JP2021114390A - Negative electrode active material, negative electrode, non-aqueous electrolyte power storage element, and manufacturing method of the same - Google Patents
Negative electrode active material, negative electrode, non-aqueous electrolyte power storage element, and manufacturing method of the same Download PDFInfo
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- JP2021114390A JP2021114390A JP2020005993A JP2020005993A JP2021114390A JP 2021114390 A JP2021114390 A JP 2021114390A JP 2020005993 A JP2020005993 A JP 2020005993A JP 2020005993 A JP2020005993 A JP 2020005993A JP 2021114390 A JP2021114390 A JP 2021114390A
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- negative electrode
- electrode active
- active material
- oxygen
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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
Abstract
Description
本発明は、負極活物質、負極、非水電解質蓄電素子及びその製造方法に関する。 The present invention relates to a negative electrode active material, a negative electrode, a non-aqueous electrolyte power storage element, and a method for producing the same.
リチウムイオン二次電池に代表される非水電解質二次電池は、エネルギー密度の高さから、パーソナルコンピュータ、通信端末等の電子機器、自動車等に多用されている。上記非水電解質二次電池は、一般的には、セパレータで電気的に隔離された一対の電極と、この電極間に介在する非水電解質とを有し、両電極間でイオンの受け渡しを行うことで充放電するよう構成される。また、非水電解質二次電池以外の非水電解質蓄電素子として、リチウムイオンキャパシタや電気二重層キャパシタ等のキャパシタも広く普及している。 Non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries are widely used in electronic devices such as personal computers and communication terminals, automobiles, etc. due to their high energy density. The non-aqueous electrolyte secondary battery generally has a pair of electrodes electrically separated by a separator and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the two electrodes. It is configured to charge and discharge. In addition, capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as non-aqueous electrolyte storage elements other than non-aqueous electrolyte secondary batteries.
上記非水電解質蓄電素子の負極活物質には、黒鉛、非黒鉛質炭素等の炭素材料が広く用いられている。これら従来の炭素材料の放電容量は４００ｍＡｈ／ｇ以下程度であり、負極活物質の大容量化等のための様々な開発が行われている。特許文献１には、「炭素粒子を含むリチウムイオン電池用アノード材料であって、前記炭素粒子は、酸素を官能基の形態で含み、該酸素の含有量は、前記炭素粒子の最表面から深さ１５ｎｍまでの表面領域に８．５質量％〜１３．０質量％、残りの内部領域に６．０質量％〜１２．０質量％と段階的に分布しており、該表面領域における酸素含有量は、該内部領域における酸素含有量よりも大きく、かつ、前記炭素粒子は、０．３３５７ｎｍよりも大きな層間間隔ｄ００２を有するグラファイト相を含む、アノード材料。」が記載されている。上記特許文献１には、具体的には実施例１として、層間間隔ｄ００２が０．３４０１ｎｍ、格子定数ａ０（１１０）が０．２４５０ｎｍ（すなわちｄ１１０が０．１２２５ｎｍ）である炭素材料が得られたことが記載されている。
Carbon materials such as graphite and non-graphitic carbon are widely used as the negative electrode active material of the non-aqueous electrolyte power storage element. The discharge capacity of these conventional carbon materials is about 400 mAh / g or less, and various developments have been made to increase the capacity of the negative electrode active material.
非水電解質蓄電素子のエネルギー密度を大きくするためには、負極活物質の放電容量が大きいことに加えて、放電容量全体に対する比較的低い電位範囲（例えば、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下）における放電容量の比が大きいことが重要である。しかし、上記特許文献１等の大容量化が報告された炭素材料は、比較的高い電位範囲で大きい放電容量を示し、従来の炭素材料に置き換わる負極活物質として必ずしも好適であるとは言えない。
In order to increase the energy density of the non-aqueous electrolyte power storage element, in addition to the large discharge capacity of the negative electrode active material, a relatively low potential range with respect to the entire discharge capacity (for example, 1.2 V vs. Li / Li + or less) It is important that the ratio of the discharge capacity in) is large. However, the carbon material reported to have a large capacity such as
本発明は、以上のような事情に基づいてなされたものであり、その目的は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比（２．０Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量に対する１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量の比）が高い負極活物質、上記負極活物質を有する負極及び非水電解質蓄電素子、並びに上記非水電解質蓄電素子の製造方法を提供することである。
なお、本明細書において、非水電解質から負極活物質に充放電反応に関与するイオン（リチウムイオン非水電解質二次電池の場合はリチウムイオン）が吸蔵される還元反応を「充電」、負極活物質から充放電反応に関与するイオンが放出される酸化反応を「放電」という。
The present invention has been made based on the above circumstances, and an object of the present invention is to have a large discharge capacity and 1.2 V vs. Discharge capacity ratio at Li / Li + less potential range (discharge capacity at 1.2V vs.Li/Li + following potential range to the discharge capacity at 2.0V vs.Li/Li + following potential range It is an object of the present invention to provide a negative electrode active material having a high ratio), a negative electrode having the negative electrode active material, a non-aqueous electrolyte power storage element, and a method for manufacturing the non-aqueous electrolyte power storage element.
In the present specification, the reduction reaction in which ions (lithium ions in the case of a lithium ion non-aqueous electrolyte secondary battery) involved in the charge / discharge reaction from the non-aqueous electrolyte to the negative electrode active material is stored is “charged”, and the negative electrode activity is performed. An oxidation reaction in which ions involved in a charge / discharge reaction are released from a substance is called "discharge".
本発明の一態様は、炭素材料であり、加熱して脱離する酸素を含有し、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上であり、平均格子面間隔ｄ１１０が０．１２２６ｎｍ超である非水電解質蓄電素子用の負極活物質（Ａ）である。 One aspect of the present invention is a carbon material, which contains oxygen to be desorbed by heating, and the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is higher than that of the carbon material before heating. It is a negative electrode active material (A) for a non-aqueous electrolyte power storage element having an average lattice plane spacing d 110 of more than 0.1226 nm and 4% by mass or more.
本発明の他の一態様は、炭素材料であり、加熱して脱離する酸素を含有し、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上１３質量％以下であり、上記４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上である非水電解質蓄電素子用の負極活物質（Ｂ）である。 Another aspect of the present invention is a carbon material, which contains oxygen to be desorbed by heating, and the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2,500 ° C. or lower is the carbon material before heating. The content of oxygen desorbed at a temperature of more than 1,000 ° C and 2,500 ° C or less with respect to oxygen desorbed at a temperature of 400 ° C or more and 2,500 ° C or less, which is 4% by mass or more and 13% by mass or less. It is a negative electrode active material (B) for a non-aqueous electrolyte power storage element having a quantity ratio of 0.45 or more.
本発明の他の一態様は、当該負極活物質（Ａ）又は当該負極活物質（Ｂ）を備える非水電解質蓄電素子用の負極である。 Another aspect of the present invention is a negative electrode for a non-aqueous electrolyte power storage element including the negative electrode active material (A) or the negative electrode active material (B).
本発明の他の一態様は、当該負極を備える非水電解質蓄電素子である。 Another aspect of the present invention is a non-aqueous electrolyte power storage device including the negative electrode.
本発明の他の一態様は、当該負極活物質（Ａ）又は当該負極活物質（Ｂ）を用いて負極を作製することを備える非水電解質蓄電素子の製造方法である。 Another aspect of the present invention is a method for manufacturing a non-aqueous electrolyte power storage element, which comprises producing a negative electrode using the negative electrode active material (A) or the negative electrode active material (B).
本発明によれば、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い負極活物質、上記負極活物質を有する負極及び非水電解質蓄電素子、並びに上記非水電解質蓄電素子の製造方法を提供することができる。 According to the present invention, the discharge capacity is large, 1.2 V vs. It is possible to provide a negative electrode active material having a high discharge capacity ratio in a potential range of Li / Li + or less, a negative electrode having the negative electrode active material, a non-aqueous electrolyte storage element, and a method for manufacturing the non-aqueous electrolyte storage element.
初めに、本明細書によって開示される負極活物質、負極、非水電解質蓄電素子及びその製造方法の概要について説明する。 First, an outline of a negative electrode active material, a negative electrode, a non-aqueous electrolyte power storage element disclosed by the present specification, and a method for manufacturing the same will be described.
本発明の一態様に係る負極活物質は、炭素材料であり、加熱して脱離する酸素を含有し、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上であり、平均格子面間隔ｄ１１０が０．１２２６ｎｍ超である非水電解質蓄電素子用の負極活物質（Ａ）である。 The negative electrode active material according to one aspect of the present invention is a carbon material, contains oxygen that is desorbed by heating, and the content of oxygen that is desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is before heating. It is a negative electrode active material (A) for a non-aqueous electrolyte power storage element, which is 4% by mass or more with respect to the carbon material and has an average lattice plane spacing d 110 of more than 0.1226 nm.
当該負極活物質（Ａ）は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い。当該負極活物質（Ａ）においてこのような効果が生じる理由は定かでは無いが、以下の理由が推測される。炭素材料においては、後述する実施例で示されているように、８００℃超２，５００℃以下の温度で脱離する酸素の含有率（加熱前の炭素材料に対する含有率。本明細書における炭素材料、すなわち負極活物質中の各所定温度範囲で脱離する酸素の含有率について、以下同様である。）と放電容量との間に高い相関性があり、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が高いほど放電容量が大きくなる傾向がある（図３参照）。この理由は定かではないが、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が高い炭素材料は、リチウムイオン等を吸蔵しやすい構造等となっていることが推測される。当該負極活物質（Ａ）においては、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が４質量％以上であるため、放電容量が大きい。
ところで、炭素材料の平均格子面間隔ｄ１１０は、グラフェン層中の炭素−炭素結合の距離と関連し、表面に存在する官能基が多いとグラフェン層が歪んで平均格子面間隔ｄ１１０は小さくなると考えられる。そして、表面に存在する官能基は、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋超の比較的高電位における放電に寄与していると考えられる。このため、酸素を含む官能基が表面領域に多く存在することを特徴とし、平均格子面間隔ｄ１１０が小さい上記特許文献１の炭素材料においては、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が相対的に低いこととなる。上記表面に存在する官能基が含む酸素は、１，０００℃以下で脱離すると考えられる。
これに対し、バルク内で安定化して存在している酸素は、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の比較的低電位における放電に寄与していると考えられる。このようなことから、平均格子面間隔ｄ１１０が大きいと、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高くなる傾向となる（図４参照）。当該負極活物質（Ａ）においては、平均格子面間隔ｄ１１０が０．１２２６ｎｍ超であることから、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高くなっていると推測される。上記バルク内で安定化して存在している酸素は、１，０００℃超で脱離すると考えられる。
The negative electrode active material (A) has a large discharge capacity and is 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is high. The reason why such an effect occurs in the negative electrode active material (A) is not clear, but the following reasons are presumed. In the carbon material, as shown in Examples described later, the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less (content rate with respect to the carbon material before heating. Carbon in the present specification. The same applies to the content of oxygen desorbed in each predetermined temperature range in the material, that is, the negative electrode active material.) There is a high correlation between the discharge capacity and the temperature of more than 800 ° C and 2,500 ° C or less. The higher the content of oxygen desorbed at temperature, the larger the discharge capacity tends to be (see FIG. 3). The reason for this is not clear, but it is presumed that a carbon material with a high oxygen content that desorbs at a temperature of more than 800 ° C and 2,500 ° C or less has a structure that easily occludes lithium ions and the like. .. The negative electrode active material (A) has a large discharge capacity because the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or lower is 4% by mass or more.
By the way, the average lattice spacing d 110 of the carbon material is related to the distance of carbon-carbon bonds in the graphene layer, and when there are many functional groups present on the surface, the graphene layer is distorted and the average lattice spacing d 110 becomes smaller. Conceivable. And the functional group existing on the surface is 1.2V vs. It is considered that it contributes to the discharge at a relatively high potential of Li / Li +. Therefore, in the carbon material of
On the other hand, the oxygen that is stabilized and present in the bulk is 1.2 V vs. It is considered that it contributes to the discharge at a relatively low potential of Li / Li + or less. Therefore, when the average lattice spacing d 110 is large, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less tends to be high (see FIG. 4). In the negative electrode active material (A), since the average lattice plane spacing d 110 is more than 0.1226 nm, 1.2 V vs. It is presumed that the discharge capacity ratio in the potential range of Li / Li + or less is high. Oxygen that is stabilized and present in the bulk is considered to be desorbed at more than 1,000 ° C.
なお、「炭素材料における酸素の含有率」は、ＨＯＲＩＢＡ社製の酸素・窒素・水素分析装置「ＥＭＧＡ−９３０」を用いた以下の方法により測定される。上記測定は、充放電前の炭素材料に対して行うか、非水電解質蓄電素子の負極として組み込まれている炭素材料に対しては、以下の手順で処理したものに対して行う。まず、非水電解質蓄電素子を０．０５Ｃの電流で通常使用時の下限電圧まで定電流放電する。解体し、負極を取り出し、金属リチウム電極を対極とした試験電池を組み立て、負極合剤１ｇあたり５０ｍＡの電流値で、負極電位が３．０Ｖ ｖｓ．Ｌｉ／Ｌｉ＋となるまで定電流放電を行い、負極を完全放電状態（充放電反応に関与するイオンが脱離した状態）に調整する。再解体し、負極を取り出す。取り出した負極を、エタノールを用いて十分に洗浄し、室温にて一昼夜乾燥させる。その後、負極活物質である炭素材料を含む負極合剤を剥離し、不活性雰囲気下８００℃で５時間の熱処理を施す。非水電解質蓄電素子の解体から測定までの作業は露点−６０℃以下のアルゴン雰囲気中で行う。ここで、通常使用時とは、当該非水電解質蓄電素子について推奨され、又は指定される充放電条件を採用して当該非水電解質蓄電素子を使用する場合をいう。ここで、不活性雰囲気下８００℃で５時間の熱処理を施す理由は、充放電によって生成したＳＥＩを除去するためである。
［測定方法］
酸素測定方法：不活性ガス融解−非分散型赤外線吸収法（ＮＤＩＲ）
ガス抽出炉電力：インパルス炉出力 ０から８．０ｋＷ（あらかじめ各設定温度に対応する好適な出力値がプログラムされており、設定温度が変わるたびに対応する出力値が適用される。）
キャリアガス：ヘリウム
校正方法：標準試料を用いた１点校正
［測定手順］
ヘリウム雰囲気下、上記分析装置指定の黒鉛製るつぼを抽出炉中に設置し、３２３１℃で３０秒、次いで４００℃で２０秒の空焼きすることで、黒鉛るつぼに含まれる酸素を除去する。この黒鉛るつぼを大気下に取り出し、試料（炭素材料）２０から２５ｍｇを黒鉛るつぼ中に入れ、再度ヘリウム雰囲気下の抽出炉中に設置する。設定温度４００℃で５０秒保持、設定温度を６００℃に変更し５０秒保持、設定温度を８００℃に変更し５０秒保持、設定温度を１，０００℃に変更し５０秒保持、設定温度を１，２００℃に変更し５０秒保持、設定温度を２，５００℃に変更し５０秒保持という昇温プログラムを実行して、段階的に昇温、加熱し、この間に試料から脱離する酸素を上記設定温度ごとに定量する。なお、黒鉛製るつぼに酸素が吸着していることを考慮して、空焼き後に大気に暴露した黒鉛るつぼ単体から脱離する酸素の量についても測定し、その分を除去する。また、設定温度に加熱してから、生成したガスがセンサー部に到着するまでの時間差を考慮し、昇温プログラムが実行された時間を０秒としたときの積算時間が以下に示す期間に定量される酸素量を、各設定温度において脱離する酸素量とする。
４００℃：０秒から５５秒
６００℃：５５秒から１０５秒
８００℃：１０５秒から１５５秒
１，０００℃：１５５秒から２０５秒
１，２００℃：２０５秒から２５５秒
２，５００℃：２５５秒から３３０秒
「炭素材料における８００℃超２，５００℃以下の温度で脱離する酸素の含有率」は、予め測定しておいた抽出炉での加熱前の試料（炭素材料）の質量に対する、１，０００℃、１，２００℃及び２，５００℃の設定温度で測定された合計酸素量（積算時間１５５秒から３３０秒の間で測定された合計酸素量）の割合として求められる。
The "oxygen content in the carbon material" is measured by the following method using an oxygen / nitrogen / hydrogen analyzer "EMGA-930" manufactured by HORIBA. The above measurement is performed on the carbon material before charging / discharging, or on the carbon material incorporated as the negative electrode of the non-aqueous electrolyte power storage element, which has been treated by the following procedure. First, the non-aqueous electrolyte power storage element is constantly discharged with a current of 0.05 C to the lower limit voltage during normal use. It was disassembled, the negative electrode was taken out, a test battery with a metallic lithium electrode as the counter electrode was assembled, and the negative electrode potential was 3.0 V vs. at a current value of 50 mA per 1 g of the negative electrode mixture. A constant current discharge is performed until Li / Li + , and the negative electrode is adjusted to a completely discharged state (a state in which ions involved in the charge / discharge reaction are desorbed). Re-disassemble and take out the negative electrode. The removed negative electrode is thoroughly washed with ethanol and dried at room temperature for 24 hours. Then, the negative electrode mixture containing the carbon material which is the negative electrode active material is peeled off, and heat treatment is performed at 800 ° C. for 5 hours in an inert atmosphere. The work from disassembly of the non-aqueous electrolyte power storage element to measurement is performed in an argon atmosphere with a dew point of -60 ° C or lower. Here, the term "normal use" refers to a case where the non-aqueous electrolyte power storage element is used by adopting the charge / discharge conditions recommended or specified for the non-aqueous electrolyte power storage element. Here, the reason for performing the heat treatment at 800 ° C. for 5 hours in an inert atmosphere is to remove the SEI generated by charging / discharging.
[Measuring method]
Oxygen measurement method: Inert gas melting-non-dispersive infrared absorption method (NDIR)
Gas extraction furnace power:
Carrier gas: Helium Calibration method: One-point calibration using a standard sample [Measurement procedure]
In a helium atmosphere, a graphite crucible designated by the above analyzer is placed in an extraction furnace and air-baked at 3231 ° C. for 30 seconds and then at 400 ° C. for 20 seconds to remove oxygen contained in the graphite crucible. The graphite crucible is taken out to the atmosphere, 20 to 25 mg of a sample (carbon material) is put into the graphite crucible, and the sample (carbon material) is placed again in the extraction furnace under a helium atmosphere. Hold at
400 ° C: 0 seconds to 55
また、炭素材料の平均格子面間隔ｄ１１０、並びに後述するその他の平均格子面間隔及び平均結晶子サイズは、以下のＸ線回折測定により決定される値である。上記Ｘ線回折測定は、充放電前の炭素材料に対して行うか、上記した酸素の含有率の測定と同様に、非水電解質蓄電素子の負極として組み込まれている炭素材料に対しては、上記の処理をしたものに対して行う。炭素材料のＸ線回折測定は、Ｘ線回折装置（Ｒｉｇａｋｕ社の「ＭｉｎｉＦｌｅｘ ＩＩ」）を用いた粉末Ｘ線回折測定によって、線源はＣｕＫα線、管電圧は３０ｋＶ、管電流は１５ｍＡとして行う。このとき、回折Ｘ線は、厚み３０μｍのＫβフィルターを通り、高速一次元検出器（Ｄ／ｔｅＸ Ｕｌｔｒａ ２）にて検出される。また、サンプリング幅は０．０１°、スキャンスピードは５°／ｍｉｎ、発散スリット幅は０．６２５°、受光スリット幅は１３ｍｍ（ＯＰＥＮ）、散乱スリット幅は８ｍｍとする。得られるＸ線回折データに基づいて、「ＲＩＥＴＡＮ２０００」プログラム（Ｆ．Ｉｚｕｍｉ ａｎｄ Ｔ．Ｉｋｅｄａ，Ｍａｔｅｒ．Ｓｃｉ．Ｆｏｒｕｍ，１９８（２０００）．）を用いたリートベルト解析により、結晶構造を解析し、平均格子面間隔及び平均結晶子サイズを求めることができる。平均格子面間隔及び平均結晶子サイズは、総合粉末Ｘ線解析ソフトウェア「ＰＤＸＬ」（Ｒｉｇａｋｕ社製）を用いても同じ結果が得られる。 The average lattice spacing d 110 of the carbon material, and other average lattice spacing and average crystallite size described later are values determined by the following X-ray diffraction measurements. The X-ray diffraction measurement is performed on the carbon material before charging and discharging, or on the carbon material incorporated as the negative electrode of the non-aqueous electrolyte power storage element in the same manner as the measurement of the oxygen content described above. Perform the above processing. The X-ray diffraction measurement of the carbon material is performed by powder X-ray diffraction measurement using an X-ray diffractometer (“MiniFlex II” manufactured by Rigaku Co., Ltd.) with a CuKα ray as the radiation source, a tube voltage of 30 kV, and a tube current of 15 mA. At this time, the diffracted X-rays pass through a Kβ filter having a thickness of 30 μm and are detected by a high-speed one-dimensional detector (D / teX Ultra 2). The sampling width is 0.01 °, the scan speed is 5 ° / min, the divergent slit width is 0.625 °, the light receiving slit width is 13 mm (OPEN), and the scattering slit width is 8 mm. Based on the obtained X-ray diffraction data, the crystal structure was analyzed by Rietveld analysis using the "RIETAN2000" program (F. Izumi and T. Ikeda, Matter. Sci. Forum, 198 (2000).), And the crystal structure was analyzed and averaged. The lattice spacing and average crystallite size can be determined. The same results can be obtained for the average lattice spacing and the average crystallite size by using the comprehensive powder X-ray analysis software "PDXL" (manufactured by Rigaku).
当該負極活物質（Ａ）において、平均格子面間隔ｄ００２が０．３３７ｎｍ以上であることが好ましい。炭素材料中の酸素含有量が多い場合、立体障害により、平均格子面間隔ｄ００２が大きくなる傾向にある。従って、当該負極活物質（Ａ）において、平均格子面間隔ｄ００２が０．３３７ｎｍ以上である場合、放電容量がより大きくなる。 In the negative electrode active material (A), the average lattice plane spacing d 002 is preferably 0.337 nm or more. When the oxygen content in the carbon material is high, the average lattice spacing d 002 tends to be large due to steric hindrance. Therefore, in the negative electrode active material (A), when the average lattice plane spacing d 002 is 0.337 nm or more, the discharge capacity becomes larger.
当該負極活物質（Ａ）において、平均結晶子サイズＬａが３１ｎｍ以下であることが好ましい。炭素材料中の酸素含有量が大きい場合、ひずみが生じて平均結晶子サイズＬａが小さくなる傾向にある。従って、当該負極活物質（Ａ）において、平均結晶子サイズＬａが３１ｎｍ以下である場合、放電容量がより大きくなる。 In the negative electrode active material (A), it is preferred that the average crystallite size L a is less than 31 nm. If a large oxygen content in the carbon material tends to average crystallite size L a in strain occurs is reduced. Therefore, in the negative electrode active material (A), in the case where the average crystallite size L a is less than 31 nm, the discharge capacity becomes larger.
本発明の他の一態様に係る負極活物質は、炭素材料であり、加熱して脱離する酸素を含有し、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上１３質量％以下であり、上記４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上である非水電解質蓄電素子用の負極活物質（Ｂ）である。 The negative electrode active material according to another aspect of the present invention is a carbon material, contains oxygen that is desorbed by heating, and the content of oxygen that is desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is heated. It is 4% by mass or more and 13% by mass or less with respect to the above-mentioned carbon material, and is desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less with respect to oxygen desorbed at the above-mentioned temperature of 400 ° C. or more and 2,500 ° C. or less. It is a negative electrode active material (B) for a non-aqueous electrolyte power storage element having an oxygen content ratio of 0.45 or more to be separated.
当該負極活物質（Ｂ）は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い。当該負極活物質（Ｂ）においてこのような効果が生じる理由は定かでは無いが、以下の理由が推測される。炭素材料においては、後述する実施例で示されているように、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が高いほど放電容量が大きくなる傾向がある（図５参照）。当該負極活物質（Ｂ）においては、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が４質量％以上であるため、放電容量が大きい。また、上述した１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋超の比較的高電位における放電に寄与していると考えられる表面に存在する官能基は、１，０００℃以下で脱離しやすく、一方、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の比較的低電位における放電に寄与していると考えられるバルク内で安定化して存在している酸素は、１，０００℃超で脱離する傾向にある。このようなことから、４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が高いと、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高くなる傾向となる（図６参照）。当該負極活物質（Ｂ）においては、４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上であるため、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高くなっていると推測される。 The negative electrode active material (B) has a large discharge capacity and is 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is high. The reason why such an effect occurs in the negative electrode active material (B) is not clear, but the following reasons are presumed. In the carbon material, as shown in Examples described later, the discharge capacity tends to increase as the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower increases (see FIG. 5). ). The negative electrode active material (B) has a large discharge capacity because the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is 4% by mass or more. In addition, the above-mentioned 1.2V vs. The functional groups present on the surface, which are considered to contribute to the discharge at a relatively high potential of Li / Li + or more, are easily desorbed at 1,000 ° C. or lower, while 1.2 V vs. Oxygen, which is stabilized and present in the bulk, which is considered to contribute to the discharge at a relatively low potential of Li / Li + or less, tends to be desorbed at more than 1,000 ° C. Therefore, if the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or lower to oxygen desorbed at a temperature of 400 ° C. or higher and 2,500 ° C. or lower is high, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less tends to be high (see FIG. 6). In the negative electrode active material (B), the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less to oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is 0. Since it is 45 or more, 1.2 V vs. It is presumed that the discharge capacity ratio in the potential range of Li / Li + or less is high.
なお、炭素材料における４００℃以上２，５００℃以下の温度で脱離する酸素の含有量は、上記「炭素材料における酸素の含有率」の測定において、４００℃から２，５００℃までの設定温度で測定された全ての合計酸素量（積算時間０秒から３３０秒の間で測定された合計酸素量）とする。但し、上記測定は、充放電前の炭素材料に対して行うものとする。「炭素材料における４００℃以上２，５００℃以下の温度で脱離する酸素の含有率」は、予め測定しておいた抽出炉での加熱前の試料（炭素材料）の質量に対する上記全ての合計酸素量（４００℃以上２，５００℃以下の温度で脱離する酸素の含有量）の割合として求められる。また、「４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比」は、質量比であり、上記全ての合計酸素量（４００℃以上２，５００℃以下の温度で脱離する酸素の量）に対する、１，２００℃及び２，５００℃の設定温度で測定された合計酸素量（積算時間２０５秒から３３０秒の間で測定された合計酸素量）の比として求められる。 The oxygen content desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower in the carbon material is the set temperature from 400 ° C. to 2500 ° C. in the above-mentioned measurement of "oxygen content in carbon material". Let it be the total amount of oxygen measured in (total oxygen amount measured between 0 seconds and 330 seconds of integration time). However, the above measurement shall be performed on the carbon material before charging / discharging. The "content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower in the carbon material" is the sum of all the above with respect to the mass of the sample (carbon material) before heating in the extraction furnace, which was measured in advance. It is determined as a ratio of the amount of oxygen (the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower). Further, "the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or lower to oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower" is a mass ratio, and all of the above. Total amount of oxygen measured at set temperatures of 1,200 ° C and 2,500 ° C (from an integrated time of 205 seconds) with respect to the total amount of oxygen (the amount of oxygen desorbed at a temperature of 400 ° C or higher and 2500 ° C or lower). It is calculated as the ratio of the total amount of oxygen measured during 330 seconds.
本発明の一態様に係る負極は、当該負極活物質（Ａ）又は当該負極活物質（Ｂ）を備える非水電解質蓄電素子用の負極である。当該負極は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い。 The negative electrode according to one aspect of the present invention is a negative electrode for a non-aqueous electrolyte power storage element including the negative electrode active material (A) or the negative electrode active material (B). The negative electrode has a large discharge capacity and is 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is high.
本発明の一態様に係る非水電解質蓄電素子は、当該負極を備える非水電解質蓄電素子（以下、単に「蓄電素子」ともいう。）である。当該蓄電素子は、本発明の一態様に係る負極活物質（Ａ）又は負極活物質（Ｂ）が用いられているため、放電容量の大きい蓄電素子となり得る。 The non-aqueous electrolyte storage element according to one aspect of the present invention is a non-aqueous electrolyte storage element (hereinafter, also simply referred to as “storage element”) including the negative electrode. Since the negative electrode active material (A) or the negative electrode active material (B) according to one aspect of the present invention is used in the power storage element, it can be a power storage element having a large discharge capacity.
本発明の一態様に係る非水電解質蓄電素子の製造方法は、当該負極活物質（Ａ）又は当該負極活物質（Ｂ）を用いて負極を作製することを備える非水電解質蓄電素子の製造方法である。当該製造方法は、本発明の一態様に係る負極活物質（Ａ）又は負極活物質（Ｂ）を用いるため、放電容量の大きい非水電解質蓄電素子を製造することが可能となる。 The method for manufacturing a non-aqueous electrolyte power storage element according to one aspect of the present invention includes manufacturing a negative electrode using the negative electrode active material (A) or the negative electrode active material (B). Is. Since the manufacturing method uses the negative electrode active material (A) or the negative electrode active material (B) according to one aspect of the present invention, it is possible to manufacture a non-aqueous electrolyte power storage element having a large discharge capacity.
以下、本発明の一実施形態に係る負極活物質、負極、非水電解質蓄電素子及びその製造方法について詳説する。なお、各実施形態に用いられる各構成部材（各構成要素）の名称は、背景技術に用いられる各構成部材（各構成要素）の名称と異なる場合がある。 Hereinafter, the negative electrode active material, the negative electrode, the non-aqueous electrolyte power storage element, and the manufacturing method thereof according to the embodiment of the present invention will be described in detail. The name of each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background technology.
＜負極活物質（Ａ）＞
（構成元素）
本発明の一実施形態に係る負極活物質（Ａ）は、炭素材料である。炭素材料とは、質量基準で最も含有量が多い元素が炭素である材料をいう。当該負極活物質（Ａ）は、炭素以外に酸素を含み、その他、水素、窒素等の他の元素をさらに含んでいてもよい。当該負極活物質（Ａ）における炭素の含有量としては、７０質量％以上９６質量％以下が好ましく、８０質量％以上９４質量％以下がより好ましく、８５質量％以上９２質量％以下がさらに好ましい。
<Negative electrode active material (A)>
(Constituent element)
The negative electrode active material (A) according to the embodiment of the present invention is a carbon material. The carbon material is a material in which the element having the highest content on a mass basis is carbon. The negative electrode active material (A) contains oxygen in addition to carbon, and may further contain other elements such as hydrogen and nitrogen. The carbon content in the negative electrode active material (A) is preferably 70% by mass or more and 96% by mass or less, more preferably 80% by mass or more and 94% by mass or less, and further preferably 85% by mass or more and 92% by mass or less.
当該負極活物質（Ａ）は、加熱して脱離する酸素を含有する炭素材料である。当該負極活物質（Ａ）（炭素材料）における４００℃以上２，５００℃以下の温度で脱離する酸素の含有率としては、例えば３質量％以上１５質量％以下であってもよいが、４質量％以上１３質量％以下が好ましく、６質量％以上１２質量％以下がより好ましく、８質量％以上１１質量％以下がさらに好ましい。４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が上記下限以上であることで、放電容量がより大きくなる。一方、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が上記上限以下であることで、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高まる。 The negative electrode active material (A) is a carbon material containing oxygen that is desorbed by heating. The content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower in the negative electrode active material (A) (carbon material) may be, for example, 3% by mass or more and 15% by mass or less, but 4 It is preferably 3% by mass or more and 13% by mass or less, more preferably 6% by mass or more and 12% by mass or less, and further preferably 8% by mass or more and 11% by mass or less. When the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is equal to or higher than the above lower limit, the discharge capacity becomes larger. On the other hand, when the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is equal to or lower than the above upper limit, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less increases.
当該負極活物質（Ａ）は、８００℃超２，５００℃以下の温度で脱離する酸素を含有する。当該負極活物質（Ａ）における上記８００℃超２，５００℃以下の温度で脱離する酸素の含有率の下限は４質量％である。８００℃超２，５００℃以下の温度で脱離する酸素の含有率は、５質量％以上１２質量％以下が好ましく、６質量％以上１１質量％以下がより好ましいことがあり、７．０質量％以上１０．５質量％以下がさらに好ましいことがある。８００℃超２，５００℃以下の温度で脱離する酸素の含有率が上記下限以上であることで、放電容量が大きくなる。一方、生産性等の観点から、８００℃超２，５００℃以下の温度で脱離する酸素の含有率は、上記上限以下が好ましい。 The negative electrode active material (A) contains oxygen that is desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or lower. The lower limit of the content of oxygen desorbed at the temperature above 800 ° C. and 2,500 ° C. or lower in the negative electrode active material (A) is 4% by mass. The content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is preferably 5% by mass or more and 12% by mass or less, more preferably 6% by mass or more and 11% by mass or less, and 7.0% by mass. % Or more and 10.5% by mass or less may be more preferable. When the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or lower is equal to or higher than the above lower limit, the discharge capacity becomes large. On the other hand, from the viewpoint of productivity and the like, the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or lower is preferably not more than the above upper limit.
当該負極活物質（Ａ）は、４００℃以上１，０００℃以下の温度で脱離する酸素を含有していてもよい。当該負極活物質（Ａ）における４００℃以上１，０００℃以下の温度で脱離する酸素の含有率は、１質量％以上６質量％以下が好ましく、１．５質量％以上５質量％以下がより好ましい。このように４００℃以上１，０００℃以下の温度で脱離する酸素の含有率が比較的少ない場合、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比がより高まる。なお、上述した、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋超の比較的高電位における放電に寄与する表面領域に存在する酸素を含む官能基は、４００℃以上１，０００℃以下の温度で脱離する傾向にある。すなわち、４００℃以上１，０００℃以下の温度で脱離する酸素の含有率が低い場合、上記官能基が少なく、平均格子面間隔ｄ１１０は大きくなる傾向にある。 The negative electrode active material (A) may contain oxygen that is desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower. The content of oxygen desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower in the negative electrode active material (A) is preferably 1% by mass or more and 6% by mass or less, and 1.5% by mass or more and 5% by mass or less. More preferred. When the content of oxygen desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower is relatively small, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is further increased. In addition, as mentioned above, 1.2V vs. Oxygen-containing functional groups present in the surface region that contribute to discharge at relatively high potentials above Li / Li + tend to be desorbed at temperatures of 400 ° C. and above and 1,000 ° C. and below. That is, when the content of oxygen desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower is low, the functional groups tend to be small and the average lattice spacing d 110 tends to be large.
なお、当該負極活物質（Ａ）（炭素材料）における４００℃以上１，０００℃以下の温度で脱離する酸素の含有率は、上述した「炭素材料における８００℃超２，５００℃以下の温度で脱離する酸素の含有率」を求める方法に準じ、予め測定しておいた抽出炉での加熱前の試料（炭素材料）の質量に対する、４００℃、６００℃、８００℃及び１，０００℃の設定温度で測定された合計酸素量（積算時間０秒から２０５秒の間で測定された合計酸素量）の割合として求められる。 The content of oxygen desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower in the negative electrode active material (A) (carbon material) is the above-mentioned "temperature of more than 800 ° C. and 2500 ° C. or lower in the carbon material". 400 ° C, 600 ° C, 800 ° C and 1,000 ° C with respect to the mass of the sample (carbon material) before heating in the extraction furnace, which was measured in advance, according to the method for determining the "content of oxygen desorbed in". It is obtained as a ratio of the total oxygen amount measured at the set temperature of (the total oxygen amount measured between 0 seconds and 205 seconds of the integration time).
当該負極活物質（Ａ）において、４００℃以上２，５００℃以下の温度で脱離する酸素に対する、１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比は、質量比で、例えば０．４０以上０．９５以下であってよいが、０．４５以上０．９０以下が好ましく、０．５０以上０．８５以下がより好ましい。上記１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が上記下限以上であることで、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比がより高まる。一方、上記１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が上記上限以下であることで、放電容量がより大きくなる。 In the negative electrode active material (A), the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less to oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is mass. The ratio may be, for example, 0.40 or more and 0.95 or less, but 0.45 or more and 0.90 or less is preferable, and 0.50 or more and 0.85 or less is more preferable. When the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or lower is equal to or higher than the above lower limit, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is further increased. On the other hand, when the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or lower is not more than the above upper limit, the discharge capacity becomes larger.
（格子面間隔等）
当該負極活物質（Ａ）における平均格子面間隔ｄ１１０は、０．１２２６ｎｍ超である。すなわち当該負極活物質（Ａ）は、上述した方法にて平均格子面間隔ｄ１１０を測定可能な炭素材料である。この平均格子面間隔ｄ１１０は、０．１２２８ｎｍ以上０．１２４０ｎｍ以下が好ましく、０．１２２９ｎｍ以上０．１２３６ｎｍ以下がより好ましく、０．１２３０ｎｍ以上０．１２３４ｎｍ以下がさらに好ましい。当該負極活物質（Ａ）における平均格子面間隔ｄ１１０が上記下限以上であることで、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高まる。一方、生産性等の観点から、上記平均格子面間隔ｄ１１０は、上記上限以下が好ましい。
(Lattice surface spacing, etc.)
The average lattice spacing d 110 in the negative electrode active material (A) is more than 0.1226 nm. That is, the negative electrode active material (A) is a carbon material whose average lattice spacing d 110 can be measured by the method described above. The average lattice spacing d 110 is preferably 0.1228 nm or more and 0.1240 nm or less, more preferably 0.1229 nm or more and 0.1236 nm or less, and further preferably 0.1230 nm or more and 0.1234 nm or less. When the average lattice plane spacing d 110 in the negative electrode active material (A) is equal to or greater than the above lower limit, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less increases. On the other hand, from the viewpoint of productivity and the like, the average lattice plane spacing d 110 is preferably equal to or less than the upper limit.
当該負極活物質（Ａ）における平均格子面間隔ｄ００２は、例えば０．３３５ｎｍ以上０．４００ｎｍ以下であってよいが、０．３３７ｎｍ以上０．３７０ｎｍ以下が好ましく、さらには０．３５０ｎｍ以下又は０．３４５ｎｍ以下がより好ましいこともある。平均格子面間隔ｄ００２が上記下限以上であることで、放電容量がより大きくなる。一方、平均格子面間隔ｄ００２が上記上限以下であることで、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比がより高まる。 The average lattice spacing d 002 in the negative electrode active material (A) may be, for example, 0.335 nm or more and 0.400 nm or less, preferably 0.337 nm or more and 0.370 nm or less, and further 0.350 nm or less or 0. .345 nm or less may be more preferred. When the average lattice spacing d 002 is equal to or greater than the above lower limit, the discharge capacity becomes larger. On the other hand, when the average lattice plane spacing d 002 is equal to or less than the above upper limit, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is further increased.
当該負極活物質（Ａ）における平均結晶子サイズＬａは、例えば１４ｎｍ以上３４ｎｍ以下であってよいが、１５ｎｍ以上３１ｎｍ以下が好ましく、１７ｎｍ以上３０ｎｍ以下がより好ましい。平均結晶子サイズＬａが上記下限以上であることで、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比がより高まる。一方、平均結晶子サイズＬａが上記上限以下であることで、放電容量がより大きくなる。 The average crystallite size L a in the negative electrode active material (A) is, for example, may be at 14nm or more 34nm or less, preferably 15nm or more 31nm or less, more preferably 30nm or more 17 nm. When the average crystallite size L a is the lower limit or more, 1.2V vs. The discharge capacity ratio in the potential range of Li / Li + or less is further increased. On the other hand, when the average crystallite size L a is less than the above upper limit, the discharge capacity becomes larger.
（用途・形状）
当該負極活物質（Ａ）は、非水電解質蓄電素子の負極活物質として用いられる。当該負極活物質（Ａ）は、通常、粉末状である。当該負極活物質（Ａ）は、例えば他の負極活物質と複合化されて用いられてもよいが、好適な形態としては、当該負極活物質のみの粉末として用いられる。
(Use / shape)
The negative electrode active material (A) is used as the negative electrode active material of the non-aqueous electrolyte power storage element. The negative electrode active material (A) is usually in the form of powder. The negative electrode active material (A) may be used in combination with, for example, another negative electrode active material, but as a preferable form, it is used as a powder of only the negative electrode active material.
当該負極活物質（Ａ）の平均粒径は、例えば、１ｎｍ以上１００μｍ以下とすることができ、１μｍ以上１００μｍ以下が好ましい場合がある。負極活物質（Ａ）の平均粒径を上記下限以上とすることで、製造又は取り扱いが容易になる。負極活物質（Ａ）の平均粒径を上記上限以下とすることで、活物質層の電子伝導性が向上する。「平均粒径」とは、ＪＩＳ−Ｚ−８８２５（２０１３年）に準拠し、粒子を溶媒で希釈した希釈液に対しレーザ回折・散乱法により測定した粒径分布に基づき、ＪＩＳ−Ｚ−８８１９−２（２００１年）に準拠し計算される体積基準積算分布が５０％となる値（Ｄ５０）を意味する。 The average particle size of the negative electrode active material (A) can be, for example, 1 nm or more and 100 μm or less, and may be preferably 1 μm or more and 100 μm or less. By setting the average particle size of the negative electrode active material (A) to be equal to or higher than the above lower limit, production or handling becomes easy. By setting the average particle size of the negative electrode active material (A) to be equal to or less than the above upper limit, the electron conductivity of the active material layer is improved. The "average particle size" is based on JIS-Z-8825 (2013), and is based on the particle size distribution measured by the laser diffraction / scattering method for a diluted solution obtained by diluting the particles with a solvent. It means a value (D50) in which the volume-based integrated distribution calculated in accordance with -2 (2001) is 50%.
粉体を所定の粒径で得るためには粉砕機や分級機等が用いられる。粉砕方法として、例えば、乳鉢、ボールミル、サンドミル、振動ボールミル、遊星ボールミル、ジェットミル、カウンタージェットミル、旋回気流型ジェットミル又は篩等を用いる方法が挙げられる。粉砕時には水、あるいはヘキサン等の有機溶剤を共存させた湿式粉砕を用いることもできる。分級方法としては、篩や風力分級機等が、乾式、湿式ともに必要に応じて用いられる。 A crusher, a classifier, or the like is used to obtain a powder having a predetermined particle size. Examples of the crushing method include a method using a mortar, a ball mill, a sand mill, a vibrating ball mill, a planetary ball mill, a jet mill, a counter jet mill, a swirling airflow type jet mill, a sieve, and the like. At the time of pulverization, wet pulverization in which water or an organic solvent such as hexane coexists can also be used. As a classification method, a sieve, a wind power classifier, or the like is used as needed for both dry and wet types.
＜負極活物質（Ｂ）＞
本発明の一実施形態に係る負極活物質（Ｂ）は、炭素材料であり、加熱して脱離する酸素を含有し、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が４質量％以上１３質量％以下であり、上記４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上である非水電解質蓄電素子用の負極活物質である。
<Negative electrode active material (B)>
The negative electrode active material (B) according to the embodiment of the present invention is a carbon material, contains oxygen that is desorbed by heating, and contains oxygen that is desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower. Is 4% by mass or more and 13% by mass or less, and the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less to the oxygen desorbed at the above temperature of 400 ° C. or more and 2,500 ° C. or less. Is a negative electrode active material for a non-aqueous electrolyte power storage element having a temperature of 0.45 or more.
当該負極活物質（Ｂ）は、「８００℃超２，５００℃以下の温度で脱離する酸素の含有率が４質量％以上であり、平均格子面間隔ｄ１１０が０．１２２６ｎｍ超であること」を必須とせず、「４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が４質量％以上１３質量％以下であり、上記４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上であること」を必須とすること以外は、上述した負極活物質（Ａ）と同様である。当該負極活物質（Ｂ）の具体的形態及び好適形態は、上述した負極活物質（Ａ）の具体的形態及び好適形態と同様である。 The negative electrode active material (B) has "the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is 4% by mass or more, and the average lattice spacing d 110 is more than 0.1226 nm. Is not essential, and "the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is 4% by mass or more and 13% by mass or less, and the oxygen content is desorbed at the above temperature of 400 ° C. or higher and 2500 ° C. or lower. The above-mentioned negative electrode active material (A), except that it is essential that the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less to the oxygen to be desorbed is 0.45 or more. Is similar to. The specific form and preferred form of the negative electrode active material (B) are the same as the specific form and preferred form of the negative electrode active material (A) described above.
＜負極活物質の製造方法＞
当該負極活物質（Ａ）及び当該負極活物質（Ｂ）は、例えば、黒鉛を出発物質（原料）とし、以下の酸化処理及び熱処理を順に施すことにより製造することができる。なお、酸化処理と熱処理との間に、水熱処理又は還元処理を施してもよく、これらの処理は施さなくてもよい。
<Manufacturing method of negative electrode active material>
The negative electrode active material (A) and the negative electrode active material (B) can be produced, for example, by using graphite as a starting material (raw material) and subjecting the following oxidation treatment and heat treatment in order. A hydrothermal treatment or a reduction treatment may be performed between the oxidation treatment and the heat treatment, and these treatments may not be performed.
（酸化処理）
酸化処理は、発煙硝酸及び塩素酸カリウム（ＫＣｌＯ３）を用いたＢｒｏｄｉｅ法が好適に採用される。まず、粉末状の黒鉛と発煙硝酸とを混合し、懸濁液を得る。発煙硝酸の使用量としては、黒鉛１ｇに対して、例えば８から４０ｃｍ３とすることができる。次いで、例えば６０℃程度に加熱した状態の上記懸濁液に、ＫＣｌＯ３を添加し反応させる。反応条件としては例えば６０℃３時間とすることができる。ＫＣｌＯ３の添加量としては、黒鉛１ｇに対して、例えば３から１６ｇとすることができる。その後、大量の水と混合することなどで反応を停止させる。懸濁液の固形物と液体とを分離し、固形物を洗浄及び乾燥させることで酸化黒鉛が得られる。
(Oxidation treatment)
For the oxidation treatment, the Brodie method using fuming nitric acid and potassium chlorate (KClO 3 ) is preferably adopted. First, powdered graphite and fuming nitric acid are mixed to obtain a suspension. The amount of fuming nitric acid used can be, for example, 8 to 40 cm 3 with respect to 1 g of graphite. Next, KClO 3 is added to the suspension heated to, for example, about 60 ° C. and reacted. The reaction conditions can be, for example, 60 ° C. for 3 hours. The amount of KClO 3 added can be, for example, 3 to 16 g with respect to 1 g of graphite. After that, the reaction is stopped by mixing with a large amount of water. Graphite oxide is obtained by separating the solid and liquid of the suspension and washing and drying the solid.
（水熱処理）
任意の処理である水熱処理は、得られた酸化黒鉛を水と混合し、反応器中で加熱することにより行うことができる。処理条件としては例えば１８０から３００℃、１時間とすることができる。その後、固形物と液体とを分離し、固形物を洗浄及び乾燥させることで水熱処理された酸化黒鉛が得られる。水熱処理を行うことで、平均格子面間隔ｄ１１０が大きくなり、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高まる傾向にある。但し、水熱処理を行うと、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率及び８００℃超２，５００℃以下の温度で脱離する酸素の含有率が低下する傾向にあり、放電容量が小さくなる場合があるため、水熱処理を行わないことが好ましいこともある。
(Hydraulic heat treatment)
Hydrothermal treatment, which is an arbitrary treatment, can be performed by mixing the obtained graphite oxide with water and heating it in a reactor. The treatment conditions can be, for example, 180 to 300 ° C. for 1 hour. Then, the solid and the liquid are separated, and the solid is washed and dried to obtain a water-heat-treated graphite oxide. By performing the hydrothermal treatment, the average lattice spacing d 110 is increased, and 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less tends to increase. However, when hydrothermal treatment is performed, the content of oxygen desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower and the content of oxygen desorbed at a temperature of more than 800 ° C. and 2500 ° C. or lower tend to decrease. Therefore, it may be preferable not to perform hydrothermal treatment because the discharge capacity may be small.
（還元処理）
任意の処理である還元処理は、得られた酸化黒鉛をヒドラジン等の還元剤により処理することにより行うことができる。還元処理を行うことで、平均格子面間隔ｄ１１０が大きくなり、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高まる傾向にある。但し、還元処理を行うと、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が低下する傾向にあり、放電容量が小さくなる場合があるため、還元処理を行わないことが好ましいこともある。
(Reduction process)
The reduction treatment, which is an arbitrary treatment, can be performed by treating the obtained graphite oxide with a reducing agent such as hydrazine. By performing the reduction treatment, the average lattice plane spacing d 110 becomes large, and 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less tends to increase. However, when the reduction treatment is performed, the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less tends to decrease, and the discharge capacity may become smaller. Therefore, the reduction treatment may not be performed. It may be preferable.
（熱処理）
熱処理は、得られた酸化黒鉛を窒素等の不活性ガス雰囲気下で加熱することにより行うことができる。処理条件としては、例えば５００から８００℃、１時間とすることができる。熱処理が不十分である場合、平均格子面間隔ｄ１１０が小さくなる傾向にある。一方、過剰な熱処理を行った場合、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が低下する傾向にある。
(Heat treatment)
The heat treatment can be performed by heating the obtained graphite oxide in an atmosphere of an inert gas such as nitrogen. The treatment conditions can be, for example, 500 to 800 ° C. for 1 hour. When the heat treatment is insufficient, the average lattice spacing d 110 tends to be small. On the other hand, when excessive heat treatment is performed, the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less tends to decrease.
＜負極＞
本発明の一実施形態に係る負極は、上述した負極活物質（Ａ）又は負極活物質（Ｂ）を備える非水電解質蓄電素子用の負極である。当該負極は、負極基材と、上記負極基材に直接又は中間層を介して配される負極活物質層とを有する。
<Negative electrode>
The negative electrode according to the embodiment of the present invention is a negative electrode for a non-aqueous electrolyte power storage element including the above-mentioned negative electrode active material (A) or negative electrode active material (B). The negative electrode has a negative electrode base material and a negative electrode active material layer arranged directly on the negative electrode base material or via an intermediate layer.
負極基材は、導電性を有する。「導電性」を有するとは、ＪＩＳ−Ｈ−０５０５（１９７５年）に準拠して測定される体積抵抗率が１０７Ω・ｃｍ以下であることを意味し、「非導電性」とは、上記体積抵抗率が１０７Ω・ｃｍ超であることを意味する。負極基材の材質としては、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼、アルミニウム等の金属又はこれらの合金が用いられる。これらの中でも銅又は銅合金が好ましい。負極基材としては、箔、蒸着膜等が挙げられ、コストの観点から箔が好ましい。したがって、負極基材としては銅箔又は銅合金箔が好ましい。銅箔の例としては、圧延銅箔、電解銅箔等が挙げられる。 The negative electrode base material has conductivity. The A has a "conductive" means that the volume resistivity is measured according to JIS-H-0505 (1975 years) is not more than 10 7 Ω · cm, "non-conductive", means that the volume resistivity is 10 7 Ω · cm greater. As the material of the negative electrode base material, metals such as copper, nickel, stainless steel, nickel-plated steel, and aluminum, or alloys thereof are used. Among these, copper or a copper alloy is preferable. Examples of the negative electrode base material include foils and vapor-deposited films, and foils are preferable from the viewpoint of cost. Therefore, a copper foil or a copper alloy foil is preferable as the negative electrode base material. Examples of the copper foil include rolled copper foil, electrolytic copper foil and the like.
負極基材の平均厚さは、２μｍ以上３５μｍ以下が好ましく、３μｍ以上３０μｍ以下がより好ましく、４μｍ以上２５μｍ以下がさらに好ましく、５μｍ以上２０μｍ以下が特に好ましい。負極基材の平均厚さを上記の範囲とすることで、負極基材の強度を高めつつ、蓄電素子の体積当たりのエネルギー密度を高めることができる。「平均厚さ」とは、所定の面積の基材を打ち抜いた際の打ち抜き質量を、基材の真密度及び打ち抜き面積で除した値をいう。他の部材等に対して「平均厚さ」を用いる場合にも同様に定義される。 The average thickness of the negative electrode base material is preferably 2 μm or more and 35 μm or less, more preferably 3 μm or more and 30 μm or less, further preferably 4 μm or more and 25 μm or less, and particularly preferably 5 μm or more and 20 μm or less. By setting the average thickness of the negative electrode base material in the above range, it is possible to increase the strength of the negative electrode base material and the energy density per volume of the power storage element. The "average thickness" means a value obtained by dividing the punching mass when punching a base material having a predetermined area by the true density of the base material and the punching area. The same definition applies when the "average thickness" is used for other members and the like.
中間層は、負極基材と負極活物質層との間に配される層である。中間層は、炭素粒子等の導電性を有する粒子を含むことで負極基材と負極活物質層との接触抵抗を低減する。中間層の構成は特に限定されず、例えば、樹脂バインダ及び導電性を有する粒子を含む。 The intermediate layer is a layer arranged between the negative electrode base material and the negative electrode active material layer. The intermediate layer contains conductive particles such as carbon particles to reduce the contact resistance between the negative electrode base material and the negative electrode active material layer. The composition of the intermediate layer is not particularly limited, and includes, for example, a resin binder and conductive particles.
負極活物質層は、負極活物質を含む。負極活物質層は、必要に応じて、導電剤、バインダ、増粘剤、フィラー等の任意成分を含む。 The negative electrode active material layer contains a negative electrode active material. The negative electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, and a filler, if necessary.
負極活物質は、上述した負極活物質（Ａ）又は負極活物質（Ｂ）を含む。負極活物質は、さらにその他の負極活物質を含んでいてもよい。その他の負極活物質としては、公知の負極活物質の中から適宜選択できる。リチウムイオン二次電池用の負極活物質としては、通常、リチウムイオンを吸蔵及び放出することができる材料が用いられる。その他の負極活物質としては、例えば、金属Ｌｉ；Ｓｉ、Ｓｎ等の金属又は半金属；Ｓｉ酸化物、Ｔｉ酸化物、Ｓｎ酸化物等の金属酸化物又は半金属酸化物；Ｌｉ４Ｔｉ５Ｏ１２、ＬｉＴｉＯ２、ＴｉＮｂ２Ｏ７等のチタン含有酸化物；ポリリン酸化合物；炭化ケイ素；負極活物質（Ａ）又は負極活物質（Ｂ）以外の従来公知の炭素材料（黒鉛、非黒鉛質炭素等）等が挙げられる。 The negative electrode active material includes the negative electrode active material (A) or the negative electrode active material (B) described above. The negative electrode active material may further contain other negative electrode active materials. As the other negative electrode active material, a known negative electrode active material can be appropriately selected. As the negative electrode active material for a lithium ion secondary battery, a material capable of occluding and releasing lithium ions is usually used. Other negative electrode active materials include, for example, metal Li; metal or semi-metal such as Si, Sn; metal oxide or semi-metal oxide such as Si oxide, Ti oxide, Sn oxide; Li 4 Ti 5 O. Titanium-containing oxides such as 12 , LiTIO 2, TiNb 2 O 7 ; polyphosphate compounds; silicon carbide; conventionally known carbon materials (graphite, non-graphitic carbon) other than the negative electrode active material (A) or the negative electrode active material (B). Etc.) etc.
負極活物質層中の全ての負極活物質に対する負極活物質（Ａ）又は負極活物質（Ｂ）の含有量は、８０質量％以上が好ましく、９０質量％以上がより好ましく、９９質量％以上がさらに好ましく、実質的に１００質量％であってよい。このように、負極活物質として負極活物質（Ａ）又は負極活物質（Ｂ）を主に用いることにより、放電容量がより大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い負極となり得る。 The content of the negative electrode active material (A) or the negative electrode active material (B) with respect to all the negative electrode active materials in the negative electrode active material layer is preferably 80% by mass or more, more preferably 90% by mass or more, and 99% by mass or more. More preferably, it may be substantially 100% by mass. As described above, by mainly using the negative electrode active material (A) or the negative electrode active material (B) as the negative electrode active material, the discharge capacity is larger and 1.2 V vs. It can be a negative electrode having a high discharge capacity ratio in the potential range of Li / Li + or less.
負極活物質層における全ての負極活物質の含有量は、６０質量％以上９９質量％以下が好ましく、７０質量％以上９５質量％以下がより好ましい。負極活物質の含有量を上記の範囲とすることで、負極活物質層の高エネルギー密度化と製造性を両立できる。同様の理由等から、負極活物質層における負極活物質（Ａ）又は負極活物質（Ｂ）の含有量は、６０質量％以上９９質量％以下が好ましく、７０質量％以上９５質量％以下がより好ましい。 The content of all the negative electrode active materials in the negative electrode active material layer is preferably 60% by mass or more and 99% by mass or less, and more preferably 70% by mass or more and 95% by mass or less. By setting the content of the negative electrode active material within the above range, it is possible to achieve both high energy density and manufacturability of the negative electrode active material layer. For the same reason, the content of the negative electrode active material (A) or the negative electrode active material (B) in the negative electrode active material layer is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less. preferable.
導電剤は、導電性を有する材料であれば特に限定されない。このような導電剤としては、例えば、炭素質材料、金属、導電性セラミックス等が挙げられる。炭素質材料としては、黒鉛化炭素、非黒鉛化炭素、グラフェン系炭素等が挙げられる。非黒鉛化炭素としては、カーボンナノファイバー、ピッチ系炭素繊維、カーボンブラック等が挙げられる。カーボンブラックとしては、ファーネスブラック、アセチレンブラック、ケッチェンブラック等が挙げられる。グラフェン系炭素としては、グラフェン、カーボンナノチューブ（ＣＮＴ）、フラーレン等が挙げられる。導電剤の形状としては、粉状、繊維状等が挙げられる。導電剤としては、これらの材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。また、これらの材料を複合化して用いてもよい。例えば、カーボンブラックとＣＮＴとを複合化した材料を用いてもよい。これらの中でも、電子伝導性及び塗工性の観点よりカーボンブラックが好ましく、中でもアセチレンブラックが好ましい。 The conductive agent is not particularly limited as long as it is a conductive material. Examples of such a conductive agent include carbonaceous materials, metals, conductive ceramics and the like. Examples of the carbonaceous material include graphitized carbon, non-graphitized carbon, graphene-based carbon and the like. Examples of non-graphitized carbon include carbon nanofibers, pitch-based carbon fibers, and carbon black. Examples of carbon black include furnace black, acetylene black, and ketjen black. Examples of graphene-based carbon include graphene, carbon nanotubes (CNT), and fullerenes. Examples of the shape of the conductive agent include powder and fibrous. As the conductive agent, one of these materials may be used alone, or two or more of these materials may be mixed and used. Further, these materials may be used in combination. For example, a material in which carbon black and CNT are composited may be used. Among these, carbon black is preferable from the viewpoint of electron conductivity and coatability, and acetylene black is particularly preferable.
負極活物質層における導電剤の含有量は、０．１質量％以上１０質量％以下が好ましい。導電剤の含有量を上記の範囲とすることで、蓄電素子のエネルギー密度を高めることができる。本発明の一態様においては、負極活物質層は導電剤を含まないことが好ましい場合もある。 The content of the conductive agent in the negative electrode active material layer is preferably 0.1% by mass or more and 10% by mass or less. By setting the content of the conductive agent in the above range, the energy density of the power storage element can be increased. In one aspect of the present invention, it may be preferable that the negative electrode active material layer does not contain a conductive agent.
バインダとしては、例えば、フッ素樹脂（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）等）、ポリエチレン、ポリプロピレン、ポリアクリル、ポリイミド等の熱可塑性樹脂；エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のエラストマー；多糖類高分子等が挙げられる。 Examples of the binder include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyacrylic, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfone. Elastomers such as chemicalized EPDM, styrene butadiene rubber (SBR), fluororubber; and thermoplastic polymers can be mentioned.
負極活物質層におけるバインダの含有量は、１質量％以上４０質量％以下が好ましく、３質量％以上３０質量％以下がより好ましい。バインダの含有量を上記の範囲とすることで、活物質を安定して保持することができる。 The binder content in the negative electrode active material layer is preferably 1% by mass or more and 40% by mass or less, and more preferably 3% by mass or more and 30% by mass or less. By setting the binder content within the above range, the active material can be stably retained.
増粘剤としては、例えば、カルボキシメチルセルロース（ＣＭＣ）、メチルセルロース等の多糖類高分子が挙げられる。増粘剤がリチウム等と反応する官能基を有する場合、予めメチル化等によりこの官能基を失活させてもよい。 Examples of the thickener include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose. When the thickener has a functional group that reacts with lithium or the like, this functional group may be deactivated in advance by methylation or the like.
フィラーは、特に限定されない。フィラーとしては、ポリプロピレン、ポリエチレン等のポリオレフィン、二酸化ケイ素、酸化アルミニウム、二酸化チタン、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の無機酸化物、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物、炭酸カルシウム等の炭酸塩、フッ化カルシウム、フッ化バリウム、硫酸バリウム等の難溶性のイオン結晶、窒化アルミニウム、窒化ケイ素等の窒化物、タルク、モンモリロナイト、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、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。本発明の一態様においては、負極活物質層はフィラーを含まないことが好ましい場合もある。 The filler is not particularly limited. Fillers include polyolefins such as polypropylene and polyethylene, silicon dioxide, aluminum oxide, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, inorganic oxides such as aluminosilicate, magnesium hydroxide, calcium hydroxide, and water. Hydroxides such as aluminum oxide, carbonates such as calcium carbonate, sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, zeolite , Apatite, kaolin, mulite, spinel, olivine, sericite, bentonite, mica and other mineral resource-derived substances, or man-made products thereof. In one aspect of the present invention, it may be preferable that the negative electrode active material layer does not contain a filler.
負極活物質層は、Ｂ、Ｎ、Ｐ、Ｆ、Ｃｌ、Ｂｒ、Ｉ等の典型非金属元素、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｎ、Ｓｒ、Ｂａ等の典型金属元素、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｚｒ、Ｔａ、Ｈｆ、Ｎｂ、Ｗ等の遷移金属元素を負極活物質、導電剤、バインダ、増粘剤、フィラー以外の成分として含有してもよい。 The negative electrode active material layer includes typical non-metal elements such as B, N, P, F, Cl, Br, I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba and the like. Typical metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Ta, Hf, Nb, W, etc. It may be contained as a component other than the viscous agent and the filler.
＜負極の製造方法＞
当該負極の製造は、例えば、負極基材に直接又は中間層を介して負極活物質層を積層することにより得ることができる。上記中間層は、負極基材に、中間層形成材料を塗工することにより得ることができる。
<Manufacturing method of negative electrode>
The negative electrode can be manufactured, for example, by laminating the negative electrode active material layer directly on the negative electrode base material or via an intermediate layer. The intermediate layer can be obtained by applying an intermediate layer forming material to the negative electrode base material.
上記負極活物質層は、負極活物質層形成用材料（負極合剤ペースト）の塗工により形成することができる。上記負極活物質層形成用材料は、負極活物質（Ａ）又は負極活物質（Ｂ）、その他の負極活物質層の各成分、及び分散媒を含む。上記分散媒としては、水やＮ−メチルピロリドン（ＮＭＰ）等の有機溶媒を適宜選択して用いればよい。負極活物質層形成用材料の塗工は公知の方法により行うことができる。通常、塗工後、塗膜を乾燥させて、分散媒を揮発させる。その後、塗膜を厚さ方向にプレスすることが好ましい。 The negative electrode active material layer can be formed by coating a material for forming the negative electrode active material layer (negative electrode mixture paste). The material for forming the negative electrode active material layer includes the negative electrode active material (A) or the negative electrode active material (B), other components of the negative electrode active material layer, and a dispersion medium. As the dispersion medium, water or an organic solvent such as N-methylpyrrolidone (NMP) may be appropriately selected and used. The coating of the material for forming the negative electrode active material layer can be performed by a known method. Usually, after coating, the coating film is dried to volatilize the dispersion medium. After that, it is preferable to press the coating film in the thickness direction.
＜非水電解質蓄電素子＞
本発明の一実施形態に係る蓄電素子は、正極と、負極と、非水電解質とを備える。正極及び負極は、通常、セパレータを介して積層又は巻回された電極体を形成する。この電極体は容器に収納され、この容器内に非水電解質が充填される。非水電解質は、正極と負極との間に介在する。蓄電素子の一例として、非水電解質二次電池（以下、単に「二次電池」ともいう。）について説明する。
<Non-aqueous electrolyte power storage element>
The power storage element according to an embodiment of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte. The positive electrode and the negative electrode usually form an electrode body laminated or wound via a separator. The electrode body is housed in a container, and the container is filled with a non-aqueous electrolyte. The non-aqueous electrolyte is interposed between the positive electrode and the negative electrode. As an example of the power storage element, a non-aqueous electrolyte secondary battery (hereinafter, also simply referred to as “secondary battery”) will be described.
（正極）
正極は、正極基材と、当該正極基材に直接又は中間層を介して配される正極活物質層とを有する。中間層の構成は特に限定されず、例えば上記負極で例示した構成から選択することができる。
(Positive electrode)
The positive electrode has a positive electrode base material and a positive electrode active material layer arranged directly on the positive electrode base material or via an intermediate layer. The configuration of the intermediate layer is not particularly limited, and can be selected from, for example, the configurations exemplified by the negative electrode.
正極基材は、導電性を有する。正極基材の材質としては、アルミニウム、チタン、タンタル、ステンレス鋼等の金属又はこれらの合金が用いられる。これらの中でも、耐電位性、導電性の高さ、及びコストの観点からアルミニウム又はアルミニウム合金が好ましい。正極基材としては、箔、蒸着膜等が挙げられ、コストの観点から箔が好ましい。したがって、正極基材としてはアルミニウム箔又はアルミニウム合金箔が好ましい。アルミニウム又はアルミニウム合金としては、ＪＩＳ−Ｈ−４０００（２０１４年）に規定されるＡ１０８５、Ａ３００３等が例示できる。 The positive electrode base material has conductivity. As the material of the positive electrode base material, metals such as aluminum, titanium, tantalum, and stainless steel, or alloys thereof are used. Among these, aluminum or an aluminum alloy is preferable from the viewpoint of potential resistance, high conductivity, and cost. Examples of the positive electrode base material include foils and vapor-deposited films, and foils are preferable from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode base material. Examples of aluminum or aluminum alloy include A1085 and A3003 specified in JIS-H-4000 (2014).
正極基材の平均厚さは、３μｍ以上５０μｍ以下が好ましく、５μｍ以上４０μｍ以下がより好ましく、８μｍ以上３０μｍ以下がさらに好ましく、１０μｍ以上２５μｍ以下が特に好ましい。正極基材の平均厚さを上記の範囲とすることで、正極基材の強度を高めつつ、二次電池の体積当たりのエネルギー密度を高めることができる。 The average thickness of the positive electrode base material is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less, further preferably 8 μm or more and 30 μm or less, and particularly preferably 10 μm or more and 25 μm or less. By setting the average thickness of the positive electrode base material within the above range, it is possible to increase the energy density per volume of the secondary battery while increasing the strength of the positive electrode base material.
正極活物質層は、正極活物質を含む。正極活物質層は、必要に応じて、導電剤、バインダ、増粘剤、フィラー等の任意成分を含む。導電剤、バインダ、増粘剤、フィラー等の任意成分は、上記負極で例示した材料から選択できる。 The positive electrode active material layer contains a positive electrode active material. The positive electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, and a filler, if necessary. Optional components such as a conductive agent, a binder, a thickener, and a filler can be selected from the materials exemplified by the negative electrode.
正極活物質としては、公知の正極活物質の中から適宜選択できる。リチウムイオン二次電池用の正極活物質としては、通常、リチウムイオンを吸蔵及び放出することができる材料が用いられる。正極活物質としては、例えば、α−ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物、スピネル型結晶構造を有するリチウム遷移金属酸化物、ポリアニオン化合物、カルコゲン化合物、硫黄等が挙げられる。α−ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物として、例えば、Ｌｉ［ＬｉｘＮｉ１−ｘ］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＣｏ１−ｘ−γ］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＣｏ１−ｘ］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＭｎ１−ｘ−γ］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＮｉγＭｎβＣｏ１−ｘ−γ−β］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β＜１）、Ｌｉ［ＬｉｘＮｉγＣｏβＡｌ１−ｘ−γ−β］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β＜１）等が挙げられる。スピネル型結晶構造を有するリチウム遷移金属酸化物として、ＬｉｘＭｎ２Ｏ４、ＬｉｘＮｉγＭｎ２−γＯ４等が挙げられる。ポリアニオン化合物として、ＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４、ＬｉＮｉＰＯ４、ＬｉＣｏＰＯ４、Ｌｉ３Ｖ２（ＰＯ４）３、Ｌｉ２ＭｎＳｉＯ４、Ｌｉ２ＣｏＰＯ４Ｆ等が挙げられる。カルコゲン化合物として、二硫化チタン、二硫化モリブデン、二酸化モリブデン等が挙げられる。これらの材料中の原子又はポリアニオンは、他の元素からなる原子又はアニオン種で一部が置換されていてもよい。これらの材料は表面が他の材料で被覆されていてもよい。正極活物質層においては、これら材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The positive electrode active material can be appropriately selected from known positive electrode active materials. As the positive electrode active material for a lithium ion secondary battery, a material capable of occluding and releasing lithium ions is usually used. Examples of the positive electrode active material include a lithium transition metal composite oxide having an α-NaFeO type 2 crystal structure, a lithium transition metal oxide having a spinel type crystal structure, a polyanion compound, a chalcogen compound, sulfur and the like. Examples of the lithium transition metal composite oxide having an α-NaFeO type 2 crystal structure include Li [Li x Ni 1-x ] O 2 (0 ≦ x <0.5) and Li [Li x Ni γ Co 1-x. −γ ] O 2 (0 ≦ x <0.5, 0 <γ <1), Li [Li x Co 1-x ] O 2 (0 ≦ x <0.5), Li [Li x Ni γ Mn 1) -x-γ] O 2 (0 ≦ x <0.5,0 <γ <1), Li [Li x Ni γ Mn β Co 1-x-γ-β] O 2 (0 ≦ x <0.5 , 0 <γ, 0 <β, 0.5 <γ + β <1), Li [Li x Ni γ Co β Al 1-x-γ-β ] O 2 (0 ≦ x <0.5, 0 <γ, Examples thereof include 0 <β, 0.5 <γ + β <1). Examples of the lithium transition metal oxide having a spinel-type crystal structure include Li x Mn 2 O 4 , Li x Ni γ Mn 2-γ O 4, and the like. Examples of the polyanion compound include LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , Li 2 CoPO 4 F and the like. Examples of the chalcogen compound include titanium disulfide, molybdenum disulfide, molybdenum dioxide and the like. The atoms or polyanions in these materials may be partially substituted with atoms or anion species consisting of other elements. The surface of these materials may be coated with other materials. In the positive electrode active material layer, one of these materials may be used alone, or two or more of these materials may be mixed and used.
正極活物質は、通常、粒子（粉体）である。正極活物質の平均粒径は、例えば、０．１μｍ以上２０μｍ以下とすることが好ましい。正極活物質の平均粒径を上記下限以上とすることで、正極活物質の製造又は取り扱いが容易になる。正極活物質の平均粒径を上記上限以下とすることで、正極活物質層の電子伝導性が向上する。なお、正極活物質と他の材料との複合体を用いる場合、該複合体の平均粒径を正極活物質の平均粒径とする。 The positive electrode active material is usually particles (powder). The average particle size of the positive electrode active material is preferably 0.1 μm or more and 20 μm or less, for example. By setting the average particle size of the positive electrode active material to the above lower limit or more, the production or handling of the positive electrode active material becomes easy. By setting the average particle size of the positive electrode active material to the above upper limit or less, the electron conductivity of the positive electrode active material layer is improved. When a composite of a positive electrode active material and another material is used, the average particle size of the complex is taken as the average particle size of the positive electrode active material.
粉体を所定の粒径で得るためには粉砕機や分級機等が用いられる。粉砕方法及び粉級方法は、例えば、上記負極活物質（Ａ）で例示した方法から選択できる。 A crusher, a classifier, or the like is used to obtain a powder having a predetermined particle size. The pulverization method and the powder grade method can be selected from, for example, the methods exemplified in the negative electrode active material (A).
正極活物質層における正極活物質の含有量は、５０質量％以上９９質量％以下が好ましく、７０質量％以上９８質量％以下がより好ましく、８０質量％以上９５質量％以下がさらに好ましい。正極活物質の含有量を上記の範囲とすることで、正極活物質層の高エネルギー密度化と製造性を両立できる。 The content of the positive electrode active material in the positive electrode active material layer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and further preferably 80% by mass or more and 95% by mass or less. By setting the content of the positive electrode active material within the above range, it is possible to achieve both high energy density and manufacturability of the positive electrode active material layer.
正極活物質層は、Ｂ、Ｎ、Ｐ、Ｆ、Ｃｌ、Ｂｒ、Ｉ等の典型非金属元素、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｎ、Ｓｒ、Ｂａ等の典型金属元素、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｚｒ、Ｎｂ、Ｗ等の遷移金属元素を正極活物質、導電剤、バインダ、増粘剤、フィラー以外の成分として含有してもよい。 The positive electrode active material layer includes typical non-metal elements such as B, N, P, F, Cl, Br, I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba and the like. Typical metal elements of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, W and other transition metal elements are used as positive electrode active materials, conductive agents, binders, thickeners, fillers. It may be contained as a component other than.
（負極）
当該二次電池に備わる負極は、上述した本発明の一実施形態に係る負極である。
(Negative electrode)
The negative electrode provided in the secondary battery is the negative electrode according to the above-described embodiment of the present invention.
（セパレータ）
セパレータは、公知のセパレータの中から適宜選択できる。セパレータとして、例えば、基材層のみからなるセパレータ、基材層の一方の面又は双方の面に耐熱粒子とバインダとを含む耐熱層が形成されたセパレータ等を使用することができる。セパレータの基材層の材質としては、例えば、織布、不織布、多孔質樹脂フィルム等が挙げられる。これらの材質の中でも、強度の観点から多孔質樹脂フィルムが好ましく、非水電解質の保液性の観点から不織布が好ましい。セパレータの基材層の材料としては、シャットダウン機能の観点から例えばポリエチレン、ポリプロピレン等のポリオレフィンが好ましく、耐酸化分解性の観点から例えばポリイミドやアラミド等が好ましい。セパレータの基材層として、これらの樹脂を複合した材料を用いてもよい。
(Separator)
The separator can be appropriately selected from known separators. As the separator, for example, a separator composed of only a base material layer, a separator in which a heat-resistant layer containing heat-resistant particles and a binder is formed on one surface or both surfaces of the base material layer can be used. Examples of the material of the base material layer of the separator include woven fabrics, non-woven fabrics, and porous resin films. Among these materials, a porous resin film is preferable from the viewpoint of strength, and a non-woven fabric is preferable from the viewpoint of liquid retention of a non-aqueous electrolyte. As the material of the base material layer of the separator, polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of shutdown function, and polyimide and aramid are preferable from the viewpoint of oxidative decomposition resistance. As the base material layer of the separator, a material in which these resins are composited may be used.
耐熱層に含まれる耐熱粒子は、大気下で５００℃にて質量減少が５％以下であるものが好ましく、大気下で８００℃にて質量減少が５％以下であるものがさらに好ましい。質量減少が所定以下である材料として無機化合物が挙げられる。無機化合物として、例えば、酸化鉄、酸化ケイ素、酸化アルミニウム、酸化チタン、チタン酸バリウム、酸化ジルコニウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の酸化物；水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物；窒化アルミニウム、窒化ケイ素等の窒化物；炭酸カルシウム等の炭酸塩；硫酸バリウム等の硫酸塩；フッ化カルシウム、フッ化バリウム等の難溶性のイオン結晶；シリコン、ダイヤモンド等の共有結合性結晶；タルク、モンモリロナイト、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、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。無機化合物として、これらの物質の単体又は複合体を単独で用いてもよく、２種以上を混合して用いてもよい。これらの無機化合物の中でも、安全性の観点から、酸化ケイ素、酸化アルミニウム、又はアルミノケイ酸塩が好ましい。 The heat-resistant particles contained in the heat-resistant layer preferably have a mass loss of 5% or less at 500 ° C. in the atmosphere, and more preferably 5% or less in mass loss at 800 ° C. in the air. Inorganic compounds can be mentioned as materials whose mass reduction is less than or equal to a predetermined value. Examples of inorganic compounds include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium oxide, barium titanate, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, and aluminosilicate; magnesium hydroxide, water. Hydroxides such as calcium oxide and aluminum hydroxide; nitrides such as aluminum nitride and silicon nitride; carbonates such as calcium carbonate; sulfates such as barium sulfate; sparingly soluble ion crystals such as calcium fluoride and barium fluoride Covalently bonded crystals such as silicon and diamond; talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mulite, spinel, olivine, sericite, bentonite, mica and other mineral resource-derived substances or man-made products thereof. .. As the inorganic compound, a simple substance or a complex of these substances may be used alone, or two or more kinds thereof may be mixed and used. Among these inorganic compounds, silicon oxide, aluminum oxide, or aluminosilicate is preferable from the viewpoint of safety.
セパレータの空孔率は、強度の観点から８０体積％以下が好ましく、放電性能の観点から２０体積％以上が好ましい。ここで、「空孔率」とは、体積基準の値であり、水銀ポロシメータでの測定値を意味する。 The porosity of the separator is preferably 80% by volume or less from the viewpoint of strength, and preferably 20% by volume or more from the viewpoint of discharge performance. Here, the "porosity" is a volume-based value, and means a value measured by a mercury porosity meter.
セパレータとして、ポリマーと非水電解質とで構成されるポリマーゲルを用いてもよい。ポリマーとして、例えば、ポリアクリロニトリル、ポリエチレンオキシド、ポリプロピレンオキシド、ポリメチルメタアクリレート、ポリビニルアセテート、ポリビニルピロリドン、ポリフッ化ビニリデン等が挙げられる。ポリマーゲルを用いると、漏液を抑制する効果がある。セパレータとして、上述したような多孔質樹脂フィルム又は不織布等とポリマーゲルを併用してもよい。 As the separator, a polymer gel composed of a polymer and a non-aqueous electrolyte may be used. Examples of the polymer include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polymethylmethacrylate, polyvinylacetate, polyvinylpyrrolidone, polyvinylidene fluoride and the like. The use of polymer gel has the effect of suppressing liquid leakage. As the separator, a polymer gel may be used in combination with the above-mentioned porous resin film or non-woven fabric.
（非水電解質）
非水電解質としては、公知の非水電解質の中から適宜選択できる。非水電解質には、非水電解液を用いることができる。非水電解液は、非水溶媒と、この非水溶媒に溶解されている電解質塩とを含む。
(Non-aqueous electrolyte)
The non-aqueous electrolyte can be appropriately selected from known non-aqueous electrolytes. As the non-aqueous electrolyte, a non-aqueous electrolyte solution can be used. The non-aqueous electrolyte solution contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
非水溶媒としては、公知の非水溶媒の中から適宜選択できる。非水溶媒としては、環状カーボネート、鎖状カーボネート、カルボン酸エステル、リン酸エステル、スルホン酸エステル、エーテル、アミド、ニトリル等が挙げられる。非水溶媒として、これらの化合物に含まれる水素原子の一部がハロゲンに置換されたものを用いてもよい。 The non-aqueous solvent can be appropriately selected from known non-aqueous solvents. Examples of the non-aqueous solvent include cyclic carbonate, chain carbonate, carboxylic acid ester, phosphoric acid ester, sulfonic acid ester, ether, amide, nitrile and the like. As the non-aqueous solvent, those in which some of the hydrogen atoms contained in these compounds are replaced with halogen may be used.
環状カーボネートとしては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）、クロロエチレンカーボネート、フルオロエチレンカーボネート（ＦＥＣ）、ジフルオロエチレンカーボネート（ＤＦＥＣ）、スチレンカーボネート、１−フェニルビニレンカーボネート、１，２−ジフェニルビニレンカーボネート等が挙げられる。これらの中でもＥＣが好ましい。 Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinylethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), and difluoroethylene carbonate. (DFEC), styrene carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate and the like can be mentioned. Of these, EC is preferable.
鎖状カーボネートとしては、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）、ジフェニルカーボネート、トリフルオロエチルメチルカーボネート、ビス（トリフルオロエチル）カーボネート等が挙げられる。これらの中でもＤＭＣ及びＥＭＣが好ましい。 Examples of the chain carbonate include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diphenyl carbonate, trifluoroethyl methyl carbonate, and bis (trifluoroethyl) carbonate. Of these, DMC and EMC are preferable.
非水溶媒として、環状カーボネート及び鎖状カーボネートの少なくとも一方を用いることが好ましく、環状カーボネートと鎖状カーボネートとを併用することがより好ましい。環状カーボネートを用いることで、電解質塩の解離を促進して非水電解液のイオン伝導度を向上させることができる。鎖状カーボネートを用いることで、非水電解液の粘度を低く抑えることができる。環状カーボネートと鎖状カーボネートとを併用する場合、環状カーボネートと鎖状カーボネートとの体積比率（環状カーボネート：鎖状カーボネート）としては、例えば、５：９５から５０：５０の範囲とすることが好ましい。 As the non-aqueous solvent, at least one of the cyclic carbonate and the chain carbonate is preferably used, and it is more preferable to use the cyclic carbonate and the chain carbonate in combination. By using the cyclic carbonate, the dissociation of the electrolyte salt can be promoted and the ionic conductivity of the non-aqueous electrolyte solution can be improved. By using the chain carbonate, the viscosity of the non-aqueous electrolytic solution can be kept low. When the cyclic carbonate and the chain carbonate are used in combination, the volume ratio of the cyclic carbonate to the chain carbonate (cyclic carbonate: chain carbonate) is preferably in the range of, for example, 5:95 to 50:50.
電解質塩としては、公知の電解質塩から適宜選択できる。電解質塩としては、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、オニウム塩等が挙げられる。これらの中でもリチウム塩が好ましい。 The electrolyte salt can be appropriately selected from known electrolyte salts. Examples of the electrolyte salt include lithium salt, sodium salt, potassium salt, magnesium salt, onium salt and the like. Of these, lithium salts are preferred.
リチウム塩としては、ＬｉＰＦ６、ＬｉＰＯ２Ｆ２、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＳＯ２Ｆ）２等の無機リチウム塩、ＬｉＳＯ３ＣＦ３、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２、ＬｉＮ（ＳＯ２ＣＦ３）（ＳＯ２Ｃ４Ｆ９）、ＬｉＣ（ＳＯ２ＣＦ３）３、ＬｉＣ（ＳＯ２Ｃ２Ｆ５）３等のハロゲン化炭化水素基を有するリチウム塩等が挙げられる。これらの中でも、無機リチウム塩が好ましく、ＬｉＰＦ６がより好ましい。 Examples of the lithium salt include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2). C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiC (SO 2 C 2 F 5 ) 3 and other halogenated hydrocarbon groups Examples thereof include lithium salts having. Among these, an inorganic lithium salt is preferable, and LiPF 6 is more preferable.
非水電解液における電解質塩の含有量は、０．１ｍｏｌ／ｄｍ３以上２．５ｍｏｌ／ｄｍ３以下であると好ましく、０．３ｍｏｌ／ｄｍ３以上２．０ｍｏｌ／ｄｍ３以下であるとより好ましく、０．５ｍｏｌ／ｄｍ３以上１．７ｍｏｌ／ｄｍ３以下であるとさらに好ましく、０．７ｍｏｌ／ｄｍ３以上１．５ｍｏｌ／ｄｍ３以下であると特に好ましい。電解質塩の含有量を上記の範囲とすることで、非水電解液のイオン伝導度を高めることができる。 The content of the electrolyte salt in the nonaqueous electrolytic solution, preferable to be 0.1 mol / dm 3 or more 2.5 mol / dm 3 or less, more preferable to be 0.3 mol / dm 3 or more 2.0 mol / dm 3 or less , more preferable to be 0.5 mol / dm 3 or more 1.7 mol / dm 3 or less, and particularly preferably 0.7 mol / dm 3 or more 1.5 mol / dm 3 or less. By setting the content of the electrolyte salt in the above range, the ionic conductivity of the non-aqueous electrolyte solution can be increased.
非水電解液は、添加剤を含んでもよい。添加剤としては、例えばビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、ｔ−ブチルベンゼン、ｔ−アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物；２−フルオロビフェニル、ｏ−シクロヘキシルフルオロベンゼン、ｐ−シクロヘキシルフルオロベンゼン等の上記芳香族化合物の部分ハロゲン化物；２，４−ジフルオロアニソール、２，５−ジフルオロアニソール、２，６−ジフルオロアニソール、３，５−ジフルオロアニソール等のハロゲン化アニソール化合物；無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸、無水グルタコン酸、無水イタコン酸、シクロヘキサンジカルボン酸無水物；亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、４，４’−ビス（２，２−ジオキソ−１，３，２−ジオキサチオラン）、４−メチルスルホニルオキシメチル−２，２−ジオキソ−１，３，２−ジオキサチオラン、チオアニソール、ジフェニルジスルフィド、ジピリジニウムジスルフィド、パーフルオロオクタン、ホウ酸トリストリメチルシリル、リン酸トリストリメチルシリル、チタン酸テトラキストリメチルシリル等が挙げられる。これら添加剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The non-aqueous electrolyte solution may contain additives. Additives include, for example, biphenyls, alkylbiphenyls, terphenyls, partially hydrides of terphenyls, aromatic compounds such as cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ethers, dibenzofurans; 2-fluorobiphenyls, o. Partial halides of the above aromatic compounds such as −cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; Anisole halide compounds; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfite, dimethyl sulfite, ethylene sulfate, Sulfolane, dimethylsulfone, diethylsulfone, dimethylsulfoxide, diethylsulfoxide, tetramethylenesulfoxide, diphenylsulfide, 4,4'-bis (2,2-dioxo-1,3,2-dioxathiolane), 4-methylsulfonyloxymethyl- Examples thereof include 2,2-dioxo-1,3,2-dioxathiolane, thioanisole, diphenyldisulfide, dipyridinium disulfide, perfluorooctane, tristrimethylsilyl borate, tristrimethylsilyl phosphate, tetraxtrimethylsilyl titanate and the like. These additives may be used alone or in combination of two or more.
非水電解液に含まれる添加剤の含有量は、非水電解液全体の質量に対して０．０１質量％以上１０質量％以下が好ましく、０．１質量％以上７質量％以下がより好ましく、０．２質量％以上５質量％以下がさらに好ましく、０．３質量％以上３質量％以下が特に好ましい。添加剤の含有量を上記の範囲とすることで、高温保存後の容量維持性能又は充放電サイクル性能を向上させたり、安全性をより向上させたりすることができる。 The content of the additive contained in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 7% by mass or less with respect to the total mass of the non-aqueous electrolytic solution. , 0.2% by mass or more and 5% by mass or less is more preferable, and 0.3% by mass or more and 3% by mass or less is particularly preferable. By setting the content of the additive in the above range, it is possible to improve the capacity maintenance performance or charge / discharge cycle performance after high-temperature storage, and further improve the safety.
非水電解質には、固体電解質を用いてもよく、非水電解液と固体電解質とを併用してもよい。 As the non-aqueous electrolyte, a solid electrolyte may be used, or a non-aqueous electrolyte solution and a solid electrolyte may be used in combination.
固体電解質としては、リチウム、ナトリウム、カルシウム等のイオン伝導性を有し、常温（例えば１５℃から２５℃）において固体である任意の材料から選択できる。固体電解質としては、例えば、硫化物固体電解質、酸化物固体電解質、及び酸窒化物固体電解質、ポリマー固体電解質等が挙げられる。 The solid electrolyte can be selected from any material having ionic conductivity such as lithium, sodium and calcium and being solid at room temperature (for example, 15 ° C. to 25 ° C.). Examples of the solid electrolyte include sulfide solid electrolytes, oxide solid electrolytes, oxynitride solid electrolytes, polymer solid electrolytes and the like.
硫化物固体電解質としては、リチウムイオン二次電池の場合、例えば、Ｌｉ２Ｓ−Ｐ２Ｓ５、ＬｉＩ−Ｌｉ２Ｓ−Ｐ２Ｓ５、Ｌｉ１０Ｇｅ−Ｐ２Ｓ１２等が挙げられる。 Examples of the lithium ion secondary battery include Li 2 SP 2 S 5 , Li I-Li 2 SP 2 S 5 , Li 10 Ge-P 2 S 12 and the like as the sulfide solid electrolyte.
＜非水電解質蓄電素子の製造方法＞
本発明の一実施形態に係る非水電解質蓄電素子の製造方法は、本発明の一実施形態に係る負極活物質（Ａ）又は負極活物質（Ｂ）を用いて負極を作製することを備える。当該製造方法は、負極活物質として本発明の一実施形態に係る負極活物質（Ａ）又は負極活物質（Ｂ）を用いること以外は、従来公知の方法により行うことができる。本発明の一実施形態に係る非水電解質蓄電素子の製造方法は、具体的には例えば、正極を作製すること、負極を作製すること、非水電解質を調製すること、正極及び負極を、セパレータを介して積層又は巻回することにより交互に重畳された電極体を形成すること、正極及び負極（電極体）を容器に収容すること、並びに非水電解質を容器に注入することを備えていてよい。これらの工程の後、注入口を封止することにより二次電池（蓄電素子）を得ることができる。
<Manufacturing method of non-aqueous electrolyte power storage element>
The method for manufacturing a non-aqueous electrolyte power storage element according to an embodiment of the present invention includes producing a negative electrode using the negative electrode active material (A) or the negative electrode active material (B) according to the embodiment of the present invention. The production method can be carried out by a conventionally known method except that the negative electrode active material (A) or the negative electrode active material (B) according to the embodiment of the present invention is used as the negative electrode active material. Specifically, the method for manufacturing a non-aqueous electrolyte power storage element according to an embodiment of the present invention includes, for example, producing a positive electrode, producing a negative electrode, preparing a non-aqueous electrolyte, and separating the positive electrode and the negative electrode. It is provided to form an electrode body which is alternately superposed by laminating or winding through, accommodating a positive electrode and a negative electrode (electrode body) in a container, and injecting a non-aqueous electrolyte into the container. good. After these steps, a secondary battery (storage element) can be obtained by sealing the injection port.
＜その他の実施形態＞
本発明は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加えてもよい。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成又は周知技術に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。また、ある実施形態の構成に対して周知技術を付加することができる。
<Other Embodiments>
The present invention is not limited to the above embodiment, and various modifications may be made without departing from the gist of the present invention. For example, the configuration of one embodiment can be added to the configuration of another embodiment, and a part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a well-known technique. In addition, some of the configurations of certain embodiments can be deleted. Further, a well-known technique can be added to the configuration of a certain embodiment.
また、上記実施の形態においては、非水電解質蓄電素子が非水電解質二次電池である形態を中心に説明したが、その他の非水電解質蓄電素子であってもよい。その他の非水電解質蓄電素子としては、キャパシタ（電気二重層キャパシタ、リチウムイオンキャパシタ）等が挙げられる。 Further, in the above-described embodiment, the non-aqueous electrolyte storage element is mainly a non-aqueous electrolyte secondary battery, but other non-aqueous electrolyte storage elements may be used. Examples of other non-aqueous electrolyte storage elements include capacitors (electric double layer capacitors, lithium ion capacitors) and the like.
図１に、本発明に係る非水電解質蓄電素子の一実施形態である矩形状の非水電解質蓄電素子１（非水電解質二次電池）の概略図を示す。なお、同図は、容器内部を透視した図としている。図１に示す非水電解質蓄電素子１は、電極体２が容器３に収納されている。電極体２は、正極活物質を備える正極と、負極活物質を備える負極とが、セパレータを介して捲回されることにより形成されている。正極は、正極リード４’を介して正極端子４と電気的に接続され、負極は、負極リード５’を介して負極端子５と電気的に接続されている。また、容器３には、非水電解質が注入されている。
FIG. 1 shows a schematic view of a rectangular non-aqueous electrolyte storage element 1 (non-aqueous electrolyte secondary battery) which is an embodiment of the non-aqueous electrolyte storage element according to the present invention. The figure is a perspective view of the inside of the container. In the non-aqueous electrolyte
本発明に係る非水電解質蓄電素子の構成については特に限定されるものではなく、円筒型電池、角型電池（矩形状の電池）、扁平型電池等が一例として挙げられる。本発明は、上記の非水電解質蓄電素子を複数備える蓄電装置としても実現することができる。蓄電装置の一実施形態を図２に示す。図２において、蓄電装置３０は、複数の蓄電ユニット２０を備えている。それぞれの蓄電ユニット２０は、複数の非水電解質蓄電素子１を備えている。上記蓄電装置３０は、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）等の自動車用電源として搭載することができる。
The configuration of the non-aqueous electrolyte power storage element according to the present invention is not particularly limited, and examples thereof include a cylindrical battery, a square battery (rectangular battery), and a flat battery. The present invention can also be realized as a power storage device including a plurality of the above-mentioned non-aqueous electrolyte power storage elements. An embodiment of the power storage device is shown in FIG. In FIG. 2, the
以下、実施例によって本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［比較例１］
黒鉛Ａ（鱗片状黒鉛、Ｄ５０＝８．８μｍ）を比較例１の負極活物質として準備した。
[Comparative Example 1]
Graphite A (scaly graphite, D50 = 8.8 μm) was prepared as the negative electrode active material of Comparative Example 1.
［実施例１］
出発物質としての黒鉛Ａ（鱗片状黒鉛、Ｄ５０＝８．８μｍ）３ｇを、発煙硝酸（Ｗａｋｏ社製）２５ｃｍ３中に添加し、懸濁液とした。この懸濁液を６０℃に加熱し、マグネチックスターラーにより３００ｒｐｍで撹拌しながらＫＣｌＯ３（Ｗａｋｏ社製）１０ｇを少しずつ加えた。６０℃で３時間反応させた後、水７５０ｃｍ３中に投入して反応を停止させた。懸濁液について、吸引ろ過により液体を分離し、水で洗浄した。その後６０℃で一晩乾燥し、酸化黒鉛を得た。
得られた酸化黒鉛４ｇをアルミナ製るつぼに入れ、これを卓上真空・ガス置換炉（デンケン・ハイデンタル社製「ＫＤＦ７５」）に設置した。次いで、０．６ｄｍ３／ｍｉｎの窒素流中、常圧下、昇温速度１℃／ｍｉｎで常温から１７０℃まで、昇温速度０．１℃／ｍｉｎで１７０から２５０℃まで、昇温速度１℃／ｍｉｎで２５０℃から８００℃まで昇温し、８００℃で５時間保持することにより熱処理を施した。このようにして、炭素材料である実施例１の負極活物質を得た。
[Example 1]
3 g of graphite A (scaly graphite, D50 = 8.8 μm) as a starting material was added to 25 cm 3 of fuming nitric acid (manufactured by Wako) to prepare a suspension. This suspension was heated to 60 ° C., and 10 g of KClO 3 (manufactured by Wako) was added little by little while stirring at 300 rpm with a magnetic stirrer. After reacting at 60 ° C. for 3 hours, the reaction was stopped by pouring into 750 cm 3 of water. For the suspension, the liquid was separated by suction filtration and washed with water. Then, it was dried at 60 degreeC overnight to obtain graphite oxide.
4 g of the obtained graphite oxide was placed in an alumina crucible and placed in a tabletop vacuum / gas replacement furnace (“KDF75” manufactured by Denken Hydental Co., Ltd.). Then, in a nitrogen flow of 0.6 dm 3 / min, under normal pressure, the temperature rise rate was 1 ° C./min from room temperature to 170 ° C., and the temperature rise rate was 0.1 ° C./min from 170 to 250 ° C. The heat treatment was performed by raising the temperature from 250 ° C. to 800 ° C. at ° C./min and holding at 800 ° C. for 5 hours. In this way, the negative electrode active material of Example 1 which is a carbon material was obtained.
［実施例２から９、比較例２］
出発物質、酸化処理の際の発煙硝酸及びＫＣｌＯ３の使用量、並びに熱処理の際の温度を表１に示す通りとしたこと以外は実施例１と同様にして、実施例２から９及び比較例２の各負極活物質を得た。
なお、表１中の「黒鉛Ｂ」は、鱗片状黒鉛（Ｄ５０＝３．５μｍ）である。
[Examples 2 to 9, Comparative Example 2]
Examples 2 to 9 and Comparative Examples are the same as in Example 1 except that the starting material, the amount of fuming nitric acid and KClO 3 used in the oxidation treatment, and the temperature in the heat treatment are as shown in Table 1. Each negative electrode active material of 2 was obtained.
In addition, "graphite B" in Table 1 is scaly graphite (D50 = 3.5 μm).
［実施例１０］
酸化処理の際の発煙硝酸及びＫＣｌＯ３の使用量を表１に示す通りとしたこと以外は実施例１と同様にして、酸化黒鉛を得た。
得られた酸化黒鉛４ｇを水２５０ｃｍ３と共に、ポータブルリアクター（耐圧硝子工業社製「ＴＰＲ−１」）中に入れた。窒素雰囲気に置換後、３００ｒｐｍで撹拌しながら、常温から１８０℃に昇温して１時間保持することにより水熱処理を施した。水熱処理後、吸引ろ過により液体を分離し、水で洗浄した。その後６０℃で一晩乾燥し、酸化黒鉛の水熱処理物を得た。
得られた水熱処理物に対して、実施例１と同様の熱処理を施し、実施例１０の負極活物質を得た。
[Example 10]
Graphite oxide was obtained in the same manner as in Example 1 except that the amounts of fuming nitric acid and KClO 3 used in the oxidation treatment were as shown in Table 1.
4 g of the obtained graphite oxide was placed in a portable reactor (“TPR-1” manufactured by Pressure Resistant Glass Industry Co., Ltd.) together with 250 cm 3 of water. After replacement with a nitrogen atmosphere, hydrothermal treatment was performed by raising the temperature from room temperature to 180 ° C. and holding for 1 hour while stirring at 300 rpm. After hydrothermal treatment, the liquid was separated by suction filtration and washed with water. Then, it was dried overnight at 60 ° C. to obtain a hydrothermally treated product of graphite oxide.
The obtained hydrothermally treated product was subjected to the same heat treatment as in Example 1 to obtain the negative electrode active material of Example 10.
［実施例１１、１２］
酸化処理の際の発煙硝酸及びＫＣｌＯ３の使用量、並びに水熱処理温度を表１に示す通りとしたこと以外は実施例１０と同様にして、実施例１１、１２の各負極活物質を得た。
[Examples 11 and 12]
The negative electrode active materials of Examples 11 and 12 were obtained in the same manner as in Example 10 except that the amounts of fuming nitric acid and KClO 3 used in the oxidation treatment and the hydrothermal treatment temperature were as shown in Table 1. ..
［実施例１３］
酸化処理の際の発煙硝酸及びＫＣｌＯ３の使用量を表１に示す通りとしたこと以外は実施例１と同様にして、酸化黒鉛を得た。
得られた酸化黒鉛４ｇを水１．２ｄｍ３中に入れ、常温で撹拌しながら、水０．１ｄｍ３にヒドラジン一水和物（Ｗａｋｏ社製）０．４ｃｍ３を加えた水溶液を滴下した。滴下終了後に１８時間撹拌することにより、還元処理を施した。還元処理後、吸引ろ過により液体を分離し、水で洗浄した。その後６０℃で一晩乾燥し、酸化黒鉛の還元処理物を得た。
得られた還元処理物に対して、実施例１と同様の熱処理を施し、実施例１３の負極活物質を得た。
[Example 13]
Graphite oxide was obtained in the same manner as in Example 1 except that the amounts of fuming nitric acid and KClO 3 used in the oxidation treatment were as shown in Table 1.
The resulting graphite oxide 4g placed in water 1.2Dm 3, with stirring at room temperature, was added dropwise hydrazine monohydrate in water 0.1Dm 3 aqueous solution was added (Wako Co.) 0.4 cm 3. The reduction treatment was carried out by stirring for 18 hours after the completion of the dropping. After the reduction treatment, the liquid was separated by suction filtration and washed with water. Then, it was dried at 60 ° C. overnight to obtain a reduced graphite oxide product.
The obtained reduction-treated product was subjected to the same heat treatment as in Example 1 to obtain the negative electrode active material of Example 13.
［比較例３］
還元処理の際のヒドラジン一水和物（表１中は「ヒドラジン」と表記）の使用量を表１に示す通りとしたこと以外は実施例１３と同様にして、比較例３の負極活物質を得た。
[Comparative Example 3]
The negative electrode active material of Comparative Example 3 was the same as in Example 13 except that the amount of hydrazine monohydrate used in the reduction treatment (denoted as “hydrazine” in Table 1) was as shown in Table 1. Got
［比較例４］
黒鉛Ａ ３ｇを濃硫酸（ナカライテスク社製、硫酸、９５％以上）１３８ｃｍ３中に入れ、氷水浴中で過マンガン酸カリウム（Ｗａｋｏ社製）１８ｇを加えた。これをマグネチックスターラーにより３００ｒｐｍで撹拌しながら、３５℃で３０分間反応させた。その後、水２７６ｃｍ３中にゆっくりと加えて、さらに９８℃で１５分間反応させた。得られた懸濁液を、水８４０ｃｍ３に過酸化水素水（ナカライテスク社製、３０％）５４ｃｍ３を加えた水溶液中に投入して、酸化反応を停止させた。吸引ろ過により液体を分離し、希塩酸及び水で洗浄した。その後８０℃で乾燥することにより酸化黒鉛を得た。
得られた酸化黒鉛２ｇをアルミナ製るつぼに入れ、これを卓上真空・ガス置換炉（デンケン・ハイデンタル社製「ＫＤＦ７５」）に設置した。次いで、０．６ｄｍ３／ｍｉｎの窒素流中、常圧下、常温から昇温速度１℃／ｍｉｎで３００℃に昇温し３０分間保持することにより熱処理を施した。このようにして、比較例４の負極活物質を得た。
[Comparative Example 4]
Graphite A 3 g of concentrated sulfuric acid was added placed in a (Nacalai Tesque, sulfate, 95%) 138cm 3, in an ice-water bath of potassium permanganate (Wako Co.) 18 g. This was reacted at 35 ° C. for 30 minutes while stirring with a magnetic stirrer at 300 rpm. Then, it was slowly added to 276 cm 3 of water, and the reaction was further carried out at 98 ° C. for 15 minutes. The obtained suspension was put into an aqueous solution prepared by adding 54 cm 3 of hydrogen peroxide solution (manufactured by Nacalai Tesque, Inc.) to 840 cm 3 of water to stop the oxidation reaction. The liquid was separated by suction filtration and washed with dilute hydrochloric acid and water. Then, it was dried at 80 ° C. to obtain graphite oxide.
2 g of the obtained graphite oxide was placed in an alumina crucible and placed in a tabletop vacuum / gas replacement furnace (“KDF75” manufactured by Denken Hydental Co., Ltd.). Next, heat treatment was performed by raising the temperature from room temperature to 300 ° C. at a heating rate of 1 ° C./min under normal pressure in a nitrogen stream of 0.6 dm 3 / min and holding it for 30 minutes. In this way, the negative electrode active material of Comparative Example 4 was obtained.
（測定）
得られた実施例及び比較例の各負極活物質（炭素材料）に対して上記した方法にて、設定温度毎に脱離する酸素の量を測定し、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率（以下、「酸素含有率（Ｔｏｔａｌ）」と示すこともある。）、８００℃超２，５００℃以下の温度で脱離する酸素の含有率（以下、「酸素含有率（＞８００℃）」と示すこともある。）、４００℃以上１，０００℃以下の温度で脱離する酸素の含有率（以下、「酸素含有率（≦１，０００℃）」と示すこともある。）、及び４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比（以下、「酸素含有量比（＞１，０００℃／Ｔｏｔａｌ）」と示すこともある。）を求めた。測定結果を表２に示す。
(measurement)
The amount of oxygen desorbed at each set temperature was measured for each of the obtained negative electrode active materials (carbon materials) of Examples and Comparative Examples by the above-mentioned method, and the temperature was 400 ° C. or higher and 2500 ° C. or lower. The content of oxygen desorbed in (hereinafter, also referred to as "oxygen content (Total)"), the content of oxygen desorbed at a temperature of more than 800 ° C. and 2,500 ° C. (hereinafter, "oxygen"). The content rate (> 800 ° C.) ”), and the oxygen content rate desorbed at a temperature of 400 ° C. or higher and 1,000 ° C. or lower (hereinafter,“ oxygen content rate (≦ 1,000 ° C.) ”. (May be shown), and the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C and 2,500 ° C or less to oxygen desorbed at a temperature of 400 ° C or more and 2,500 ° C or less (hereinafter, "oxygen"). The content ratio (> 1,000 ° C./Total) ”may be indicated.) Was determined. The measurement results are shown in Table 2.
得られた実施例及び比較例の各負極活物質（炭素材料）に対して上記した方法にて、平均格子面間隔ｄ００２、ｄ１１０及び平均結晶子サイズＬａを求めた。測定結果を表２に示す。 At resulting embodiments and methods described above for each negative electrode active material of Comparative Example (carbon material), to obtain an average lattice spacing d 002, d 110 and an average crystallite size L a. The measurement results are shown in Table 2.
（負極の作製）
実施例及び比較例の各負極活物質とＰＶＤＦとを質量比８８：１２（固形物換算）で含有し、ＮＭＰを分散媒とする負極合剤ペーストを調製した。各負極合剤ペーストを銅箔基材に塗布し、上記分散媒を揮発させ、プレスし、実施例１〜１３及び比較例１〜３の各負極（作用極）を得た。また、比較例４の負極活物質とＰＶＤＦとの質量比を７０：３０としたこと以外は同様にして、比較例４の負極（作用極）を得た。
(Preparation of negative electrode)
A negative electrode mixture paste containing NMP as a dispersion medium was prepared by containing each of the negative electrode active materials of Examples and Comparative Examples and PVDF in a mass ratio of 88:12 (in terms of solid matter). Each negative electrode mixture paste was applied to a copper foil base material, the dispersion medium was volatilized, and pressed to obtain each negative electrode (working electrode) of Examples 1 to 13 and Comparative Examples 1 to 3. Further, the negative electrode (working electrode) of Comparative Example 4 was obtained in the same manner except that the mass ratio of the negative electrode active material of Comparative Example 4 to PVDF was 70:30.
（セル（非水電解質蓄電素子）の作製）
得られた上記各負極を用いて、非水電解質蓄電素子であるセルを作製した。対極及び参照極には、金属リチウムを用いた。セパレータにはポリエチレン製の微多孔膜を用いた。非水電解質としては、エチレンカーボネート、エチルメチルカーボネート及びジメチルカーボネートを体積比が６：７：７となるように混合した溶媒に、ＬｉＰＦ６を１ｍｏｌ／ｄｍ３となるように溶解させた電解液を用いた。セパレータを介して、負極と対極（金属リチウム）とを対向させ、各集電端子が外部に露出するようにして、袋状に加工したアルミニウム樹脂複合フィルムの内部に収納し、電解液を注入後、気密封止した。これにより各非水電解質蓄電素子（セル）を得た。
(Manufacturing of cells (non-aqueous electrolyte power storage elements))
Using each of the obtained negative electrodes, a cell which is a non-aqueous electrolyte power storage element was produced. Metallic lithium was used for the counter electrode and the reference electrode. A polyethylene microporous membrane was used as the separator. As the non-aqueous electrolyte, an electrolytic solution prepared by dissolving LiPF 6 at a volume ratio of 1 mol / dm 3 in a solvent obtained by mixing ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate at a volume ratio of 6: 7: 7 is used. Using. The negative electrode and the counter electrode (metallic lithium) are opposed to each other via a separator, and each current collecting terminal is exposed to the outside. , Airtightly sealed. As a result, each non-aqueous electrolyte power storage element (cell) was obtained.
（充放電試験）
上記セルを用い、２５℃の環境下、以下の条件にて充放電試験を行った。充電は定電流定電圧（ＣＣＣＶ）充電とし、充電下限電位は０．０１Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）とした。充電終止条件は、充電下限電位に到達してから１２時間を経過した時点とした。放電は定電流（ＣＣ）放電とし、放電終止電位は２．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）とした。充電及び放電の定電流値は、負極が含有する負極活物質の質量に対して５０ｍＡ／ｇとした。また、充電後に１０分間の休止時間を設定した。上記充放電試験における放電容量、及び１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比（０．０１から２．０Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量に対する、０．０１から１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量の比）を表２に示す。
(Charge / discharge test)
Using the above cell, a charge / discharge test was conducted under the following conditions in an environment of 25 ° C. Charging was constant current constant voltage (CCCV) charging, and the lower limit potential of charging was 0.01 V (vs. Li / Li +). The charging termination condition was set to the time when 12 hours had passed after reaching the lower limit charging potential. The discharge was a constant current (CC) discharge, and the discharge end potential was 2.0 V (vs. Li / Li +). The constant current value for charging and discharging was set to 50 mA / g with respect to the mass of the negative electrode active material contained in the negative electrode. In addition, a rest time of 10 minutes was set after charging. The discharge capacity in the above charge / discharge test, and 1.2 V vs. From the discharge capacity ratio (0.01 at Li / Li + less potential range to the discharge capacity at 2.0V vs.Li/Li + potential range from 0.01 1.2V vs.Li/Li + of The ratio of discharge capacities in the potential range) is shown in Table 2.
また、これらの試験結果に基づいた、負極活物質の８００℃超２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（＞８００℃））と放電容量との関係を示すグラフを図３に、負極活物質の平均格子面間隔ｄ１１０と０．０１から１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量比との関係を示すグラフを図４に、負極活物質の４００℃以上２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（Ｔｏｔａｌ））と放電容量との関係を示すグラフを図５に、負極活物質の４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比（酸素含有量比（＞１，０００℃／Ｔｏｔａｌ））と０．０１から１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量比との関係を示すグラフを図６に示す。 Further, based on these test results, the relationship between the oxygen content (oxygen content (> 800 ° C.)) of the negative electrode active material desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less and the discharge capacity is shown. The graph is shown in FIG. 3, where the average lattice spacing of the negative electrode active material is d 110 and 0.01 to 1.2 V vs. A graph showing the relationship with the discharge capacity ratio in the Li / Li + potential range is shown in FIG. 4, which shows the oxygen content of the negative electrode active material desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower (oxygen content rate (oxygen content rate). A graph showing the relationship between Total)) and the discharge capacity is shown in FIG. 5 at a temperature of more than 1,000 ° C and 2,500 ° C or less with respect to oxygen desorbed from the negative electrode active material at a temperature of 400 ° C or more and 2,500 ° C or less. Desorbed oxygen content ratio (oxygen content ratio (> 1,000 ° C / Total)) and 0.01 to 1.2 V vs. A graph showing the relationship with the discharge capacity ratio in the potential range of Li / Li + is shown in FIG.
表２及び図３に示されるように、負極活物質の８００℃超２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（＞８００℃））が高いと、放電容量が大きくなる。なお、図３中、他とは異なる傾向を示す比較例４は、製造方法及び物性（酸素含有率（Ｔｏｔａｌ）、（１１０）回折線の有無など）が他とは異なるため同様には比較することができない。また、表２及び図４に示されるように、負極活物質の平均格子面間隔ｄ１１０が大きいと、０．０１から１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量比が高くなる。従って、８００℃超２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（＞８００℃））が４質量％以上であり、平均格子面間隔ｄ１１０が０．１２２６ｎｍ超である実施例１から１３の各負極活物質は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い。 As shown in Table 2 and FIG. 3, when the oxygen content (oxygen content (> 800 ° C.)) of the negative electrode active material desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or lower is high, the discharge capacity becomes high. growing. In FIG. 3, Comparative Example 4 showing a tendency different from the others is compared in the same manner because the production method and physical properties (oxygen content (Total), presence / absence of (110) diffraction line, etc.) are different from the others. Can't. Further, as shown in Table 2 and FIG. 4, when the average lattice spacing d 110 of the negative electrode active material is large, 0.01 to 1.2 V vs. The discharge capacity ratio in the Li / Li + potential range becomes high. Therefore, the oxygen content (oxygen content (> 800 ° C.)) desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is 4% by mass or more, and the average lattice spacing d 110 is more than 0.1226 nm. Each of the negative electrode active materials of Examples 1 to 13 has a large discharge capacity, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is high.
同様に、表２及び図５に示されるように、負極活物質の４００℃以上２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（Ｔｏｔａｌ））が高いと、放電容量が大きくなる。また、表２及び図６に示されるように、負極活物質の４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比（酸素含有量比（＞１，０００℃／Ｔｏｔａｌ））が高いと、０．０１から１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋の電位範囲での放電容量比が高くなる。従って、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率（酸素含有率（Ｔｏｔａｌ））が４質量％以上であり、４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比（酸素含有量比（＞１，０００℃／Ｔｏｔａｌ））が０．４５以上である実施例１から１３の各負極活物質は、放電容量が大きく、１．２Ｖ ｖｓ．Ｌｉ／Ｌｉ＋以下の電位範囲での放電容量比が高い。 Similarly, as shown in Table 2 and FIG. 5, when the oxygen content (oxygen content (Total)) of the negative electrode active material desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is high, the discharge capacity is high. Becomes larger. Further, as shown in Table 2 and FIG. 6, oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less with respect to oxygen desorbed at a temperature of 400 ° C. or higher and 2,500 ° C. or lower of the negative electrode active material. When the content ratio (oxygen content ratio (> 1,000 ° C / Total)) is high, 0.01 to 1.2 V vs. The discharge capacity ratio in the Li / Li + potential range becomes high. Therefore, the oxygen content (oxygen content (Total)) desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is 4% by mass or more, and desorption is performed at a temperature of 400 ° C. or higher and 2500 ° C. or lower. Examples 1 to 13 in which the oxygen content ratio (oxygen content ratio (> 1,000 ° C / Total)) desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or lower with respect to oxygen is 0.45 or more. Each negative electrode active material has a large discharge capacity, 1.2 V vs. The discharge capacity ratio in the potential range of Li / Li + or less is high.
本発明は、パーソナルコンピュータ、通信端末等の電子機器、自動車等の電源として使用される非水電解質蓄電素子等に適用できる。 The present invention can be applied to electronic devices such as personal computers and communication terminals, non-aqueous electrolyte power storage elements used as power sources for automobiles, and the like.
１ 非水電解質蓄電素子
２ 電極体
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
1 Non-aqueous electrolyte
Claims (7)
加熱して脱離する酸素を含有し、８００℃超２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上であり、
平均格子面間隔ｄ１１０が０．１２２６ｎｍ超である非水電解質蓄電素子用の負極活物質。 It is a carbon material
It contains oxygen that is desorbed by heating, and the content of oxygen that is desorbed at a temperature of more than 800 ° C. and 2,500 ° C. or less is 4% by mass or more with respect to the carbon material before heating.
A negative electrode active material for a non-aqueous electrolyte power storage element having an average lattice spacing d 110 of more than 0.1226 nm.
加熱して脱離する酸素を含有し、４００℃以上２，５００℃以下の温度で脱離する酸素の含有率が加熱前の上記炭素材料に対して４質量％以上１３質量％以下であり、
上記４００℃以上２，５００℃以下の温度で脱離する酸素に対する１，０００℃超２，５００℃以下の温度で脱離する酸素の含有量比が０．４５以上である非水電解質蓄電素子用の負極活物質。 It is a carbon material
The content of oxygen that contains oxygen that is desorbed by heating and is desorbed at a temperature of 400 ° C. or higher and 2500 ° C. or lower is 4% by mass or more and 13% by mass or less with respect to the carbon material before heating.
A non-aqueous electrolyte power storage element in which the content ratio of oxygen desorbed at a temperature of more than 1,000 ° C. and 2,500 ° C. or less to oxygen desorbed at a temperature of 400 ° C. or higher and 2,500 ° C. or lower is 0.45 or more. Negative electrode active material for.
A method for manufacturing a non-aqueous electrolyte power storage element, comprising producing a negative electrode using the negative electrode active material according to any one of claims 1 to 4.
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