JP2020013680A - Electrolytic solution - Google Patents
Electrolytic solution Download PDFInfo
- Publication number
- JP2020013680A JP2020013680A JP2018134437A JP2018134437A JP2020013680A JP 2020013680 A JP2020013680 A JP 2020013680A JP 2018134437 A JP2018134437 A JP 2018134437A JP 2018134437 A JP2018134437 A JP 2018134437A JP 2020013680 A JP2020013680 A JP 2020013680A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- negative electrode
- active material
- electrode active
- electrolytic solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 66
- 239000011737 fluorine Substances 0.000 claims abstract description 66
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- 150000002148 esters Chemical class 0.000 claims abstract description 16
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims description 53
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 9
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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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、蓄電装置に用いられる電解液に関するものである。 The present invention relates to an electrolytic solution used for a power storage device.
一般に、二次電池等の蓄電装置は、主な構成要素として、正極、負極及び電解液を備える。そして、負極には、充放電に関与する負極活物質が具備されている。産業界からは蓄電装置の高容量化が求められており、その対応として、各種の技術が検討されている。具体的な高容量化技術の一つに、蓄電装置の負極活物質として、リチウムなどの電荷担体の吸蔵能力に優れるＳｉを含有するＳｉ含有負極活物質を採用することが知られている。 In general, a power storage device such as a secondary battery includes a positive electrode, a negative electrode, and an electrolyte as main components. The negative electrode is provided with a negative electrode active material involved in charge and discharge. The industry has been demanding an increase in the capacity of a power storage device, and various technologies are being studied to meet the demand. As one of specific technologies for increasing the capacity, it has been known to employ a Si-containing negative electrode active material containing Si, which has an excellent ability to occlude charge carriers such as lithium, as a negative electrode active material of a power storage device.
例えば、特許文献１及び特許文献２には、負極活物質がＳｉＯであるリチウムイオン二次電池が記載されている。 For example, Patent Literature 1 and Patent Literature 2 describe a lithium ion secondary battery in which a negative electrode active material is SiO.
特許文献３には、ＣａＳｉ２を酸と反応させてＣａを除去した層状ポリシランを主成分とする層状シリコン化合物を合成し、当該層状シリコン化合物を３００℃以上で加熱して水素を離脱させたシリコン材料を製造したこと、及び、当該シリコン材料を負極活物質として具備するリチウムイオン二次電池が記載されている。 Patent Document 3 discloses a silicon obtained by synthesizing a layered silicon compound containing a layered polysilane whose main component is Ca by removing Ca by reacting CaSi 2 with an acid and heating the layered silicon compound at 300 ° C. or more to release hydrogen. It describes that the material was manufactured, and a lithium ion secondary battery including the silicon material as a negative electrode active material.
蓄電装置に用いられる一般的な電解液は電解質及び非水溶媒を含有する。ここで、電解質としてはＬｉＰＦ６を採用するのが一般的であり、非水溶媒としてはエチルメチルカーボネート、ジメチルカーボネート、ジエチルカーボネートなどの鎖状カーボネートを採用するのが一般的である。実際に、特許文献１〜特許文献３には、電解質としてＬｉＰＦ６を採用し、非水溶媒としてエチルメチルカーボネート、ジメチルカーボネート、ジエチルカーボネートなどの鎖状カーボネートを採用したリチウムイオン二次電池が具体的に記載されている。 A common electrolytic solution used for a power storage device contains an electrolyte and a non-aqueous solvent. Here, LiPF 6 is generally used as the electrolyte, and a chain carbonate such as ethyl methyl carbonate, dimethyl carbonate, or diethyl carbonate is generally used as the non-aqueous solvent. Actually, Patent Literatures 1 to 3 specifically disclose a lithium ion secondary battery that employs LiPF 6 as an electrolyte and a chain carbonate such as ethyl methyl carbonate, dimethyl carbonate, or diethyl carbonate as a nonaqueous solvent. It is described in.
また、非水溶媒の一部として、フルオロエチレンカーボネートやジフルオロエチレンカーボネートなどのフッ素含有環状カーボネートを採用することも知られている。実際に特許文献４には、Ｓｉ含有負極活物質を備える二次電池における電解液の非水溶媒として、フルオロエチレンカーボネートやジフルオロエチレンカーボネートなどのフッ素含有環状カーボネートを用いることで、二次電池の容量維持率が好適化したことが記載されている（表１７を参照。）。 It is also known that a fluorine-containing cyclic carbonate such as fluoroethylene carbonate and difluoroethylene carbonate is used as a part of the non-aqueous solvent. In fact, Patent Document 4 discloses that the capacity of a secondary battery is increased by using a fluorine-containing cyclic carbonate such as fluoroethylene carbonate or difluoroethylene carbonate as a nonaqueous solvent for an electrolyte in a secondary battery including a Si-containing negative electrode active material. It is stated that the retention was optimized (see Table 17).
産業界からは、容量を好適に維持し得る蓄電装置が求められている。
本発明はかかる事情に鑑みて為されたものであり、蓄電装置の容量を好適に維持し得る、フッ素含有環状カーボネートを含有する新たな電解液を提供することを目的とする。
The industry demands a power storage device capable of maintaining a suitable capacity.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a new electrolytic solution containing a fluorine-containing cyclic carbonate, which can appropriately maintain the capacity of a power storage device.
本発明者は、フルオロエチレンカーボネートなどのフッ素含有環状カーボネートを含有する電解液が蓄電装置の容量維持率を好適化する理由を、以下のとおり考察した。 The present inventor considered the reason why the electrolytic solution containing a fluorine-containing cyclic carbonate such as fluoroethylene carbonate optimizes the capacity retention of the power storage device as follows.
フルオロエチレンカーボネートなどのフッ素含有環状カーボネートは、蓄電装置の充電時に負極界面で還元分解して、負極の表面にＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｐｈａｓｅ）被膜を形成する。そして、ＳＥＩ被膜の存在に因り、電解液や負極活物質の劣化が抑制されるため、蓄電装置の容量は好適に維持される。ここで、好適なＳＥＩには、ＬｉＦが形成されていると考えられる。 Fluorine-containing cyclic carbonate such as fluoroethylene carbonate undergoes reductive decomposition at the negative electrode interface during charging of the power storage device, and forms a SEI (Solid Electrolyte Interphase) film on the surface of the negative electrode. Then, the deterioration of the electrolytic solution and the negative electrode active material is suppressed due to the presence of the SEI film, so that the capacity of the power storage device is preferably maintained. Here, it is considered that LiF is formed in the suitable SEI.
ＬｉＦの形成には、Ｌｉ源とＦ源が不可欠である。Ｆ源はフッ素含有環状カーボネートであり、Ｌｉ源は電解液に溶解されている電解質であるリチウム塩である。 For the formation of LiF, a Li source and an F source are indispensable. The F source is a fluorine-containing cyclic carbonate, and the Li source is a lithium salt which is an electrolyte dissolved in an electrolyte.
本発明者は、ＬｉＦを好適に形成させるためには、リチウムとフッ素含有環状カーボネートの錯体が、負極界面で還元分解するのが好ましいと考えた。ここで、ＬｉＦ形成の点のみを考慮すると、電解液に含有される非水溶媒としてはフッ素含有環状カーボネートのみを採用すれば足りるが、多量のフッ素含有環状カーボネートを含有する非水溶媒を電解液に採用した場合には、蓄電装置の性能低下が生じることがある。そのため、フッ素含有環状カーボネートと共に、他の非水溶媒を併用するのが好ましいといえる。
そうすると、電解液中では、リチウムに対する、フッ素含有環状カーボネートと他の非水溶媒との配位競争（配位子交換反応）が生じているといえる。
The present inventor has considered that in order to suitably form LiF, it is preferable that a complex of lithium and a fluorine-containing cyclic carbonate is reductively decomposed at the negative electrode interface. Here, considering only the point of LiF formation, it is sufficient to employ only the fluorine-containing cyclic carbonate as the non-aqueous solvent contained in the electrolytic solution, but the non-aqueous solvent containing a large amount of the fluorine-containing cyclic carbonate is used as the electrolytic solution. In some cases, the performance of the power storage device may be reduced. Therefore, it can be said that it is preferable to use another non-aqueous solvent together with the fluorine-containing cyclic carbonate.
Then, it can be said that coordination competition (ligand exchange reaction) between the fluorine-containing cyclic carbonate and another non-aqueous solvent with respect to lithium occurs in the electrolytic solution.
そこで、本発明者は、リチウムとフッ素含有環状カーボネートの錯体の割合を増加させるには、フッ素含有環状カーボネート以外の非水溶媒の配位能を低下させることが効果的ではないかとの仮説を立てた。 Therefore, the present inventors hypothesized that it would be effective to decrease the coordination ability of a non-aqueous solvent other than the fluorine-containing cyclic carbonate in order to increase the ratio of the complex of lithium and the fluorine-containing cyclic carbonate. Was.
フッ素含有環状カーボネートや一般的な鎖状カーボネートがリチウムと配位する際には、Ｃ＝Ｏ結合における酸素の非共有電子対がリチウムに配位していると考えられる。
そこで、本発明者は、フッ素含有環状カーボネートと共に併用される非水溶媒のＣ＝Ｏ結合における酸素の非共有電子対の電子密度を低下させることを想起した。具体的には、Ｃ＝Ｏ結合における炭素に強力な電子吸引基が結合している非水溶媒を、フッ素含有環状カーボネートの併用溶媒として採用することを想起した。
When a fluorine-containing cyclic carbonate or a general chain carbonate coordinates with lithium, it is considered that an unshared electron pair of oxygen in a C ＝ O bond is coordinated with lithium.
Thus, the present inventor has conceived of reducing the electron density of the lone pair of oxygen at the C ＝ O bond of the non-aqueous solvent used in combination with the fluorine-containing cyclic carbonate. Specifically, the present inventor recalled that a non-aqueous solvent in which a strong electron-withdrawing group is bonded to carbon in a CＣO bond was used as a combined solvent for a fluorine-containing cyclic carbonate.
そして、本発明者は、フルオロエチレンカーボネートと、Ｃ＝Ｏ結合における炭素にトリフルオロメチル基が結合したフッ素含有鎖状エステルとを併用した混合溶媒を調製して、当該混合溶媒に、一般的な電解質であるＬｉＰＦ６を溶解させようとした。しかしながら、上述の混合溶媒にＬｉＰＦ６を所望の濃度で溶解させることはできなかった。 Then, the present inventor prepared a mixed solvent using a combination of fluoroethylene carbonate and a fluorine-containing chain ester in which a trifluoromethyl group is bonded to carbon at a C ＝ O bond, and used a general mixed solvent as the mixed solvent. An attempt was made to dissolve LiPF 6 as an electrolyte. However, LiPF 6 could not be dissolved at the desired concentration in the above-mentioned mixed solvent.
そこで、本発明者は、電解質についても検討を重ねて、ＬｉＢＦ３ＣＦ３やＬｉＢＦ２（ＣＦ３）２が上述の混合溶媒に溶解することを見出した。そして、ＬｉＢＦ３ＣＦ３やＬｉＢＦ２（ＣＦ３）２を上述の混合溶媒に溶解させた電解液を用いてリチウムイオン二次電池を製造し、試験を行ったところ、当該リチウムイオン二次電池が容量を好適に維持することを確認した。 Therefore, the present inventors have repeatedly studied the electrolyte and found that LiBF 3 CF 3 and LiBF 2 (CF 3 ) 2 are dissolved in the above-mentioned mixed solvent. Then, a lithium ion secondary battery was manufactured using an electrolyte solution in which LiBF 3 CF 3 or LiBF 2 (CF 3 ) 2 was dissolved in the above-mentioned mixed solvent, and a test was performed. It was confirmed that the capacity was suitably maintained.
これらの知見に基づき、本発明は完成された。 The present invention has been completed based on these findings.
本発明の電解液は、ＬｉＢＦ４−ａ（ＣＦ３）ａ（ａは１、２、３又は４である。）、フッ素含有環状カーボネート及び下記一般式（１）で表されるフッ素含有鎖状エステルを含有することを特徴とする。
一般式（１） Ｒ１ＣＯ２Ｒ２
Ｒ１は、フッ素含有アルキル基である。Ｒ２は、フッ素で置換されていてもよいアルキル基である。
The electrolyte solution of the present invention includes LiBF 4-a (CF 3 ) a (a is 1, 2, 3, or 4), a fluorine-containing cyclic carbonate, and a fluorine-containing chain represented by the following general formula (1). It is characterized by containing an ester.
General formula (1) R 1 CO 2 R 2
R 1 is a fluorine-containing alkyl group. R 2 is an alkyl group optionally substituted by fluorine.
本発明の電解液は、蓄電装置の容量を好適に維持し得るものである。 The electrolytic solution of the present invention can suitably maintain the capacity of the power storage device.
以下に、本発明を実施するための形態を説明する。なお、特に断らない限り、本明細書に記載された数値範囲「ａ〜ｂ」は、下限ａ及び上限ｂをその範囲に含む。そして、これらの上限値及び下限値、ならびに実施例中に列記した数値も含めてそれらを任意に組み合わせることで数値範囲を構成し得る。さらに、これらの数値範囲内から任意に選択した数値を、新たな上限や下限の数値とすることができる。 Hereinafter, embodiments for implementing the present invention will be described. Unless otherwise specified, the numerical range “ab” described in this specification includes the lower limit a and the upper limit b in the range. A numerical range can be formed by arbitrarily combining these upper and lower limits and the numerical values listed in the examples. Further, numerical values arbitrarily selected from within these numerical ranges can be set as new upper and lower numerical values.
本発明の電解液は、ＬｉＢＦ４−ａ（ＣＦ３）ａ（ａは１、２、３又は４である。）、フッ素含有環状カーボネート及び下記一般式（１）で表されるフッ素含有鎖状エステルを含有することを特徴とする。
一般式（１） Ｒ１ＣＯ２Ｒ２
Ｒ１は、フッ素含有アルキル基である。Ｒ２は、フッ素で置換されていてもよいアルキル基である。
The electrolyte solution of the present invention includes LiBF 4-a (CF 3 ) a (a is 1, 2, 3, or 4), a fluorine-containing cyclic carbonate, and a fluorine-containing chain represented by the following general formula (1). It is characterized by containing an ester.
General formula (1) R 1 CO 2 R 2
R 1 is a fluorine-containing alkyl group. R 2 is an alkyl group optionally substituted by fluorine.
本発明の電解液は、蓄電装置の電解液として使用できる。蓄電装置としては、リチウムイオン二次電池や、リチウムイオンキャパシタなどのキャパシタを例示できる。以下、本発明の電解液を備える蓄電装置を本発明の蓄電装置といい、本発明の電解液を備えるリチウムイオン二次電池を本発明のリチウムイオン二次電池という。 The electrolytic solution of the present invention can be used as an electrolytic solution for a power storage device. Examples of the power storage device include a lithium ion secondary battery and a capacitor such as a lithium ion capacitor. Hereinafter, a power storage device including the electrolytic solution of the present invention is referred to as a power storage device of the present invention, and a lithium ion secondary battery including the electrolytic solution of the present invention is referred to as a lithium ion secondary battery of the present invention.
本発明の電解液におけるＬｉＢＦ４−ａ（ＣＦ３）ａの濃度は、特に制限されない。好適な濃度範囲として、０．５〜４ｍｏｌ／Ｌ、０．６〜３ｍｏｌ／Ｌ、０．７〜２ｍｏｌ／Ｌ、０．８〜１．７ｍｏｌ／Ｌ、０．９〜１．５ｍｏｌ／Ｌを例示できる。 The concentration of LiBF 4-a (CF 3 ) a in the electrolytic solution of the present invention is not particularly limited. Suitable concentration ranges are 0.5 to 4 mol / L, 0.6 to 3 mol / L, 0.7 to 2 mol / L, 0.8 to 1.7 mol / L, and 0.9 to 1.5 mol / L. Can be illustrated.
また、本発明の電解液には、本発明の趣旨を逸脱しない範囲で、公知の電解質を併用してもよい。本発明の電解液に含まれる電解質全体に対するＬｉＢＦ４−ａ（ＣＦ３）ａの割合として、５０〜１００モル％、７０〜１００モル％、９０〜１００モル％を例示できる。 A known electrolyte may be used in combination with the electrolytic solution of the present invention without departing from the spirit of the present invention. Examples of the ratio of LiBF 4-a (CF 3 ) a to the entire electrolyte contained in the electrolyte solution of the present invention include 50 to 100 mol%, 70 to 100 mol%, and 90 to 100 mol%.
本発明の電解液はフッ素含有環状カーボネートを含む。フッ素含有環状カーボネートとは、フッ素を分子内に有する環状カーボネートを意味する。フッ素含有環状カーボネートは、耐酸化能に優れるが、還元条件下でたやすく分解する。従って、フッ素含有環状カーボネートは、本発明の蓄電装置の充放電条件下において、負極と電解液との界面において優先的に分解する。その結果、負極の表面に、フッ素含有環状カーボネートの分解物に由来する被膜が形成される。かかる被膜の存在に因り、負極に対する電解液の直接的な接触を防ぐことができるため、電解液の構成成分の過剰な分解を抑制できる。その結果、本発明の蓄電装置の劣化を抑制できる。 The electrolyte of the present invention contains a fluorine-containing cyclic carbonate. The fluorine-containing cyclic carbonate means a cyclic carbonate having fluorine in a molecule. Fluorine-containing cyclic carbonates have excellent oxidation resistance, but readily decompose under reducing conditions. Therefore, the fluorine-containing cyclic carbonate is preferentially decomposed at the interface between the negative electrode and the electrolyte under the charge and discharge conditions of the power storage device of the present invention. As a result, a film derived from the decomposition product of the fluorine-containing cyclic carbonate is formed on the surface of the negative electrode. Due to the presence of such a coating, direct contact of the electrolyte with the negative electrode can be prevented, so that excessive decomposition of the components of the electrolyte can be suppressed. As a result, deterioration of the power storage device of the present invention can be suppressed.
フッ素含有環状カーボネートの具体例としては、下記一般式（Ａ）で表される化合物を挙げることができる。 Specific examples of the fluorine-containing cyclic carbonate include a compound represented by the following general formula (A).
Ｒ１、Ｒ２はそれぞれ独立に、水素、アルキル基、ハロゲン含有アルキル基又はハロゲンである。ただし、各Ｒ１及び各Ｒ２のうち、少なくとも一つはＦを含む。 R 1 and R 2 are each independently hydrogen, an alkyl group, a halogen-containing alkyl group or halogen. However, at least one of R 1 and R 2 includes F.
一般式（Ａ）で表されるフッ素含有環状カーボネートを具体的な化合物名で示すと、フルオロエチレンカーボネート、４−（トリフルオロメチル）−１，３−ジオキソラン−２−オン、４，４−ジフルオロ−１，３−ジオキソラン−２−オン、４−フルオロ−４−メチル−１，３−ジオキソラン−２−オン、４−（フルオロメチル）−１，３−ジオキソラン−２−オン、４，５−ジフルオロ−１，３−ジオキソラン−２−オン、４−フルオロ−５−メチル−１，３−ジオキソラン−２−オン、４，５−ジフルオロ−４，５−ジメチル−１，３−ジオキソラン−２−オンを挙げることができ、中でもフルオロエチレンカーボネートが好ましい。 Specific examples of the fluorine-containing cyclic carbonate represented by the general formula (A) include fluoroethylene carbonate, 4- (trifluoromethyl) -1,3-dioxolan-2-one, and 4,4-difluoro -1,3-dioxolan-2-one, 4-fluoro-4-methyl-1,3-dioxolan-2-one, 4- (fluoromethyl) -1,3-dioxolan-2-one, 4,5- Difluoro-1,3-dioxolan-2-one, 4-fluoro-5-methyl-1,3-dioxolan-2-one, 4,5-difluoro-4,5-dimethyl-1,3-dioxolan-2- ON can be mentioned, and among them, fluoroethylene carbonate is preferable.
次に、一般式（１） Ｒ１ＣＯ２Ｒ２で表されるフッ素含有鎖状エステルについて説明する。一般式（１）において、Ｒ１はフッ素含有アルキル基であり、Ｒ２はフッ素で置換されていてもよいアルキル基である。 Next, the fluorine-containing chain ester represented by the general formula (1) R 1 CO 2 R 2 will be described. In the general formula (1), R 1 is a fluorine-containing alkyl group, and R 2 is an alkyl group which may be substituted with fluorine.
Ｒ１は強力な電子吸引性を示すフッ素含有アルキル基である。そのため、フッ素含有鎖状エステルのＣ＝Ｏ結合における酸素の非共有電子対の電子密度が低下するので、フッ素含有鎖状エステルのリチウムに対する配位能は比較的低いといえる。
そうすると、リチウムとフッ素含有環状カーボネートの錯体は、電解液中で、相対的に安定に存在できるといえる。
R 1 is a fluorine-containing alkyl group having a strong electron-withdrawing property. Therefore, since the electron density of the lone pair of oxygen at the CＯO bond of the fluorine-containing chain ester decreases, the coordination ability of the fluorine-containing chain ester with lithium is relatively low.
Then, it can be said that the complex of lithium and the fluorine-containing cyclic carbonate can be relatively stably present in the electrolytic solution.
蓄電装置の充電時には、静電的に負極に引き付けられるリチウムと共にフッ素含有環状カーボネートが負極に接近する。そして、リチウムとフッ素含有環状カーボネートが配位又は近接した状況下で、フッ素含有環状カーボネートが還元分解されると考えられる。その結果、ＳＥＩの一部としてＬｉＦが好適に形成されると推定される。 When the power storage device is charged, the fluorine-containing cyclic carbonate approaches the negative electrode together with lithium which is electrostatically attracted to the negative electrode. Then, it is considered that the fluorine-containing cyclic carbonate is reductively decomposed in a state where lithium and the fluorine-containing cyclic carbonate are coordinated or close to each other. As a result, it is presumed that LiF is suitably formed as a part of SEI.
一般式（１）において、Ｒ１及びＲ２の炭素数は、それぞれ独立に、１〜４が好ましく、１〜３がより好ましい。 In the general formula (1), R 1 and R 2 each independently preferably have 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.
より好適なフッ素含有鎖状エステルとして、ＣａＨｂＦｃＣＯ２ＣｄＨｅＦｆ（ａは１、２又は３であり、ｂは０〜６の整数であり、ｃは１〜７の整数であり、２ａ＋１＝ｂ＋ｃを満足する。ｄは１、２又は３であり、ｅは０〜７の整数であり、ｆは０〜７の整数であり、２ｄ＋１＝ｅ＋ｆを満足する。）を例示できる。 As a more preferred fluorine-containing chain ester, C a H b F c CO 2 C d H e F f (a is 1, 2 or 3, b is an integer of Less than six, c is 1-7 Satisfies 2a + 1 = b + c. D is 1, 2, or 3, e is an integer of 0 to 7, f is an integer of 0 to 7, and satisfies 2d + 1 = e + f.) Can be exemplified.
フッ素含有鎖状エステルの具体例としては、フルオロ酢酸メチル、ジフルオロ酢酸メチル、トリフルオロ酢酸メチル、フルオロ酢酸エチル、ジフルオロ酢酸エチル、トリフルオロ酢酸エチル、フルオロ酢酸プロピル、ジフルオロ酢酸プロピル、トリフルオロ酢酸プロピル、２−フルオロプロピオン酸メチル、２，２−ジフルオロプロピオン酸メチル、３，３，３−トリフルオロプロピオン酸メチル、２，３，３，３−テトラフルオロプロピオン酸メチル、２，２，３，３，３−ペンタフルオロプロピオン酸メチル、２−フルオロプロピオン酸エチル、２，２−ジフルオロプロピオン酸エチル、３，３，３−トリフルオロプロピオン酸エチル、２，３，３，３−テトラフルオロプロピオン酸エチル、２，２，３，３，３−ペンタフルオロプロピオン酸エチル、２−フルオロプロピオン酸プロピル、２，２−ジフルオロプロピオン酸プロピル、３，３，３−トリフルオロプロピオン酸プロピル、２，３，３，３−テトラフルオロプロピオン酸プロピル、２，２，３，３，３−ペンタフルオロプロピオン酸プロピル、トリフルオロ酢酸２−フルオロエチル、トリフルオロ酢酸２，２−ジフルオロエチル、トリフルオロ酢酸２，２，２−トリフルオロエチルを例示できる。 Specific examples of the fluorine-containing chain ester, methyl fluoroacetate, methyl difluoroacetate, methyl trifluoroacetate, ethyl fluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, propyl fluoroacetate, propyl difluoroacetate, propyl trifluoroacetate, Methyl 2-fluoropropionate, methyl 2,2-difluoropropionate, methyl 3,3,3-trifluoropropionate, methyl 2,3,3,3-tetrafluoropropionate, 2,2,3,3 Methyl 3-pentafluoropropionate, ethyl 2-fluoropropionate, ethyl 2,2-difluoropropionate, ethyl 3,3,3-trifluoropropionate, ethyl 2,3,3,3-tetrafluoropropionate, 2,2,3,3,3-pentafluoropropyl Ethyl acetate, propyl 2-fluoropropionate, propyl 2,2-difluoropropionate, propyl 3,3,3-trifluoropropionate, propyl 2,3,3,3-tetrafluoropropionate, 2,2,2 Examples thereof include propyl 3,3,3-pentafluoropropionate, 2-fluoroethyl trifluoroacetate, 2,2-difluoroethyl trifluoroacetate, and 2,2,2-trifluoroethyl trifluoroacetate.
本発明の電解液は、フッ素含有環状カーボネートとフッ素含有鎖状エステルを体積比５：９５〜５０：５０の範囲内で含有するのが好ましい。フッ素含有環状カーボネートとフッ素含有鎖状エステルの体積比は、８：９２〜４０：６０の範囲内がより好ましく、１０：９０〜３０：７０の範囲内がさらに好ましく、１５：８５〜２５：７５の範囲内が特に好ましい。 The electrolytic solution of the present invention preferably contains a fluorine-containing cyclic carbonate and a fluorine-containing chain ester in a volume ratio of 5:95 to 50:50. The volume ratio of the fluorine-containing cyclic carbonate to the fluorine-containing chain ester is more preferably in the range of 8:92 to 40:60, further preferably in the range of 10:90 to 30:70, and is preferably 15:85 to 25:75. Is particularly preferred.
また、本発明の電解液には、本発明の趣旨を逸脱しない範囲で、フッ素含有環状カーボネートとフッ素含有鎖状エステル以外の公知の非水溶媒を併用してもよい。本発明の電解液に含まれる非水溶媒全体に対するフッ素含有環状カーボネート及びフッ素含有鎖状エステルの合計量の割合として、５０〜１００体積％、７０〜１００体積％、９０〜１００体積％を例示できる。 In addition, a known non-aqueous solvent other than the fluorine-containing cyclic carbonate and the fluorine-containing chain ester may be used in the electrolyte solution of the present invention without departing from the spirit of the present invention. The ratio of the total amount of the fluorine-containing cyclic carbonate and the fluorine-containing chain ester to the entire nonaqueous solvent contained in the electrolytic solution of the present invention can be exemplified by 50 to 100% by volume, 70 to 100% by volume, and 90 to 100% by volume. .
本発明の電解液には、本発明の趣旨を逸脱しない範囲で、公知の添加剤を配合してもよい。 Known additives may be added to the electrolytic solution of the present invention without departing from the spirit of the present invention.
次に、本発明の蓄電装置の代表例として、本発明のリチウムイオン二次電池の説明を行う。本発明のリチウムイオン二次電池は、本発明の電解液と、負極と正極を備える。
負極の具体的な態様は、集電体と、集電体の表面に形成された負極活物質層とを具備する。
Next, a lithium ion secondary battery of the present invention will be described as a typical example of the power storage device of the present invention. A lithium ion secondary battery of the present invention includes the electrolytic solution of the present invention, a negative electrode and a positive electrode.
A specific embodiment of the negative electrode includes a current collector and a negative electrode active material layer formed on a surface of the current collector.
集電体は、リチウムイオン二次電池などの二次電池の放電又は充電の間、電極に電流を流し続けるための化学的に不活性な電子伝導体をいう。集電体の材料は、使用する活物質に適した電圧に耐え得る金属であれば特に制限はない。集電体の材料としては、銀、銅、金、アルミニウム、タングステン、コバルト、亜鉛、ニッケル、鉄、白金、錫、インジウム、チタン、ルテニウム、タンタル、クロム、モリブデンから選ばれる少なくとも一種、並びにステンレス鋼などの金属材料を例示することができる。集電体は公知の保護層で被覆されていても良い。集電体の表面を公知の方法で処理したものを集電体として用いても良い。 The current collector refers to a chemically inert electronic conductor for continuously supplying a current to an electrode during discharging or charging of a secondary battery such as a lithium ion secondary battery. The material of the current collector is not particularly limited as long as it is a metal that can withstand a voltage suitable for the active material to be used. As the material of the current collector, at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel And other metal materials. The current collector may be covered with a known protective layer. A current collector whose surface is treated by a known method may be used as the current collector.
集電体は箔、シート、フィルム、線状、棒状、メッシュなどの形態をとることができる。そのため、集電体として、例えば、銅箔、ニッケル箔、アルミニウム箔、ステンレス箔などの金属箔を好適に用いることができる。集電体が箔、シート、フィルム形態の場合は、その厚みが１μｍ〜１００μｍの範囲内であることが好ましい。 The current collector may be in the form of a foil, sheet, film, wire, rod, mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector. When the current collector is in the form of a foil, sheet, or film, the thickness is preferably in the range of 1 μm to 100 μm.
負極活物質層は、負極活物質、並びに必要に応じて結着剤及び導電助剤を含む。 The negative electrode active material layer contains a negative electrode active material and, if necessary, a binder and a conductive auxiliary.
本発明の電解液は、本発明のリチウムイオン二次電池の充電時に分解して、負極の表面にリチウム及びフッ素を含有する被膜を形成する。かかる被膜は、電解液の過剰な分解を抑制するとともに、劣化の可能性がある負極活物質の保護膜としても作用する。特に、負極活物質としてＳｉ含有負極活物質を採用した場合の好適な保護膜として作用する。よって、負極活物質としてはＳｉ含有負極活物質を採用するのが好ましい。負極活物質層には、Ｓｉ含有負極活物質以外の公知の負極活物質を含んでもよい。 The electrolyte of the present invention decomposes at the time of charging the lithium ion secondary battery of the present invention to form a film containing lithium and fluorine on the surface of the negative electrode. Such a coating suppresses excessive decomposition of the electrolytic solution and also acts as a protective film for the negative electrode active material that may be deteriorated. In particular, it functions as a suitable protective film when a Si-containing negative electrode active material is adopted as the negative electrode active material. Therefore, it is preferable to employ a Si-containing negative electrode active material as the negative electrode active material. The negative electrode active material layer may include a known negative electrode active material other than the Si-containing negative electrode active material.
Ｓｉ含有負極活物質としては、リチウムイオンを吸蔵及び放出し得るＳｉ含有材料が使用可能である。 As the Si-containing negative electrode active material, a Si-containing material capable of inserting and extracting lithium ions can be used.
Ｓｉ含有材料の具体例として、Ｓｉ単体や、ＳｉＯｘ（０．３≦ｘ≦１．６）を例示できる。ＳｉＯｘのｘが下限値未満であると、Ｓｉの比率が過大になるため、充放電時の体積変化が大きくなりすぎて二次電池のサイクル特性が低下する場合がある。一方、ｘが上限値を超えると、Ｓｉ比率が過小になってエネルギー密度が低下する。ｘの範囲は０．５≦ｘ≦１．５であるのがより好ましく、０．７≦ｘ≦１．２であるのがさらに好ましい。 Specific examples of the Si-containing material include Si alone and SiO x (0.3 ≦ x ≦ 1.6). When x of SiO x is less than the lower limit, the ratio of Si becomes excessively large, so that the volume change at the time of charging and discharging becomes too large, and the cycle characteristics of the secondary battery may deteriorate. On the other hand, if x exceeds the upper limit, the Si ratio becomes too small and the energy density decreases. The range of x is more preferably 0.5 ≦ x ≦ 1.5, and even more preferably 0.7 ≦ x ≦ 1.2.
Ｓｉ含有材料の具体例として、国際公開第２０１４／０８０６０８号などに開示されるシリコン材料（以下、単に「シリコン材料」という。）を挙げることができる。 Specific examples of the Si-containing material include a silicon material disclosed in WO 2014/080608 (hereinafter, simply referred to as “silicon material”).
シリコン材料は、複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有するものである。シリコン材料は、例えば、ＣａＳｉ２と酸とを反応させてポリシランを主成分とする層状シリコン化合物を合成する工程、さらに、当該層状シリコン化合物を３００℃以上で加熱して水素を離脱させる工程を経て製造されるものである。 The silicon material has a structure in which a plurality of plate-like silicon bodies are stacked in the thickness direction. The silicon material undergoes, for example, a step of reacting CaSi 2 with an acid to synthesize a layered silicon compound containing polysilane as a main component, and a step of heating the layered silicon compound at 300 ° C. or higher to release hydrogen. It is manufactured.
シリコン材料の製造方法を、酸として塩化水素を用いた場合の理想的な反応式で示すと以下のとおりとなる。
３ＣａＳｉ２＋６ＨＣｌ → Ｓｉ６Ｈ６＋３ＣａＣｌ２
Ｓｉ６Ｈ６ → ６Ｓｉ＋３Ｈ２↑
An ideal reaction formula for a method of manufacturing a silicon material using hydrogen chloride as an acid is as follows.
3CaSi 2 + 6HCl → Si 6 H 6 + 3CaCl 2
Si 6 H 6 → 6Si + 3H 2 ↑
ただし、ポリシランであるＳｉ６Ｈ６を合成する上段の反応では、副生物や不純物除去の観点から、通常、反応溶媒として水が用いられる。そして、Ｓｉ６Ｈ６は水と反応し得るため、上段の反応を含む層状シリコン化合物を合成する工程において、層状シリコン化合物がＳｉ６Ｈ６のみを含むものとして製造されることはほとんどなく、層状シリコン化合物はＳｉ６Ｈｓ(ＯＨ)ｔＸｕ（Ｘは酸のアニオン由来の元素若しくは基、ｓ＋ｔ＋ｕ＝６、０＜ｓ＜６、０＜ｔ＜６、０＜ｕ＜６）で表されるものとして製造される。なお、上記の化学式においては、残存し得るＣａなどの不可避不純物については、考慮していない。そして、当該層状シリコン化合物を加熱して得られるシリコン材料も、酸素や酸のアニオン由来の元素を含む。 However, in the upper reaction of synthesizing Si 6 H 6 as polysilane, water is usually used as a reaction solvent from the viewpoint of removing by-products and impurities. Since Si 6 H 6 can react with water, in the step of synthesizing the layered silicon compound including the upper reaction, the layered silicon compound is hardly produced as containing only Si 6 H 6 , The silicon compound is represented by Si 6 H s (OH) t X u (X is an element or group derived from an anion of an acid, s + t + u = 6, 0 <s <6, 0 <t <6, 0 <u <6). Manufactured as such. In the above chemical formula, inevitable impurities such as Ca that may remain are not considered. The silicon material obtained by heating the layered silicon compound also contains elements derived from oxygen and anions of acids.
既述のとおり、シリコン材料は、複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有する。リチウムイオンが効率的に吸蔵及び放出されるためには、板状シリコン体は厚さが１０ｎｍ〜１００ｎｍの範囲内のものが好ましく、２０ｎｍ〜５０ｎｍの範囲内のものがより好ましい。板状シリコン体の長手方向の長さは、０．１μｍ〜５０μｍの範囲内のものが好ましい。また、板状シリコン体は、（長手方向の長さ）／（厚さ）が２〜１０００の範囲内であるのが好ましい。板状シリコン体の積層構造は走査型電子顕微鏡などによる観察で確認できる。また、この積層構造は、原料のＣａＳｉ２におけるＳｉ層の名残りであると考えられる。 As described above, the silicon material has a structure in which a plurality of plate-like silicon bodies are stacked in the thickness direction. In order to efficiently store and release lithium ions, the plate-like silicon body preferably has a thickness in the range of 10 nm to 100 nm, more preferably 20 nm to 50 nm. The length in the longitudinal direction of the plate-like silicon body is preferably in the range of 0.1 μm to 50 μm. Moreover, it is preferable that (length in the longitudinal direction) / (thickness) of the plate-shaped silicon body is in the range of 2 to 1,000. The laminated structure of the plate-like silicon body can be confirmed by observation with a scanning electron microscope or the like. This laminated structure is considered to be a remnant of the Si layer in the raw material CaSi 2 .
シリコン材料には、アモルファスシリコン及び／又はシリコン結晶子が含まれるのが好ましい。特に、上記板状シリコン体において、アモルファスシリコンをマトリックスとし、シリコン結晶子が当該マトリックス中に点在している状態が好ましい。シリコン結晶子のサイズは、０．５ｎｍ〜３００ｎｍの範囲内が好ましく、１ｎｍ〜１００ｎｍの範囲内がより好ましく、１ｎｍ〜５０ｎｍの範囲内がさらに好ましく、１ｎｍ〜１０ｎｍの範囲内が特に好ましい。なお、シリコン結晶子のサイズは、シリコン材料に対してＸ線回折測定を行い、得られたＸ線回折チャートのＳｉ（１１１）面の回折ピークの半値幅を用いたシェラーの式から算出される。 Preferably, the silicon material includes amorphous silicon and / or silicon crystallites. In particular, in the plate-like silicon body, it is preferable that amorphous silicon is used as a matrix and silicon crystallites are scattered in the matrix. The size of the silicon crystallite is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, still more preferably in the range of 1 nm to 50 nm, and particularly preferably in the range of 1 nm to 10 nm. The size of the silicon crystallite is calculated from Scherrer's formula using the half-value width of the diffraction peak of the Si (111) plane in the obtained X-ray diffraction chart by performing X-ray diffraction measurement on the silicon material. .
シリコン材料に含まれる板状シリコン体、アモルファスシリコン及びシリコン結晶子の存在量や大きさは、主に加熱温度や加熱時間に左右される。加熱温度は、３５０℃〜９５０℃の範囲内が好ましく、４００℃〜９００℃の範囲内がより好ましい。 The abundance and size of the silicon plate, amorphous silicon, and silicon crystallite contained in the silicon material mainly depend on the heating temperature and the heating time. The heating temperature is preferably in the range of 350C to 950C, more preferably in the range of 400C to 900C.
Ｓｉ含有負極活物質は、粒子の集合体である粉末状のものが好ましい。Ｓｉ含有負極活物質の平均粒子径は、１〜３０μｍの範囲内が好ましく、２〜２０μｍの範囲内がより好ましい。平均粒子径が小さすぎるＳｉ含有負極活物質を用いると、製造作業が困難になる場合がある。他方、平均粒子径が大きすぎるＳｉ含有負極活物質を用いた負極を具備するリチウムイオン二次電池は、好適な充放電ができない場合がある。
なお、本明細書における平均粒子径とは、一般的なレーザー回折式粒度分布測定装置で試料を測定した場合におけるＤ５０を意味する。
The Si-containing negative electrode active material is preferably in the form of a powder, which is an aggregate of particles. The average particle diameter of the Si-containing negative electrode active material is preferably in the range of 1 to 30 μm, and more preferably in the range of 2 to 20 μm. When a Si-containing negative electrode active material having an average particle diameter that is too small is used, the manufacturing operation may be difficult. On the other hand, a lithium ion secondary battery provided with a negative electrode using a Si-containing negative electrode active material having an average particle diameter that is too large may not be able to suitably charge and discharge.
The average particle diameter herein means a D 50 in the case of measuring a sample in a conventional laser diffraction particle size distribution analyzer.
Ｓｉ含有負極活物質として、Ｓｉ含有負極活物質を炭素層で被覆した炭素層被覆−Ｓｉ含有負極活物質を採用してもよい。炭素層被覆−Ｓｉ含有負極活物質は、炭素層とＳｉ含有負極活物質とが一体化しているものが好ましい。そのような炭素層被覆−Ｓｉ含有負極活物質の製造方法としては、Ｓｉ含有負極活物質及び炭素粉末の混合物に対して、強い圧力を付した上で撹拌して一体化するメカニカルミリング法や、炭素源から生じる炭素をＳｉ含有負極活物質に蒸着させるＣＶＤ（ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）法を例示できる。 As the Si-containing negative electrode active material, a carbon layer-coated Si-containing negative electrode active material in which a Si-containing negative electrode active material is coated with a carbon layer may be employed. The carbon layer-coated Si-containing negative electrode active material is preferably one in which the carbon layer and the Si-containing negative electrode active material are integrated. As a method for producing such a carbon layer coating-Si-containing negative electrode active material, a mechanical milling method of applying a strong pressure to a mixture of a Si-containing negative electrode active material and carbon powder and stirring and integrating the mixture, A CVD (chemical vapor deposition) method in which carbon generated from a carbon source is deposited on a Si-containing negative electrode active material can be exemplified.
Ｓｉ含有負極活物質の表面を薄い炭素層で均一に被覆できる点から、ＣＶＤ法が好ましい。そして、ＣＶＤ法のうち、炭素源である気体状態の有機物を熱で分解して炭素を発生させる熱ＣＶＤ法が好ましい。 The CVD method is preferred because the surface of the Si-containing negative electrode active material can be uniformly coated with a thin carbon layer. Among the CVD methods, a thermal CVD method in which a gaseous organic substance as a carbon source is decomposed by heat to generate carbon is preferable.
熱ＣＶＤ法を用いて炭素層被覆−Ｓｉ含有負極活物質を製造する、熱ＣＶＤ工程について具体的に説明する。詳細に述べると、熱ＣＶＤ工程は、非酸化性雰囲気下及び加熱条件下にて、Ｓｉ含有負極活物質を有機物と接触させて、Ｓｉ含有負極活物質の表面に有機物が炭素化してなる炭素層を形成させる工程である。熱ＣＶＤ工程を行う場合には、ホットウォール型、コールドウォール型、横型、縦型などの型式の、流動層反応炉、回転炉、トンネル炉、バッチ式焼成炉、ロータリーキルンなどの公知のＣＶＤ装置を用いればよい。 The thermal CVD process for producing the carbon layer-coated Si-containing negative electrode active material using the thermal CVD method will be specifically described. More specifically, in the thermal CVD process, the Si-containing negative electrode active material is brought into contact with an organic substance under a non-oxidizing atmosphere and under heating conditions to form a carbon layer formed by carbonizing the organic substance on the surface of the Si-containing negative electrode active material. Is a step of forming When performing the thermal CVD process, a known CVD device such as a fluidized-bed reactor, a rotary furnace, a tunnel furnace, a batch-type firing furnace, or a rotary kiln of a type such as a hot wall type, a cold wall type, a horizontal type, or a vertical type is used. It may be used.
有機物としては、非酸化性雰囲気下での加熱によって熱分解して炭化し得るものが用いられ、例えば、メタン、エタン、プロパン、ブタン、イソブタン、ペンタン、ヘキサンなどの飽和脂肪族炭化水素、エチレン、プロピレン、アセチレンなどの不飽和脂肪族炭化水素、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、ベンゼン、トルエン、キシレン、スチレン、エチルベンゼン、ジフェニルメタン、ナフタレン、フェノール、クレゾール、ニトロベンゼン、クロルベンゼン、インデン、ベンゾフラン、ピリジンなどの芳香族炭化水素、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル類、脂肪酸類などから選択される一種又は混合物が挙げられる。 As the organic substance, those which can be thermally decomposed and carbonized by heating under a non-oxidizing atmosphere are used, for example, methane, ethane, propane, butane, isobutane, pentane, saturated aliphatic hydrocarbons such as hexane, ethylene, Unsaturated aliphatic hydrocarbons such as propylene and acetylene, alcohols such as methanol, ethanol, propanol and butanol, benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene and benzofuran And a mixture or a mixture selected from aromatic hydrocarbons such as pyridine, esters such as ethyl acetate, butyl acetate, and amyl acetate, and fatty acids.
熱ＣＶＤ工程における処理温度は、有機物の種類によって異なるが、有機物が熱分解する温度より５０℃以上高い温度とすることが望ましい。しかし、加熱温度が過度に高いと、系内に遊離炭素（煤）が発生する場合があるので、遊離炭素（煤）が発生しない条件を選択することが好ましい。形成される炭素層の厚さは、処理時間によって制御することができる。 The processing temperature in the thermal CVD step varies depending on the type of the organic substance, but is preferably set to a temperature higher than the temperature at which the organic substance is thermally decomposed by 50 ° C. or more. However, if the heating temperature is excessively high, free carbon (soot) may be generated in the system. Therefore, it is preferable to select a condition under which free carbon (soot) is not generated. The thickness of the formed carbon layer can be controlled by the processing time.
熱ＣＶＤ工程は、Ｓｉ含有負極活物質を流動状態にして行うことが望ましい。このようにすることで、Ｓｉ含有負極活物質の全表面を有機物と接触させることができ、より均一な炭素層を形成することができる。Ｓｉ含有負極活物質を流動状態にするには、流動床を用いるなど各種方法があるが、Ｓｉ含有負極活物質を撹拌しながら有機物と接触させるのが好ましい。例えば、内部に邪魔板をもつ回転炉を用いれば、邪魔板に留まったＳｉ含有負極活物質が回転炉の回転に伴って所定高さから落下することで撹拌され、その際に有機物と接触して炭素層が形成されるので、Ｓｉ含有負極活物質の全体にいっそう均一な炭素層を形成することができる。 It is desirable that the thermal CVD process be performed with the Si-containing negative electrode active material in a fluid state. By doing so, the entire surface of the Si-containing negative electrode active material can be brought into contact with the organic substance, and a more uniform carbon layer can be formed. There are various methods for bringing the Si-containing negative electrode active material into a fluidized state, for example, using a fluidized bed. However, it is preferable to bring the Si-containing negative electrode active material into contact with an organic substance while stirring. For example, if a rotary furnace having a baffle plate inside is used, the Si-containing negative electrode active material remaining on the baffle plate is agitated by falling from a predetermined height with the rotation of the rotary furnace, and at that time comes into contact with organic matter. As a result, a more uniform carbon layer can be formed over the entire Si-containing negative electrode active material.
炭素層被覆−Ｓｉ含有負極活物質の炭素層は非晶質及び／又は結晶質であり、そして、当該炭素層はＳｉ含有負極活物質粒子の表面全体を被覆しているのが好ましい。炭素層の厚みは、１ｎｍ〜１００ｎｍの範囲内が好ましく、５〜５０ｎｍの範囲内がより好ましく、１０〜３０ｎｍの範囲内がさらに好ましい。 Carbon Layer Coating-The carbon layer of the Si-containing negative electrode active material is preferably amorphous and / or crystalline, and the carbon layer preferably covers the entire surface of the Si-containing negative electrode active material particles. The thickness of the carbon layer is preferably in the range of 1 nm to 100 nm, more preferably in the range of 5 to 50 nm, and even more preferably in the range of 10 to 30 nm.
負極活物質層には、負極活物質が負極活物質層全体の質量に対して、６０〜９９質量％で含まれるのが好ましく、７０〜９５質量％で含まれるのがより好ましい。 The anode active material layer preferably contains the anode active material in an amount of 60 to 99% by mass, more preferably 70 to 95% by mass, based on the mass of the entire anode active material layer.
結着剤としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレン等の熱可塑性樹脂、ポリイミド、ポリアミドイミド等のイミド系樹脂、アルコキシシリル基含有樹脂、カルボキシメチルセルロース、スチレンブタジエンゴムなどの公知のものを採用すればよい。 Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, fluorine-containing resins such as fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide-based resins such as polyimide and polyamideimide, resins containing an alkoxysilyl group, and carboxymethylcellulose. A known material such as styrene-butadiene rubber may be used.
また、国際公開第２０１６／０６３８８２号に開示される、ポリアクリル酸やポリメタクリル酸などのカルボキシル基含有ポリマーをジアミンなどのポリアミンで架橋した架橋ポリマーを、結着剤として用いてもよい。 Further, a cross-linked polymer disclosed in WO 2016/063882 in which a carboxyl group-containing polymer such as polyacrylic acid or polymethacrylic acid is cross-linked with a polyamine such as diamine may be used as the binder.
架橋ポリマーに用いられるジアミンとしては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等のアルキレンジアミン、１，４−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、イソホロンジアミン、ビス（４−アミノシクロヘキシル）メタン等の含飽和炭素環ジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、ビス（４−アミノフェニル）スルホン、ベンジジン、ｏ−トリジン、２，４−トリレンジアミン、２，６−トリレンジアミン、キシリレンジアミン、ナフタレンジアミン等の芳香族ジアミンが挙げられる。 Examples of the diamine used for the crosslinked polymer include alkylenediamines such as ethylenediamine, propylenediamine, and hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, isophoronediamine, and bis (4-aminocyclohexyl) methane. Saturated carbocyclic diamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, bis (4-aminophenyl) sulfone, benzidine, o-tolidine, 2,4- Aromatic diamines such as tolylenediamine, 2,6-tolylenediamine, xylylenediamine, and naphthalenediamine are exemplified.
負極活物質層中の結着剤の配合割合は、質量比で、負極活物質：結着剤＝１：０．００５〜１：０．３であるのが好ましい。結着剤が少なすぎると電極の成形性が低下し、また、結着剤が多すぎると電極のエネルギー密度が低くなるためである。 The mixing ratio of the binder in the negative electrode active material layer is preferably from 1: 0.005 to 1: 0.3 in terms of mass ratio. If the amount of the binder is too small, the moldability of the electrode is reduced, and if the amount of the binder is too large, the energy density of the electrode is reduced.
導電助剤は、電極の導電性を高めるために添加される。そのため、導電助剤は、電極の導電性が不足する場合に任意に加えればよく、電極の導電性が十分に優れている場合には加えなくても良い。導電助剤としては化学的に不活性な電子高伝導体であれば良く、炭素質微粒子であるカーボンブラック、黒鉛、気相法炭素繊維（Vapor Grown Carbon Fiber）、および各種金属粒子などが例示される。カーボンブラックとしては、アセチレンブラック、ケッチェンブラック（登録商標）、ファーネスブラック、チャンネルブラックなどが例示される。これらの導電助剤を単独又は二種以上組み合わせて活物質層に添加することができる。 The conductive additive is added to increase the conductivity of the electrode. Therefore, the conductive assistant may be arbitrarily added when the conductivity of the electrode is insufficient, and may not be added when the conductivity of the electrode is sufficiently excellent. The conductive additive may be any chemically inert high electron conductor, and examples thereof include carbon black, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber), and various metal particles. You. Examples of the carbon black include acetylene black, Ketjen Black (registered trademark), furnace black, and channel black. These conductive assistants can be added to the active material layer alone or in combination of two or more.
負極活物質層中の導電助剤の配合割合は、質量比で、負極活物質：導電助剤＝１：０．０１〜１：０．５であるのが好ましい。導電助剤が少なすぎると効率のよい導電パスを形成できず、また、導電助剤が多すぎると活物質層の成形性が悪くなるとともに電極のエネルギー密度が低くなるためである。 It is preferable that the compounding ratio of the conductive auxiliary in the negative electrode active material layer is negative electrode active material: conductive auxiliary = 1: 0.01 to 1: 0.5 by mass ratio. If the amount of the conductive assistant is too small, an efficient conductive path cannot be formed, and if the amount of the conductive assistant is too large, the moldability of the active material layer deteriorates and the energy density of the electrode decreases.
集電体の表面に負極活物質層を形成させるには、ロールコート法、ダイコート法、ディップコート法、ドクターブレード法、スプレーコート法、カーテンコート法などの従来から公知の方法を用いて、集電体の表面に負極活物質を塗布すればよい。具体的には、負極活物質、結着剤、溶剤、並びに必要に応じて導電助剤を混合してスラリーにしてから、当該スラリーを集電体の表面に塗布後、乾燥する。溶剤としては、Ｎ−メチル−２−ピロリドン、メタノール、メチルイソブチルケトン、水を例示できる。電極密度を高めるべく、乾燥後のものを圧縮しても良い。 To form the negative electrode active material layer on the surface of the current collector, a conventionally known method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, and a curtain coating method is used. The negative electrode active material may be applied to the surface of the electric body. Specifically, a negative electrode active material, a binder, a solvent, and, if necessary, a conductive auxiliary are mixed to form a slurry, and then the slurry is applied to the surface of the current collector and then dried. Examples of the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. The dried product may be compressed to increase the electrode density.
本発明のリチウムイオン二次電池の一態様は、負極、正極、セパレータ及び本発明の電解液を具備する。
正極は、集電体と集電体の表面に形成された正極活物質層とを具備する。集電体としては、負極で説明したものを適宜適切に採用すればよい。
One embodiment of the lithium ion secondary battery of the present invention includes a negative electrode, a positive electrode, a separator, and the electrolytic solution of the present invention.
The positive electrode includes a current collector and a positive electrode active material layer formed on a surface of the current collector. As the current collector, those described for the negative electrode may be appropriately used as appropriate.
正極の電位をリチウム基準で４Ｖ以上とする場合には、正極用集電体としてアルミニウムを採用するのが好ましい。 When the potential of the positive electrode is 4 V or more on the basis of lithium, it is preferable to use aluminum as the positive electrode current collector.
具体的には、正極用集電体として、アルミニウム又はアルミニウム合金からなるものを用いるのが好ましい。ここでアルミニウムは、純アルミニウムを指し、純度９９．０％以上のアルミニウムを純アルミニウムと称する。純アルミニウムに種々の元素を添加して合金としたものをアルミニウム合金と称する。アルミニウム合金としては、Ａｌ−Ｃｕ系、Ａｌ−Ｍｎ系、Ａｌ−Ｆｅ系、Ａｌ−Ｓｉ系、Ａｌ−Ｍｇ系、Ａｌ−Ｍｇ−Ｓｉ系、Ａｌ−Ｚｎ−Ｍｇ系が挙げられる。 Specifically, it is preferable to use a collector made of aluminum or an aluminum alloy as the positive electrode current collector. Here, aluminum refers to pure aluminum, and aluminum having a purity of 99.0% or more is referred to as pure aluminum. An alloy obtained by adding various elements to pure aluminum is referred to as an aluminum alloy. Examples of the aluminum alloy include Al-Cu, Al-Mn, Al-Fe, Al-Si, Al-Mg, Al-Mg-Si, and Al-Zn-Mg.
また、アルミニウム又はアルミニウム合金として、具体的には、例えばＪＩＳ Ａ１０８５、Ａ１Ｎ３０等のＡ１０００系合金（純アルミニウム系)、ＪＩＳ Ａ３００３、Ａ３００４等のＡ３０００系合金（Ａｌ−Ｍｎ系）、ＪＩＳ Ａ８０７９、Ａ８０２１等のＡ８０００系合金（Ａｌ−Ｆｅ系）が挙げられる。 Specific examples of aluminum or aluminum alloy include, for example, A1000 series alloys (pure aluminum series) such as JIS A1085 and A1N30, A3000 series alloys (Al-Mn series) such as JIS A3003 and A3004, JIS A8079, A8021 and the like. A8000-based alloy (Al-Fe-based).
正極活物質層は、リチウムイオンを吸蔵及び放出し得る正極活物質、並びに必要に応じて結着剤及び導電助剤を含む。正極活物質層には、正極活物質が正極活物質層全体の質量に対して、６０〜９９質量％で含まれるのが好ましく、７０〜９５質量％で含まれるのがより好ましい。結着剤及び導電助剤としては、負極で説明したものを適宜適切な量で採用すればよい。 The positive electrode active material layer contains a positive electrode active material capable of occluding and releasing lithium ions, and, if necessary, a binder and a conductive assistant. The positive electrode active material layer preferably contains the positive electrode active material in an amount of 60 to 99% by mass, and more preferably 70 to 95% by mass, based on the total mass of the positive electrode active material layer. What is necessary is just to employ | adopt what was demonstrated by the negative electrode in a suitable quantity suitably as a binder and a conductive auxiliary agent.
正極活物質としては、層状岩塩構造の一般式：ＬｉａＮｉｂＣｏｃＭｄＤｅＯｆ(ＭはＭｎ及びＡｌから選択される。ＤはＷ、Ｍｏ、Ｒｅ、Ｐｄ、Ｂａ、Ｃｒ、Ｂ、Ｓｂ、Ｓｒ、Ｐｂ、Ｇａ、Ｎｂ、Ｍｇ、Ｔａ、Ｔｉ、Ｌａ、Ｚｒ、Ｃｕ、Ｃａ、Ｉｒ、Ｈｆ、Ｒｈ、Ｆｅ、Ｇｅ、Ｚｎ、Ｒｕ、Ｓｃ、Ｓｎ、Ｉｎ、Ｙ、Ｂｉ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ｐ、Ｖから選ばれる少なくとも１の元素である。ａ、ｂ、ｃ、ｄ、ｅ、ｆは０．２≦ａ≦２、ｂ＋ｃ＋ｄ＋ｅ＝１、０≦ｅ＜１、１．７≦ｆ≦３を満足する。)で表されるリチウム複合金属酸化物、Ｌｉ２ＭｎＯ３を挙げることができる。また、正極活物質として、ＬｉＭｎ２Ｏ４等のスピネル構造の金属酸化物、スピネル構造の金属酸化物と層状化合物の混合物で構成される固溶体、ＬｉＭＰＯ４、ＬｉＭＶＯ４又はＬｉ２ＭＳｉＯ４（式中のＭはＣｏ、Ｎｉ、Ｍｎ、Ｆｅのうちの少なくとも一種から選択される）などで表されるポリアニオン系化合物を挙げることができる。さらに、正極活物質として、ＬｉＦｅＰＯ４ＦなどのＬｉＭＰＯ４Ｆ（Ｍは遷移金属）で表されるタボライト系化合物、ＬｉＦｅＢＯ３などのＬｉＭＢＯ３（Ｍは遷移金属）で表されるボレート系化合物を挙げることができる。正極活物質として用いられるいずれの金属酸化物も上記の組成式を基本組成とすればよく、基本組成に含まれる金属元素を他の金属元素で置換したものも使用可能である。また、正極活物質として、リチウムイオンを含まないものを用いても良い。例えば、硫黄単体、硫黄と炭素を複合化した化合物、ＴｉＳ２などの金属硫化物、Ｖ２Ｏ５、ＭｎＯ２などの酸化物、ポリアニリン及びアントラキノン並びにこれら芳香族を化学構造に含む化合物、共役二酢酸系有機物などの共役系材料、その他公知の材料を用いることもできる。さらに、ニトロキシド、ニトロニルニトロキシド、ガルビノキシル、フェノキシルなどの安定なラジカルを有する化合物を正極活物質として採用してもよい。リチウムイオンを含まない正極活物質材料を用いる場合には、正極及び／又は負極に、公知の方法により、予めリチウムを添加しておくのが好ましい。 As the positive electrode active material, the general formula of the layered rock salt structure: Li a Ni b Co c M d D e O f (M is .D selected from Mn and Al W, Mo, Re, Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, Rh, Fe, Ge, Zn, Ru, Sc, Sn, In, Y, Bi, At least one element selected from S, Si, Na, K, P, and V. a, b, c, d, e, and f are 0.2 ≦ a ≦ 2, b + c + d + e = 1, and 0 ≦ e <1. Satisfying 1.7 ≦ f ≦ 3), and a lithium composite metal oxide represented by the formula: Li 2 MnO 3 . As the positive electrode active material, a metal oxide having a spinel structure such as LiMn 2 O 4 , a solid solution composed of a mixture of a metal oxide having a spinel structure and a layered compound, LiMPO 4 , LiMVO 4, or Li 2 MSiO 4 (wherein M is selected from at least one of Co, Ni, Mn, and Fe). Furthermore, as the positive electrode active material, tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to. Any of the metal oxides used as the positive electrode active material may have the above composition formula as the basic composition, and those obtained by replacing the metal element contained in the basic composition with another metal element can also be used. Alternatively, a material containing no lithium ion may be used as the positive electrode active material. For example, elemental sulfur, a compound of sulfur and carbon, metal sulfides such as TiS 2 , oxides such as V 2 O 5 and MnO 2 , polyaniline and anthraquinone, compounds containing these aromatics in their chemical structures, conjugated compounds Conjugated materials such as acetic acid-based organic substances and other known materials can also be used. Further, a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, and phenoxyl may be employed as the positive electrode active material. When a positive electrode active material containing no lithium ions is used, it is preferable to add lithium to the positive electrode and / or the negative electrode in advance by a known method.
高容量及び耐久性などに優れる点から、正極活物質として、層状岩塩構造の一般式：ＬｉａＮｉｂＣｏｃＭｄＤｅＯｆ(ＭはＭｎ及びＡｌから選択される。ＤはＷ、Ｍｏ、Ｒｅ、Ｐｄ、Ｂａ、Ｃｒ、Ｂ、Ｓｂ、Ｓｒ、Ｐｂ、Ｇａ、Ｎｂ、Ｍｇ、Ｔａ、Ｔｉ、Ｌａ、Ｚｒ、Ｃｕ、Ｃａ、Ｉｒ、Ｈｆ、Ｒｈ、Ｆｅ、Ｇｅ、Ｚｎ、Ｒｕ、Ｓｃ、Ｓｎ、Ｉｎ、Ｙ、Ｂｉ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ｐ、Ｖから選ばれる少なくとも１の元素である。ａ、ｂ、ｃ、ｄ、ｅ、ｆは０．２≦ａ≦２、ｂ＋ｃ＋ｄ＋ｅ＝１、０≦ｅ＜１、１．７≦ｆ≦３を満足する。) で表されるリチウム複合金属酸化物を採用することが好ましい。 From the viewpoint of excellent and high capacity, and durability, as the positive electrode active material, the general formula of the layered rock salt structure: Li a Ni b Co c M d D e O f (M is .D selected from Mn and Al W, Mo, Re, Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, Rh, Fe, Ge, Zn, Ru, At least one element selected from Sc, Sn, In, Y, Bi, S, Si, Na, K, P, and V. a, b, c, d, e, and f are 0.2 ≦ a ≦ 2. , B + c + d + e = 1, 0 ≦ e <1, 1.7 ≦ f ≦ 3.) It is preferable to employ a lithium composite metal oxide represented by the following formula:
上記一般式において、ｂ、ｃ、ｄの値は、上記条件を満足するものであれば特に制限はないが、０＜ｂ＜１、０＜ｃ＜１、０＜ｄ＜１であるものが良く、また、ｂ、ｃ、ｄの少なくともいずれか一つが１０／１００＜ｂ＜９０／１００、１０／１００＜ｃ＜９０／１００、５／１００＜ｄ＜７０／１００の範囲であることが好ましく、２０／１００＜ｂ＜８０／１００、１２／１００＜ｃ＜７０／１００、１０／１００＜ｄ＜６０／１００の範囲であることがより好ましく、３０／１００＜ｂ＜７０／１００、１５／１００＜ｃ＜５０／１００、１２／１００＜ｄ＜５０／１００の範囲であることがさらに好ましい。 In the above general formula, the values of b, c, and d are not particularly limited as long as they satisfy the above conditions, but those satisfying 0 <b <1, 0 <c <1, and 0 <d <1. In addition, at least one of b, c, and d may be in the range of 10/100 <b <90/100, 10/100 <c <90/100, and 5/100 <d <70/100. More preferably, it is more preferably in the range of 20/100 <b <80/100, 12/100 <c <70/100, 10/100 <d <60/100, and 30/100 <b <70/100, It is more preferable that the range of 15/100 <c <50/100 and the range of 12/100 <d <50/100 are satisfied.
ａ、ｅ、ｆについては、上記一般式で規定する範囲内の数値であればよく、好ましくは０．５≦ａ≦１．５、０≦ｅ＜０．２、１．８≦ｆ≦２．５、より好ましくは０．８≦ａ≦１．３、０≦ｅ＜０．１、１．９≦ｆ≦２．１をそれぞれ例示することができる。 a, e, and f may be numerical values within the range defined by the above general formula, and are preferably 0.5 ≦ a ≦ 1.5, 0 ≦ e <0.2, and 1.8 ≦ f ≦ 2. 0.5, more preferably 0.8 ≦ a ≦ 1.3, 0 ≦ e <0.1, and 1.9 ≦ f ≦ 2.1.
高容量及び耐久性などに優れる点から、正極活物質として、スピネル構造のＬｉｘＭｎ２―ｙＡｙＯ４（Ａは、Ｃａ、Ｍｇ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ａｌ、Ｐ、Ｇａ、Ｇｅから選ばれる少なくとも１の元素、及び、Ｎｉなどの遷移金属元素から選ばれる少なくとも１種の金属元素から選択される。０＜ｘ≦２．２、０≦ｙ≦１）を例示できる。ｘの値の範囲としては、０．５≦ｘ≦１．８、０．７≦ｘ≦１．５、０．９≦ｘ≦１．２を例示でき、ｙの値の範囲としては、０≦ｙ≦０．８、０≦ｙ≦０．６を例示できる。具体的なスピネル構造の化合物として、ＬｉＭｎ２Ｏ４、ＬｉＭｎ１．５Ｎｉ０．５Ｏ４を例示できる。 From the viewpoint of excellent and high capacity, and durability, as a positive electrode active material, the Li x Mn 2-y A y O 4 (A spinel structure, Ca, Mg, S, Si , Na, K, Al, P, Ga , Ge, and at least one metal element selected from transition metal elements such as Ni, and 0 <x ≦ 2.2, 0 ≦ y ≦ 1). The range of the value of x can be exemplified by 0.5 ≦ x ≦ 1.8, 0.7 ≦ x ≦ 1.5, 0.9 ≦ x ≦ 1.2, and the range of the value of y is 0 ≦ y ≦ 0.8 and 0 ≦ y ≦ 0.6. Specific examples of the compound having a spinel structure include LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
具体的な正極活物質として、ＬｉＦｅＰＯ４、Ｌｉ２ＦｅＳｉＯ４、ＬｉＣｏＰＯ４、Ｌｉ２ＣｏＰＯ４、Ｌｉ２ＭｎＰＯ４、Ｌｉ２ＭｎＳｉＯ４、Ｌｉ２ＣｏＰＯ４Ｆを例示できる。他の具体的な正極活物質として、Ｌｉ２ＭｎＯ３−ＬｉＣｏＯ２を例示できる。 Specific positive electrode active material can be exemplified by LiFePO 4, Li 2 FeSiO 4, LiCoPO 4, Li 2 CoPO 4, Li 2 MnPO 4, Li 2 MnSiO 4, Li 2 CoPO 4 F. As another specific positive electrode active material can be exemplified by Li 2 MnO 3 -LiCoO 2.
セパレータは、正極と負極とを隔離し、両極の接触による短絡を防止しつつ、リチウムイオンを通過させるものである。セパレータとしては、公知のものを採用すればよく、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミド、ポリアラミド（Ａｒｏｍａｔｉｃ ｐｏｌｙａｍｉｄｅ）、ポリエステル、ポリアクリロニトリル等の合成樹脂、セルロース、アミロース等の多糖類、フィブロイン、ケラチン、リグニン、スベリン等の天然高分子、セラミックスなどの電気絶縁性材料を１種若しくは複数用いた多孔体、不織布、織布などを挙げることができる。また、セパレータは多層構造としてもよい。 The separator separates the positive electrode and the negative electrode, and prevents lithium ions from passing through while preventing a short circuit due to contact between the two electrodes. Known separators may be used as the separator, and synthetic resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polyamide), polyester, and polyacrylonitrile; polysaccharides such as cellulose and amylose; and fibroin. , Natural polymers such as keratin, lignin, suberin, and the like, porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as ceramics. Further, the separator may have a multilayer structure.
本発明のリチウムイオン二次電池の具体的な製造方法について述べる。
例えば、正極と負極とでセパレータを挟持して電極体とする。電極体は、正極、セパレータ及び負極を重ねた積層型、又は、正極、セパレータ及び負極の積層体を捲いた捲回型のいずれの型にしても良い。正極の集電体および負極の集電体から外部に通ずる正極端子および負極端子までを、集電用リード等を用いて接続した後に、電極体に本発明の電解液を加えてリチウムイオン二次電池とするとよい。
A specific method for manufacturing the lithium ion secondary battery of the present invention will be described.
For example, an electrode body is formed by sandwiching a separator between a positive electrode and a negative electrode. The electrode body may be any of a stacked type in which a positive electrode, a separator, and a negative electrode are stacked, or a wound type in which a stacked body of a positive electrode, a separator, and a negative electrode is wound. After connecting the current collector of the positive electrode and the current collector of the negative electrode to the positive electrode terminal and the negative electrode terminal leading to the outside using a current collecting lead or the like, the electrolytic solution of the present invention is added to the electrode body, and lithium ion secondary Use a battery.
本発明のリチウムイオン二次電池の形状は特に限定されるものでなく、円筒型、角型、コイン型、ラミネート型等、種々の形状を採用することができる。 The shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical type, a square type, a coin type, and a laminate type can be adopted.
本発明のリチウムイオン二次電池は、車両に搭載してもよい。車両は、その動力源の全部あるいは一部にリチウムイオン二次電池による電気エネルギーを使用している車両であればよく、例えば、電気車両、ハイブリッド車両などであるとよい。車両にリチウムイオン二次電池を搭載する場合には、リチウムイオン二次電池を複数直列に接続して組電池とするとよい。リチウムイオン二次電池を搭載する機器としては、車両以外にも、パーソナルコンピュータ、携帯通信機器など、電池で駆動される各種の家電製品、オフィス機器、産業機器などが挙げられる。さらに、本発明のリチウムイオン二次電池は、風力発電、太陽光発電、水力発電その他電力系統の蓄電装置及び電力平滑化装置、船舶等の動力及び／又は補機類の電力供給源、航空機、宇宙船等の動力及び／又は補機類の電力供給源、電気を動力源に用いない車両の補助用電源、移動式の家庭用ロボットの電源、システムバックアップ用電源、無停電電源装置の電源、電動車両用充電ステーションなどにおいて充電に必要な電力を一時蓄える蓄電装置に用いてもよい。 The lithium ion secondary battery of the present invention may be mounted on a vehicle. The vehicle may be a vehicle that uses electric energy from a lithium ion secondary battery for all or a part of its power source, such as an electric vehicle or a hybrid vehicle. When a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery. Examples of devices on which a lithium ion secondary battery is mounted include various home appliances, office devices, industrial devices, and the like, other than vehicles, such as personal computers and portable communication devices, which are driven by batteries. Further, the lithium ion secondary battery of the present invention is a wind power generation, a photovoltaic power generation, a hydroelectric power generation, a power storage device and a power smoothing device of a power system, a power supply source for motive power of ships and / or accessories, an aircraft, Power supply for spacecraft and other power supplies and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, The present invention may be applied to a power storage device for temporarily storing power required for charging at a charging station for an electric vehicle or the like.
以上、本発明の実施形態を説明したが、本発明は、上記実施形態に限定されるものではない。本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。 The embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be implemented in various forms with modifications, improvements, and the like that can be made by those skilled in the art without departing from the gist of the present invention.
以下に、実施例及び比較例などを示し、本発明をより具体的に説明する。なお、本発明は、これらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Note that the present invention is not limited by these examples.
（実施例１）
フルオロエチレンカーボネート及びトリフルオロ酢酸エチルを体積比２０：８０で混合して混合溶媒とした。混合溶媒にＬｉＢＦ３ＣＦ３のジメチルカーボネート錯体（東京化成工業株式会社）を溶解して、ＬｉＢＦ３ＣＦ３の濃度が１ｍｏｌ／Ｌである実施例１の電解液を製造した。
(Example 1)
Fluoroethylene carbonate and ethyl trifluoroacetate were mixed at a volume ratio of 20:80 to obtain a mixed solvent. A dimethyl carbonate complex of LiBF 3 CF 3 (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in the mixed solvent to produce an electrolyte of Example 1 in which the concentration of LiBF 3 CF 3 was 1 mol / L.
実施例１の電解液を用いて、実施例１のリチウムイオン二次電池を以下のとおり製造した。 Using the electrolyte solution of Example 1, the lithium ion secondary battery of Example 1 was manufactured as follows.
撹拌条件下の０℃の濃塩酸溶液に、ＣａＳｉ２を加えて１時間反応させた。反応液に水を加え、濾過を行い、黄色の粉体を濾取した。黄色の粉体を水洗し、さらにエタノール洗浄した後に、減圧乾燥して、層状ポリシランを含有する層状シリコン化合物を得た。次いで、層状シリコン化合物をアルゴン雰囲気下、８００℃で加熱して、水素を離脱させて、シリコン材料を製造した。プロパンガス雰囲気下、シリコン材料を８８０℃で加熱することで、炭素層被覆−Ｓｉ含有負極活物質である炭素被覆シリコン材料を製造した。 CaSi 2 was added to a concentrated hydrochloric acid solution at 0 ° C. under stirring conditions and reacted for 1 hour. Water was added to the reaction solution, the mixture was filtered, and a yellow powder was collected by filtration. The yellow powder was washed with water, further washed with ethanol, and dried under reduced pressure to obtain a layered silicon compound containing a layered polysilane. Next, the layered silicon compound was heated at 800 ° C. in an argon atmosphere to release hydrogen, thereby producing a silicon material. By heating the silicon material at 880 ° C. in a propane gas atmosphere, a carbon-coated silicon material as a carbon layer-coated negative electrode active material containing Si was produced.
重量平均分子量８０万のポリアクリル酸をＮ−メチル−２−ピロリドンに溶解して、ポリアクリル酸が１０質量％で含有されるポリアクリル酸溶液を製造した。また、４，４’−ジアミノジフェニルメタン０．２ｇ（１．０ｍｍｏｌ）を０．４ｍＬのＮ−メチル−２−ピロリドンに溶解して、４，４’−ジアミノジフェニルメタン溶液を製造した。撹拌条件下、ポリアクリル酸溶液７ｍＬ（アクリル酸モノマー換算で、９．５ｍｍｏｌに該当する。）に、４，４’−ジアミノジフェニルメタン溶液の全量を滴下して、得られた混合物を室温で３０分間撹拌した。その後、ディーンスターク装置を用いて、混合物を１３０℃で３時間撹拌して脱水反応を進行させることで、結着剤溶液を製造した。 Polyacrylic acid having a weight average molecular weight of 800,000 was dissolved in N-methyl-2-pyrrolidone to prepare a polyacrylic acid solution containing 10% by mass of polyacrylic acid. Further, 0.2 g (1.0 mmol) of 4,4'-diaminodiphenylmethane was dissolved in 0.4 mL of N-methyl-2-pyrrolidone to prepare a 4,4'-diaminodiphenylmethane solution. Under stirring conditions, the entire amount of the 4,4′-diaminodiphenylmethane solution was added dropwise to 7 mL of the polyacrylic acid solution (equivalent to 9.5 mmol in terms of acrylic acid monomer), and the resulting mixture was allowed to stand at room temperature for 30 minutes. Stirred. Thereafter, using a Dean-Stark apparatus, the mixture was stirred at 130 ° C. for 3 hours to advance a dehydration reaction, thereby producing a binder solution.
Ｓｉ含有負極活物質として炭素被覆シリコン材料７２．５質量部、導電助剤としてアセチレンブラック１３．５質量部、結着剤として固形分が１４質量部となる量の上記結着剤溶液、及び、適量のＮ−メチル−２−ピロリドンを混合して、スラリーを製造した。負極用集電体として厚み１０μｍの銅箔を準備した。この銅箔の表面に、ドクターブレードを用いて、上記スラリーを膜状に塗布した。スラリーが塗布された銅箔を８０℃、１５分間乾燥することで、Ｎ−メチル−２−ピロリドンを除去した。その後、プレスすることで、厚み２５μｍの負極活物質層が形成された負極を製造した。 72.5 parts by mass of a carbon-coated silicon material as a Si-containing negative electrode active material, 13.5 parts by mass of acetylene black as a conductive additive, an amount of the binder solution in which the solid content becomes 14 parts by mass as a binder, and An appropriate amount of N-methyl-2-pyrrolidone was mixed to produce a slurry. A 10-μm-thick copper foil was prepared as a negative electrode current collector. The slurry was applied to the surface of the copper foil in the form of a film using a doctor blade. The copper foil coated with the slurry was dried at 80 ° C. for 15 minutes to remove N-methyl-2-pyrrolidone. Thereafter, by pressing, a negative electrode on which a 25 μm-thick negative electrode active material layer was formed was manufactured.
ＬｉＮｉ０．５Ｃｏ０．３Ｍｎ０．２Ｏ２で表される層状岩塩構造のリチウム金属複合酸化物９４質量部、導電助剤としてアセチレンブラック３質量部、結着剤としてポリフッ化ビニリデン３質量部、及び、適量のＮ−メチル−２−ピロリドンを混合して、スラリーを製造した。正極用集電体としてアルミニウム箔を準備した。このアルミニウム箔の表面に、ドクターブレードを用いて上記スラリーが膜状になるように塗布した。スラリーが塗布されたアルミニウム箔を乾燥することで、Ｎ−メチル−２−ピロリドンを除去した。その後、当該アルミニウム箔をプレスし接合物を得た。得られた接合物を真空乾燥機で加熱乾燥して、正極活物質層が形成された正極を製造した。 94 parts by mass of a lithium metal composite oxide having a layered rock salt structure represented by LiNi 0.5 Co 0.3 Mn 0.2 O 2 , 3 parts by mass of acetylene black as a conductive aid, and 3 parts by mass of polyvinylidene fluoride as a binder And a suitable amount of N-methyl-2-pyrrolidone to prepare a slurry. An aluminum foil was prepared as a current collector for the positive electrode. The slurry was applied on the surface of the aluminum foil using a doctor blade so as to form a film. The N-methyl-2-pyrrolidone was removed by drying the aluminum foil on which the slurry was applied. Thereafter, the aluminum foil was pressed to obtain a joined product. The obtained bonded article was dried by heating with a vacuum drier to produce a positive electrode on which a positive electrode active material layer was formed.
セパレータとして、ポリプロピレン製多孔質膜を準備した。 A polypropylene porous membrane was prepared as a separator.
正極と負極とでセパレータを挟持し、極板群とした。この極板群を二枚一組のラミネートフィルムで覆い、三辺をシールした後、袋状となったラミネートフィルムに電解液を注入した。その後、残りの一辺をシールすることで、四辺が気密にシールされ、極板群および電解液が密閉された実施例１のリチウムイオン二次電池を製造した。 A separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group. The electrode group was covered with a set of two laminated films, and after sealing three sides, an electrolyte was injected into the bag-shaped laminated film. Thereafter, by sealing the remaining one side, the four sides were hermetically sealed, and the lithium ion secondary battery of Example 1 in which the electrode plate group and the electrolyte were sealed was manufactured.
（実施例２）
トリフルオロ酢酸エチルに替えてトリフルオロ酢酸イソプロピルを採用した以外は、実施例１と同様の方法で、実施例２の電解液を製造した。
実施例２の電解液を用いた以外は、実施例１と同様の方法で、実施例２のリチウムイオン二次電池を製造した。
(Example 2)
An electrolytic solution of Example 2 was produced in the same manner as in Example 1, except that isopropyl trifluoroacetate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Example 2 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Example 2 was used.
（実施例３）
フルオロエチレンカーボネート及びトリフルオロ酢酸エチルを体積比２０：８０で混合して混合溶媒とした。混合溶媒にＬｉＢＦ２（ＣＦ３）２を溶解して、ＬｉＢＦ２（ＣＦ３）２の濃度が１ｍｏｌ／Ｌである実施例３の電解液を製造した。
実施例３の電解液を用いた以外は、実施例１と同様の方法で、実施例３のリチウムイオン二次電池を製造した。
(Example 3)
Fluoroethylene carbonate and ethyl trifluoroacetate were mixed at a volume ratio of 20:80 to obtain a mixed solvent. LiBF 2 (CF 3 ) 2 was dissolved in the mixed solvent to prepare an electrolyte solution of Example 3 in which the concentration of LiBF 2 (CF 3 ) 2 was 1 mol / L.
A lithium ion secondary battery of Example 3 was manufactured in the same manner as in Example 1, except that the electrolytic solution of Example 3 was used.
（実施例４）
トリフルオロ酢酸エチルに替えてトリフルオロ酢酸イソプロピルを採用した以外は、実施例３と同様の方法で、実施例４の電解液を製造した。
実施例４の電解液を用いた以外は、実施例１と同様の方法で、実施例４のリチウムイオン二次電池を製造した。
(Example 4)
An electrolytic solution of Example 4 was produced in the same manner as in Example 3, except that isopropyl trifluoroacetate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Example 4 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Example 4 was used.
（比較例１）
フルオロエチレンカーボネート及びトリフルオロ酢酸エチルを体積比２０：８０で混合して混合溶媒とした。混合溶媒にＬｉＰＦ６を混合して、ＬｉＰＦ６の濃度が１ｍｏｌ／Ｌである比較例１の電解液を製造しようとしたが、目的の濃度でＬｉＰＦ６を溶解させることができなかった。
(Comparative Example 1)
Fluoroethylene carbonate and ethyl trifluoroacetate were mixed at a volume ratio of 20:80 to obtain a mixed solvent. LiPF 6 was mixed with the mixed solvent to produce an electrolyte of Comparative Example 1 in which the concentration of LiPF 6 was 1 mol / L, but LiPF 6 could not be dissolved at the desired concentration.
（比較例２）
フルオロエチレンカーボネート及びトリフルオロ酢酸エチルを体積比２０：８０で混合して混合溶媒とした。混合溶媒にＬｉＢＦ４を混合して、ＬｉＢＦ４の濃度が１ｍｏｌ／Ｌである比較例２の電解液を製造しようとしたが、目的の濃度でＬｉＢＦ４を溶解させることができなかった。
(Comparative Example 2)
Fluoroethylene carbonate and ethyl trifluoroacetate were mixed at a volume ratio of 20:80 to obtain a mixed solvent. LiBF 4 was mixed with the mixed solvent to produce an electrolyte solution of Comparative Example 2 in which the concentration of LiBF 4 was 1 mol / L, but LiBF 4 could not be dissolved at the desired concentration.
（比較例３）
トリフルオロ酢酸エチルに替えて酢酸エチルを採用した以外は、実施例１と同様の方法で、比較例３の電解液を製造した。
比較例３の電解液を用いた以外は、実施例１と同様の方法で、比較例３のリチウムイオン二次電池を製造した。
(Comparative Example 3)
An electrolytic solution of Comparative Example 3 was produced in the same manner as in Example 1, except that ethyl acetate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Comparative Example 3 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Comparative Example 3 was used.
（比較例４）
トリフルオロ酢酸エチルに替えてジメチルカーボネートを採用した以外は、実施例１と同様の方法で、比較例４の電解液を製造した。
比較例４の電解液を用いた以外は、実施例１と同様の方法で、比較例４のリチウムイオン二次電池を製造した。
(Comparative Example 4)
An electrolytic solution of Comparative Example 4 was produced in the same manner as in Example 1, except that dimethyl carbonate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Comparative Example 4 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Comparative Example 4 was used.
（比較例５）
トリフルオロ酢酸エチルに替えて酢酸エチルを採用した以外は、実施例３と同様の方法で、比較例５の電解液を製造した。
比較例５の電解液を用いた以外は、実施例１と同様の方法で、比較例５のリチウムイオン二次電池を製造した。
(Comparative Example 5)
An electrolytic solution of Comparative Example 5 was produced in the same manner as in Example 3, except that ethyl acetate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Comparative Example 5 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Comparative Example 5 was used.
（比較例６）
トリフルオロ酢酸エチルに替えてジメチルカーボネートを採用した以外は、実施例３と同様の方法で、比較例６の電解液を製造した。
比較例６の電解液を用いた以外は、実施例１と同様の方法で、比較例６のリチウムイオン二次電池を製造した。
(Comparative Example 6)
An electrolytic solution of Comparative Example 6 was produced in the same manner as in Example 3, except that dimethyl carbonate was used instead of ethyl trifluoroacetate.
A lithium ion secondary battery of Comparative Example 6 was manufactured in the same manner as in Example 1 except that the electrolytic solution of Comparative Example 6 was used.
（評価例１）
各リチウムイオン二次電池を３．９Ｖまで０．３Ｃレートで充電して、６０℃で２０時間保存した。その後、各リチウムイオン二次電池に対して、１Ｃレートで４．２４Ｖまで充電して３Ｖまで放電するとの充放電サイクルを３０回繰り返した。
初回の充放電サイクルの放電容量に対する、３０回目の充放電サイクルの放電容量の割合を、容量維持率として算出した。
(Evaluation Example 1)
Each lithium ion secondary battery was charged to 3.9 V at a rate of 0.3 C and stored at 60 ° C. for 20 hours. Thereafter, a charge / discharge cycle of charging each lithium ion secondary battery to 4.24 V at a 1 C rate and discharging it to 3 V was repeated 30 times.
The ratio of the discharge capacity of the 30th charge / discharge cycle to the discharge capacity of the first charge / discharge cycle was calculated as a capacity retention ratio.
以上の結果を表１に示す。表１において、ＦＥＣとはフルオロエチレンカーボネートの略称である。ＤＭＣとはジメチルカーボネートの略称である。 Table 1 shows the above results. In Table 1, FEC is an abbreviation for fluoroethylene carbonate. DMC is an abbreviation for dimethyl carbonate.
表１から、本発明の電解液を用いた実施例のリチウムイオン二次電池は、いずれも高い容量維持率を示したことがわかる。本発明者の仮説が正しいことが試験結果で裏付けられたといえる。 Table 1 shows that the lithium ion secondary batteries of Examples using the electrolytic solution of the present invention all exhibited high capacity retention rates. It can be said that the test results confirmed that the inventor's hypothesis was correct.
Claims (5)
一般式（１） Ｒ１ＣＯ２Ｒ２
Ｒ１は、フッ素含有アルキル基である。Ｒ２は、フッ素で置換されていてもよいアルキル基である。 LiBF 4-a (CF 3 ) a (a is 1, 2, 3 or 4), a fluorine-containing cyclic carbonate and a fluorine-containing chain ester represented by the following general formula (1). Electrolyte solution.
General formula (1) R 1 CO 2 R 2
R 1 is a fluorine-containing alkyl group. R 2 is an alkyl group optionally substituted by fluorine.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4164019A4 (en) * | 2021-06-25 | 2024-04-03 | LG Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| JPWO2024090573A1 (en) * | 2022-10-27 | 2024-05-02 |
-
2018
- 2018-07-17 JP JP2018134437A patent/JP2020013680A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4164019A4 (en) * | 2021-06-25 | 2024-04-03 | LG Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| JPWO2024090573A1 (en) * | 2022-10-27 | 2024-05-02 |
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