperature, for example, the shutdown is started at a temperature slightly lower than the temperature at which the shutdown is started in a non-aqueous secondary battery having a separator composed of a polyethylene microporous membrane. Therefore, a non-aqueous secondary battery with higher safety can be obtained. If it is the combination of the crosslinking agent and polysaccharide which are mentioned later, crosslinking start temperature can be made into the above temperature.
前記の架橋開始温度は、架橋剤と多糖類との混合物について、示差走査熱量計（ＤＳＣ）を使用して昇温試験を行うことで発熱挙動を観察した際の、発熱反応の立ち上がり時点での温度を意味している。なお、層（Ａ）の形成には、後述するように、架橋剤、多糖類および溶剤などを含む層（Ａ）形成用組成物を使用することが通常であるが、架橋開始温度の測定に用いる試料（架橋剤と多糖類との混合物）には、この層（Ａ）形成用組成物を使用してもよい。 The crosslinking initiation temperature is determined at the time of exothermic reaction when the exothermic behavior is observed by performing a temperature rise test using a differential scanning calorimeter (DSC) for a mixture of a crosslinking agent and a polysaccharide. It means temperature. In order to form the layer (A), as will be described later, it is usual to use a composition for forming the layer (A) containing a crosslinking agent, a polysaccharide and a solvent. You may use this layer (A) formation composition for the sample (mixture of a crosslinking agent and a polysaccharide) to be used.
本明細書でいう架橋開始温度は、具体的には以下の方法により求められる値である。Ａｒ雰囲気内でＤＳＣ測定用のステンレス鋼（ＳＵＳ）製密閉容器に、試料３.５ｍｇを入れて密閉をして測定サンプルを作製する。基準サンプルには、前記ＤＳＣ測定用のＳＵＳ製密閉容器にＡｒガスを封入したものを使用する。これらを、ＤＳＣを用いて昇温開始温度を３０℃として、昇温速度５℃／ｍｉｎで２５０℃まで加熱を行い、基準サンプルとの温度差から測定サンプルの発熱反応の立ち上がり時点での温度を検出し、これを架橋開始温度とする。 The crosslinking initiation temperature as used herein is specifically a value determined by the following method. In an Ar atmosphere, 3.5 mg of a sample is put into a stainless steel (SUS) sealed container for DSC measurement and sealed to prepare a measurement sample. As the reference sample, an SUS sealed container for DSC measurement in which Ar gas is sealed is used. These are heated to 250 ° C. at a rate of temperature increase of 5 ° C./min using DSC at a temperature rise start temperature of 30 ° C., and the temperature at the start of the exothermic reaction of the measurement sample is determined from the temperature difference from the reference sample. It detects and makes this a crosslinking start temperature.
層（Ａ）は、正極と負極との間に配されていればよく、例えば、セパレータが層（Ａ）を含有していてもよく、また、正極または負極の表面に層（Ａ）が形成されていてもよい。セパレータが層（Ａ）とは別に２以上の層を有する多層構造の場合、層（Ａ）はセパレータの表面層であってもよく、表面層以外の層であってもよいが、表面層とすることがより好ましい。 The layer (A) may be disposed between the positive electrode and the negative electrode. For example, the separator may contain the layer (A), and the layer (A) is formed on the surface of the positive electrode or the negative electrode. May be. When the separator has a multilayer structure having two or more layers apart from the layer (A), the layer (A) may be a surface layer of the separator or a layer other than the surface layer, More preferably.
層（Ａ）に係る多糖類は、熱によって架橋剤で架橋し得るものであり、具体的には、例えば、（Ｃ６Ｈ１１ＮＯ４）ｎ（ｎは１以上の整数）で表されるもののうちの１種または２種以上が使用される。これらの中でも、キトサン誘導体（ヒドロキシエチルキトサン、ヒドロキシプロピルキトサン、ヒドロキシブチルキトサンおよびグリセリル化キトサンなど）が好ましい。 The polysaccharide according to the layer (A) can be cross-linked with a cross-linking agent by heat, and is specifically represented by, for example, (C 6 H 11 NO 4 ) n (n is an integer of 1 or more). One or more of those are used. Among these, chitosan derivatives (such as hydroxyethyl chitosan, hydroxypropyl chitosan, hydroxybutyl chitosan, and glycerylated chitosan) are preferable.
非水二次電池では、例えば、金属製の混入異物があった場合、電池内で溶解し、これが負極に析出して成長することで、セパレータを突き破り短絡を引き起こす場合がある。また、非水二次電池では、高温環境下で長期間貯蔵を行ったり、充放電を繰り返したりすることによって、正極活物質の金属がイオンとなって非水電解質中に溶出し、これが充放電の過程において負極上に金属として析出することがある。この負極上に析出した金属は、非水電解質中のリチウムイオンと反応して、電池の容量低下を引き起こす場合がある。そして、負極上に析出した正極活物質由来の金属も、セパレータを突き破って短絡を引き起こすことがある。 In a non-aqueous secondary battery, for example, when there is a metallic foreign matter, it dissolves in the battery, and this precipitates on the negative electrode and grows, which may break through the separator and cause a short circuit. Also, in non-aqueous secondary batteries, the positive electrode active material metal becomes ions and elutes into the non-aqueous electrolyte by long-term storage in a high-temperature environment or repeated charge and discharge, which is charged and discharged. In this process, it may be deposited as a metal on the negative electrode. The metal deposited on the negative electrode may react with lithium ions in the non-aqueous electrolyte to cause a reduction in battery capacity. And the metal derived from the positive electrode active material deposited on the negative electrode may break through the separator and cause a short circuit.
キトサン誘導体は、分子内に有するアミノ基の作用によって、非水電解質中に溶出した金属イオンを効果的にトラップすることができる一方で、電池の充放電に関与するリチウムイオンはあまりトラップしない。よって、層（Ａ）に係る多糖類として、キトサンやその誘導体を用いた場合には、前記の容量低下や短絡の発生を抑制し得ることから、非水二次電池の信頼性、貯蔵特性（特に高温環境下での貯蔵特性）および充放電サイクル特性を高めることができる。 The chitosan derivative can effectively trap metal ions eluted in the non-aqueous electrolyte by the action of the amino group in the molecule, but does not trap lithium ions involved in charge / discharge of the battery so much. Therefore, when chitosan or a derivative thereof is used as the polysaccharide according to the layer (A), it is possible to suppress the above-described reduction in capacity and occurrence of short-circuiting. Therefore, the reliability and storage characteristics of the non-aqueous secondary battery ( In particular, storage characteristics in a high temperature environment) and charge / discharge cycle characteristics can be enhanced.
層（Ａ）に係る架橋剤は、熱によって多糖類と架橋構造を形成し得るものであり、具体的には、有機カルボン酸、有機カルボン酸無水物、有機カルボン酸の塩、有機カルボン酸誘導体などが使用できる。このような架橋剤を使用し、かつ多糖類にキトサン誘導体を使用した場合には、電池内の温度が上昇した際に、層（Ａ）内において、アミノ基を有する三次元的な網目構造（架橋構造）が形成される。 The crosslinking agent according to the layer (A) is capable of forming a crosslinked structure with a polysaccharide by heat. Specifically, organic carboxylic acid, organic carboxylic acid anhydride, organic carboxylic acid salt, organic carboxylic acid derivative Etc. can be used. When such a cross-linking agent is used and a chitosan derivative is used as the polysaccharide, when the temperature in the battery rises, a three-dimensional network structure having amino groups in the layer (A) ( A crosslinked structure) is formed.
有機カルボン酸としては、例えば、コハク酸、リンゴ酸、クエン酸、マレイン酸、１，２，３，４−ブタンテトラカルボン酸などの脂肪族多価カルボン酸；サリチル酸などの芳香族モノカルボン酸；フタル酸、トリメリット酸、ピロメリット酸などの芳香族多価カルボン酸；ピロリドンカルボン酸などの複素環式カルボン酸；などが挙げられる。 Examples of organic carboxylic acids include aliphatic polycarboxylic acids such as succinic acid, malic acid, citric acid, maleic acid and 1,2,3,4-butanetetracarboxylic acid; aromatic monocarboxylic acids such as salicylic acid; And aromatic polycarboxylic acids such as phthalic acid, trimellitic acid and pyromellitic acid; and heterocyclic carboxylic acids such as pyrrolidone carboxylic acid.
有機カルボン酸無水物としては、前記例示の各有機カルボン酸の無水物が挙げられる。また、有機カルボン酸の塩としては、前記例示の各有機カルボン酸のアンモニウム塩やアミン塩などが挙げられる。なお、有機多価カルボン酸の塩の場合には、有機多価カルボン酸の有するカルボキシル基の一部のみが塩を形成していてもよく、全てが塩を形成していてもよい。 Examples of the organic carboxylic acid anhydride include the anhydrides of the organic carboxylic acids exemplified above. Examples of the organic carboxylic acid salt include ammonium salts and amine salts of the organic carboxylic acids exemplified above. In the case of a salt of an organic polyvalent carboxylic acid, only a part of the carboxyl groups of the organic polyvalent carboxylic acid may form a salt, or all may form a salt.
有機カルボン酸誘導体としては、前記例示の各有機カルボン酸の誘導体（アルキルエステル；アミド；イミド；アミドイミド；Ｎ−ヒドロキシスクシンイミド、Ｎ−ヒドロキシスルホスクシンイミドまたはこれらの誘導体によって修飾した修飾物；など）が挙げられる。なお、有機多価カルボン酸の誘導体の場合には、有機多価カルボン酸の有するカルボキシル基の一部が誘導体形成に使用されていてもよく、全てが誘導体形成に使用されていてもよい。 Examples of the organic carboxylic acid derivative include derivatives of the above-mentioned organic carboxylic acids (alkyl ester; amide; imide; amide imide; N-hydroxysuccinimide, N-hydroxysulfosuccinimide, or a modified product modified with these derivatives, etc.). It is done. In the case of a derivative of an organic polyvalent carboxylic acid, a part of the carboxyl group possessed by the organic polyvalent carboxylic acid may be used for forming the derivative, or all may be used for forming the derivative.
前記例示の架橋剤の中でも、有機カルボン酸または有機カルボン酸無水物がより好ましく、架橋性がより良好である点で、３価以上の芳香族多価カルボン酸であるピロメリット酸、トリメリット酸、およびこれらの無水物が特に好ましい。 Among the exemplified cross-linking agents, organic carboxylic acid or organic carboxylic acid anhydride is more preferable, and pyromellitic acid and trimellitic acid which are trivalent or higher aromatic polyvalent carboxylic acids in terms of better crosslinkability. And their anhydrides are particularly preferred.
層（Ａ）は、架橋剤および多糖類のみで構成してもよいが、層（Ａ）のイオン透過性をより高めるなどの目的で、無機微粒子、樹脂微粒子および樹脂製の極細繊維よりなる群から選択される少なくとも１種の材料を含有させてもよい。 The layer (A) may be composed only of a cross-linking agent and a polysaccharide, but for the purpose of enhancing the ion permeability of the layer (A), the group consisting of inorganic fine particles, resin fine particles, and resin-made ultrafine fibers. You may contain the at least 1 sort (s) of material selected from these.
無機微粒子としては、電気化学的に安定で、かつ電気絶縁性のものであればよく、例えば、酸化鉄（ＦｅｘＯｙ；ＦｅＯ、Ｆｅ２Ｏ３など）、ＳｉＯ２、Ａｌ２Ｏ３、ＴｉＯ２、ＢａＴｉＯ２、ＺｒＯ２などの無機酸化物の微粒子；窒化アルミニウム、窒化ケイ素などの無機窒化物の微粒子；フッ化カルシウム、フッ化バリウム、硫酸バリウム、炭化カルシウムなどの難溶性のイオン結晶の微粒子；シリコン、ダイヤモンドなどの共有結合性結晶の微粒子；モンモリロナイトなどの粘土の微粒子；などが挙げられる。ここで、前記無機酸化物の微粒子は、ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、マイカなどの鉱物資源由来物質またはこれらの人造物などの微粒子であってもよい。また、金属、ＳｎＯ２、スズ−インジウム酸化物（ＩＴＯ）などの導電性酸化物、カーボンブラック、グラファイトなどの炭素質材料などで例示される導電性材料の表面を、電気絶縁性を有する材料（例えば、前記の無機酸化物など）で被覆することにより電気絶縁性を持たせた粒子であってもよい。
As the inorganic fine particles, electrochemically stable, and as long as the electrical insulation, for example, iron oxide (Fe x O y; FeO, such Fe 2 O 3), SiO 2 , Al 2
樹脂微粒子としては、耐熱性および電気絶縁性を有しており、非水電解質に対して安定であり、更に、電池の作動電圧範囲において酸化還元されにくい電気化学的に安定な材料により構成された微粒子が好ましく、このような材料としては、例えば、樹脂架橋体が挙げられる。より具体的には、スチレン樹脂〔ポリスチレン（ＰＳ）など〕、スチレンブタジエンゴム（ＳＢＲ）、アクリル樹脂〔ポリメチルメタクリレート（ＰＭＭＡ）など〕、ポリアルキレンオキシド〔ポリエチレンオキシド（ＰＥＯ）など〕、フッ素樹脂〔ポリフッ化ビニリデン（ＰＶＤＦ）など〕およびこれらの誘導体よりなる群から選ばれる少なくとも１種の樹脂の架橋体；尿素樹脂；ポリウレタン；などが例示できる。樹脂微粒子には、前記例示の樹脂を１種単独で用いてもよく、２種以上を併用してもよい。また、有機微粒子は、必要に応じて、樹脂に添加される公知の各種添加剤、例えば、酸化防止剤などを含有していても構わない。 The resin fine particles have heat resistance and electrical insulation, are stable with respect to non-aqueous electrolytes, and are made of an electrochemically stable material that is not easily oxidized or reduced in the operating voltage range of the battery. Fine particles are preferable, and examples of such a material include a crosslinked resin. More specifically, styrene resin (polystyrene (PS), etc.), styrene butadiene rubber (SBR), acrylic resin (polymethyl methacrylate (PMMA), etc.), polyalkylene oxide (polyethylene oxide (PEO), etc.), fluororesin [ Polyvinylidene fluoride (PVDF) and the like] and a crosslinked product of at least one resin selected from the group consisting of these derivatives; urea resin; polyurethane; and the like. For the resin fine particles, the above-exemplified resins may be used alone or in combination of two or more. Moreover, the organic fine particles may contain various known additives that are added to the resin, for example, an antioxidant, if necessary.
樹脂製の極細繊維としては、例えば、ポリイミド、ポリアクリロニトリル、アラミド、ポリプロピレン（ＰＰ）、塩素化ＰＰ、ＰＥＯ、ポリエチレン（ＰＥ）、セルロース、セルロース誘導体、ポリサルフォン、ポリエーテルサルフォン、ポリフッ化ビニリデン（ＰＶＤＦ）、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体などの樹脂や、これらの樹脂の誘導体で構成された極細繊維が挙げられる。 Examples of the resin-made ultrafine fibers include polyimide, polyacrylonitrile, aramid, polypropylene (PP), chlorinated PP, PEO, polyethylene (PE), cellulose, cellulose derivatives, polysulfone, polyethersulfone, and polyvinylidene fluoride (PVDF). ), Resins such as vinylidene fluoride-hexafluoropropylene copolymer, and ultrafine fibers composed of derivatives of these resins.
前記例示の無機微粒子、樹脂微粒子、および樹脂製の極細繊維の中でも、Ａｌ２Ｏ３、ＳｉＯ２、ベーマイト、ＰＭＭＡ（架橋ＰＭＭＡ）の各微粒子が特に好ましく用いられる。 Among the inorganic fine particles, resin fine particles, and ultrafine fibers made of resin, Al 2 O 3 , SiO 2 , boehmite, and PMMA (crosslinked PMMA) fine particles are particularly preferably used.
無機微粒子および樹脂微粒子の形状は、球状、板状、板状以外の多面体形状などいずれの形状であってもよい。 The shape of the inorganic fine particles and the resin fine particles may be any shape such as a spherical shape, a plate shape, and a polyhedral shape other than the plate shape.
また、無機微粒子および樹脂微粒子の粒子径としては、一次粒子の平均粒子径で、０．１μｍ以上であることが好ましく、０．２μｍ以上であることがより好ましく、３μｍ以下であることが好ましく、２μｍ以下であることがより好ましい。無機微粒子や樹脂微粒子の一次粒子の平均粒子径が小さすぎると、表面積が大きくなって、層（Ａ）の形成に使用する組成物（溶剤を含む組成物。詳しくは後述する。）において、溶剤中への分散が困難となり、また、前記組成物が凝集しやすくなることから好ましくない。また、無機微粒子や樹脂微粒子の一次粒子の平均粒子径が大きすぎると、層（Ａ）内でのリチウムイオンの運動を、層（Ａ）の面方向に対して均一にし難くなり、電池の充放電時のリチウムイオンの移動障壁となる虞がある。 The particle diameter of the inorganic fine particles and the resin fine particles is preferably an average particle diameter of primary particles of 0.1 μm or more, more preferably 0.2 μm or more, and preferably 3 μm or less. More preferably, it is 2 μm or less. If the average particle size of the primary particles of the inorganic fine particles or resin fine particles is too small, the surface area becomes large, and the composition used in the formation of the layer (A) (a composition containing a solvent; details will be described later) is a solvent. Dispersion into the inside becomes difficult and the composition tends to aggregate, which is not preferable. If the average particle size of the primary particles of the inorganic fine particles or resin fine particles is too large, it becomes difficult to make the movement of lithium ions in the layer (A) uniform with respect to the surface direction of the layer (A). There is a risk of becoming a lithium ion migration barrier during discharge.
本明細書でいう各種微粒子の平均粒子径、レーザー散乱粒度分布計（例えば、ＨＯＲＩＢＡ社製「ＬＡ−９２０」）を用い、耐熱性微粒子を膨潤させたり溶解させたりしない媒体（例えば水）に分散させて測定した体積基準の積算分率における５０％での粒径（Ｄ５０）である。 The average particle diameter of various fine particles referred to in this specification, a laser scattering particle size distribution meter (for example, “LA-920” manufactured by HORIBA), and dispersed in a medium (for example, water) that does not swell or dissolve the heat-resistant fine particles. The particle size (D50) at 50% of the volume-based integrated fraction measured in this way.
また、樹脂製の極細繊維の形態としては、平均繊維径が０．０１〜１０μｍであることが好ましく、平均繊維長が１〜１０００μｍであることが好ましい。 Moreover, as a form of resin-made ultrafine fiber, it is preferable that an average fiber diameter is 0.01-10 micrometers, and it is preferable that an average fiber length is 1-1000 micrometers.
本明細書でいう極細繊維の平均繊維径および平均繊維長は、極細繊維の走査型電子顕微鏡（ＳＥＭ）写真を撮影し、撮影した写真上において任意の位置に線を引き、線と交差する全ての繊維径および繊維長（それぞれｎ＝２０以上）をカウントして、それらの平均値（数平均）を算出することにより求められる値である。 The average fiber diameter and average fiber length of the ultrafine fibers referred to in this specification are obtained by taking a scanning electron microscope (SEM) photograph of the ultrafine fiber, drawing a line at an arbitrary position on the photographed photograph, and crossing the line. This is a value obtained by counting the fiber diameter and the fiber length (each n = 20 or more) and calculating the average value (number average) thereof.
層（Ａ）において、多糖類および架橋剤の含有量は、例えば、電池内が温度上昇した際に、層（Ａ）内でより良好に架橋構造を形成し得るようにする観点から、多糖類１００質量部に対して、架橋剤を１０〜５０質量部とすることが好ましい。 In the layer (A), the content of the polysaccharide and the cross-linking agent is, for example, from the viewpoint of enabling a better cross-linked structure to be formed in the layer (A) when the temperature in the battery rises. It is preferable that a crosslinking agent shall be 10-50 mass parts with respect to 100 mass parts.
また、層（Ａ）に、無機微粒子、樹脂微粒子、および樹脂製の極細繊維よりなる群から選択される少なくとも１種の材料を含有させる場合には、前記材料１００質量部に対して、多糖類の含有量を、０．０１〜５質量部とすることが好ましく、これにより、層（Ａ）のリチウムイオン透過性を良好にしつつ、多糖類および架橋剤による架橋構造の形成を良好に進め、それによる前記の効果を良好に確保することができる。 Further, when the layer (A) contains at least one material selected from the group consisting of inorganic fine particles, resin fine particles, and resin ultrafine fibers, the polysaccharide is used with respect to 100 parts by mass of the material. The content of is preferably 0.01 to 5 parts by mass, thereby improving the lithium ion permeability of the layer (A), while favorably promoting the formation of a crosslinked structure with a polysaccharide and a crosslinking agent, As a result, the above-mentioned effects can be secured satisfactorily.
層（Ａ）の厚みは、層（Ａ）の形成による前記の効果をより良好に確保する観点から、０．１μｍ以上であることが好ましく、３．０μｍ以上であることがより好ましい。ただし、層（Ａ）が厚すぎると、電池の容量が小さくなる虞があることから、層（Ａ）の厚みは、１０．０μｍ以下であることが好ましく、６．０μｍ以下であることがより好ましい。 The thickness of the layer (A) is preferably 0.1 μm or more, and more preferably 3.0 μm or more, from the viewpoint of better ensuring the above-described effect due to the formation of the layer (A). However, if the layer (A) is too thick, the capacity of the battery may be reduced. Therefore, the thickness of the layer (A) is preferably 10.0 μm or less, and more preferably 6.0 μm or less. preferable.
本発明の非水二次電池に係る正極には、例えば、正極活物質、導電助剤およびバインダを含有する正極合剤層を、集電体の片面または両面に有する構造のものを使用することができる。 For the positive electrode according to the non-aqueous secondary battery of the present invention, for example, a positive electrode mixture layer containing a positive electrode active material, a conductive additive and a binder is used on one or both sides of the current collector. Can do.
正極活物質には、例えば、従来から知られているリチウムイオン二次電池などの非水二次電池に用いられている正極活物質、すなわち、Ｌｉイオンを吸蔵放出可能な正極活物質を特に制限なく使用できる。正極活物質の具体例としては、ＬｉＭ１ ｘＭｎ２−ｘＯ４（Ｍ１は、Ｌｉ、Ｂ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｌ、Ｓｎ、Ｓｂ、Ｉｎ、Ｎｂ、Ｍｏ、Ｗ、Ｙ、ＲｕおよびＲｈよりなる群から選択される少なくとも１種の元素であり、０．０１≦ｘ≦０．６である。）で表されるスピネル型リチウムマンガン複合酸化物、ＬｉａＭｎ（１−ｂ−ｃ）ＮｉｂＭ２ ｃＯ（２−ｄ）Ｆｅ（Ｍ２は、Ｃｏ、Ｍｇ、Ａｌ、Ｂ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｕ、Ｚｎ、Ｚｒ、Ｍｏ、Ｓｎ、Ｃａ、ＳｒおよびＷよりなる群から選択される少なくとも１種の元素であり、０．８≦ａ≦１．２、０＜ｂ＜０．５、０≦ｃ≦０．５、ｄ＋ｅ＜１、−０．１≦ｄ≦０．２、０≦ｅ≦０．１である。）で表される層状化合物、ＬｉＣｏ１−ｙＭ３ ｙＯ２（ただし、Ｍ３は、Ａｌ、Ｍｇ、Ｔｉ、Ｚｒ、Ｆｅ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｎｂ、Ｍｏ、Ｓｎ、ＳｂおよびＢａよりなる群から選択される少なくとも１種の元素であり、０≦ｙ≦０．５）で表されるリチウムコバルト複合酸化物、ＬｉＮｉ１−ｚＭ４ ｚＯ２（ただし、Ｍ４は、Ａｌ、Ｍｇ、Ｔｉ、Ｚｒ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｎｂ、Ｍｏ、Ｓｎ、ＳｂおよびＢａよりなる群から選択される少なくとも１種の元素であり、０≦ｚ≦０．５）で表されるリチウムニッケル複合酸化物、ＬｉＭ５ １−ｆＭ６ ｆＯ２（ただし、Ｍ５は、Ｆｅ、ＭｎおよびＣｏよりなる群から選択される少なくとも１種の元素で、Ｍ６は、Ａｌ、Ｍｇ、Ｔｉ、Ｚｒ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ｎｂ、Ｍｏ、Ｓｎ、ＳｂおよびＢａよりなる群から選択される少なくとも１種の元素であり、０≦ｆ≦０．５）で表されるオリビン型複合酸化物などが挙げられ、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。 For the positive electrode active material, for example, a positive electrode active material that is conventionally used in a non-aqueous secondary battery such as a lithium ion secondary battery, that is, a positive electrode active material capable of occluding and releasing Li ions is particularly limited. Can be used without Specific examples of the positive electrode active material, LiM 1 x Mn 2-x O 4 (M 1 is, Li, B, Mg, Ca , Sr, Ba, Ti, V, Cr, Fe, Co, Ni, Cu, Al , Sn, Sb, In, Nb, Mo, W, Y, Ru, and Rh, at least one element selected from 0.01 ≦ x ≦ 0.6. Spinel-type lithium-manganese composite oxide, Li a Mn (1-bc) Ni b M 2 c O (2-d) Fe (M 2 is Co, Mg, Al, B, Ti, V, Cr, At least one element selected from the group consisting of Fe, Cu, Zn, Zr, Mo, Sn, Ca, Sr and W, 0.8 ≦ a ≦ 1.2, 0 <b <0.5, 0 ≦ c ≦ 0.5, d + e <1, −0.1 ≦ d ≦ 0.2, and 0 ≦ e ≦ 0.1.) LiCo 1-y M 3 y O 2 (M 3 is made of Al, Mg, Ti, Zr, Fe, Ni, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb and Ba) Lithium cobalt composite oxide represented by 0 ≦ y ≦ 0.5, which is at least one element selected from the group, LiNi 1-z M 4 z O 2 (where M 4 is Al, Mg) , Ti, Zr, Fe, Co, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb and Ba, and at least one element selected from 0 ≦ z ≦ 0.5) Lithium nickel composite oxide, LiM 5 1-f M 6 f O 2 (wherein M 5 is at least one element selected from the group consisting of Fe, Mn and Co, and M 6 is Al Mg, Ti, Zr, Ni, Cu, Zn An olivine type complex oxide represented by 0 ≦ f ≦ 0.5), which is at least one element selected from the group consisting of Ga, Ge, Nb, Mo, Sn, Sb and Ba, Only one of these may be used, or two or more may be used in combination.
正極合剤層に係る導電助剤には、例えば、カーボンブラックなどの炭素材料が使用できる。また、正極合剤層に係るバインダには、ＰＶＤＦなどのフッ素樹脂が使用できる。 For example, a carbon material such as carbon black can be used as the conductive additive for the positive electrode mixture layer. Moreover, fluororesins, such as PVDF, can be used for the binder which concerns on a positive mix layer.
正極合剤層は、例えば、前記の正極活物質、導電助剤およびバインダをＮ−メチル−２−ピロリドン（ＮＭＰ）などの溶媒に溶解または分散させて正極合剤含有スラリーを調製し、これを正極集電体の片面または両面に塗布して乾燥し、必要に応じてプレス処理を施すことにより形成することができる。なお、正極に係る正極合剤層は、前記の方法以外の方法により形成してもよい。正極合剤層の厚みは、集電体の片面あたり、２０〜２００μｍとすることが好ましい。 The positive electrode mixture layer is prepared by, for example, preparing a positive electrode mixture-containing slurry by dissolving or dispersing the positive electrode active material, the conductive additive and the binder in a solvent such as N-methyl-2-pyrrolidone (NMP). It can form by apply | coating to the single side | surface or both surfaces of a positive electrode electrical power collector, drying, and performing a press process as needed. In addition, you may form the positive mix layer concerning a positive electrode by methods other than the said method. The thickness of the positive electrode mixture layer is preferably 20 to 200 μm per one side of the current collector.
正極の集電体としては、アルミニウムなどの金属の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、厚みが１０〜３０μｍのアルミニウム箔が好適に用いられる。 As the current collector of the positive electrode, a metal foil such as aluminum, a punching metal, a net, an expanded metal, or the like can be used. Usually, an aluminum foil having a thickness of 10 to 30 μm is preferably used.
正極側のリード部は、通常、正極作製時に、集電体の一部に正極合剤層を形成せずに集電体の露出部を残し、そこをリード部とすることによって設けられる。ただし、リード部は必ずしも当初から集電体と一体化されたものであることは要求されず、集電体にアルミニウム製の箔などを後から接続することによって設けてもよい。 The lead portion on the positive electrode side is normally provided by leaving the exposed portion of the current collector without forming the positive electrode mixture layer on a part of the current collector and forming the lead portion at the time of producing the positive electrode. However, the lead portion is not necessarily integrated with the current collector from the beginning, and may be provided by connecting an aluminum foil or the like to the current collector later.
正極に係る正極合剤層においては、正極活物質の含有量を８７〜９７質量％とし、導電助剤の含有量を１．５〜６．５質量％とし、バインダの含有量を１．５〜６．５質量％とすることが好ましい。 In the positive electrode mixture layer related to the positive electrode, the content of the positive electrode active material is 87 to 97% by mass, the content of the conductive auxiliary agent is 1.5 to 6.5% by mass, and the content of the binder is 1.5%. It is preferable to set it to -6.5 mass%.
本発明の非水二次電池に係る負極には、従来から知られているリチウムイオン二次電池などの非水二次電池に用いられている負極、すなわち、Ｌｉイオンを吸蔵放出可能な活物質を含有する負極であれば特に制限はない。例えば、活物質として、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（ＭＣＭＢ）、炭素繊維などの、リチウムを吸蔵、放出可能な炭素系材料の１種または２種以上の混合物が用いられる。また、Ｓｉ、Ｓｎ、Ｇｅ、Ｂｉ、Ｓｂ、Ｉｎなどの元素を含む単体、化合物およびその合金、リチウム含有窒化物、または酸化物などのリチウム金属に近い低電圧で充放電できる化合物、もしくはリチウム金属やリチウム／アルミニウム合金、更にはＬｉ４Ｔｉ５Ｏ１２で表されるようなＴｉ酸化物も負極活物質として用いることができる。これらの負極活物質に導電助剤（カーボンブラックなどの炭素材料など）やＰＶＤＦなどのバインダなどを適宜添加した負極合剤を、集電体を芯材として、その片面または両面に成形体（負極合剤層）に仕上げたもの、または前記の各種合金やリチウム金属の箔を単独、もしくは集電体上に負極剤層として積層したものなどが用いられる。 The negative electrode according to the non-aqueous secondary battery of the present invention includes a negative electrode used in a conventionally known non-aqueous secondary battery such as a lithium ion secondary battery, that is, an active material capable of occluding and releasing Li ions. If it is a negative electrode containing this, there will be no restriction | limiting in particular. For example, carbon that can occlude and release lithium, such as graphite, pyrolytic carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads (MCMB), and carbon fibers as active materials One type or a mixture of two or more types of system materials is used. In addition, simple compounds containing elements such as Si, Sn, Ge, Bi, Sb, and In, compounds and alloys thereof, lithium-containing nitrides, oxides and other compounds that can be charged and discharged at a low voltage close to lithium metal, or lithium metal Alternatively, a lithium / aluminum alloy, or a Ti oxide represented by Li 4 Ti 5 O 12 can also be used as the negative electrode active material. A negative electrode mixture in which a conductive additive (carbon material such as carbon black) or a binder such as PVDF is appropriately added to these negative electrode active materials, and a molded body (negative electrode) on one or both sides of the current collector as a core material A mixture layer) or the above-described various alloys or lithium metal foils alone or laminated as a negative electrode layer on a current collector is used.
なお、負極合剤層を有する負極の場合には、例えば、前記の負極活物質やバインダなどをＮＭＰや水などの溶媒に溶解または分散させて負極合剤含有スラリーを調製し、これを負極集電体の片面または両面に塗布して乾燥し、必要に応じてプレス処理を施すことにより形成することができる。ただし、負極に係る負極合剤層は、前記の方法以外の方法により形成してもよい。 In the case of a negative electrode having a negative electrode mixture layer, for example, a negative electrode mixture-containing slurry is prepared by dissolving or dispersing the negative electrode active material, binder, or the like in a solvent such as NMP or water. It can be formed by applying to one side or both sides of the electrical conductor and drying, and if necessary, press treatment. However, you may form the negative mix layer concerning a negative electrode by methods other than the said method.
集電体の片面または両面に負極合剤層を形成する場合には、負極合剤層の厚みは、集電体の片面あたり、２０〜２００μｍとすることが好ましい。 When the negative electrode mixture layer is formed on one side or both sides of the current collector, the thickness of the negative electrode mixture layer is preferably 20 to 200 μm per one side of the current collector.
負極に集電体を用いる場合には、集電体としては、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。この負極集電体は、高エネルギー密度の電池を得るために負極全体の厚みを薄くする場合、厚みの上限は３０μｍであることが好ましく、下限は５μｍであることが望ましい。また、負極側のリード部は、正極側のリード部と同様にして形成すればよい。 When a current collector is used for the negative electrode, a copper or nickel foil, a punching metal, a net, an expanded metal, or the like can be used as the current collector, but a copper foil is usually used. In the negative electrode current collector, when the thickness of the entire negative electrode is reduced in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 30 μm, and the lower limit is preferably 5 μm. Further, the lead portion on the negative electrode side may be formed in the same manner as the lead portion on the positive electrode side.
負極に係る負極合剤層においては、負極活物質の含有量を８８〜９９質量％とし、バインダの含有量を１〜１２質量％とすることが好ましく、また、導電助剤を使用する場合には、その含有量を０．５〜６質量％とすることが好ましい。 In the negative electrode mixture layer related to the negative electrode, the content of the negative electrode active material is preferably 88 to 99% by mass, and the content of the binder is preferably 1 to 12% by mass. When a conductive additive is used, The content is preferably 0.5 to 6% by mass.
層（Ａ）を正極または負極の表面に形成する場合には、例えば、層（Ａ）の構成材料（架橋剤および多糖類、更には、必要に応じて使用される無機微粒子、樹脂微粒子または樹脂製の極細繊維）を溶剤に分散（架橋剤および多糖類は溶解していてもよい）させて層（Ａ）形成用組成物を調製し、これを正極の表面（少なくとも正極合剤層の表面）または負極の負極剤層の表面（少なくとも負極剤層の表面）に塗布し、乾燥して溶剤を除去する方法が採用できる。 When the layer (A) is formed on the surface of the positive electrode or the negative electrode, for example, the constituent material of the layer (A) (crosslinking agent and polysaccharide, as well as inorganic fine particles, resin fine particles or resin used as necessary) The layer (A) forming composition is prepared by dispersing the ultrafine fibers made in a solvent (the crosslinking agent and the polysaccharide may be dissolved), and this is prepared on the surface of the positive electrode (at least the surface of the positive electrode mixture layer). ) Or the surface of the negative electrode agent layer of the negative electrode (at least the surface of the negative electrode agent layer), and drying to remove the solvent.
層（Ａ）形成用組成物の溶剤には、ＮＭＰなどの有機溶剤や水を使用することができる。 An organic solvent such as NMP or water can be used as the solvent of the layer (A) forming composition.
本発明の非水二次電池に係るセパレータには、例えば、ポリオレフィン、ポリエステル、ポリイミド、ポリアミド、ポリウレタンなどの樹脂で構成された多孔質膜を使用することができるが、セパレータにシャットダウン機能を持たせる観点から、ポリオレフィン製の多孔質膜を使用することが好ましい。 For the separator according to the non-aqueous secondary battery of the present invention, for example, a porous film made of a resin such as polyolefin, polyester, polyimide, polyamide, polyurethane can be used, but the separator has a shutdown function. From the viewpoint, it is preferable to use a porous film made of polyolefin.
ポリオレフィンとしては、低密度ポリエチレン、高密度ポリエチレン、超高分子量ポリエチレンなどのＰＥ；ＰＰなどが挙げられ、これらのうちの１種のみを用いてもよく、２種以上を併用してもよい。例えば、２種以上のポリオレフィンを使用した多孔質膜としては、例えば、ＰＰ層上にＰＥ層を介してＰＰ層を積層した三層構造の多孔質膜が挙げられる。 Examples of the polyolefin include PE such as low density polyethylene, high density polyethylene, and ultrahigh molecular weight polyethylene; PP, etc., and only one of these may be used, or two or more may be used in combination. For example, as a porous film using two or more kinds of polyolefin, for example, a porous film having a three-layer structure in which a PP layer is laminated on a PP layer via a PE layer can be mentioned.
これらのポリオレフィンの中でも、融点、すなわち、ＪＩＳ Ｋ ７１２１の規定に準じて、示差走査熱量計（ＤＳＣ）を用いて測定される融解温度が、８０〜１５０℃のものを使用することが好ましい。このような融点のポリオレフィンを含有する多孔質膜であれば、前記ポリオレフィンが軟化してセパレータの空孔が閉塞されるシャットダウン特性の開始温度が８０〜１５０℃のセパレータとすることができるため、かかるセパレータを使用することで、非水二次電池の安全性を更に高めることが可能となる。 Among these polyolefins, those having a melting point of 80 to 150 ° C. measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121 are preferably used. Such a porous film containing a polyolefin having a melting point can be a separator having a shutdown characteristic starting temperature of 80 to 150 ° C. in which the polyolefin is softened and the pores of the separator are closed. By using the separator, the safety of the non-aqueous secondary battery can be further increased.
セパレータに使用する多孔質膜としては、例えば、従来から知られている溶剤抽出法や、乾式または湿式延伸法などにより形成された孔を多数有するイオン透過性の多孔質膜（電池のセパレータとして汎用されている微多孔膜）を用いることができる。 Examples of porous membranes used in separators include ion-permeable porous membranes having a large number of pores formed by a conventionally known solvent extraction method, dry type or wet drawing method (generally used as battery separators). A microporous film) can be used.
また、セパレータに層（Ａ）を形成する場合、多孔質膜には、前記の微多孔膜以外にも、前記例示の樹脂で構成された不織布などを用いてもよい。 Moreover, when forming a layer (A) in a separator, you may use the nonwoven fabric etc. which were comprised with the said resin other than the said microporous film for a porous film.
セパレータに層（Ａ）を形成する場合には、前記のような樹脂製の多孔質膜の表面に、前記の層（Ａ）形成用組成物を塗布し、乾燥して溶剤を除去する方法が採用できる。 When the layer (A) is formed on the separator, there is a method in which the layer (A) forming composition is applied to the surface of the resin porous membrane as described above, and the solvent is removed by drying. Can be adopted.
本発明の非水二次電池において、前記の正極と前記の負極とは、前記のセパレータを介して積層した積層体（積層電極体）や、更にこの積層体を巻回した巻回体（巻回電極体）の形態で用いることができる。 In the non-aqueous secondary battery of the present invention, the positive electrode and the negative electrode include a laminated body (laminated electrode body) laminated via the separator, and a wound body (winding) obtained by winding the laminated body. It can be used in the form of a rotating electrode body).
本発明の非水二次電池に係る非水電解質には、例えば、リチウム塩を有機溶媒に溶解した溶液（非水電解液）が使用される。リチウム塩としては、溶媒中で解離してＬｉ＋イオンを形成し、電池として使用される電圧範囲で分解などの副反応を起こしにくいものであれば特に制限はない。例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６などの無機リチウム塩；ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、Ｌｉ２Ｃ２Ｆ４（ＳＯ３）２、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｎＦ２ｎ＋１ＳＯ３（ｎ≧２）、ＬｉＮ（ＲｆＯＳＯ２）２［ここでＲｆはフルオロアルキル基］などの有機リチウム塩；などを用いることができる。 For the nonaqueous electrolyte according to the nonaqueous secondary battery of the present invention, for example, a solution (nonaqueous electrolyte) in which a lithium salt is dissolved in an organic solvent is used. The lithium salt is not particularly limited as long as it dissociates in a solvent to form Li + ions and hardly causes side reactions such as decomposition in a voltage range used as a battery. For example, inorganic lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ≧ 2), LiN (R f OSO 2 ) 2 [where R f is a fluoroalkyl group] and the like; Can be used.
非水電解質に用いる有機溶媒としては、前記のリチウム塩を溶解し、電池として使用される電圧範囲で分解などの副反応を起こさないものであれば特に限定されない。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、ビニレンカーボネートなどの環状カーボネート；ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネートなどの鎖状カーボネート；プロピオン酸メチルなどの鎖状エステル；γ−ブチロラクトンといった環状エステル；ジメトキシエタン、ジエチルエーテル、１，３−ジオキソラン、ジグライム、トリグライム、テトラグライムなどの鎖状エーテル；ジオキサン、テトラヒドロフラン、２−メチルテトラヒドロフランなどの環状エーテル；アセトニトリル、プロピオニトリル、メトキシプロピオニトリルといったニトリル類；エチレングリコールサルファイトなどの亜硫酸エステル類；などが挙げられ、これらを１種単独で用いてもよいし、２種以上を併用しても構わない。なお、より良好な特性の電池とするためには、エチレンカーボネートと鎖状カーボネートの混合溶媒など、高い導電率を得ることができる組み合わせで用いることが望ましい。 The organic solvent used for the non-aqueous electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause a side reaction such as decomposition in a voltage range used as a battery. For example, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; chain esters such as methyl propionate; cyclic esters such as γ-butyrolactone; Chain ethers such as ethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme; cyclic ethers such as dioxane, tetrahydrofuran and 2-methyltetrahydrofuran; nitriles such as acetonitrile, propionitrile and methoxypropionitrile; Sulfites such as ethylene glycol sulfite; and the like, and these may be used alone. , It may be used in combination of two or more thereof. In order to obtain a battery with better characteristics, it is desirable to use a combination that can obtain high conductivity, such as a mixed solvent of ethylene carbonate and chain carbonate.
また、これらの非水電解質に安全性や充放電サイクル性、高温貯蔵性といった特性を向上させる目的で、ビニレンカーボネート類、１，３−プロパンサルトン、ジフェニルジスルフィド、シクロヘキシルベンゼン、ビフェニル、フルオロベンゼン、ｔ−ブチルベンゼンなどの添加剤を適宜加えることもできる。 In addition, for the purpose of improving the safety, charge / discharge cycleability, and high-temperature storage properties of these nonaqueous electrolytes, vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, Additives such as t-butylbenzene can be added as appropriate.
このリチウム塩の非水電解質中の濃度としては、０．５〜１．５ｍｏｌ／ｌとすることが好ましく、０．９〜１．２５ｍｏｌ／ｌとすることがより好ましい。 The concentration of the lithium salt in the nonaqueous electrolyte is preferably 0.5 to 1.5 mol / l, and more preferably 0.9 to 1.25 mol / l.
また、前記の非水電解質（非水電解液）に、ポリマーなどの公知のゲル化剤を加えてゲル状（ゲル状電解質）として用いてもよい。 Further, a known gelling agent such as a polymer may be added to the non-aqueous electrolyte (non-aqueous electrolyte solution) to form a gel (gel electrolyte).
本発明の非水二次電池の形態としては、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）などが挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。 Examples of the form of the non-aqueous secondary battery of the present invention include a cylindrical shape (such as a rectangular tube shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
本発明の非水二次電池は、自動車用途や電動工具の電源用途などの用途に好適である他、各種電子機器の電源用途など、従来から知られているリチウムイオン二次電池などの非水二次電池が用いられている各種用途と同じ用途にも適用することができる。 The non-aqueous secondary battery of the present invention is suitable for applications such as automobile applications and power supply applications for electric tools, and also non-aqueous secondary batteries such as lithium ion secondary batteries that have been conventionally known, such as power supply applications for various electronic devices. The present invention can also be applied to the same uses as those for which secondary batteries are used.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
＜層（Ａ）形成用組成物の調製＞
〔層（Ａ）形成用組成物（１）〕
ＮＭＰ：１０００ｇ中に、無機微粒子である多面体形状のベーマイト合成品（アスペクト比：１．４、Ｄ５０：０．６３μｍ）：２００ｇと、グリセリル化キトサン（無機微粒子：１００質量部に対して１．５質量部）と、ピロメリット酸（無機微粒子：１００質量部に対して１．５質量部）とを、スリーワンモーターを用いて１時間攪拌して分散させて、均一な層（Ａ）形成用組成物（１）を調製した。
<Preparation of composition for forming layer (A)>
[Layer (A) forming composition (1)]
NMP: In 1000 g, polyhedron-shaped boehmite synthetic product (aspect ratio: 1.4, D50: 0.63 μm): 200 g and glycerylated chitosan (inorganic fine particles: 1.5 parts per 100 parts by mass) Composition) and pyromellitic acid (inorganic fine particles: 1.5 parts by mass with respect to 100 parts by mass) are dispersed by stirring for 1 hour using a three-one motor to form a uniform layer (A). A product (1) was prepared.
〔層（Ａ）形成用組成物（２）〕
ＮＭＰ：１０００ｇ中に、グリセリル化キトサン：１ｇとピロメリット酸：１ｇとを、スリーワンモーターを用いて１時間攪拌して分散させて、層（Ａ）形成用組成物（２）を調製した。
[Layer (A) forming composition (2)]
In 1 g of NMP, 1 g of glycerylated chitosan and 1 g of pyromellitic acid were stirred and dispersed using a three-one motor for 1 hour to prepare a composition (2) for forming a layer (A).
〔層（Ａ）形成用組成物（３）〕
ＮＭＰ：１０００ｇ中に、無機微粒子である多面体形状のベーマイト合成品（アスペクト比：１．４、Ｄ５０：０．６３μｍ）：２００ｇと、グリセリル化キトサン（無機微粒子：１００質量部に対して１．５質量部）と、トリメリット酸（無機微粒子：１００質量部に対して１．５質量部）とを、スリーワンモーターを用いて１時間攪拌して分散させて、均一な層（Ａ）形成用組成物（３）を調製した。
[Layer (A) forming composition (3)]
NMP: In 1000 g, polyhedron-shaped boehmite synthetic product (aspect ratio: 1.4, D50: 0.63 μm): 200 g and glycerylated chitosan (inorganic fine particles: 1.5 parts per 100 parts by mass) Composition) and trimellitic acid (inorganic fine particles: 1.5 parts by mass with respect to 100 parts by mass) are dispersed by stirring for 1 hour using a three-one motor to form a uniform layer (A). A product (3) was prepared.
〔層（Ａ）形成用組成物（４）〕
ＮＭＰ：１０００ｇ中に、樹脂微粒子である架橋ＰＭＭＡ粒子（Ｄ５０：０．５０μｍ、ガラス転移温度：１０５℃）：２００ｇと、グリセリル化キトサン（無機微粒子：１００質量部に対して１．５質量部）と、ピロメリット酸（無機微粒子：１００質量部に対して１．５質量部）とを、スリーワンモーターを用いて１時間攪拌して分散させて、均一な層（Ａ）形成用組成物（４）を調製した。
[Layer (A) forming composition (4)]
NMP: Cross-linked PMMA particles (D50: 0.50 μm, glass transition temperature: 105 ° C.): 200 g and glycerylated chitosan (inorganic fine particles: 1.5 parts by mass with respect to 100 parts by mass) in 1000 g of resin And pyromellitic acid (inorganic fine particles: 1.5 parts by mass with respect to 100 parts by mass) are stirred and dispersed using a three-one motor for 1 hour to form a uniform layer (A) forming composition (4 ) Was prepared.
〔層（Ａ）形成用組成物（５）〕
ＮＭＰ：１０００ｇ中に、樹脂製の極細繊維であるセルロース繊維（平均繊維径：０．３μｍ、平均繊維長：４２０μｍ）：５０ｇと、グリセリル化キトサン（樹脂製の極細繊維：１００質量部に対して０．５質量部）と、ピロメリット酸（樹脂製の極細繊維：１００質量部に対して０．５質量部）とを、スリーワンモーターを用いて１時間攪拌して分散させて、均一な層（Ａ）形成用組成物（５）を調製した。
[Layer (A) forming composition (5)]
NMP: In 1000 g, cellulose fiber (average fiber diameter: 0.3 μm, average fiber length: 420 μm): 50 g and glycerylated chitosan (resin ultrafine fiber: 100 parts by mass) 0.5 parts by mass) and pyromellitic acid (resin-made ultrafine fiber: 0.5 parts by mass with respect to 100 parts by mass) were stirred and dispersed using a three-one motor for 1 hour to form a uniform layer. (A) A forming composition (5) was prepared.
実施例１
＜負極の作製＞
負極活物質である天然黒鉛：９０質量％と、導電助剤であるアセチレンブラック：４．７質量％とを混合し、ここに、負極活物質、導電助剤および結着剤からなる負極合剤中において５．３質量％となる量のＰＶＤＦ（バインダ）を含むＮＭＰ溶液を加え、よく混練して負極合剤含有スラリーを調製した。負極集電体となる厚み２０μｍの圧延銅箔の両面に、乾燥後の負極合剤層の質量が、負極集電体の片面あたり５．０ｍｇ／ｃｍ２となる量で前記のスラリーを均一に塗布し、その後８０℃で乾燥し、更にロールプレス機で圧縮成形して負極を得た。なお、負極合剤含有スラリーを圧延銅箔に塗布する際には、圧延銅箔の一部が露出するようにした。前記負極の負極合剤層の厚みは、集電体（圧延銅箔）の片面あたり、２１μｍであった。
Example 1
<Production of negative electrode>
Natural graphite as a negative electrode active material: 90% by mass and acetylene black as a conductive auxiliary agent: 4.7% by mass are mixed, and here, a negative electrode mixture comprising a negative electrode active material, a conductive auxiliary agent and a binder. An NMP solution containing PVDF (binder) in an amount of 5.3% by mass was added and kneaded well to prepare a negative electrode mixture-containing slurry. Uniformly distribute the slurry on both sides of a 20 μm-thick rolled copper foil serving as the negative electrode current collector in an amount such that the mass of the negative electrode mixture layer after drying is 5.0 mg / cm 2 per side of the negative electrode current collector. It was coated, then dried at 80 ° C., and further compression molded with a roll press to obtain a negative electrode. When applying the negative electrode mixture-containing slurry to the rolled copper foil, a part of the rolled copper foil was exposed. The thickness of the negative electrode mixture layer of the negative electrode was 21 μm per one side of the current collector (rolled copper foil).
前記の負極を、負極合剤層の大きさが８５０ｍｍ×５２ｍｍで、かつ圧延銅箔の露出部を含むように切断し、更に、電流を取り出すためのニッケル製リード片を、圧延銅箔の露出部に溶接した。 The negative electrode is cut so that the size of the negative electrode mixture layer is 850 mm × 52 mm and includes the exposed portion of the rolled copper foil, and a nickel lead piece for taking out a current is exposed to the rolled copper foil. Welded to the part.
更に、得られた負極の負極合剤層上に、層（Ａ）形成用組成物（１）を、バーコーターを用いて、乾燥後の層（Ａ）の厚みが５．０μｍになるように均一に塗布し、乾燥して負極の負極合剤層上に層（Ａ）を形成した。 Further, on the negative electrode mixture layer of the obtained negative electrode, the layer (A) forming composition (1) is dried using a bar coater so that the thickness of the layer (A) after drying becomes 5.0 μm. It apply | coated uniformly and dried and formed the layer (A) on the negative mix layer of a negative electrode.
＜正極の作製＞
正極活物質であるＬｉＮｉ０．６Ｍｎ０．２Ｃｏ０．２Ｏ２：８６．２質量％と、導電助剤である黒鉛：９．０質量％およびアセチレンブラック：１．８質量％とを混合し、ここに、正極活物質、導電助剤および結着剤からなる正極合剤中において３質量％となる量のＰＶＤＦ（バインダ）を含むＮＭＰ溶液を加え、よく混練して正極合剤含有スラリーを調製した。正極集電体となる厚みが２０μｍのアルミニウム箔の両面に、乾燥後の正極合剤層の質量量が、正極集電体の片面あたり１１．６ｍｇ／ｃｍ２となる量で前記のスラリーを均一に塗布し、その後８０℃で乾燥し、更にロールプレス機で圧縮成形して正極を得た。なお、正極合剤含有スラリーをアルミニウム箔に塗布する際には、アルミニウム箔の一部が露出するようにした。前記正極の正極合剤層の厚みは、集電体（アルミニウム箔）の片面あたり、２６μｍであった。
<Preparation of positive electrode>
LiNi 0.6 Mn 0.2 Co 0.2 O 2 as positive electrode active material: 86.2% by mass, graphite as a conductive additive: 9.0% by mass, and acetylene black: 1.8% by mass Mix, add NMP solution containing PVDF (binder) in an amount of 3% by mass in the positive electrode mixture consisting of the positive electrode active material, the conductive additive and the binder, and knead well to contain the positive electrode mixture A slurry was prepared. Uniformly mix the slurry in such an amount that the mass of the positive electrode mixture layer after drying is 11.6 mg / cm 2 on one side of the positive electrode current collector on both sides of an aluminum foil with a thickness of 20 μm to be the positive electrode current collector. Then, it was dried at 80 ° C., and further compression molded with a roll press to obtain a positive electrode. When applying the positive electrode mixture-containing slurry to the aluminum foil, a part of the aluminum foil was exposed. The thickness of the positive electrode mixture layer of the positive electrode was 26 μm per one side of the current collector (aluminum foil).
前記の正極を、正極合剤層の大きさが８００ｍｍ×４８ｍｍで、かつアルミニウム箔の露出部を含むように裁断し、更に、電流を取り出すためのアルミニウム製リード片を、アルミニウム箔の露出部に溶接した。 The positive electrode is cut so that the size of the positive electrode mixture layer is 800 mm × 48 mm and includes the exposed portion of the aluminum foil, and an aluminum lead piece for taking out an electric current is formed on the exposed portion of the aluminum foil. Welded.
＜セパレータ＞
厚みが１６μｍ、空孔率が４５％で、両面にコロナ放電処理を施したＰＥ製微多孔膜を、セパレータとして用意した。
<Separator>
A PE microporous membrane having a thickness of 16 μm and a porosity of 45% and subjected to corona discharge treatment on both sides was prepared as a separator.
＜電池の組み立て＞
前記の正極と前記の負極とを、間に前記のセパレータを介在させつつ重ね合わせ、渦巻状に巻回して巻回電極体とした。この巻回電極体を、アルミニウム外装体に挿入し、非水電解液（エチレンカーボネートとジメチルカーボネートとメチルエチルカーボネートとを２：４：４の体積比で混合した溶媒に、ＬｉＰＦ６を１ｍｏｌ／ｌの濃度で溶解させた溶液）を外装体内に注入した後に、外装体の開口部を封止して、長さ６５ｍｍ、直径１８ｍｍの円筒形の巻回電極体を内部に有し、図１に示す構造の非水二次電池（リチウムイオン二次電池）を作製した。
<Battery assembly>
The positive electrode and the negative electrode were overlapped with the separator interposed therebetween, and wound in a spiral shape to obtain a wound electrode body. This wound electrode body was inserted into an aluminum outer casing, and a non-aqueous electrolyte (LiPF 6 was added at 1 mol / l in a solvent in which ethylene carbonate, dimethyl carbonate, and methyl ethyl carbonate were mixed at a volume ratio of 2: 4: 4). 1) is injected into the exterior body, the opening of the exterior body is sealed, and a cylindrical wound electrode body having a length of 65 mm and a diameter of 18 mm is provided inside. A non-aqueous secondary battery (lithium ion secondary battery) having the structure shown was produced.
ここで、図１に示す電池について説明すると、図１に示す非水二次電池では、正極１と負極２とがセパレータ３を介して渦巻状に巻回され、巻回電極体として非水電解液４と共に外装体５内に収容されている。なお、図１では、繁雑化を避けるため、正極１や負極２の作製にあたって使用した集電体などは図示していない。
Here, the battery shown in FIG. 1 will be described. In the nonaqueous secondary battery shown in FIG. 1, the positive electrode 1 and the
外装体５の底部には前記巻回電極体の挿入に先立って、ＰＰからなる絶縁体６が配置されている。封口板７は、アルミニウム製で円板状をしていて、その中央部に薄肉部７ａが設けられ、かつ前記薄肉部７ａの周囲に電池内圧を防爆弁９に作用させるための圧力導入口７ｂとしての孔が設けられている。そして、この薄肉部７ａの上面に防爆弁９の突出部９ａが溶接され、溶接部分１１を構成している。なお、前記の封口板７に設けた薄肉部７ａや防爆弁９の突出部９ａなどは、図面上での理解がしやすいように、切断面のみを図示しており、切断面後方の輪郭は図示を省略している。また、封口板７の薄肉部７ａと防爆弁９の突出部９ａの溶接部分１１も、図面上での理解が容易なように、実際よりは誇張した状態に図示している。
Prior to the insertion of the wound electrode body, an
端子板８は、圧延鋼製で表面にニッケルメッキが施され、周縁部が鍔状になった帽子状をしており、この端子板８にはガス排出口８ａが設けられている。防爆弁９は、アルミニウム製で円板状をしており、その中央部には発電要素側（図１では、下側）に先端部を有する突出部９ａが設けられ、かつ薄肉部９ｂが設けられ、前記突出部９ａの下面が、前記のように、封口板７の薄肉部７ａの上面に溶接され、溶接部分１１を構成している。絶縁パッキング１０は、ＰＰ製で環状をしており、封口板７の周縁部の上部に配置され、その上部に防爆弁９が配置していて、封口板７と防爆弁９とを絶縁するとともに、両者の間から非水電解液が漏れないように両者の間隙を封止している。環状ガスケット１２はＰＰ製で、リード体１３はアルミニウム製で、前記封口板７と正極１とを接続し、巻回電極体の上部には絶縁体１４が配置され、負極２と外装体５の底部とはニッケル製のリード体１５で接続されている。
The terminal plate 8 is made of rolled steel, has a nickel plating on the surface, and has a hat shape with a peripheral edge portion having a hook shape. The terminal plate 8 is provided with a
この非水電解液二次電池においては、封口板７の薄肉部７ａと防爆弁９の突出部９ａとが溶接部分１１で接触し、防爆弁９の周縁部と端子板８の周縁部とが接触し、正極１と封口板７とは正極側のリード体１３で接続されているので、通常の状態では、正極１と端子板８とはリード体１３、封口板７、防爆弁９およびそれらの溶接部分１１によって電気的接続が得られ、電路として正常に機能する。
In this non-aqueous electrolyte secondary battery, the
そして、電池が高温にさらされるなど、電池に異常事態が起こり、電池内部にガスが発生して電池の内圧が上昇した場合には、その内圧上昇により、防爆弁９の中央部が内圧方向（図１では、上側の方向）に変形し、それに伴って溶接部分１１で一体化されている薄肉部７ａに剪断力が働いて該薄肉部７ａが破断するか、または防爆弁９の突出部９ａと封口板７の薄肉部７ａとの溶接部分１１が剥離した後、この防爆弁９に設けられている薄肉部９ｂが開裂してガスを端子板８のガス排出口８ａから電池外部に排出させて電池の破裂を防止することができるように設計されている。
When the battery is exposed to a high temperature and an abnormal situation occurs, gas is generated inside the battery and the internal pressure of the battery rises, the internal pressure increases, so that the central portion of the explosion-proof valve 9 moves in the internal pressure direction ( In FIG. 1, the thin-
得られた非水二次電池は、設計容量をもとに、０．０５Ｃ（５７．５ｍＡｈ）の電流値で４．１Ｖまで定電流充電を行い、引き続いて４．１Ｖで定電流充電の開始から３．０時間になるまで定電圧充電を行う予備充電を実施した。そして、予備充電後の電池について、０．２Ｃ（２３０ｍＡｈ）の電流値で４．２Ｖまで定電流充電を行い、引き続いて４．２Ｖで定電流充電の開始から７．５時間になるまで定電圧充電を行い、更に０．２Ｃの電流値で３．０Ｖまで定電流放電を行う一連の操作を１サイクルとし、これを２サイクル繰り返して、定格容量を設定した。この定格容量は１１５０ｍＡｈであった（後記の全ての実施例および比較例の非水二次電池も、実施例１の電池と同じ条件で定格容量の設定を行い、それらの定格容量は１１５０ｍＡｈである）。 The obtained non-aqueous secondary battery is charged with a constant current of up to 4.1 V at a current value of 0.05 C (57.5 mAh) based on the design capacity, and then starts constant current charging at 4.1 V. From this time, preliminary charging was performed in which constant voltage charging was performed until 3.0 hours. Then, the battery after the preliminary charge is charged with a constant current of up to 4.2 V at a current value of 0.2 C (230 mAh), and then at a constant voltage of 4.2 V until 7.5 hours from the start of the constant current charge. A series of operations in which charging was performed and constant current discharging was performed up to 3.0 V at a current value of 0.2 C was defined as one cycle, and this was repeated two cycles to set the rated capacity. This rated capacity was 1150 mAh (the non-aqueous secondary batteries of all examples and comparative examples described later were also set to the rated capacity under the same conditions as the battery of Example 1, and the rated capacity was 1150 mAh. ).
実施例２
実施例１で用いたものと同じセパレータの片面に、層（Ａ）形成用組成物（１）を、バーコーターを用いて、乾燥後の層（Ａ）の厚みが５．０μｍになるように均一に塗布し、乾燥して、セパレータ上に層（Ａ）を形成した。
Example 2
On one side of the same separator as that used in Example 1, the layer (A) forming composition (1) is dried using a bar coater so that the thickness of the layer (A) after drying is 5.0 μm. It apply | coated uniformly and dried and formed the layer (A) on the separator.
実施例１で作製したものと同じ正極と、実施例１で作製したものと同じ負極〔層（Ａ）を形成していない負極〕とを、前記セパレータを介して重ね合わせて渦巻状に巻回して巻回電極体とした。なお、この巻回電極体においては、セパレータ上に形成した層（Ａ）が、正極と対向するようにした。そして、この巻回電極体を用いた以外は、実施例１と同様にして非水二次電池を作製した。 The same positive electrode as that produced in Example 1 and the same negative electrode as that produced in Example 1 (negative electrode without forming the layer (A)) were overlapped with each other and wound into a spiral shape. Thus, a wound electrode body was obtained. In this wound electrode body, the layer (A) formed on the separator was made to face the positive electrode. And the non-aqueous secondary battery was produced like Example 1 except having used this winding electrode body.
実施例３
実施例１で作製したものと同じ正極の正極合剤層上に、層（Ａ）形成用組成物（１）を、バーコーターを用いて、乾燥後の層（Ａ）の厚みが５．０μｍになるように均一に塗布し、乾燥して、正極の正極合剤層上に層（Ａ）を形成した。
Example 3
On the positive electrode mixture layer of the same positive electrode as that prepared in Example 1, the layer (A) forming composition (1) was dried using a bar coater, and the thickness of the layer (A) after drying was 5.0 μm. The layer (A) was formed on the positive electrode mixture layer of the positive electrode.
前記正極と、実施例１で作製したものと同じ負極〔層（Ａ）を形成していない負極〕とを、実施例１で使用したものと同じセパレータを介して重ね合わせ渦巻状に巻回して巻回電極体とした。そして、この巻回電極体を用いた以外は、実施例１と同様にして非水二次電池を作製した。 The positive electrode and the same negative electrode (negative electrode without forming the layer (A)) produced in Example 1 were overlapped and wound in a spiral shape through the same separator as used in Example 1 A wound electrode body was obtained. And the non-aqueous secondary battery was produced like Example 1 except having used this winding electrode body.
実施例４
実施例１で作製したものと同じ負極〔層（Ａ）を形成していない負極〕上に、層（Ａ）形成用組成物（２）を、ディップコーターを用いて、乾燥後の層（Ａ）の厚みが５．０μｍになるように均一に塗布し、乾燥して、負極上に層（Ａ）を形成した。
Example 4
On the same negative electrode [negative electrode in which layer (A) is not formed] as prepared in Example 1, the layer (A) forming composition (2) was dried using a dip coater (A ) Was uniformly applied to a thickness of 5.0 μm and dried to form a layer (A) on the negative electrode.
前記負極と、実施例１で作製したものと同じ正極とを、実施例１で使用したものと同じセパレータを介して重ね合わせ、渦巻状に巻回して巻回電極体とした。そして、この積層電極体を用いた以外は、実施例１と同様にして非水二次電池を作製した。 The negative electrode and the same positive electrode as that prepared in Example 1 were overlapped through the same separator as that used in Example 1, and wound into a spiral shape to obtain a wound electrode body. And the non-aqueous secondary battery was produced like Example 1 except having used this laminated electrode body.
実施例５
層（Ａ）形成用組成物（１）に代えて層（Ａ）形成用組成物（３）を用いた以外は、実施例１と同様にして負極の負極合剤層上に層（Ａ）を形成した。そして、この負極を用いた以外は、実施例１と同様にして非水二次電池を作製した。
Example 5
The layer (A) is formed on the negative electrode mixture layer of the negative electrode in the same manner as in Example 1, except that the layer (A) forming composition (3) is used instead of the layer (A) forming composition (1). Formed. And the non-aqueous secondary battery was produced like Example 1 except having used this negative electrode.
実施例６
層（Ａ）形成用組成物（１）に代えて層（Ａ）形成用組成物（４）を用いた以外は、実施例１と同様にして負極の負極合剤層上に層（Ａ）を形成した。そして、この負極を用いた以外は、実施例１と同様にして非水二次電池を作製した。
Example 6
The layer (A) is formed on the negative electrode mixture layer of the negative electrode in the same manner as in Example 1 except that the layer (A) forming composition (4) is used instead of the layer (A) forming composition (1). Formed. And the non-aqueous secondary battery was produced like Example 1 except having used this negative electrode.
実施例７
層（Ａ）形成用組成物（２）に代えて層（Ａ）形成用組成物（５）を用いた以外は、実施例４と同様にして負極上に層（Ａ）を形成した。そして、この負極を用いた以外は、実施例１と同様にして非水二次電池を作製した。
Example 7
A layer (A) was formed on the negative electrode in the same manner as in Example 4 except that the layer (A) forming composition (5) was used instead of the layer (A) forming composition (2). And the non-aqueous secondary battery was produced like Example 1 except having used this negative electrode.
比較例１
水：１０００ｇ中に、無機微粒子であるベーマイト合成品（アスペクト比：１．４、Ｄ５０：０．６３μｍ）：２００ｇと、バインダであるアクリレート共重合体（モノマー成分としてブチルアクリレートを主成分とする市販のアクリレート共重合体。無機微粒子：１００質量部に対して３質量部。）とを、スリーワンモーターを用いて１時間攪拌して分散させ、均一な多孔質層形成用組成物を調製した。
Comparative Example 1
Water: 1000 g boehmite synthetic product (aspect ratio: 1.4, D50: 0.63 μm): 200 g and binder acrylate copolymer (commercially composed mainly of butyl acrylate as a monomer component) An inorganic fine particle: 3 parts by mass with respect to 100 parts by mass) was dispersed by stirring for 1 hour using a three-one motor to prepare a uniform porous layer forming composition.
実施例１で作製したものと同じ負極〔層（Ａ）を形成していない負極〕の負極合剤層上に、前記の多孔質層形成用組成物を、バーコーターを用いて、乾燥後の多孔質層の厚みが５．０μｍになるように均一に塗布し、乾燥して負極の負極合剤層上に多孔質層を形成した。そして、この負極を用いた以外は、実施例１と同様にして非水二次電池を作製した。 On the negative electrode mixture layer of the same negative electrode [negative electrode not forming layer (A)] as prepared in Example 1, the porous layer forming composition was dried using a bar coater. It apply | coated uniformly so that the thickness of a porous layer might be set to 5.0 micrometers, and it dried and formed the porous layer on the negative mix layer of a negative electrode. And the non-aqueous secondary battery was produced like Example 1 except having used this negative electrode.
比較例２
実施例１で使用したものと同じセパレータの片面に、比較例１で調製したものと同じ多孔質層形成用組成物を、バーコーターを用いて、乾燥後の多孔質層の厚みが５．０μｍになるように均一に塗布し、乾燥してセパレータ上に多孔質層を形成した。そして、このセパレータを用いた以外は、実施例２と同様にして非水二次電池を作製した。
Comparative Example 2
Using the same porous layer forming composition as that prepared in Comparative Example 1 on one side of the same separator as that used in Example 1, using a bar coater, the thickness of the porous layer after drying was 5.0 μm. Then, it was uniformly applied and dried to form a porous layer on the separator. And the non-aqueous secondary battery was produced like Example 2 except having used this separator.
比較例３
実施例１で作製したものと同じ正極と、実施例１で作製したものと同じ負極〔層（Ａ）を形成していない負極〕とを、実施例１で使用したものと同じセパレータを介して重ね合わせて渦巻状に巻回して巻回電極体とした。そして、この巻回電極体を用いた以外は、実施例１と同様にして非水二次電池を作製した。
Comparative Example 3
The same positive electrode as that produced in Example 1 and the same negative electrode as that produced in Example 1 [negative electrode without forming the layer (A)] were passed through the same separator as that used in Example 1. They were superposed and wound in a spiral shape to obtain a wound electrode body. And the non-aqueous secondary battery was produced like Example 1 except having used this winding electrode body.
実施例１〜７および比較例１〜３の非水二次電池およびこれらの非水二次電池の作製に用いた多孔質層形成用組成物について、以下の各評価を行った。 The following evaluation was performed about the non-aqueous secondary battery of Examples 1-7 and Comparative Examples 1-3 and the composition for porous layer formation used for preparation of these non-aqueous secondary batteries.
＜釘刺し試験＞
定格容量まで充電した各電池の、中央側面の近傍に熱電対をテープで止め、更に厚み６ｍｍのグラスウールを巻きつけ、直径３０ｍｍの円筒形のラミネートで外装して、電池を断熱状態にした。そして、電池の電圧および表面温度をモニタリングしつつ、２０℃の環境下で、充電状態の電池の中央に、直径３ｍｍのステンレス製の釘を１ｍｍ／ｓｅｃの速度で突き刺した。ここで、短絡によって電圧降下が観測された時点で釘の降下を停止して保持した。
<Nail penetration test>
Each battery charged to the rated capacity was fixed with a thermocouple in the vicinity of the central side, further wrapped with glass wool having a thickness of 6 mm, and packaged with a cylindrical laminate having a diameter of 30 mm to make the battery insulative. Then, while monitoring the voltage and surface temperature of the battery, a stainless steel nail having a diameter of 3 mm was pierced at a speed of 1 mm / sec in the center of the charged battery in an environment of 20 ° C. Here, the drop of the nail was stopped and held when a voltage drop was observed due to a short circuit.
試験における評価基準としては、電池の温度上昇がないことが要求される。電池電圧が５０ｍＶ以上の電圧降下が観測された時点から、電池表面が５秒以内に２００℃以上まで上昇した場合を０点とし、１０秒以内に２００℃以上まで上昇した場合を１点、これ該当しない場合を２点と点数付けした。 As an evaluation standard in the test, it is required that the temperature of the battery does not increase. When the battery voltage drop of 50 mV or more is observed, 0 points when the battery surface rises to 200 ° C or higher within 5 seconds, 1 point when the battery voltage rises to 200 ° C or higher within 10 seconds, The case where it did not correspond was scored as 2 points.
更に電池電圧が５０ｍＶ以上の電圧降下が観測された時点から１分の間の電池表面最高温度を到達温度とし、到達温度「０点：３００℃以上」、「１点：１００℃以上３００℃未満」、これ該当しない場合を「２点：１００℃未満」とし、この点数の合計から安全性について総合判断をした。 Furthermore, the highest temperature on the surface of the battery for 1 minute from the time when a voltage drop of 50 mV or more is observed is regarded as the ultimate temperature, and the ultimate temperature is “0 point: 300 ° C. or higher”, “1 point: 100 ° C. or higher and lower than 300 ° C. “If this is not the case, the score was“ 2 points: less than 100 ° C. ”, and the safety was comprehensively determined from the sum of the scores.
＜昇温試験＞
充電前の各電池を５℃／ｍｉｎで昇温し、抵抗の変化を観測して、抵抗上昇が２倍以上となる温度を測定し、これをシャットダウン温度とした。
<Temperature test>
Each battery before charging was heated at 5 ° C./min, the change in resistance was observed, the temperature at which the resistance increase was doubled or more was measured, and this was taken as the shutdown temperature.
＜架橋開始温度＞
実施例および比較例１、２の電池の作製に用いた多孔質層形成用組成物について、前記の方法で「架橋開始温度」を測定した。
<Crosslinking start temperature>
About the composition for porous layer formation used for preparation of the battery of an Example and Comparative Examples 1 and 2, "crosslinking start temperature" was measured by the said method.
＜充放電サイクル特性評価＞
実施例および比較例の各非水二次電池（前記の各試験を行っていない電池）について、２５℃の環境下で、０．５Ｃ（５７５ｍＡｈ）の電流値で４．２Ｖまで定電流充電を行い、引き続いて、４．２Ｖに到達した時点で一定電圧充電に移行し電流値が１Ｃに対して、１／２０まで減少した時点で終了させた。更に０．２Ｃ（２３０ｍＡ）の電流値で３．０Ｖまで定電流放電を行う一連の操作を１サイクルとし、これを２００サイクル繰り返して、１サイクル目の放電容量と２００サイクル目の放電容量を求めた。そして、各電池について、２００サイクル目の放電容量を１サイクル目の放電容量で除した値を百分率で表して、２００サイクル目の放電容量維持率を算出した。
<Charge / discharge cycle characteristics evaluation>
For each of the non-aqueous secondary batteries of Examples and Comparative Examples (batteries not subjected to each of the above tests), constant current charging was performed up to 4.2 V at a current value of 0.5 C (575 mAh) in an environment of 25 ° C. Then, when the voltage reached 4.2V, the voltage was changed to constant voltage charging and terminated when the current value decreased to 1/20 with respect to 1C. Further, a series of operations for performing constant current discharge to 3.0 V at a current value of 0.2 C (230 mA) is defined as one cycle, and this is repeated 200 cycles to obtain the discharge capacity at the first cycle and the discharge capacity at the 200th cycle. It was. For each battery, the value obtained by dividing the discharge capacity at the 200th cycle by the discharge capacity at the first cycle was expressed as a percentage, and the discharge capacity maintenance rate at the 200th cycle was calculated.
＜貯蔵特性評価＞
前記の充放電サイクル特性の評価を行った各電池を、０．２Ｃ（２３０ｍＡ）の電流値で４．２Ｖまで充電した後に、６０℃に調節した恒温槽内に入れて５日間貯蔵した。その後恒温槽の加熱を止め、１日経過してから各電池を取り出し、０．２Ｃ（２３０ｍＡ）の電流値で３．０Ｖまで定電流放電を行って放電容量（貯蔵直後の放電容量）を求め、これらの値と、充放電サイクル特性評価時の１サイクル目の放電容量（初期放電容量）とから、下記式に従って容量維持率（％）を求めた。
<Storage characteristics evaluation>
Each battery for which the charge / discharge cycle characteristics were evaluated was charged to 4.2 V at a current value of 0.2 C (230 mA), and then stored in a thermostat adjusted to 60 ° C. and stored for 5 days. Thereafter, the heating of the thermostatic chamber was stopped, and after 1 day, each battery was taken out and discharged at a constant current of up to 3.0 V at a current value of 0.2 C (230 mA) to obtain the discharge capacity (discharge capacity immediately after storage). From these values and the discharge capacity (initial discharge capacity) of the first cycle at the time of charge / discharge cycle characteristics evaluation, the capacity retention rate (%) was determined according to the following formula.
容量維持率 ＝ （貯蔵直後の放電容量／初期放電容量）×１００ Capacity retention rate = (discharge capacity immediately after storage / initial discharge capacity) × 100
また、貯蔵直後の放電容量測定後の各電池について、充放電サイクル特性評価時と同じ条件での充放電を２サイクル繰り返して、放電容量（貯蔵後２サイクル目の放電容量）を求めた。そして、各電池の貯蔵後２サイクル目の放電容量と、充放電サイクル特性評価時の１サイクル目の放電容量（初期放電容量）とから、下記式に従って容量回復率（％）を求めた。 Moreover, about each battery after the discharge capacity measurement immediately after storage, charging / discharging on the same conditions as the time of charging / discharging cycle characteristic evaluation was repeated 2 cycles, and discharge capacity (discharge capacity of the 2nd cycle after storage) was calculated | required. And the capacity | capacitance recovery rate (%) was calculated | required according to the following formula from the discharge capacity of the 2nd cycle after storage of each battery, and the discharge capacity (initial discharge capacity) of the 1st cycle at the time of charge / discharge cycle characteristic evaluation.
容量回復率 ＝ （貯蔵後２サイクル目の放電容量／初期放電容量）×１００ Capacity recovery rate = (discharge capacity at the second cycle after storage / initial discharge capacity) × 100
前記の各評価結果を表１に示す。 Each evaluation result is shown in Table 1.
表１に示す通り、架橋剤と、熱によって前記架橋剤で架橋でき、かつ架橋開始温度が９０〜１３０℃の多糖類とを含む層（Ａ）を、正極と負極との間に有する実施例１〜７の非水二次電池は、釘刺し試験時の温度上昇が抑制できており、また、シャットダウン温度も、セパレータの素材として使用されているＰＥの融点よりも少し低い温度とすることができており、優れた安全性を確保できている。また、実施例１〜７の非水二次電池では、層（Ａ）に係る多糖類としてキトサン誘導体を使用しており、その作用によって、充放電サイクル特性評価時の２００サイクル後の容量維持率、並びに貯蔵特性評価時の容量維持率および容量回復率が高く、充放電サイクル特性および貯蔵特性も優れている。 As shown in Table 1, an embodiment having a layer (A) between a positive electrode and a negative electrode that includes a cross-linking agent and a polysaccharide that can be cross-linked with the cross-linking agent by heat and has a cross-linking start temperature of 90 to 130 ° C. The non-aqueous secondary batteries 1 to 7 can suppress the temperature rise during the nail penetration test, and the shutdown temperature should be slightly lower than the melting point of PE used as a separator material. It is possible to secure excellent safety. Moreover, in the non-aqueous secondary battery of Examples 1-7, the chitosan derivative is used as the polysaccharide which concerns on a layer (A), The capacity | capacitance maintenance factor after 200 cycles at the time of charge / discharge cycle characteristic evaluation by the effect | action In addition, the capacity retention rate and capacity recovery rate at the time of storage characteristics evaluation are high, and the charge / discharge cycle characteristics and storage characteristics are also excellent.
これに対し、層（Ａ）を有していない比較例３の電池では、釘刺し試験時に温度上昇が認められており、安全性が劣っている。また、層（Ａ）に代えて架橋剤および多糖類を含有しない多孔質層を、正極と負極との間に有する比較例１、２の電池では、釘刺し試験時の温度上昇を、比較例３の電池に比べると抑制できているものの、実施例の電池よりは温度上昇抑制効果が小さく、安全性が劣っている。 On the other hand, in the battery of Comparative Example 3 that does not have the layer (A), a temperature increase was observed during the nail penetration test, and the safety was poor. In addition, in the batteries of Comparative Examples 1 and 2 having a porous layer that does not contain a crosslinking agent and a polysaccharide between the positive electrode and the negative electrode instead of the layer (A), the temperature increase during the nail penetration test is Although it can be suppressed as compared with the battery of 3, the temperature rise suppressing effect is smaller than that of the battery of the example, and the safety is inferior.
１ 正極
２ 負極
３ セパレータ
７ 封口板
７ａ 封口板の薄肉部
８ 端子板
８ａ 端子板のガス排出口
９ 防爆弁
９ａ 防爆弁の突出部
９ｂ 防爆弁の薄肉部
DESCRIPTION OF SYMBOLS 1
Claims (4)
前記正極と前記負極との間に、架橋剤と、熱によって前記架橋剤で架橋でき、かつ架橋開始温度が９０〜１３０℃の多糖類とを含む層（Ａ）を有することを特徴とする非水二次電池。 A non-aqueous secondary battery having a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte as constituent elements,
Between the positive electrode and the negative electrode, there is a layer (A) including a crosslinking agent and a polysaccharide that can be crosslinked with the crosslinking agent by heat and has a crosslinking initiation temperature of 90 to 130 ° C. Water secondary battery.
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