JP2022135234A - Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery having the same - Google Patents
Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery having the same Download PDFInfo
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- JP2022135234A JP2022135234A JP2021034904A JP2021034904A JP2022135234A JP 2022135234 A JP2022135234 A JP 2022135234A JP 2021034904 A JP2021034904 A JP 2021034904A JP 2021034904 A JP2021034904 A JP 2021034904A JP 2022135234 A JP2022135234 A JP 2022135234A
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 30
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 15
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- -1 allyl ester compound Chemical class 0.000 claims description 72
- 239000008151 electrolyte solution Substances 0.000 claims description 70
- 239000007774 positive electrode material Substances 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000007773 negative electrode material Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 10
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- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
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- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- FCFMKFHUNDYKEG-UHFFFAOYSA-N thietane 1,1-dioxide Chemical class O=S1(=O)CCC1 FCFMKFHUNDYKEG-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ARUIMKUOHIINGI-UHFFFAOYSA-N trifluoro(methylsulfonyl)methane Chemical compound CS(=O)(=O)C(F)(F)F ARUIMKUOHIINGI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Description
本発明は、非水系電解液及び該非水系電解液を備える非水系電解液二次電池に関する。 TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte.
含リチウム遷移金属酸化物を正極に用い、非水溶媒を電解液に用いるリチウム非水系電解液二次電池は、高いエネルギー密度を実現できることから、携帯電話、ラップトップコンピュータ等の小型電源から、自動車や鉄道、ロードレベリング用の大型電源まで広範な用途に適用されている。しかしながら、近年の非水系電解液二次電池に対する高性能化の要求はますます高まっており、各種特性の向上が強く要求されている。 Lithium non-aqueous electrolyte secondary batteries that use a lithium-containing transition metal oxide for the positive electrode and a non-aqueous solvent for the electrolyte can achieve high energy density. It is used in a wide range of applications, including large power supplies for railroads, railroads, and load leveling. However, in recent years, there has been an increasing demand for higher performance of non-aqueous electrolyte secondary batteries, and there is a strong demand for improvements in various characteristics.
これまでに、特定の添加剤を電解液中に含有させたり、特定の電解液と電極を組み合わせたりすることで、エネルギーデバイスの電池特性を向上する方法が提案されている。例えば、特許文献1は、蓄電デバイス用、特にSi系の負極活物質を含有するリチウムイオン蓄電池用の電解液に関し、Si系の負極活物質を含有する負極及び特定の炭素-炭素二重結合を有するエステル化合物を含有する非水系電解液を備えることにより蓄電デバイスのサイクル時の放電容量維持率を向上させることが提案されている。 So far, methods have been proposed to improve the battery characteristics of energy devices by including specific additives in the electrolyte or by combining specific electrolytes and electrodes. For example, Patent Document 1 relates to an electrolytic solution for an electric storage device, particularly a lithium ion storage battery containing a Si-based negative electrode active material, and a negative electrode containing a Si-based negative electrode active material and a specific carbon-carbon double bond. It has been proposed to improve the discharge capacity retention rate during cycling of an electricity storage device by providing a non-aqueous electrolytic solution containing an ester compound having a
特許文献2には、非水電解液電池の充放電サイクルにおける放電容量維持率の向上のために、特定の飽和鎖状カルボン酸エステル及び不飽和鎖状カルボン酸エステルを含有する電解液が提案されている。 Patent Document 2 proposes an electrolytic solution containing a specific saturated chain carboxylic acid ester and an unsaturated chain carboxylic acid ester in order to improve the discharge capacity retention rate in charge-discharge cycles of a non-aqueous electrolyte battery. ing.
特許文献3には、高温保存時の電池の膨張を抑制しつつ、サイクル時の放電容量維持率を向上させるために、電解液中に特定の不飽和カルボン酸エステルを含有させ、特定の外装部材に収容し非水電解液二次電池とすることが提案されている。 In Patent Document 3, in order to improve the discharge capacity retention rate during cycling while suppressing the expansion of the battery during high-temperature storage, the electrolyte contains a specific unsaturated carboxylic acid ester, and a specific exterior member It has been proposed that the non-aqueous electrolyte secondary battery is made by housing the non-aqueous electrolyte secondary battery.
特許文献4には、スピネル型マンガン酸リチウムを正極活物質とするリチウム二次電池において、高温特性や保存特性を向上させるために、特定の重合性有機化合物を含有する非水系電解液が提案されている。 Patent Document 4 proposes a non-aqueous electrolytic solution containing a specific polymerizable organic compound in order to improve high-temperature characteristics and storage characteristics in a lithium secondary battery using spinel-type lithium manganate as a positive electrode active material. ing.
近年の非水系電解液二次電池は、特に電池搭載自動車が求める要求特性がますます高くなり、高温保存後の電池容量の向上が高いレベルで求められている。これまでに、例えば、ジフルオロリン酸リチウムなどのリン酸塩が非水系電解液二次電池の添加剤として検討されている。
しかしながら、特許文献1では、特定の負極活物質を含有する負極、炭素-炭素二重結合を有するエステル化合物を含有する非水電解液を組み合わせることによる非水系電解液二次電池のサイクル時の容量維持率の向上が検討されているが、高温保存後の電池抵抗に関しては着目されておらず検討されていない。また、特許文献2では、サイクル試験時の放電容量維持率の向上が検討されているが、高温保存後の電池抵抗に関しては着目されて
おらず、検討されていない。さらに、特許文献3では、特定の外装部材と特定の不飽和カルボン酸エステルを有する電解液を組み合わせることによるサイクル特性の向上が検討されているが、特定の不飽和カルボン酸エステル以外の電解液の成分としては、溶媒と、溶媒に溶解された電解質塩とを含むこと、並びにハロゲン化炭酸エステルまたは炭素-炭素多重結合を有する炭酸エステルを含有することが好ましいことが記載されているのみである。さらに、特許文献4では、飽和鎖状カルボン酸エステルに適した添加剤を選択することにより、充放電サイクルにおける放電容量維持率を向上させることが検討されているが、非水電解液の成分として、特定の飽和および不飽和鎖状カルボン酸エステル以外には、溶媒と、溶媒に溶解された電解質塩とを含むことが記載されているのみである。
In recent years, non-aqueous electrolyte secondary batteries have been required to have higher and higher performance, especially for battery-equipped vehicles, and a high level of improvement in battery capacity after high-temperature storage has been demanded. So far, for example, phosphates such as lithium difluorophosphate have been studied as additives for non-aqueous electrolyte secondary batteries.
However, in Patent Document 1, a negative electrode containing a specific negative electrode active material and a non-aqueous electrolyte containing an ester compound having a carbon-carbon double bond are combined. Although the improvement of the retention rate has been studied, the battery resistance after high-temperature storage has not been paid attention to and studied. Further, in Patent Literature 2, improvement of the discharge capacity retention rate during the cycle test is studied, but the battery resistance after high-temperature storage is not paid attention to and studied. Furthermore, in Patent Document 3, improvement of cycle characteristics is studied by combining a specific exterior member and an electrolytic solution having a specific unsaturated carboxylic acid ester, but an electrolytic solution other than the specific unsaturated carboxylic acid ester is used. It only states that the components include a solvent and an electrolyte salt dissolved in the solvent, and that it preferably includes a halogenated carbonate or a carbonate having a carbon-carbon multiple bond. Furthermore, in Patent Document 4, it is studied to improve the discharge capacity retention rate in charge-discharge cycles by selecting an additive suitable for the saturated chain carboxylic acid ester, but as a component of the non-aqueous electrolyte , other than specific saturated and unsaturated linear carboxylic acid esters, are only described to include a solvent and an electrolyte salt dissolved in the solvent.
本発明では、高温保存後の非水系電解液二次電池の直流抵抗(DCR)の増加を抑制し得る非水系電解液を提供することを課題とする。 An object of the present invention is to provide a non-aqueous electrolyte that can suppress an increase in direct current resistance (DCR) of a non-aqueous electrolyte secondary battery after high-temperature storage.
本発明者は、上記の課題を解決すべく鋭意検討した結果、非水系電解液に特定の炭素-炭素不飽和結合を有するエステル化合物と、特定のリン酸塩、スルホン酸塩又はホウ酸塩とを含有することで、上記課題を解決できることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have found that an ester compound having a specific carbon-carbon unsaturated bond in a non-aqueous electrolytic solution, and a specific phosphate, sulfonate or borate By containing, it was found that the above problems can be solved, and the present invention was achieved.
即ち、本発明の要旨は、以下に存する。
[1]式(I)で表される化合物(A)と、P-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、並びにB-F結合及び/又はオキサラート基を有するホウ酸塩からなる群より選ばれる1種以上の化合物(B)と、を含有することを特徴とする非水系電解液。
(式(I)中、R1~R6は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R1とR2、R1とR3、R4とR5、及びR5とR6は互いに結合し環状構造を形成していてもよい。nは0~4の整数である。)
[2]前記式(I)中、R1~R6が、それぞれ独立に、水素原子、ハロゲン原子、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、炭素数6~12のアリール基、又は炭素数7~18のアラルキル基である、[1]に記載の非水系電解液。
[3]前記式(I)で表される化合物(A)が、下記式(II)で表されるビニルエステル化合物及び/又は式(III)で表されるアリルエステル化合物である、[1]又は[2]に記載の非水電解液。
(式(II)中、R7~R9は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R7とR8、R7とR9は互いに結合し環状構造を形成していてもよい。)
(式(III)中、R10~R12は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R10とR11、R10とR12は互いに結合し環状構造を形成していてもよい。)
[4]前記式(I)で表される化合物(A)がメタクリル酸アリルである、[1]~[3]のいずれかに記載の非水系電解液。
[5]前記式(I)で表される化合物(A)を0.01質量%以上、10質量%以下含有する、[1]~[4]のいずれかに記載の非水系電解液。
[6]前記P-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、B-F結合を有するホウ酸塩及びオキサラート基を有するホウ酸塩からなる群より選ばれる1種以上の化合物(B)を、0.01質量%以上、10質量%以下含有する、[1]~[5]のいずれかに記載の非水系電解液。
[7]金属イオンを吸蔵及び放出しうる正極活物質を有する正極と、金属イオンを吸蔵及び放出しうる負極活物質を有する負極と、[1]~[6]のいずれかに記載の非水系電解液と、を備える非水系電解液二次電池。
That is, the gist of the present invention resides in the following.
[1] a compound (A) represented by formula (I), a phosphate having a PF bond and a P=O bond, a sulfonate having an SF bond, and a BF bond and/or and one or more compounds (B) selected from the group consisting of borates having an oxalate group.
(In Formula (I), R 1 to R 6 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 1 and R 2 , R 1 and R 3 , R 4 and R 5 , and R 5 and R 6 may combine with each other to form a cyclic structure, and n is an integer of 0 to 4.)
[2] In formula (I), R 1 to R 6 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 6 to 12 carbon atoms. or an aralkyl group having 7 to 18 carbon atoms, the non-aqueous electrolytic solution according to [1].
[3] The compound (A) represented by the formula (I) is a vinyl ester compound represented by the following formula (II) and/or an allyl ester compound represented by the formula (III) [1] Or the non-aqueous electrolytic solution according to [2].
(In Formula (II), R 7 to R 9 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 7 and R 8 and R 7 and R 9 are bonded to each other to form a cyclic structure. may be.)
(In Formula (III), R 10 to R 12 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 10 and R 11 and R 10 and R 12 are bonded to each other to form a cyclic structure. may be.)
[4] The non-aqueous electrolytic solution according to any one of [1] to [3], wherein the compound (A) represented by formula (I) is allyl methacrylate.
[5] The non-aqueous electrolytic solution according to any one of [1] to [4], containing 0.01% by mass or more and 10% by mass or less of the compound (A) represented by the formula (I).
[6] from the group consisting of a phosphate having a PF bond and a P=O bond, a sulfonate having an SF bond, a borate having a BF bond and a borate having an oxalate group The non-aqueous electrolytic solution according to any one of [1] to [5], containing 0.01% by mass or more and 10% by mass or less of one or more selected compounds (B).
[7] A positive electrode having a positive electrode active material capable of absorbing and releasing metal ions, a negative electrode having a negative electrode active material capable of absorbing and releasing metal ions, and the non-aqueous system according to any one of [1] to [6]. A non-aqueous electrolyte secondary battery comprising an electrolyte.
本発明によれば、高温保存後の非水系電解液二次電池のDCRの増加を抑制し得る非水系電解液を提供できる。また、当該非水系電解液を備えた非水系電解液二次電池を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the non-aqueous electrolyte solution which can suppress the increase in DCR of the non-aqueous electrolyte secondary battery after high temperature storage can be provided. Also, a non-aqueous electrolyte secondary battery comprising the non-aqueous electrolyte can be provided.
以下に、本発明を実施するための形態を詳細に説明する。ただし、以下に記載する説明は本発明の実施形態の一例(代表例)であり、本発明はこれらの内容に限定されるものではない。また、本発明は、その要旨を逸脱しない範囲内で任意に変更して実施することができる。 EMBODIMENT OF THE INVENTION Below, the form for implementing this invention is demonstrated in detail. However, the description given below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents. In addition, the present invention can be arbitrarily changed and implemented without departing from the gist thereof.
[1.非水系電解液]
本発明の実施形態に係る非水系電解液二次電池に用いる非水系電解液は、一般的な非水系電解液と同様に、電解質、これを溶解する非水溶媒を含有し、さらに、式(I)で表される化合物(A)(以下、炭素-炭素不飽和結合を有するエステル化合物と記す場合がある)、且つP-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、並びにB-F結合及び/又はオキサラート基を有するホウ酸塩からなる群より選ばれる1種以上の化合物(B)(以下、「併用添加剤」と記す場合がある)を含有する非水系電解液である。
(式(I)中、R1~R6は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R1とR3、又はR4とR5は互いに結合し環状構造を形成していてもよい。nは0~4の整数である。)
本発明に係る非水系電解液は、高温保存後の電池容量を改善し得る。このような優れた
効果を奏する理由について、本発明者は以下のように推測する。
二次電池の充放電に伴い、式(I)で表される化合物(A)の炭素-炭素不飽和結合が電極上で反応して化合物(A)が多量化し、さらにP-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、並びにB-F結合及び/又はオキサラート基を有するホウ酸塩からなる群より選ばれる1種以上の化合物(B)と反応し、電極上で難溶解性かつ強固な共被膜を形成することで、電極活物質と溶媒等との副反応を抑制すると考える。
すなわち、本発明は、非水系電解液中に、炭素-炭素不飽和結合を有するエステル化合物とP-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、並びにB-F結合及び/又はオキサラート基を有するホウ酸塩からなる群より選ばれる1種以上の化合物とを含有させることで、従来より高いレベルまで、高温保存後のDCR増加を抑制できると考える。
以下、各構成について説明する。
[1. Non-aqueous electrolyte]
The non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery according to the embodiment of the present invention contains an electrolyte, a non-aqueous solvent for dissolving it, as well as a general non-aqueous electrolyte, and further has the formula ( Compound (A) represented by I) (hereinafter sometimes referred to as an ester compound having a carbon-carbon unsaturated bond), and a phosphate having a PF bond and a P=O bond, and an SF bond and one or more compounds (B) selected from the group consisting of sulfonates having It is a non-aqueous electrolytic solution containing.
(In Formula (I), R 1 to R 6 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 1 and R 3 or R 4 and R 5 are bonded to each other to form a cyclic structure. may be formed, n is an integer from 0 to 4.)
The non-aqueous electrolytic solution according to the present invention can improve battery capacity after high-temperature storage. The inventor of the present invention presumes the reason for such excellent effects as follows.
As the secondary battery is charged and discharged, the carbon-carbon unsaturated bond of the compound (A) represented by the formula (I) reacts on the electrode to increase the amount of the compound (A), and further the PF bond and P = reacting with one or more compounds (B) selected from the group consisting of phosphates having an O bond, sulfonates having an SF bond, and borates having a BF bond and/or an oxalate group However, it is thought that side reactions between the electrode active material and the solvent or the like can be suppressed by forming a hard and insoluble co-film on the electrode.
That is, the present invention provides, in a non-aqueous electrolytic solution, an ester compound having a carbon-carbon unsaturated bond, a phosphate having a PF bond and a P=O bond, a sulfonate having an SF bond, and By containing one or more compounds selected from the group consisting of borates having a BF bond and/or an oxalate group, it is believed that the increase in DCR after high-temperature storage can be suppressed to a higher level than before.
Each configuration will be described below.
[1-1.式(I)で表される化合物(A)(炭素-炭素不飽和結合を有するエステル化合物)]
式(I)中、R1~R6は、それぞれ独立に、水素原子、ハロゲン原子又は炭化水素基である。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、又はヨウ素原子が挙げられる。なかでも、フッ素原子が、電解液への安定性の点で好ましい。
炭化水素基としては、アルキル基、アルケニル基、アルキニル基、アリール基又はアラルキル基が挙げられる。なかでも、アルキル基、アルケニル基、アリール基、及びアラルキル基が好ましく、アルキル基及びアルケニル基がより好ましく、アルキル基が特に好ましい。なお、炭化水素基はフッ素原子等の置換基を有していてもよい。また、アリール基は、任意の環原子がヘテロ原子で置換されているヘテロアリール基も含むものとする。
アルキル基としては、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、tert-ブチル基、n-ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、及びデシル基等が挙げられる。なかでも、炭素数が1~6のアルキル基が、電解液への溶解性の点で好ましい。
アルケニル基としては、ビニル基、アリル基、メタリル基、2-ブテニル基、3-メチル2-ブテニル基、3-ブテニル基、4-ペンテニル基、5-ヘキセニル基、6-ヘプテニル基、及び7-オクテニル基等が挙げられる。なかでも、炭素数が2~6のアルケニル基が電解液への溶解性の点で好ましい。
アルキニル基としては、エチニル基、2-プロピニル基、2-ブチニル基、3-ブチニル基、4-ペンチニル基、5-ヘキシニル基、6-ヘプチニル基、及び7-オクチニル基等が挙げられる。なかでも、炭素数が2~6のアルキニル基が電解液への溶解性の点で好ましい。
アリール基としては、フェニル基、1-ナフチル基、2-ナフチル基、2-チエニル基、3-チエニル基、2-フリル基、3-フリル基、2-ピロリル基、3-ピロリル基、及びベンジル基等が挙げられる。なかでも、炭素原子数が6~12のアリール基が好ましく、フェニル基、1-ナフチル基、及び2-ナフチル基が電解液への溶解性の点で特に好ましい。
アラルキル基としては、フェニルメチル基(ベンジル基)、フェニルエチル基(フェネチル基)、フェニルプロピル基、フェニルブチル基、及びフェニルイソプロピル基等が挙
げられる。なかでも、ベンジル基及びフェネチル基が好ましく、ベンジル基が電解液への安定性の点で特に好ましい。
式(I)中のR1とR2、R1とR3、R4とR5、又はR5とR6はそれぞれ互いに結合し環状構造を形成していてもよい。本明細書では、R1~R6は、R1とR2、R1とR3、R4とR5、又はR5とR6が互いに結合して形成した環において、1つのC-C結合を切断した場合に生成する基も含む。
R1、R2並びにR1及びR2が結合する炭素、又はR5、R6並びにR5及びR6が結合する炭素から構成される環状構造としては、シクロヘキセン環、シクロペンテン環等の脂環式炭素環が挙げられる。なかでも、シクロヘキセン環が電解液への安定性の点で好ましい。
R1、R3並びに、R1及びR2が結合する炭素とR3及びエステル基が結合する炭素との炭素-炭素二重結合、R4、R5並びに、R4及びメチレン基若しくはエステル基の酸素原子が結合する炭素とR5及びR6が結合する炭素との炭素-炭素二重結合から構成される環状構造としては、シクロヘキセン環、シクロペンテン環等の脂環式炭素環;ベンゼン環、ナフタレン環等の芳香環;等が挙げられる。なかでも、シクロヘキセン環、ベンゼン環、ナフタレン環が電解液への安定性の点で好ましく、シクロヘキセン環、ベンゼン環、及びナフタレン環がより好ましく、シクロヘキセン環、及びベンゼン環がさらに好ましい。また、環状構造の水素原子がフッ素原子等のハロゲン原子に置換されてもよい。
R1~R6としては水素原子、炭素数1~6のアルキル基が好ましい。
nは0~4の整数であり、電解液への溶解性の点で好ましくは0~2の整数であり、より好ましくは0又は1であり、さらに好ましくは1である。
In formula (I), R 1 to R 6 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group.
A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among them, a fluorine atom is preferable from the viewpoint of stability to the electrolytic solution.
Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups and aralkyl groups. Among them, an alkyl group, an alkenyl group, an aryl group, and an aralkyl group are preferable, an alkyl group and an alkenyl group are more preferable, and an alkyl group is particularly preferable. Incidentally, the hydrocarbon group may have a substituent such as a fluorine atom. Aryl groups are also meant to include heteroaryl groups in which any ring atom is substituted with a heteroatom.
Alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl. and the like. Among them, an alkyl group having 1 to 6 carbon atoms is preferable from the standpoint of solubility in the electrolytic solution.
Examples of alkenyl groups include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 6-heptenyl, and 7- An octenyl group and the like can be mentioned. Among them, an alkenyl group having 2 to 6 carbon atoms is preferable in terms of solubility in the electrolytic solution.
Examples of alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, 5-hexynyl, 6-heptynyl, and 7-octynyl groups. Among them, an alkynyl group having 2 to 6 carbon atoms is preferable from the standpoint of solubility in the electrolytic solution.
Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-pyrrolyl, and benzyl and the like. Among them, an aryl group having 6 to 12 carbon atoms is preferable, and a phenyl group, a 1-naphthyl group and a 2-naphthyl group are particularly preferable from the viewpoint of solubility in the electrolytic solution.
The aralkyl group includes a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, and the like. Among them, a benzyl group and a phenethyl group are preferable, and a benzyl group is particularly preferable from the viewpoint of stability to the electrolytic solution.
R 1 and R 2 , R 1 and R 3 , R 4 and R 5 , or R 5 and R 6 in formula (I) may be bonded to each other to form a cyclic structure. In the present specification , R 1 to R 6 are one C-- It also includes groups generated when the C bond is cleaved.
The cyclic structure composed of R 1 , R 2 and the carbon to which R 1 and R 2 are bonded, or the carbon to which R 5 , R 6 and R 5 and R 6 are bonded includes an alicyclic ring such as a cyclohexene ring and a cyclopentene ring. Formula carbocycles are included. Among them, a cyclohexene ring is preferable from the viewpoint of stability to the electrolytic solution.
R 1 , R 3 and a carbon-carbon double bond between the carbon to which R 1 and R 2 are bonded and the carbon to which R 3 and the ester group are bonded, R 4 , R 5 and R 4 and a methylene or ester group The cyclic structure composed of a carbon-carbon double bond between the carbon to which the oxygen atom of and the carbon to which R 5 and R 6 are bonded includes an alicyclic carbocyclic ring such as a cyclohexene ring and a cyclopentene ring; a benzene ring, aromatic rings such as naphthalene ring; and the like. Among them, a cyclohexene ring, a benzene ring, and a naphthalene ring are preferable from the viewpoint of stability to an electrolytic solution, a cyclohexene ring, a benzene ring, and a naphthalene ring are more preferable, and a cyclohexene ring and a benzene ring are even more preferable. Also, hydrogen atoms in the ring structure may be substituted with halogen atoms such as fluorine atoms.
R 1 to R 6 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
n is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1 from the viewpoint of solubility in the electrolytic solution.
電解液中での安定性の観点から、より好ましくは、以下の一般式(II)で表されるビニルエステル化合物及び/又は一般式(III)で表されるアリルエステル化合物である。
(式(II)中、R7~R9は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R7とR8、R7とR9は互いに結合し環状構造を形成していてもよい。)
(式(III)中、R10~R12は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R10とR11、R10とR12は互いに結合し環状構造を形成していてもよい。)
一般式(II)におけるR7~R9、及び一般式(III)におけるR10~R12は、それぞれ一般式(I)におけるR1~R3と同義である。
From the viewpoint of stability in the electrolytic solution, vinyl ester compounds represented by the following general formula (II) and/or allyl ester compounds represented by general formula (III) are more preferred.
(In Formula (II), R 7 to R 9 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 7 and R 8 and R 7 and R 9 are bonded to each other to form a cyclic structure. may be.)
(In Formula (III), R 10 to R 12 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 10 and R 11 and R 10 and R 12 are bonded to each other to form a cyclic structure. may be.)
R 7 to R 9 in general formula (II) and R 10 to R 12 in general formula (III) have the same definitions as R 1 to R 3 in general formula (I).
式(I)で表される化合物としては、具体的には以下の化合物が挙げられる。
なかでも、以下の化合物が好ましい。
より好ましくは、以下の化合物が挙げられる。
より好ましくは、以下の化合物が挙げられる。
より好ましくは以下の化合物が挙げられる。
より好ましくは以下の化合物が挙げられる。電極上での過剰な反応が抑制できるためである。
式(I)で表される化合物の含有量は、特段の制限はないが、非水系電解液の全量に対して、通常0.01質量%以上、好ましくは0.05質量%以上であり、また、通常10質量%以下、好ましくは8質量%以下、より好ましく6質量%以下、さらに好ましくは4質量%以下である。式(I)で表される化合物は、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
炭素-炭素不飽和結合を有するエステル化合物の同定や含有量の測定は、核磁気共鳴(NMR)分光法により行う。
The content of the compound represented by formula (I) is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, relative to the total amount of the non-aqueous electrolytic solution, Also, it is usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less, and still more preferably 4% by mass or less. The compounds represented by formula (I) may be used singly or two or more may be used in any combination and ratio.
Identification and content measurement of the ester compound having a carbon-carbon unsaturated bond are performed by nuclear magnetic resonance (NMR) spectroscopy.
[1-2. P-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、B-F結合及び/又はオキサラート基を有するホウ酸塩:化合物(B)(併用添加
剤)]
[1-2-1.P-F結合及びP=O結合を有するリン酸塩]
P-F結合及びP=O結合を有するリン酸塩としては特に限定されないが、具体的にはモノフルオロリン酸リチウム、モノフルオロリン酸ナトリウム、モノフルオロリン酸カリ
ウム、モノフルオロリン酸ルビジウム、モノフルオロリン酸セシウム、ジフルオロリン酸リチウム、ジフルオロリン酸ナトリウム、ジフルオロリン酸カリウム、ジフルオロリン酸ルビジウム、ジフルオロリン酸セシウム、モノフルオロモノメチルリン酸リチウム、モノフルオロモノメチルリン酸ナトリウム、モノフルオロモノメチルリン酸カリウム、モノフルオロモノメチルリン酸ルビジウム、モノフルオロモノメチルリン酸セシウムが挙げられる。なかでも、モノフルオロリン酸リチウム、ジフルオロリン酸リチウムが電解液安定性の点で特に好ましい。
P-F結合及びP=O結合を有するリン酸塩の含有量は、特段の制限はないが、非水系電解液全量に対して、通常0.01質量%以上、好ましくは0.05質量%以上、より好ましくは0.1質量%以上であり、また、通常10質量%以下、好ましくは8質量%以下、より好ましくは6質量%以下である。P-F結合及びP=O結合を有するリン酸塩の同定や含有量の測定は、核磁気共鳴(NMR)分光法により行う。
[1-2. Phosphate having PF bond and P=O bond, sulfonate having SF bond, borate having BF bond and/or oxalate group: compound (B) (combined additive)]
[1-2-1. Phosphate with PF bond and P=O bond]
Phosphates having a PF bond and a P=O bond are not particularly limited, but specific examples include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, rubidium monofluorophosphate, mono Cesium fluorophosphate, lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate, rubidium difluorophosphate, cesium difluorophosphate, lithium monofluoromonomethyl phosphate, sodium monofluoromonomethyl phosphate, potassium monofluoromonomethyl phosphate , rubidium monofluoromonomethyl phosphate, and cesium monofluoromonomethyl phosphate. Among them, lithium monofluorophosphate and lithium difluorophosphate are particularly preferable in terms of electrolyte solution stability.
The content of the phosphate having a PF bond and a P=O bond is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass, based on the total amount of the non-aqueous electrolyte. Above, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less. Phosphate having PF bond and P=O bond is identified and its content is measured by nuclear magnetic resonance (NMR) spectroscopy.
[1-2-2.S-F結合を有するスルホン酸塩]
S-F結合を有するスルホン酸塩としては特に限定されないが、具体的には、フルオロスルホン酸リチウム、フルオロスルホン酸ナトリウム、フルオロスルホン酸カリウム、フルオロスルホン酸ルビジウム、フルオロスルホン酸セシウム等のフルオロスルホン酸塩;ビスフルオロスルホニルイミドリチウム等のフルオロスルホニルイミド塩;等が挙げられる。電解液安定性の点でフルオロスルホン酸塩が好ましく、フルオロスルホン酸リチウムがさらに好ましい。
S-F結合を有するスルホン酸塩の含有量は、特段の制限はないが、非水系電解全量に対して、通常0.01質量%以上、好ましくは0.05質量%以上、より好ましくは0.1質量%以上であり、また通常10質量%以下、好ましくは8質量%以下、より好ましくは6質量%以下である。
[1-2-2. Sulfonate with SF bond]
The sulfonate having an SF bond is not particularly limited, but specific examples include fluorosulfonic acids such as lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, rubidium fluorosulfonate, and cesium fluorosulfonate. salts; fluorosulfonylimide salts such as bisfluorosulfonylimide lithium; and the like. Fluorosulfonate is preferable, and lithium fluorosulfonate is more preferable from the viewpoint of electrolyte solution stability.
The content of the sulfonate having an SF bond is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0, based on the total amount of non-aqueous electrolysis. .1% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less.
[1-2-3.B-F結合及び/又はオキサラート基を有するホウ酸塩]
本発明のB-F結合及び/又はオキサラート基を有するホウ酸塩としては特に限定されないが、具体的には、テトラフルオロホウ酸リチウム、テトラフルオロホウ酸ナトリウム、テトラフルオロホウ酸カリウム、テトラフルオロホウ酸ルビジウム、テトラフルオロホウ酸セシウム、トリフルオロモノメチルホウ酸リチウム、ジフルオロジメチルホウ酸リチウム、又はトリメチルモノフルオロホウ酸リチウム等のB-F結合を有するホウ酸塩;ビスオキサラートホウ酸リチウム、ビスオキサラートホウ酸ナトリウム、ビスオキサラートホウ酸カリウム、ビスオキサラートホウ酸ルビジウム、又はビスオキサラートホウ酸セシウム等のオキサラート基を有するホウ酸塩;モノオキサラートジフルオロホウ酸リチウム、モノオキサラートジフルオロホウ酸ナトリウム、モノオキサラートジフルオロホウ酸カリウム、又はモノオキサラートジフルオロホウ酸セシウム等のB-F結合及びオキサラート基を有するホウ酸塩;等が挙げられる。なかでも、テトラフルオロホウ酸リチウム、テトラフルオロホウ酸ナトリウム、テトラフルオロホウ酸カリウム、ビスオキサラートホウ酸リチウム、及びモノオキサラートジフルオロホウ酸リチウムが、電解液安定性の点で特に好ましい。
B-F結合及び/又はオキサラート基を有するホウ酸塩の含有量は、特段の制限はないが、非水系電解液の全量に対して、0.01質量%以上、好ましくは0.05質量%以上、より好ましくは0.1質量%以上であり、また、10質量%以下、好ましくは8質量%以下、より好ましくは6質量%以下である。B-F結合及び/又はオキサラート基を有するホウ酸塩の同定や含有量の測定は、核磁気共鳴(NMR)分光法により行う。
[1-2-3. Borate with BF bond and/or oxalate group]
The borate having a BF bond and/or an oxalate group of the present invention is not particularly limited, but specific examples include lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, tetrafluoroborate Borates having a BF bond such as rubidium acid, cesium tetrafluoroborate, lithium trifluoromonomethylborate, lithium difluorodimethylborate, or lithium trimethylmonofluoroborate; lithium bisoxalate borate, bisoxa Borates having an oxalate group such as sodium oxalate borate, potassium bisoxalate borate, rubidium bisoxalate borate, or cesium bisoxalate borate; lithium monooxalate difluoroborate, monooxalate difluoroborate borates having a BF bond and an oxalate group, such as sodium, potassium monooxalate difluoroborate, or cesium monooxalate difluoroborate; Among them, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium bisoxalate borate, and lithium monooxalate difluoroborate are particularly preferable in terms of electrolyte solution stability.
The content of the borate having a BF bond and/or an oxalate group is not particularly limited, but is 0.01% by mass or more, preferably 0.05% by mass, based on the total amount of the non-aqueous electrolytic solution. Above, more preferably 0.1% by mass or more, and 10% by mass or less, preferably 8% by mass or less, and more preferably 6% by mass or less. The borate having a BF bond and/or an oxalate group is identified and its content is measured by nuclear magnetic resonance (NMR) spectroscopy.
P-F結合及びP=O結合を有するリン酸塩、S-F結合を有するスルホン酸塩、並びにB-F結合及び/又はオキサラート基を有するホウ酸塩からなる群より選ばれる化合物(B)を2種以上含有する場合の総含有量は、非水系電解液の全量に対して、通常0.01質量%以上、好ましくは0.05質量%以上、より好ましくは0.1質量%以上であり
、また、通常10質量%以下、好ましくは、8質量%以下、より好ましくは6質量%以下である。
A compound (B) selected from the group consisting of a phosphate having a PF bond and a P═O bond, a sulfonate having an SF bond, and a borate having a BF bond and/or an oxalate group The total content when two or more types are contained is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, relative to the total amount of the non-aqueous electrolytic solution. Also, it is usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less.
[1-3.電解質]
<リチウム塩>
非水系電解液における電解質としては、通常、リチウム塩が用いられる。リチウム塩としては、この用途に用いられることが知られているものであれば特に制限がなく、任意のものを用いることができ、具体的には以下のものが挙げられる。
[1-3. Electrolytes]
<Lithium salt>
A lithium salt is usually used as the electrolyte in the non-aqueous electrolytic solution. The lithium salt is not particularly limited as long as it is known to be used for this purpose, and any lithium salt can be used. Specific examples include the following.
例えば、フルオロホウ酸リチウム塩類、フルオロリン酸リチウム塩類、タングステン酸リチウム塩類、カルボン酸リチウム塩類、スルホン酸リチウム塩類、リチウムイミド塩類、リチウムメチド塩類、リチウムオキサラート塩類、及び含フッ素有機リチウム塩類等が挙げられる。 Examples include lithium fluoroborate salts, lithium fluorophosphate salts, lithium tungstate salts, lithium carboxylate salts, lithium sulfonate salts, lithium imide salts, lithium methide salts, lithium oxalate salts, and fluorine-containing organic lithium salts. .
中でも、フルオロホウ酸リチウム塩類としてLiBF4;フルオロリン酸リチウム塩類としてLiPF6;スルホン酸リチウム塩類として、CH3SO3Li;リチウムイミド塩類としてLiN(FSO2)(CF3SO2)、LiN(CF3SO2)2、LiN(C2F5SO2)2、リチウム環状1,2-パーフルオロエタンジスルホニルイミド、リチウム環状1,3-パーフルオロプロパンジスルホニルイミド;リチウムメチド塩類として、LiC(FSO2)3、LiC(CF3SO2)3、LiC(C2F5SO2)3;リチウムオキサラート塩類としてモノオキサラートジフルオロホウ酸リチウムト、ビスオキサラートホウ酸リチウム(LiBOB)、リチウムテトラフルオロオキサラトフォスフェート、リチウムジフルオロビス(オキサラト)フォスフェート、リチウムトリス(オキサラト)フォスフェート;等が、低温出力特性やハイレート充放電特性、インピーダンス特性、高温保存特性、サイクル特性等を向上させる効果がある点からより好ましい。さらに好ましくは、LiPF6又はリチウムビス(オキサラト)ボレートであり、特に好ましくはLiPF6である。また、上記電解質は、単独で用いても、2種以上を併用してもよい。ただし、[1-2-1.P-F結合及びP=O結合を有するリン酸塩]~[1-2-3.B-F結合及び/又はオキサラート基を有するホウ酸塩]記載の併用添加剤に該当するリチウム塩電解質が非水系電解液に含まれる場合、併用添加剤に該当するリチウム塩以外の電解質を必ず含有する。
2種類以上の電解質の組み合わせとして、特段の制限はないが、LiPF6及びLiBF4の組み合わせ並びにLiPF6及びLiN(CF3SO2)2の組み合わせが好ましく挙げられる。なかでも、LiPF6及びLiBF4の組み合わせが好ましい。
LiBF 4 as lithium fluoroborate; LiPF 6 as lithium fluorophosphate; CH 3 SO 3 Li as lithium sulfonate; LiN(FSO 2 ) (CF 3 SO 2 ), LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropanedisulfonylimide; 2 ) 3 , LiC(CF 3 SO 2 ) 3 , LiC(C 2 F 5 SO 2 ) 3 ; lithium oxalate salts such as lithium monooxalate difluoroborate, lithium bisoxalate borate (LiBOB), lithium tetrafluoro Oxalatophosphate, lithium difluorobis(oxalato)phosphate, lithium tris(oxalato)phosphate, etc. have the effect of improving low-temperature output characteristics, high-rate charge/discharge characteristics, impedance characteristics, high-temperature storage characteristics, cycle characteristics, etc. more preferable from the point of view. LiPF 6 or lithium bis(oxalato)borate is more preferred, and LiPF 6 is particularly preferred. Moreover, the said electrolyte may be used independently or may use 2 or more types together. However, [1-2-1. Phosphate with PF bond and P=O bond] to [1-2-3. Borate with BF bond and/or oxalate group] When the non-aqueous electrolyte contains a lithium salt electrolyte that corresponds to the combined additive described above, it must contain an electrolyte other than the lithium salt that corresponds to the combined additive. do.
The combination of two or more electrolytes is not particularly limited, but preferably includes a combination of LiPF 6 and LiBF 4 and a combination of LiPF 6 and LiN(CF 3 SO 2 ) 2 . Among them, a combination of LiPF 6 and LiBF 4 is preferred.
非水系電解液中の電解質の総濃度は、特に制限はないが、非水系電解液の全量に対して、通常8質量%以上、好ましくは8.5質量%以上、より好ましくは9質量%以上であり、また、通常18質量%以下、好ましくは17質量%以下、より好ましくは16質量%以下である。電解質の総濃度が上記範囲内であると、電気伝導率が電池動作に適正となるため、十分な出力特性が得られる傾向にある。電解質の同定や含有量の測定は、核磁気共鳴(NMR)分光法により行う。 The total concentration of the electrolyte in the non-aqueous electrolyte is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass or more, relative to the total amount of the non-aqueous electrolyte. and is usually 18% by mass or less, preferably 17% by mass or less, more preferably 16% by mass or less. When the total concentration of the electrolytes is within the above range, the electrical conductivity is appropriate for battery operation, so there is a tendency to obtain sufficient output characteristics. Identification of the electrolyte and measurement of the content are performed by nuclear magnetic resonance (NMR) spectroscopy.
[1-4.非水系溶媒]
本発明の一実施形態に係る非水系電解液は、一般的な非水系電解液と同様、通常はその主成分として、上述した電解質を溶解する非水系溶媒を含有する。用いられる非水系溶媒は上述した電解質を溶解すれば特に制限はなく、公知の有機溶媒を用いることができる。有機溶媒としては、飽和環状カーボネート、鎖状カーボネート、鎖状カルボン酸エステル(ただし、式(I)で表される化合物を除く。)、環状カルボン酸エステル、エーテル系化合物、及びスルホン系化合物等が挙げられるが、これらに特に限定されない。有機溶媒は、1種を単独で又は2種以上を組み合わせて用いることができる。
2種以上の有機溶媒の組み合わせとして、特段の制限はないが、飽和環状カーボネート及び鎖状カルボン酸エステル、環状カルボン酸エステル及び鎖状カーボネート、並びに飽和環状カーボネート、鎖状カーボネート及び鎖状カルボン酸エステルが挙げられる。なかでも、飽和環状カーボネート及び鎖状カーボネート、並びに飽和環状カーボネート、鎖状カーボネート及び鎖状カルボン酸エステルが好ましい。
[1-4. Non-aqueous solvent]
The non-aqueous electrolytic solution according to one embodiment of the present invention normally contains, as its main component, a non-aqueous solvent that dissolves the above-described electrolyte, like common non-aqueous electrolytic solutions. The non-aqueous solvent to be used is not particularly limited as long as it dissolves the electrolyte described above, and known organic solvents can be used. Examples of organic solvents include saturated cyclic carbonates, chain carbonates, chain carboxylic acid esters (excluding compounds represented by formula (I)), cyclic carboxylic acid esters, ether compounds, sulfone compounds, and the like. Examples include, but are not limited to, these. An organic solvent can be used individually by 1 type or in combination of 2 or more types.
The combination of two or more organic solvents is not particularly limited, but saturated cyclic carbonates and chain carboxylic acid esters, cyclic carboxylic acid esters and chain carbonates, and saturated cyclic carbonates, chain carbonates and chain carboxylic acid esters. is mentioned. Of these, saturated cyclic carbonates and chain carbonates, and saturated cyclic carbonates, chain carbonates and chain carboxylic acid esters are preferred.
[1-4-1.飽和環状カーボネート]
飽和環状カーボネートとしては、例えば、炭素数2~4のアルキレン基を有するものが挙げられ、リチウムイオン解離度の向上に由来する電池特性向上の点から炭素数2~3の飽和環状カーボネートが好ましく用いられる。
[1-4-1. saturated cyclic carbonate]
Examples of saturated cyclic carbonates include those having an alkylene group having 2 to 4 carbon atoms, and saturated cyclic carbonates having 2 to 3 carbon atoms are preferably used from the viewpoint of improving battery characteristics resulting from an improvement in the degree of dissociation of lithium ions. be done.
飽和環状カーボネートとしては、具体的には、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等が挙げられる。中でも、エチレンカーボネート又はプロピレンカーボネートが好ましく、酸化・還元されにくいエチレンカーボネートがより好ましい。飽和環状カーボネートは、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。 Specific examples of saturated cyclic carbonates include ethylene carbonate, propylene carbonate, and butylene carbonate. Among them, ethylene carbonate or propylene carbonate is preferable, and ethylene carbonate which is difficult to be oxidized/reduced is more preferable. Saturated cyclic carbonates may be used alone, or two or more of them may be used in any combination and ratio.
飽和環状カーボネートの含有量は、特に制限されず、本実施形態に係る発明の効果を著しく損なわない限り任意であるが、非水系電解液の非水系溶媒全量に対して、通常3体積%以上、好ましくは5体積%以上であり、一方、通常90体積%以下、好ましくは85体積%以下、より好ましくは80体積%以下である。この範囲とすることで、非水系電解液の誘電率の低下に由来する電気伝導率の低下を回避し、非水系電解液二次電池の大電流放電特性、負極に対する安定性、サイクル特性を良好な範囲としやすくなり、非水系電解液の酸化・還元耐性が向上し、高温保存時の安定性が向上する傾向にある。
なお、本実施形態における体積%とは25℃、1気圧における体積を意味する。
The content of the saturated cyclic carbonate is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the invention according to the present embodiment. The content is preferably 5% by volume or more, and is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting this range, it is possible to avoid a decrease in electrical conductivity due to a decrease in the dielectric constant of the non-aqueous electrolyte, and to improve the large current discharge characteristics of the non-aqueous electrolyte secondary battery, the stability to the negative electrode, and the cycle characteristics. range, the oxidation/reduction resistance of the non-aqueous electrolytic solution is improved, and the stability during high-temperature storage tends to be improved.
In addition, volume % in this embodiment means the volume at 25 degreeC and 1 atmospheric pressure.
[1-4-2.鎖状カーボネート]
鎖状カーボネートとしては、通常炭素数3~7のものが用いられ、電解液の粘度を適切な範囲に調整するために、炭素数3~5の鎖状カーボネートが好ましく用いられる。
[1-4-2. chain carbonate]
As the chain carbonate, those having 3 to 7 carbon atoms are usually used, and chain carbonates having 3 to 5 carbon atoms are preferably used in order to adjust the viscosity of the electrolytic solution within an appropriate range.
鎖状カーボネートとしては、具体的には、ジメチルカーボネート、ジエチルカーボネート、ジ-n-プロピルカーボネート、ジイソプロピルカーボネート、n-プロピルイソプロピルカーボネート、エチルメチルカーボネート、メチル-n-プロピルカーボネートが挙げられる。特に好ましくはジメチルカーボネート、ジエチルカーボネート又はエチルメチルカーボネートである。 Specific examples of chain carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropyl carbonate, ethylmethyl carbonate and methyl-n-propyl carbonate. Particularly preferred are dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
また、フッ素原子を有する鎖状カーボネート類(以下、「フッ素化鎖状カーボネート」と略記する場合がある。)も好適に用いることができる。フッ素化鎖状カーボネートが有するフッ素原子の数は、1以上であれば特に制限されないが、通常6以下であり、好ましくは4以下である。フッ素化鎖状カーボネートが複数のフッ素原子を有する場合、当該複数のフッ素原子は同一の炭素に結合していてもよく、異なる炭素に結合していてもよい。
フッ素化鎖状カーボネートとしては、フルオロメチルメチルカーボネート等のフッ素化ジメチルカーボネート誘導体;2-フルオロエチルメチルカーボネート等のフッ素化エチルメチルカーボネート誘導体;エチル-(2-フルオロエチル)カーボネート等のフッ素化ジエチルカーボネート誘導体;等が挙げられる。
Chain carbonates having a fluorine atom (hereinafter sometimes abbreviated as “fluorinated chain carbonate”) can also be preferably used. The number of fluorine atoms in the fluorinated linear carbonate is not particularly limited as long as it is 1 or more, but it is usually 6 or less, preferably 4 or less. When the fluorinated chain carbonate has a plurality of fluorine atoms, the plurality of fluorine atoms may be bonded to the same carbon or to different carbons.
Fluorinated linear carbonates include fluorinated dimethyl carbonate derivatives such as fluoromethylmethyl carbonate; fluorinated ethylmethyl carbonate derivatives such as 2-fluoroethylmethyl carbonate; and fluorinated diethyl carbonates such as ethyl-(2-fluoroethyl) carbonate. derivatives; and the like.
鎖状カーボネートは、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。 A chain carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
鎖状カーボネートの含有量は特に限定されないが、非水系電解液の非水系溶媒全量に対
して、通常15体積%以上であり、好ましくは20体積%以上、より好ましくは25体積%以上であり、また、通常90体積%以下、好ましくは85体積%以下、より好ましくは80体積%以下である。鎖状カーボネートの含有量を上記範囲とすることによって、非水系電解液の粘度を適切な範囲とし、イオン伝導度の低下を抑制し、ひいては非水系電解液二次電池の出力特性を良好な範囲としやすくなる。
Although the content of the chain carbonate is not particularly limited, it is usually 15% by volume or more, preferably 20% by volume or more, more preferably 25% by volume or more, relative to the total amount of the non-aqueous solvent in the non-aqueous electrolyte, Also, it is usually 90% by volume or less, preferably 85% by volume or less, more preferably 80% by volume or less. By setting the content of the chain carbonate in the above range, the viscosity of the non-aqueous electrolyte is set in an appropriate range, the decrease in ionic conductivity is suppressed, and the output characteristics of the non-aqueous electrolyte secondary battery are kept in a good range. It becomes easier to
さらに、特定の鎖状カーボネートに対して、エチレンカーボネートを特定の含有量で組み合わせることにより、電池性能を著しく向上させることができる。 Furthermore, by combining a specific linear carbonate with a specific content of ethylene carbonate, the battery performance can be significantly improved.
例えば、特定の鎖状カーボネートとしてジメチルカーボネートとエチルメチルカーボネートを選択した場合、エチレンカーボネートの含有量は、特に制限されず、本実施形態に係る発明の効果を著しく損なわない限り任意であるが、非水系電解液の非水系溶媒全量に対して、通常15体積%以上、好ましくは20体積%以上、また、通常45体積%以下、好ましくは40体積%以下であり、ジメチルカーボネートの含有量は、非水系電解液の非水系溶媒全量に対して、通常20体積%以上、好ましくは30体積%以上、また、通常50体積%以下、好ましくは45体積%以下であり、エチルメチルカーボネートの含有量は非水系電解液の非水系溶媒全量に対して、通常20体積%以上、好ましくは30体積%以上、また、通常50体積%以下、好ましくは45体積%以下である。含有量を上記範囲内とすることで、高温安定性に優れ、ガス発生が抑制される傾向がある。 For example, when dimethyl carbonate and ethyl methyl carbonate are selected as specific chain carbonates, the content of ethylene carbonate is not particularly limited, and is arbitrary as long as the effects of the invention according to the present embodiment are not significantly impaired. It is usually 15% by volume or more, preferably 20% by volume or more, and usually 45% by volume or less, preferably 40% by volume or less, based on the total amount of the non-aqueous solvent in the aqueous electrolyte. It is usually 20% by volume or more, preferably 30% by volume or more, and usually 50% by volume or less, preferably 45% by volume or less, based on the total amount of the non-aqueous solvent in the aqueous electrolyte. It is usually 20% by volume or more, preferably 30% by volume or more, and usually 50% by volume or less, preferably 45% by volume or less, relative to the total amount of the non-aqueous solvent in the aqueous electrolytic solution. By setting the content within the above range, there is a tendency that high-temperature stability is excellent and gas generation is suppressed.
[1-4-3.鎖状カルボン酸エステル]
鎖状カルボン酸エステル(ただし、式(I)で表される化合物を除く。)としては、例
えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、酪酸メチル、酪酸エチル、吉草酸メチル、イソ酪酸メチル、イソ酪酸エチル、及びピバル酸メチルが挙げられる。なかでも、酢酸メチル、酢酸エチル、酢酸プロピル、又は酢酸ブチルが電池特性向上の点から好ましい。上述の化合物の水素の一部をフッ素原子で置換した鎖状カルボン酸エステル(例えば、トリフルオロ酢酸メチル、トリフルオロ酢酸エチル等)も好適に使える。
鎖状カルボン酸エステルの含有量は、非水系溶媒全量に対して、通常1体積%以上、好ましくは5体積%以上、より好ましくは15体積%以上である。この範囲であれば、非水系電解液の電気伝導率を改善し、非水系電解液電池の大電流放電特性を向上させやすくなる。また、鎖状カルボン酸エステルの含有量は、通常70体積%以下、好ましくは50体積%以下、より好ましくは40体積%以下である。このように上限を設定することにより、非水系電解液の粘度を適切な範囲とし、電気伝導率の低下を回避し、負極抵抗の増大を抑制し、非水系電解液二次電池の大電流放電特性を良好な範囲としやすくなる。
[1-4-3. Chain carboxylic acid ester]
Chain carboxylic acid esters (excluding compounds represented by formula (I)) include, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, Methyl butyrate, ethyl butyrate, methyl valerate, methyl isobutyrate, ethyl isobutyrate, and methyl pivalate. Among them, methyl acetate, ethyl acetate, propyl acetate, or butyl acetate is preferable from the viewpoint of improving battery characteristics. Chain carboxylic acid esters (eg, methyl trifluoroacetate, ethyl trifluoroacetate, etc.) obtained by substituting fluorine atoms for part of the hydrogen atoms in the above compounds can also be used favorably.
The content of the chain carboxylic acid ester is generally 1% by volume or more, preferably 5% by volume or more, more preferably 15% by volume or more, relative to the total amount of the non-aqueous solvent. Within this range, the electrical conductivity of the non-aqueous electrolytic solution is improved, and the large current discharge characteristics of the non-aqueous electrolytic solution battery are easily improved. Moreover, the content of the chain carboxylic acid ester is usually 70% by volume or less, preferably 50% by volume or less, and more preferably 40% by volume or less. By setting the upper limit in this way, the viscosity of the non-aqueous electrolyte solution can be adjusted to an appropriate range, a decrease in electrical conductivity can be avoided, an increase in negative electrode resistance can be suppressed, and a large current discharge of the non-aqueous electrolyte secondary battery can be achieved. It becomes easier to bring the characteristics into a favorable range.
[1-4-4.環状カルボン酸エステル]
環状カルボン酸エステルとしては、例えば、γ-ブチロラクトン、及びγ-バレロラクトンが挙げられる。これらの中でも、γ-ブチロラクトンがより好ましい。また、上述の化合物の水素の一部をフッ素で置換した環状カルボン酸エステルも好適に使える。
環状カルボン酸エステルの含有量は、非水系電解液の非水系溶媒全量に対して、通常1体積%以上、好ましくは5体積%以上、より好ましくは15体積%以上である。この範囲であれば、非水系電解液の電気伝導率を改善し、非水系電解液電池の大電流放電特性を向上させやすくなる。また、環状カルボン酸エステルの含有量は、非水系溶媒全量に対して、通常70体積%以下、好ましくは50体積%以下、より好ましくは40体積%以下である。このように上限を設定することにより、非水系電解液の粘度を適切な範囲とし、電気伝導率の低下を回避し、負極抵抗の増大を抑制し、非水系電解液二次電池の大電流放電特性を良好な範囲としやすくなる。
[1-4-4. Cyclic carboxylic acid ester]
Cyclic carboxylic acid esters include, for example, γ-butyrolactone and γ-valerolactone. Among these, γ-butyrolactone is more preferred. Cyclic carboxylic acid esters obtained by substituting a portion of the hydrogen atoms of the above compounds with fluorine are also suitable for use.
The content of the cyclic carboxylic acid ester is generally 1% by volume or more, preferably 5% by volume or more, more preferably 15% by volume or more, relative to the total amount of the non-aqueous solvent in the non-aqueous electrolytic solution. Within this range, the electrical conductivity of the non-aqueous electrolytic solution is improved, and the large current discharge characteristics of the non-aqueous electrolytic solution battery are easily improved. Moreover, the content of the cyclic carboxylic acid ester is usually 70% by volume or less, preferably 50% by volume or less, more preferably 40% by volume or less, relative to the total amount of the non-aqueous solvent. By setting the upper limit in this way, the viscosity of the non-aqueous electrolyte solution can be adjusted to an appropriate range, a decrease in electrical conductivity can be avoided, an increase in negative electrode resistance can be suppressed, and a large current discharge of the non-aqueous electrolyte secondary battery can be achieved. It becomes easier to bring the characteristics into a good range.
[1-4-5.エーテル系化合物]
エーテル系化合物としては特に限定されないが、ジメトキシメタン、ジエトキシメタン、エトキシメトキシメタン、エチレングリコールジ-n-プロピルエーテル、エチレングリコールジ-n-ブチルエーテル、ジエチレングリコールジメチルエーテル等の炭素数3~10の鎖状エーテル;及びテトラヒドロフラン、2-メチルテトラヒドロフラン、3-メチルテトラヒドロフラン、1,3-ジオキサン、2-メチル-1,3-ジオキサン、4-メチル-1,3-ジオキサン、1,4-ジオキサン等の炭素数3~6の環状エーテル;が好ましい。なお、上述のエーテル系化合物の一部の水素がフッ素にて置換されていてもよい。
なかでも、炭素数3~10の鎖状エーテルとして、リチウムイオンへの溶媒和能力が高く、イオン解離性を向上させ、粘性が低く、高いイオン伝導度を与えることから、ジメトキシメタン、ジエトキシメタン、又はエトキシメトキシメタンが好ましく、炭素数3~6の環状エーテルとして、高いイオン電導度を与えることから、テトラヒドロフラン、1,3-ジオキサン、又は1,4-ジオキサン等が好ましい。
[1-4-5. Ether-based compound]
The ether-based compound is not particularly limited, but a chain having 3 to 10 carbon atoms such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether, etc. ether; and carbon number such as tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 1,4-dioxane 3 to 6 cyclic ethers; are preferred. A portion of the hydrogen atoms in the above ether-based compound may be substituted with fluorine.
Among them, as a chain ether having 3 to 10 carbon atoms, dimethoxymethane and diethoxymethane have high solvation ability for lithium ions, improve ion dissociation, have low viscosity, and provide high ionic conductivity. , or ethoxymethoxymethane is preferable, and tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, or the like is preferable as a cyclic ether having 3 to 6 carbon atoms because it gives a high degree of ionic conductivity.
エーテル系化合物の含有量は、特に制限されず、本実施形態に係る発明の効果を著しく損なわない限り任意であるが、非水系電解液の非水系溶媒全量に対して、通常1体積%以上、好ましくは2体積%以上、より好ましくは3体積%以上、また、通常30体積%以下、好ましくは25体積%以下、より好ましくは20体積%以下である。エーテル系化合物の含有量が上記範囲内であれば、リチウムイオン解離度の向上と粘度低下に由来するイオン伝導度の向上効果を確保しやすい。また、負極活物質が炭素系材料の場合、鎖状エーテルがリチウムイオンと共に共挿入される現象を抑制できることから、入出力特性や充放電レート特性を適正な範囲とすることができる。 The content of the ether-based compound is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the invention according to the present embodiment. It is preferably 2% by volume or more, more preferably 3% by volume or more, and usually 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less. When the content of the ether-based compound is within the above range, it is easy to secure the effect of improving the degree of dissociation of lithium ions and improving the ionic conductivity resulting from the decrease in viscosity. Moreover, when the negative electrode active material is a carbon-based material, the phenomenon of co-insertion of the chain ether together with the lithium ions can be suppressed, so that the input/output characteristics and the charge/discharge rate characteristics can be set within appropriate ranges.
[1-4-6.スルホン系化合物]
スルホン系化合物としては、特に制限されず、環状スルホンであってもよく、鎖状スルホンであってもよい。環状スルホンの場合、炭素数が通常3~6、好ましくは3~5であり、鎖状スルホンの場合、炭素数が通常2~6、好ましくは2~5である。また、スルホン系化合物1分子中のスルホニル基の数は、特に制限されないが、通常1又は2である。
[1-4-6. Sulfone compound]
The sulfone-based compound is not particularly limited, and may be a cyclic sulfone or a chain sulfone. Cyclic sulfones generally have 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and chain sulfones generally have 2 to 6 carbon atoms, preferably 2 to 5 carbon atoms. Although the number of sulfonyl groups in one molecule of the sulfone compound is not particularly limited, it is usually one or two.
環状スルホンとしては、モノスルホン化合物であるトリメチレンスルホン類、テトラメチレンスルホン類、ヘキサメチレンスルホン類等;ジスルホン化合物であるトリメチレンジスルホン類、テトラメチレンジスルホン類、ヘキサメチレンジスルホン類等が挙げられる。中でも誘電率と粘性の観点から、テトラメチレンスルホン類、テトラメチレンジスルホン類、ヘキサメチレンスルホン類、又はヘキサメチレンジスルホン類がより好ましく、テトラメチレンスルホン類(スルホラン類)が特に好ましい。 Cyclic sulfones include trimethylenesulfones, tetramethylenesulfones, hexamethylenesulfones, etc., which are monosulfone compounds; and trimethylenedisulfones, tetramethylenedisulfones, hexamethylenedisulfones, etc., which are disulfone compounds. Among them, tetramethylenesulfones, tetramethylenedisulfones, hexamethylenesulfones, or hexamethylenedisulfones are more preferable, and tetramethylenesulfones (sulfolanes) are particularly preferable from the viewpoint of dielectric constant and viscosity.
スルホラン類としては、スルホラン及びスルホラン誘導体が好ましい。スルホラン誘導体としては、スルホラン環を構成する炭素原子上に結合した水素原子の1以上がフッ素原子、アルキル基、フッ素置換アルキル基で置換されたものが好ましい。 As sulfolanes, sulfolane and sulfolane derivatives are preferred. As the sulfolane derivative, one in which one or more hydrogen atoms bonded to carbon atoms constituting a sulfolane ring are substituted with a fluorine atom, an alkyl group, or a fluorine-substituted alkyl group is preferable.
中でも、2-メチルスルホラン、3-メチルスルホラン、2-フルオロスルホラン、3-フルオロスルホラン、2,3-ジフルオロスルホラン、2-トリフルオロメチルスルホラン、3-トリフルオロメチルスルホラン等が、イオン伝導度が高く入出力が高い点で好ましい。 Among them, 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, 3-fluorosulfolane, 2,3-difluorosulfolane, 2-trifluoromethylsulfolane, 3-trifluoromethylsulfolane and the like have high ionic conductivity. It is preferable in terms of high input/output.
また、鎖状スルホンとしては、ジメチルスルホン、エチルメチルスルホン、ジエチルスルホン、モノフルオロメチルメチルスルホン、ジフルオロメチルメチルスルホン、トリフルオロメチルメチルスルホン、ペンタフルオロエチルメチルスルホン等が挙げられる。なかでも、ジメチルスルホン、エチルメチルスルホン、モノフルオロメチルメチルスルホンが電解液の高温保存安定性が向上する点で好ましい。 Chain sulfones include dimethylsulfone, ethylmethylsulfone, diethylsulfone, monofluoromethylmethylsulfone, difluoromethylmethylsulfone, trifluoromethylmethylsulfone, pentafluoroethylmethylsulfone and the like. Among them, dimethylsulfone, ethylmethylsulfone, and monofluoromethylmethylsulfone are preferable because they improve the high-temperature storage stability of the electrolytic solution.
スルホン系化合物の含有量は、特に制限されず、本実施形態に係る発明の効果を著しく損なわない限り任意であるが、非水系電解液の非水系溶媒全量に対して、通常0.3体積%以上、好ましくは0.5体積%以上、より好ましくは1体積%以上であり、また、通常40体積%以下、好ましくは35体積%以下、より好ましくは30体積%以下である。スルホン系化合物の含有量が上記範囲内であれば、高温保存安定性に優れた電解液が得られる傾向にある。 The content of the sulfone-based compound is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the invention according to the present embodiment. Above, it is preferably 0.5% by volume or more, more preferably 1% by volume or more, and is usually 40% by volume or less, preferably 35% by volume or less, more preferably 30% by volume or less. If the content of the sulfone-based compound is within the above range, there is a tendency to obtain an electrolytic solution with excellent high-temperature storage stability.
[1-5.助剤]
本発明の非水系電解液には、本発明の効果を著しく損なわない範囲において、各種の助剤を含有していてもよい。助剤としては、従来公知のものを任意に用いることができる。なお、助剤は、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
[1-5. Auxiliary agent]
The non-aqueous electrolytic solution of the present invention may contain various auxiliary agents as long as they do not significantly impair the effects of the present invention. As the auxiliary agent, any conventionally known one can be used. In addition, an auxiliary agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
非水系電解液に含有していてもよい助剤としては、炭素-炭素不飽和結合を有する環状カーボネート、フッ素含有環状カーボネート、イソシアネート基を有する化合物、イソシアヌル酸骨格を有する化合物、硫黄含有有機化合物、リン含有有機化合物、シアノ基を有する有機化合物、ケイ素含有化合物、芳香族化合物、フッ素非含有カルボン酸エステル、エーテル結合を有する環状化合物、カルボン酸無水物、ホウ酸塩(ただし、B-F結合及び/又はオキサラート基を有するホウ酸塩を除く。)、オキサラート塩(ただし、B-F結合
及び/又はオキサラート基を有するホウ酸塩を除く。)等が例示できる。例えば、国際公
開公報第2015/111676号に記載の化合物等が挙げられる。
エーテル結合を有する環状化合物は、非水系電解液において助剤として用いることもできるし、1-4.で示したとおり非水系溶媒としても用いることができるものも含まれる。エーテル結合を有する環状化合物を助剤として用いる場合は、4質量%未満の量で用いる。ホウ酸塩、及びオキサラート塩は、非水系電解液において助剤として用いることもできるし、1-3.で示したとおり電解質として用いることができるものも含まれる。ホウ酸塩、又はオキサラート塩を助剤として用いる場合は、3質量%未満で用いる。
Examples of auxiliary agents that may be contained in the non-aqueous electrolytic solution include cyclic carbonates having carbon-carbon unsaturated bonds, fluorine-containing cyclic carbonates, compounds having an isocyanate group, compounds having an isocyanuric acid skeleton, sulfur-containing organic compounds, Phosphorus-containing organic compounds, organic compounds having a cyano group, silicon-containing compounds, aromatic compounds, fluorine-free carboxylic acid esters, cyclic compounds having an ether bond, carboxylic acid anhydrides, borates (however, B-F bonds and /or borates having an oxalate group), oxalate salts (excluding borates having a BF bond and/or an oxalate group), and the like. Examples thereof include compounds described in International Publication No. 2015/111676.
A cyclic compound having an ether bond can also be used as an auxiliary agent in a non-aqueous electrolytic solution, and 1-4. Also included are those that can be used as non-aqueous solvents as shown in . When a cyclic compound having an ether bond is used as an auxiliary agent, it is used in an amount of less than 4% by mass. Borate and oxalate salts can also be used as auxiliary agents in non-aqueous electrolytes, and 1-3. Also included are those that can be used as electrolytes as shown in . When a borate or oxalate salt is used as an auxiliary agent, it is used at less than 3% by weight.
[2.非水系電解液二次電池]
本発明の一実施態様である非水系電解液二次電池は、金属イオンを吸蔵及び放出しうる正極活物質を有する正極と、金属イオンを吸蔵及び放出しうる負極活物質を有する負極とを備える非水系電解液二次電池であって、非水系電解液を含む。
[2. Non-aqueous electrolyte secondary battery]
A non-aqueous electrolyte secondary battery, which is one embodiment of the present invention, comprises a positive electrode having a positive electrode active material capable of absorbing and releasing metal ions, and a negative electrode having a negative electrode active material capable of absorbing and releasing metal ions. A non-aqueous electrolyte secondary battery containing a non-aqueous electrolyte.
[2-1.非水系電解液]
非水系電解液としては、上述の非水系電解液を用いる。なお、本発明の趣旨を逸脱しない範囲において、上述の非水系電解液に対し、その他の非水系電解液を混合して用いることも可能である。
[2-1. Non-aqueous electrolyte]
As the non-aqueous electrolytic solution, the non-aqueous electrolytic solution described above is used. It should be noted that other non-aqueous electrolytic solutions may be mixed with the above-described non-aqueous electrolytic solution without departing from the gist of the present invention.
[2-2.負極]
負極は、負極活物質を集電体表面の少なくとも一部に有する。
[2-2-1.負極活物質]
負極に使用される負極活物質としては、電気化学的に金属イオンを吸蔵及び放出可能なものであれば、特に制限はない。具体例としては、炭素系材料、Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料、リチウム含有金属複合酸化物材料、及びこれらの混合物等が挙げられる。これらの中でもサイクル特性及び安全性が良好でさらに連続充電特性も優れている点で、炭素系材料、Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料又はLiと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子と黒鉛粒子との混合物を使用するのが好ましい。これらは1種を単独で用いてもよく、また2種以上を任意に組み合わせて併用してもよい。
[2-2. negative electrode]
The negative electrode has a negative electrode active material on at least part of the current collector surface.
[2-2-1. Negative electrode active material]
The negative electrode active material used for the negative electrode is not particularly limited as long as it can electrochemically occlude and release metal ions. Specific examples include carbonaceous materials, materials containing metallic elements and/or metalloid elements that can be alloyed with Li, lithium-containing metal composite oxide materials, mixtures thereof, and the like. Among these, in terms of good cycle characteristics and safety and excellent continuous charging characteristics, carbon-based materials, materials containing metal elements and / or metalloid elements that can be alloyed with Li, or materials that can be alloyed with Li It is preferred to use a mixture of particles of a material containing metallic and/or semi-metallic elements and graphite particles. These may be used singly or in combination of two or more.
[2-2-2.炭素系材料]
炭素系材料としては、天然黒鉛、人造黒鉛、非晶質炭素、炭素被覆黒鉛、黒鉛被覆黒鉛及び樹脂被覆黒鉛等が挙げられる。なかでも、天然黒鉛が好ましい。炭素系材料は1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
天然黒鉛としては、鱗状黒鉛、鱗片状黒鉛及び/又はこれらに球形化や緻密化等の処理を施した黒鉛粒子等が挙げられる。これらの中でも、粒子の充填性又は充放電レート特性の観点から、球形化処理を施した球状もしくは楕円体状の黒鉛粒子が特に好ましい。
黒鉛粒子の平均粒子径(d50)は、通常1μm以上、100μm以下である。
[2-2-2. carbon-based materials]
Carbon-based materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite. Among them, natural graphite is preferable. One type of carbon-based material may be used alone, or two or more types may be used together in any combination and ratio.
Examples of natural graphite include scale-like graphite, scale-like graphite, and/or graphite particles obtained by subjecting these to a treatment such as spheroidization or densification. Among these, spherical or ellipsoidal graphite particles subjected to a spheroidizing treatment are particularly preferable from the viewpoint of the packing properties of the particles and the charge/discharge rate characteristics.
The average particle size (d50) of graphite particles is usually 1 μm or more and 100 μm or less.
[2-2-3.炭素系材料の物性]
負極活物質としての炭素系材料は、以下の(1)~(4)に示した物性及び形状等の特徴の内、少なくとも1つを満たしていることが好ましく、複数を同時に満たすことが特に好ましい。
(1)X線回折パラメータ
炭素系材料の学振法によるX線回折で求めた格子面(002面)のd値(層間距離)は、通常0.335nm以上、0.360nm以下である。また、学振法によるX線回折で求めた炭素系材料の結晶子サイズ(Lc)は、通常1.0nm以上である。
(2)体積基準平均粒径
炭素系材料の体積基準平均粒径は、レーザー回折・散乱法により求めた体積基準の平均粒径(メジアン径)であり、通常1μm以上、100μm以下である。
(3)ラマンR値、ラマン半値幅
炭素系材料のラマンR値は、アルゴンイオンレーザーラマンスペクトル法を用いて測定した値であり、通常0.01以上、1.5以下である。
また、炭素系材料の1580cm-1付近のラマン半値幅は特に制限されないが、通常10cm-1以上、100cm-1以下である。
(4)BET比表面積
炭素系材料のBET比表面積は、BET法を用いて測定した比表面積の値であり、通常0.1m2・g-1以上、100m2・g-1以下である。
また、負極活物質中に性質の異なる炭素系材料が2種以上含有されていてもよい。ここでいう性質とは、X線回折パラメータ、体積基準平均粒径、ラマンR値、ラマン半値幅又はBET比表面積を意味する。
好ましい例としては、体積基準粒度分布がメジアン径を中心としたときに左右対称とならないこと、ラマンR値が異なる炭素系材料を2種以上含有していること、及びX線パラメータが異なる炭素系材料を2種以上含有すること等が挙げられる。
[2-2-3. Physical properties of carbonaceous materials]
The carbon-based material as the negative electrode active material preferably satisfies at least one of the physical properties, shape, and other characteristics shown in the following (1) to (4), and particularly preferably satisfies a plurality of them at the same time. .
(1) X-Ray Diffraction Parameter The d value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction of the carbon-based material according to the Gakushin method is usually 0.335 nm or more and 0.360 nm or less. Moreover, the crystallite size (Lc) of the carbonaceous material determined by X-ray diffraction according to the Gakushin method is usually 1.0 nm or more.
(2) Volume-Based Average Particle Size The volume-based average particle size of the carbon-based material is the volume-based average particle size (median diameter) determined by the laser diffraction/scattering method, and is usually 1 μm or more and 100 μm or less.
(3) Raman R value and Raman half-value width The Raman R value of a carbon-based material is a value measured using an argon ion laser Raman spectroscopy, and is usually 0.01 or more and 1.5 or less.
The Raman half-value width of the carbonaceous material near 1580 cm −1 is not particularly limited, but is usually 10 cm −1 or more and 100 cm −1 or less.
(4) BET Specific Surface Area The BET specific surface area of a carbon-based material is the value of the specific surface area measured using the BET method, and is usually 0.1 m 2 ·g −1 or more and 100 m 2 ·g −1 or less.
Moreover, two or more kinds of carbon-based materials having different properties may be contained in the negative electrode active material. The property referred to here means an X-ray diffraction parameter, volume-based average particle size, Raman R value, Raman half width or BET specific surface area.
Preferred examples include that the volume-based particle size distribution is not left-right symmetrical about the median diameter, that two or more carbonaceous materials having different Raman R values are contained, and that the carbonaceous materials having different X-ray parameters are Containing 2 or more types of materials, etc. are mentioned.
[2-2-4.Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料]
Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料は、従来公知のいずれのものも使用可能であるが、容量とサイクル寿命の点から、例えば、Sb、Si、Sn、Al、As、及びZnからなる群から選ばれる金属及び/若しくは半金属元素の単体又はその化合物であることが好ましい。また、Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料が金属元素を2種類以上の元素を含有する場合、当該材料は、これらの合金からなる合金材料であってもよい。
また、Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料としては、酸化物、窒化物、炭化物等が挙げられる。これらは、Liと合金化可能な金属元素及び/若しくは半金属元素を、2種以上含有していてもよい。なかでも、金属Si(以下、Siと記載する場合がある)又はSi含有化合物が高容量化の点で、好ましい。
[2-2-4. Materials containing metallic elements and/or metalloid elements that can be alloyed with Li]
Any conventionally known material containing a metal element and/or metalloid element that can be alloyed with Li can be used. , As, and Zn. In addition, when a material containing a metal element and/or a metalloid element that can be alloyed with Li contains two or more types of metal elements, the material may be an alloy material made of these alloys. .
Materials containing a metal element and/or a metalloid element that can be alloyed with Li include oxides, nitrides, carbides, and the like. These may contain two or more kinds of metal elements and/or metalloid elements that can be alloyed with Li. Among them, metal Si (hereinafter sometimes referred to as Si) or Si-containing compounds are preferable from the viewpoint of increasing the capacity.
本明細書では、Si又はSi含有化合物を総称してSi化合物と呼ぶ。Si化合物としては、具体的には、SiOx、SiNx、SiCx、SiZx‘Oy(Z=C、N)等が
挙げられる。Si化合物としては、Si酸化物(SiOx)が、黒鉛と比較して理論容量が大きい点で好ましく、非晶質SiもしくはナノサイズのSi結晶が、リチウムイオン等のアルカリイオンの出入りがしやすく、高容量を得ることが可能である点で好ましい。
この一般式SiOxで表されるSi酸化物は、二酸化珪素(SiO2)とSiとを原料として得られるが、そのxの値は通常0<x<2である。
Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料が粒子である場合、その平均粒子径(d50)は、サイクル寿命の観点から、通常0.01μm以上、10μm以下である。
In this specification, Si or Si-containing compounds are collectively referred to as Si compounds. Specific examples of Si compounds include SiO x , SiN x , SiC x , SiZ x′ O y (Z=C, N), and the like. As the Si compound, Si oxide (SiO x ) is preferable in that it has a larger theoretical capacity than graphite, and amorphous Si or nano-sized Si crystals facilitate the entry and exit of alkali ions such as lithium ions. , is preferable in that it is possible to obtain a high capacity.
The Si oxide represented by the general formula SiO x is obtained by using silicon dioxide (SiO 2 ) and Si as raw materials, and the value of x is usually 0<x<2.
When the material containing the metal element and/or metalloid element that can be alloyed with Li is particles, the average particle diameter (d50) is usually 0.01 μm or more and 10 μm or less from the viewpoint of cycle life.
[2-2-5.Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子と黒鉛粒子との混合物]
負極活物質として用いられるLiと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子と黒鉛粒子との混合物は、前述のLiと合金化可能な金属元素及び/若しくは半金属元素を含有する粒子と前述の黒鉛粒子が互いに独立した粒子の状態で混合されている混合体でもよいしLiと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子が黒鉛粒子の表面又は内部に存在している複合体でもよい。
Liと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子と黒鉛粒子の合計に対するLiと合金化可能な金属元素及び/若しくは半金属元素を含有する材料の粒子の含有割合は、通常1質量%以上、99質量%以下である。
[2-2-5. A mixture of particles of a material containing a metallic element and/or semi-metallic element that can be alloyed with Li and graphite particles]
A mixture of graphite particles and particles of a material containing a metal element and/or metalloid element that can be alloyed with Li used as a negative electrode active material contains the metal element and/or metalloid element that can be alloyed with Li. It may be a mixture in which particles containing and the above-mentioned graphite particles are mixed in a state of independent particles, or particles of a material containing a metal element and / or metalloid element that can be alloyed with Li are graphite particles. It may be a complex existing on the surface or inside.
The content ratio of the particles of the material containing the metal element and/or metalloid element that can be alloyed with Li to the total of the particles of the material containing the metal element and/or metalloid element that can be alloyed with Li and the graphite particles , usually 1% by mass or more and 99% by mass or less.
[2-2-6.リチウム含有金属複合酸化物材料]
負極活物質として用いられるリチウム含有金属複合酸化物材料としては、リチウムイオンを吸蔵及び放出可能であれば、特に制限されないが、高電流密度充放電特性の点からチタンを含むリチウム含有金属複合酸化物材料が好ましく、リチウムとチタンの複合酸化物(以下、「リチウムチタン複合酸化物」と略記する場合がある)がより好ましく、スピネル構造を有するリチウムチタン複合酸化物が出力抵抗を大きく低減するので特に好ましい。
[2-2-6. Lithium-containing metal composite oxide material]
The lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium ions. A material is preferable, and a composite oxide of lithium and titanium (hereinafter sometimes abbreviated as "lithium-titanium composite oxide") is more preferable, and lithium-titanium composite oxide having a spinel structure greatly reduces the output resistance, so it is particularly preferable.
また、リチウムチタン複合酸化物のリチウム及び/又はチタンが、他の金属元素、例えば、Al、Ga、Cu及びZnからなる群より選ばれる少なくとも1種の元素で置換されていてもよい。
リチウムチタン複合酸化物として、Li4/3Ti5/3O4、Li1Ti2O4及びLi4/5Ti11/5O4が好ましい。また、リチウム及び/又はチタンの一部が他の元素で置換されたリチウムチタン複合酸化物として、例えば、Li4/3Ti4/3Al1/3O4が好ましい。
Also, lithium and/or titanium in the lithium-titanium composite oxide may be substituted with other metal elements such as at least one element selected from the group consisting of Al, Ga, Cu and Zn.
Li 4/3 Ti 5/3 O 4 , Li 1 Ti 2 O 4 and Li 4/5 Ti 11/5 O 4 are preferable as the lithium titanium composite oxide. Li4 / 3Ti4 / 3Al1 / 3O4 , for example, is preferable as the lithium-titanium composite oxide in which part of lithium and/or titanium is replaced with another element.
[2-2-7.負極の構成と作製法]
負極の製造は、本発明の効果を著しく損なわない限り、公知のいずれの方法を用いてもよい。例えば、負極活物質に、結着剤、溶媒、必要に応じて、増粘剤、導電材、充填材等を加えてスラリーとし、これを集電体に塗布、乾燥した後にプレスして負極活物質層を形成することによって作製することができる。
[2-2-7. Structure and manufacturing method of negative electrode]
Any known method may be used to manufacture the negative electrode as long as it does not significantly impair the effects of the present invention. For example, a binder, a solvent, and, if necessary, a binder, a solvent, a thickener, a conductive material, a filler, etc., are added to the negative electrode active material to form a slurry, which is applied to a current collector, dried, and then pressed to form a negative electrode active material. It can be made by forming a layer of material.
[2-2-7-1.集電体]
負極活物質を保持させる集電体としては、公知のものを任意に用いることができる。負極の集電体としては、例えば、アルミニウム、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の金属材料が挙げられるが、加工し易さとコストの点から特に銅が好ましい。
また、集電体の形状は、例えば、金属箔、金属円柱、金属コイル、金属板、金属薄膜、エキスパンドメタル、パンチメタル、発泡メタル等が挙げられる。中でも、好ましくは金属薄膜又は金属箔である。より好ましくは銅箔であり、更に好ましくは圧延法による圧延銅箔と、電解法による電解銅箔である。なお、金属薄膜及び金属箔は適宜メッシュ状に形
成してもよい。
負極の集電体の形状が板状や膜状等である場合、該集電体の厚さは任意であるが、通常1μm以上、1mm以下である。
[2-2-7-1. current collector]
As the current collector for holding the negative electrode active material, any known current collector can be used. Examples of the current collector for the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable in terms of ease of processing and cost.
Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punched metal, and foamed metal. Among them, a metal thin film or a metal foil is preferable. Copper foil is more preferable, and rolled copper foil obtained by a rolling method and electrolytic copper foil obtained by an electrolysis method are further preferable. Incidentally, the metal thin film and the metal foil may be appropriately formed in a mesh shape.
When the shape of the current collector of the negative electrode is plate-like, film-like, or the like, the thickness of the current collector is arbitrary, but is usually 1 μm or more and 1 mm or less.
[2-2-7-2.結着剤]
負極活物質を結着する結着剤としては、非水系電解液や電極製造時に用いる溶媒に対して安定な材料であれば、特に制限されない。
具体例としては、SBR(スチレン・ブタジエンゴム)、イソプレンゴム、ブタジエンゴム、フッ素ゴム、NBR(アクリロニトリル・ブタジエンゴム)、エチレン・プロピレンゴム等のゴム状高分子;ポリフッ化ビニリデン、ポリテトラフルオロエチレン、テトラフルオロエチレン・エチレン共重合体等のフッ素系高分子等が挙げられる。これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
負極活物質に対する結着剤の割合は、通常0.1質量%以上、20質量%以下である。
特に、SBRに代表されるゴム状高分子を主要成分に含有する場合には、負極活物質に対する結着剤の割合は、好ましくは0.1質量%以上、5質量%以下である。また、結着剤がポリフッ化ビニリデンに代表されるフッ素系高分子を主要成分に含有する場合には負極活物質に対する結着剤の割合は、好ましくは1質量%以上、15質量%以下である。
[2-2-7-2. Binder]
The binder that binds the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolytic solution and the solvent used in electrode production.
Specific examples include rubber-like polymers such as SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluororubber, NBR (acrylonitrile-butadiene rubber), ethylene-propylene rubber; polyvinylidene fluoride, polytetrafluoroethylene, Examples thereof include fluorine-based polymers such as tetrafluoroethylene/ethylene copolymers. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
The ratio of the binder to the negative electrode active material is usually 0.1% by mass or more and 20% by mass or less.
In particular, when a rubber-like polymer represented by SBR is contained as a main component, the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more and 5% by mass or less. Further, when the binder contains a fluorine-based polymer represented by polyvinylidene fluoride as a main component, the ratio of the binder to the negative electrode active material is preferably 1% by mass or more and 15% by mass or less. .
[2-2-7-3.溶媒]
スラリーを形成するための溶媒としては、負極活物質、結着剤、並びに必要に応じて使用される増粘剤、導電材、充填剤等を溶解または分散することが可能な溶媒であれば、その種類に特に制限はなく、水系溶媒と有機系溶媒のどちらを用いてもよい。
[2-2-7-3. solvent]
As the solvent for forming the slurry, any solvent capable of dissolving or dispersing the negative electrode active material, binder, and optionally used thickener, conductive material, filler, etc. can be used. The type of solvent is not particularly limited, and either an aqueous solvent or an organic solvent may be used.
[2-2-7-4.増粘剤]
増粘剤は、通常、スラリーの粘度を調整するために使用される。増粘剤としては、特に制限されないが、具体的には、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール等が挙げられる。これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
増粘剤を用いる場合には、負極活物質に対する増粘剤の割合は、通常0.1質量%以上、5質量%以下である。
[2-2-7-4. Thickener]
Thickeners are commonly used to adjust the viscosity of the slurry. The thickener is not particularly limited, but specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol and the like. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
When a thickener is used, the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more and 5% by mass or less.
[2-2-8.電極密度]
負極活物質を電極化した際の電極構造は特に制限されないが、集電体上に存在している負極活物質の密度は、通常1g・cm-3以上、2.2g・cm-3以下である。
[2-2-8. Electrode density]
The electrode structure when the negative electrode active material is formed into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is usually 1 g cm −3 or more and 2.2 g cm −3 or less. be.
[2-2-9.負極板の厚さ]
負極(「負極板」ともいう。)の厚さは用いられる正極(「正極板」ともいう。)に合わせて設計されるものであり、特に制限されないが、負極板の厚さから集電体の厚さを差し引いた負極活物質層の厚さは、通常15μm以上、300μm以下である。
[2-2-9. Thickness of negative electrode plate]
The thickness of the negative electrode (also referred to as “negative plate”) is designed according to the positive electrode (also referred to as “positive plate”) to be used, and is not particularly limited. The thickness of the negative electrode active material layer after subtracting the thickness of is usually 15 μm or more and 300 μm or less.
[2-2-10.負極板の表面被覆]
また、負極板は、その表面に、負極活物質とは異なる組成の物質が付着したもの(表面付着物質)を用いてもよい。表面付着物質としては酸化アルミニウム等の酸化物、硫酸リチウム等の硫酸塩、炭酸リチウム等の炭酸塩等が挙げられる。
[2-2-10. Surface coating of negative electrode plate]
Further, the negative electrode plate may have a surface adhered with a substance having a composition different from that of the negative electrode active material (surface adhering substance). Examples of the surface adhering substance include oxides such as aluminum oxide, sulfates such as lithium sulfate, and carbonates such as lithium carbonate.
[2-3.正極]
正極は、正極活物質を集電体表面の少なくとも一部に有する。
[2-3-1.正極活物質]
以下に正極に使用される正極活物質(リチウム遷移金属系化合物)について述べる。
[2-3. positive electrode]
The positive electrode has a positive electrode active material on at least part of the current collector surface.
[2-3-1. Positive electrode active material]
The positive electrode active material (lithium transition metal compound) used for the positive electrode is described below.
[2-3-1-1.リチウム遷移金属系化合物]
リチウム遷移金属系化合物は、リチウムイオンを脱離、挿入することが可能な構造を有する化合物であり、例えば、硫化物やリン酸塩化合物、ケイ酸化合物、ホウ酸化合物、リチウム遷移金属複合酸化物などが挙げられる。なかでも、リン酸塩化合物又はリチウム遷移金属複合酸化物が好ましく、リチウム遷移金属複合酸化物がより好ましい。
リチウム遷移金属複合酸化物としては、三次元的拡散が可能なスピネル構造や、リチウムイオンの二次元的拡散を可能にする層状構造に属するものが挙げられる。
スピネル構造を有するものは、一般的に下記組成式(1)で表される。
LixM2O4・・・(1)
(式(1)中、xは1≦x≦1.5であり、Mは1種以上の遷移金属元素を表す。)
具体的には、LiMn2O4、LiCoMnO4、LiNi0.5Mn1.5O4、LiCoVO4などが挙げられる。
層状構造を有するものは、一般的に下記組成式(2)で表される。
Lix’M’O2・・・(2)
(式(2)中、x’は-0.1≦x’≦0.5であり、M’は1種以上の遷移金属元素を表す。)
具体的には、LiCoO2、LiNiO2、LiNi0.85Co0.10Al0.05O2、LiNi0.80Co0.15Al0.05O2、LiNi0.33Co0.33Mn0.33O2、Li1.05Ni0.33Co0.33Mn0.33O2、LiNi0.5Co0.2Mn0.3O2、Li1.05Ni0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2などが挙げられる。
[2-3-1-1. Lithium transition metal compound]
A lithium transition metal compound is a compound having a structure capable of desorbing and inserting lithium ions. etc. Among them, a phosphate compound or a lithium transition metal composite oxide is preferred, and a lithium transition metal composite oxide is more preferred.
Lithium-transition metal composite oxides include those belonging to a spinel structure that enables three-dimensional diffusion and those that belong to a layered structure that enables two-dimensional diffusion of lithium ions.
Those having a spinel structure are generally represented by the following compositional formula (1).
Li x M 2 O 4 (1)
(In formula (1), x is 1≤x≤1.5, and M represents one or more transition metal elements.)
Specific examples include LiMn 2 O 4 , LiCoMnO 4 , LiNi 0.5 Mn 1.5 O 4 and LiCoVO 4 .
Those having a layered structure are generally represented by the following compositional formula (2).
Li x'M'O 2 (2)
(In formula (2), x' is -0.1 ≤ x' ≤ 0.5, and M' represents one or more transition metal elements.)
Specifically, LiCoO 2 , LiNiO 2 , LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33O2 , Li1.05Ni0.33Co0.33Mn0.33O2 , LiNi0.5Co0.2Mn0.3O2 , Li1.05Ni0.5Co0 _ _ _ _ _ _ _ .2Mn0.3O2 , LiNi0.6Co0.2Mn0.2O2 , LiNi0.8Co0.1Mn0.1O2 and the like . _ _
なかでも、電池容量を向上させる観点から、層状構造を有するリチウム遷移金属複合酸化物が好ましく、下記組成式(3)で表されるリチウム遷移金属複合酸化物であることがより好ましい。
Lia1Nib1M’c1O2・・・(3)
(式(3)中、a1、b1及びc1はそれぞれ0.90≦a1≦1.10、0.30≦b1≦0.98、0.00≦c1≦0.50を満たす数値であり、b1+c1=1を満たす。M’はCo、Mn、Al、Mg、Zr、Fe、Ti及びErからなる群より選ばれる1種以上の元素を表す。)
Among them, from the viewpoint of improving battery capacity, a lithium-transition metal composite oxide having a layered structure is preferable, and a lithium-transition metal composite oxide represented by the following compositional formula (3) is more preferable.
Li a1 Ni b1 M′ c1 O 2 (3)
(In formula (3), a1, b1 and c1 are numerical values satisfying 0.90 ≤ a1 ≤ 1.10, 0.30 ≤ b1 ≤ 0.98, 0.00 ≤ c1 ≤ 0.50, and b1 + c1 = 1. M' represents one or more elements selected from the group consisting of Co, Mn, Al, Mg, Zr, Fe, Ti and Er.)
特に、下記組成式(4)で表されるリチウム遷移金属複合酸化物であることが好ましい。
Lia2Nib2Coc2M’d2O2・・・(4)
(式(4)中、a2、b2、c2及びd2はそれぞれ、0.90≦a2≦1.10、0.33≦b2≦0.98、0.01≦c2<0.50、0.01≦d2<0.50を満たす数値であり、b2+c2+d2=1を満たす。M’はMn、Al、Mg、Zr、Fe、Ti及びErからなる群より選ばれる1種以上の元素を表す。)
組成式(4)中、d2は0.10≦d2≦0.50を満たす数値であることが好ましい。
In particular, a lithium-transition metal composite oxide represented by the following compositional formula (4) is preferred.
Li a2 Ni b2 Co c2 M′ d2 O 2 (4)
(In formula (4), a2, b2, c2 and d2 are respectively 0.90 ≤ a2 ≤ 1.10, 0.33 ≤ b2 ≤ 0.98, 0.01 ≤ c2 < 0.50, 0.01 ≤ d2 < 0.50 and satisfies b2 + c2 + d2 = 1. M' represents one or more elements selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti and Er.)
In composition formula (4), d2 is preferably a numerical value that satisfies 0.10≤d2≤0.50.
組成式(4)で表されるリチウム遷移金属複合酸化物の好適な具体例としては、例えば、LiNi0.85Co0.10Al0.05O2、LiNi0.80Co0.15Al0.05O2、LiNi0.5Co0.2Mn0.3O2、Li1.05Ni0.50Co0.20Mn0.30O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、Li1.05Ni0.34Mn0.33Co0.33O2等が挙げられる。 Suitable specific examples of the lithium-transition metal composite oxide represented by the compositional formula (4) include LiNi 0.85 Co 0.10 Al 0.05 O 2 and LiNi 0.80 Co 0.15 Al 0 .05O2 , LiNi0.5Co0.2Mn0.3O2 , Li1.05Ni0.50Co0.20Mn0.30O2 , LiNi0.6Co0.2Mn0 . _ _ _ _ _ _ 2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , Li 1.05 Ni 0.34 Mn 0.33 Co 0.33 O 2 and the like.
各組成式中、M’はMn又はAlを含むことが好ましく、Mnを含むことがより好まし
く、Mn又はAlであることがさらに好ましい。リチウム遷移金属複合酸化物の構造安定性が高まり、繰り返し充放電した際の構造劣化が抑制されるためである。
In each composition formula, M' preferably contains Mn or Al, more preferably Mn, and even more preferably Mn or Al. This is because the structural stability of the lithium-transition metal composite oxide is enhanced, and structural deterioration during repeated charging and discharging is suppressed.
[2-3-1-2.異元素導入]
また、リチウム遷移金属複合酸化物は、上述の組成式に含まれる元素以外の元素(異元素)が導入されてもよい。
[2-3-1-2. Foreign element introduction]
Further, the lithium-transition metal composite oxide may contain an element (foreign element) other than the elements included in the above composition formula.
[2-3-1-3.表面被覆]
上記正極活物質の表面に、正極活物質とは異なる組成の物質(表面付着物質)が付着したものを用いてもよい。表面付着物質としては酸化アルミニウム等の酸化物、硫酸リチウム等の硫酸塩、炭酸リチウム等の炭酸塩等が挙げられる。
これら表面付着物質は、例えば、溶媒に溶解又は懸濁させて該正極活物質に含浸添加、乾燥する方法等により該正極活物質表面に付着させることができる。
表面付着物質の量としては、該正極活物質に対して、好ましくは1μmol/g以上であり、10μmol/g以上が好ましく、また、通常1mmol/g以下で用いられる。
本明細書においては、正極活物質の表面に、上記表面付着物質が付着したものも「正極活物質」という。
[2-3-1-3. surface coating]
A positive electrode active material having a different composition (surface adhering substance) attached to the surface of the positive electrode active material may be used. Examples of the surface adhering substance include oxides such as aluminum oxide, sulfates such as lithium sulfate, and carbonates such as lithium carbonate.
These surface-attaching substances can be attached to the surface of the positive electrode active material by, for example, a method of dissolving or suspending them in a solvent, impregnating and adding them to the positive electrode active material, and drying the material.
The amount of the surface-adhering substance is preferably 1 μmol/g or more, preferably 10 μmol/g or more, and usually 1 mmol/g or less, relative to the positive electrode active material.
In the present specification, a positive electrode active material having the above-described surface-attached substance attached to its surface is also referred to as a "positive electrode active material."
[2-3-1-4.ブレンド]
なお、これらの正極活物質は1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
[2-3-1-4. blend]
In addition, these positive electrode active materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
[2-3-2.正極の構成と製造方法]
以下に、正極の構成と製造方法について述べる。本実施形態において、正極活物質を用いる正極の製造は、常法により行うことができる。即ち、正極活物質と結着剤、並びに必要に応じて導電材及び増粘剤等を乾式で混合してシート状にしたものを正極集電体に圧着するか、又はこれらの材料を液体媒体に溶解又は分散させてスラリーとして、これを正極集電体に塗布し、乾燥することにより、正極活物質層を集電体上に形成する塗布法により正極を得ることができる。また、例えば、上述の正極活物質をロール成形してシート電極としてもよいし、圧縮成形によりペレット電極としてもよい。
以下、正極集電体に順次スラリーの塗布及び乾燥する場合について説明する。
[2-3-2. Configuration and Manufacturing Method of Positive Electrode]
The configuration and manufacturing method of the positive electrode will be described below. In this embodiment, the positive electrode using the positive electrode active material can be manufactured by a conventional method. That is, a positive electrode active material, a binder, and, if necessary, a conductive material, a thickening agent, and the like are dry-mixed to form a sheet, which is pressed against a positive electrode current collector, or these materials are mixed in a liquid medium. A positive electrode can be obtained by a coating method in which a positive electrode active material layer is formed on a current collector by dissolving or dispersing it in a slurry to form a slurry, applying this to a positive electrode current collector, and drying it. Further, for example, the positive electrode active material described above may be roll-molded into a sheet electrode, or may be compression-molded into a pellet electrode.
A case where the slurry is sequentially applied to the positive electrode current collector and dried will be described below.
[2-3-2-1.活物質含有量]
正極活物質層中、正極活物質の含有量は、通常80質量%以上、98質量%以下である。
[2-3-2-1. Active material content]
The content of the positive electrode active material in the positive electrode active material layer is usually 80% by mass or more and 98% by mass or less.
[2-3-2-2.導電材]
導電材としては、公知の導電材を任意に用いることができる。具体例としては、銅、ニッケル等の金属材料;天然黒鉛、黒鉛(グラファイト)、カーボンブラック等の炭素系材料;等が挙げられる。導電材は、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。導電材は、正極活物質層中に、通常0.01質量%以上、50質量%以下含有するように用いられる。
[2-3-2-2. Conductive material]
Any known conductive material can be used as the conductive material. Specific examples include metal materials such as copper and nickel; carbon-based materials such as natural graphite, graphite, and carbon black; and the like. One type of conductive material may be used alone, or two or more types may be used together in any combination and ratio. The conductive material is used so as to be contained in the positive electrode active material layer generally in an amount of 0.01% by mass or more and 50% by mass or less.
[2-3-2-3.結着剤]
正極活物質層の製造に用いる結着剤としては、例えば、塗布法により正極活物質層を形成する場合は、スラリー用の液体媒体に対して溶解又は分散される材料であれば、その種類は特に制限されないが、耐候性、耐薬品性、耐熱性、難燃性等から、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のフッ素系樹脂;ポリアクリロニトリル、ポリビニリデンシアニド等のCN基含有ポリマー;等が好ましい。
また、上記のポリマーなどの混合物、変成体、誘導体、ランダム共重合体、交互共重合
体、グラフト共重合体、ブロック共重合体なども使用できる。なお、結着剤は、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
また、結着剤として樹脂を用いる場合、その樹脂の重量平均分子量は、本発明の効果を著しく損なわない限り任意であるが、通常1万以上300万以下である。分子量がこの範囲であると電極の強度が向上し、電極の形成を好適に行うことができる。
正極活物質層中の結着剤の割合は、通常0.1質量%以上、80質量%以下である。
[2-3-2-3. Binder]
As the binder used for producing the positive electrode active material layer, for example, when the positive electrode active material layer is formed by a coating method, if it is a material that is dissolved or dispersed in the liquid medium for slurry, the type is Fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene; CN groups such as polyacrylonitrile and polyvinylidene cyanide; containing polymer; and the like are preferred.
Mixtures, modified products, derivatives, random copolymers, alternating copolymers, graft copolymers, block copolymers, etc. of the above polymers can also be used. In addition, a binder may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
When a resin is used as the binder, the weight-average molecular weight of the resin is arbitrary as long as it does not significantly impair the effects of the present invention. When the molecular weight is within this range, the strength of the electrode is improved, and the electrode can be suitably formed.
The ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more and 80% by mass or less.
[2-3-2-4.液体媒体]
スラリーを形成するための液体媒体としては、正極活物質、導電材、結着剤、並びに必要に応じて使用される増粘剤を溶解又は分散することが可能な溶媒であれば、その種類に特に制限はなく、水系溶媒と有機系溶媒のどちらを用いてもよい。
[2-3-2-4. liquid medium]
As the liquid medium for forming the slurry, any solvent capable of dissolving or dispersing the positive electrode active material, the conductive material, the binder, and the thickening agent used as necessary may be used. There is no particular limitation, and either an aqueous solvent or an organic solvent may be used.
[2-3-2-5.集電体]
正極集電体の材質としては特に制限されず、公知のものを任意に用いることができる。具体例としては、アルミニウム、ステンレス鋼、ニッケルメッキ、チタン、タンタル等の金属材料が挙げられる。中でもアルミニウムが好ましい。
集電体の形状としては、金属箔、金属円柱、金属コイル、金属板、金属薄膜、エキスパンドメタル、パンチメタル、発泡メタル等が挙げられる。これらのうち、金属箔又は金属薄膜が好ましい。なお、金属箔及び金属薄膜は適宜メッシュ状に形成してもよい。
なお、正極の集電体の形状が板状や膜状等である場合、該集電体の厚さは任意であるが、通常1μm以上、1mm以下である。
[2-3-2-5. current collector]
The material of the positive electrode current collector is not particularly limited, and any known material can be used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum. Among them, aluminum is preferred.
Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punched metal, and foamed metal. Among these, a metal foil or a metal thin film is preferable. Incidentally, the metal foil and the metal thin film may be appropriately formed in a mesh shape.
When the shape of the current collector of the positive electrode is plate-like, film-like, or the like, the thickness of the current collector is arbitrary, but is usually 1 μm or more and 1 mm or less.
[2-3-2-6.正極板の厚さ]
正極板の厚さは特に限定されないが、高容量かつ高出力の観点から、正極板の厚さから集電体の厚さを差し引いた正極活物質層の厚さは、集電体の片面に対して通常10μm以上、500μm以下である。
[2-3-2-6. Thickness of positive electrode plate]
The thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the positive electrode active material layer obtained by subtracting the thickness of the current collector from the thickness of the positive electrode plate is On the other hand, it is usually 10 μm or more and 500 μm or less.
[2-3-2-7.正極活物質層の密度]
塗布、乾燥によって得られた正極活物質層は、正極活物質の充填密度を上げるために、ハンドプレス、ローラープレス等により圧密化することが好ましい。集電体上に存在している正極活物質層の密度は、通常1.5g/cm3以上、4.5g/cm3以下である。
[2-3-2-7. Density of positive electrode active material layer]
The positive electrode active material layer obtained by coating and drying is preferably densified by hand pressing, roller pressing, or the like in order to increase the packing density of the positive electrode active material. The density of the positive electrode active material layer present on the current collector is usually 1.5 g/cm 3 or more and 4.5 g/cm 3 or less.
[2-3-2-8.正極板の表面被覆]
また、上記正極板は、その表面に、正極板とは異なる組成の物質が付着したものを用いてもよく、当該物質としては、正極活物質の表面に付着していてもよい表面付着物質と同じ物質が用いられる。
[2-3-2-8. Surface coating of positive electrode plate]
In addition, the positive electrode plate may be one in which a substance having a composition different from that of the positive electrode plate is attached to the surface of the positive electrode plate. The same substances are used.
[2-4.セパレータ]
正極と負極との間には、短絡を防止するために、通常はセパレータを介在させる。この場合、非水系電解液は、通常はこのセパレータに含浸させて用いる。
[2-4. Separator]
A separator is usually interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the separator is usually impregnated with the non-aqueous electrolytic solution.
[2-4-1.材料]
セパレータの材料としては非水系電解液に対し安定な材料であれば特に制限されないが、好ましくは、例えば、アルミナや二酸化ケイ素等の酸化物類、窒化アルミや窒化ケイ素等の窒化物類、硫酸バリウムや硫酸カルシウム等の硫酸塩類、ガラス繊維からなるガラスフィルター等の無機物;ポリオレフィン等の樹脂が挙げられ、より好ましくはポリオレフィンであり、特に好ましくはポリエチレン又はポリプロピレンである。これらの材料は1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。また上記材料を積層させて用いてもよい。
[2-4-1. material]
The material of the separator is not particularly limited as long as it is stable against a non-aqueous electrolytic solution, but is preferably, for example, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and barium sulfate. inorganic substances such as glass filters made of glass fibers; and resins such as polyolefins, more preferably polyolefins, and particularly preferably polyethylene or polypropylene. One of these materials may be used alone, or two or more of them may be used in any combination and ratio. Further, the above materials may be laminated and used.
[2-4-2.形態]
セパレータの形態としては特に制限されないが、好ましくは、不織布、織布、微多孔性フィルム等の薄膜形状のものが用いられる。薄膜形状では、孔径が0.01~1μm、厚さが1~50μmのものが好適に用いられる。独立した薄膜形状以外に、樹脂製の結着材を用いて無機物の粒子を含有する複合多孔層を正極及び/又は負極の表層に形成させてなるセパレータを用いてもよい。セパレータの形態は、保液性に優れるため、微多孔性フィルム及び不織布であることが好ましい。
[2-4-2. form]
The shape of the separator is not particularly limited, but thin films such as non-woven fabrics, woven fabrics and microporous films are preferably used. In the form of a thin film, one having a pore diameter of 0.01 to 1 μm and a thickness of 1 to 50 μm is preferably used. In addition to the independent thin film shape, a separator may be used in which a composite porous layer containing inorganic particles is formed on the surface of the positive electrode and/or the negative electrode using a resin binder. The form of the separator is preferably a microporous film or a non-woven fabric because of its excellent liquid retention.
[2-4-3.空孔率]
セパレータとして多孔性シートや不織布等の多孔質のものを用いる場合、セパレータの空孔率は任意であるが、通常20%以上、90%以下である。
[2-4-3. Porosity]
When a porous material such as a porous sheet or non-woven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more and 90% or less.
[2-4-4.透気度]
セパレータの非水系電解液二次電池における透気度は、ガーレ値で把握することができる。ガーレ値とは、フィルム厚さ方向の空気の通り抜け難さを示し、100mLの空気が該フィルムを通過するのに必要な秒数で表される。セパレータのガーレ値は、任意ではあるが、通常10~1000秒/100mLである。
[2-4-4. air permeability]
The air permeability of the separator in the non-aqueous electrolyte secondary battery can be grasped by the Gurley value. The Gurley value indicates how difficult it is for air to pass through the film in the thickness direction, and is expressed in seconds required for 100 mL of air to pass through the film. The Gurley value of the separator is arbitrary, but usually 10-1000 seconds/100 mL.
[2-5.電池設計]
[2-5-1.電極群]
電極群は、上記の正極板と負極板とを上記のセパレータを介してなる積層構造のもの、及び上記の正極板と負極板とを上記のセパレータを介して渦巻き状に捲回した構造のもののいずれでもよい。電極群の体積が電池内容積に占める割合(以下、電極群占有率と称する)は、通常40%以上、90%以下である。
[2-5. battery design]
[2-5-1. Electrode group]
The electrode group has a laminate structure in which the positive electrode plate and the negative electrode plate are interposed between the separators, and a structure in which the positive electrode plate and the negative electrode plate are spirally wound with the separator interposed therebetween. Either is fine. The ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as electrode group occupancy) is usually 40% or more and 90% or less.
[2-5-2.集電構造]
電極群が前述の積層構造のものでは、各電極層の金属芯部分を束ねて端子に溶接して形成される構造が好適に用いられる。電極内に複数の端子を設けて抵抗を低減する構造も好適に用いられる。電極群が前述の捲回構造のものでは、正極及び負極にそれぞれ複数のリード構造を設け、端子に束ねることにより、内部抵抗を低くすることができる。
[2-5-2. Current collection structure]
When the electrode group has the above-described laminated structure, a structure in which the metal core portions of the electrode layers are bundled and welded to a terminal is preferably used. A structure in which a plurality of terminals are provided in an electrode to reduce resistance is also preferably used. When the electrode group has the wound structure described above, the internal resistance can be reduced by providing a plurality of lead structures for each of the positive electrode and the negative electrode and bundling them around the terminal.
[2-5-3.保護素子]
保護素子として、過大電流等による発熱とともに抵抗が増大するPTC(Positive Temperature Coefficient)素子、温度ヒューズ、サーミスター、異常発熱時に電池内部圧力や内部温度の急激な上昇により回路に流れる電流を遮断する弁(電流遮断弁)等を使用することができる。上記保護素子は高電流の通常使用で作動しない条件のものを選択することが好ましく、保護素子がなくても異常発熱や熱暴走に至らない設計にすることがより好ましい。
[2-5-3. Protective element]
Protective elements include PTC (Positive Temperature Coefficient) elements whose resistance increases as heat is generated by excessive current, thermal fuses, thermistors, and valves that cut off the current flowing through the circuit due to a sudden increase in battery internal pressure or internal temperature during abnormal heat generation. (current cut-off valve) or the like can be used. It is preferable to select the protective element under the condition that it does not operate under normal high-current use, and it is more preferable to design such that abnormal heat generation and thermal runaway do not occur even without the protective element.
[2-5-4.外装体]
非水系電解液二次電池は、通常、上記の非水系電解液、負極、正極、セパレータ等を外装体(外装ケース)内に収納して構成される。この外装体に制限は無く、本発明の効果を著しく損なわない限り公知のものを任意に採用することができる。
外装ケースの材質は用いられる非水系電解液に対して安定な物質であれば特に限定されるものではないが、軽量化の観点から、アルミニウム若しくはアルミニウム合金の金属又はラミネートフィルムが好適に用いられる。
上記金属類を用いる外装ケースでは、レーザー溶接、抵抗溶接、超音波溶接により金属同士を溶着して封止密閉構造とするもの、又は、樹脂製ガスケットを介して上記金属類を用いてかしめ構造とするものが挙げられる。
[2-5-4. exterior body]
A non-aqueous electrolyte secondary battery is generally configured by housing the non-aqueous electrolyte, the negative electrode, the positive electrode, the separator, and the like in an exterior body (exterior case). There is no restriction on this exterior body, and any known one can be employed as long as it does not significantly impair the effects of the present invention.
The material of the exterior case is not particularly limited as long as it is stable with respect to the non-aqueous electrolytic solution used, but from the viewpoint of weight reduction, aluminum or aluminum alloy metal or laminate film is preferably used.
The exterior case using the above metals has a sealed structure by welding the metals together by laser welding, resistance welding, or ultrasonic welding, or a crimped structure using the above metals via a resin gasket. There are things to do.
[2-5-5.形状]
また、外装ケースの形状も任意であり、例えば円筒型、角形、ラミネート型、コイン型、大型等の何れであってもよい。
[2-5-5. shape]
Moreover, the shape of the exterior case is also arbitrary, and may be cylindrical, rectangular, laminated, coin-shaped, large-sized, or the like.
次に実施例により本発明の具体的態様を更に詳細に説明するが、本発明はこれらの例によって限定されるものではない。
本実施例及び比較例に使用した化合物を以下に示す。
Specific embodiments of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.
The compounds used in Examples and Comparative Examples are shown below.
[実施例1-1~1-3、比較例1-1~1-5]
[非水系電解液二次電池の作製]
<非水系電解液の調製>
乾燥アルゴン雰囲気下、エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(体積比3:4:3)に、十分に乾燥させたLiPF6を1.0mol/L(12.3質量%、非水系電解液中の濃度として)溶解させた非水系電解液を基準電解液として、表1に記載の通り、炭素-炭素不飽和結合を有するエステル化合物(表中、「エステル化合物」と示した。)と、併用添加剤とを溶解させて実施例1-1~1-3、比較例1-2~1-5の非水系電解液を調製した。比較例1-1の非水系電解液は、基準電解液を用いた。
[Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-5]
[Preparation of non-aqueous electrolyte secondary battery]
<Preparation of non-aqueous electrolytic solution>
In a dry argon atmosphere, a mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (volume ratio 3:4:3) was added with 1.0 mol/L (12.3% by mass of non-aqueous electrolysis) of sufficiently dried LiPF6 . As the concentration in the liquid), the dissolved non-aqueous electrolytic solution is used as the reference electrolytic solution, and as shown in Table 1, an ester compound having a carbon-carbon unsaturated bond (indicated as “ester compound” in the table) and , combined additives were dissolved to prepare non-aqueous electrolytic solutions of Examples 1-1 to 1-3 and Comparative Examples 1-2 to 1-5. A reference electrolyte was used as the non-aqueous electrolyte in Comparative Example 1-1.
<正極の作製>
正極活物質としてLi1.05Ni0.34Mn0.33Co0.33O2を85質量部、導電材としてアセチレンブラックを10質量部、結着剤としてポリフッ化ビニリデン(PVdF)を5質量部を、N-メチル-2-ピロリドン中で混合してスラリー化した。これを厚さ15μmのアルミニウム箔に均一に塗布、乾燥した後、ロールプレスを行い、正極とした。なお、正極活物質層の密度は2.6g/cm3であった。
<Preparation of positive electrode>
85 parts by mass of Li 1.05 Ni 0.34 Mn 0.33 Co 0.33 O 2 as a positive electrode active material, 10 parts by mass of acetylene black as a conductive material, and 5 parts by mass of polyvinylidene fluoride (PVdF) as a binder The parts were mixed and slurried in N-methyl-2-pyrrolidone. This was uniformly applied to an aluminum foil having a thickness of 15 μm, dried, and roll-pressed to obtain a positive electrode. The density of the positive electrode active material layer was 2.6 g/cm 3 .
<負極の作製>
グラファイト粉末49質量部に、増粘剤としてカルボキシメチルセルロースナトリウムの水性ディスパージョン(カルボキシメチルセルロースナトリウムの濃度1質量%)50質量部と、結着剤としてスチレン-ブタジエンゴムの水性ディスパージョン(スチレン-ブタジエンゴムの濃度49質量%)1質量部を加え、ディスパーザーで混合してスラリー化した。得られたスラリーを厚さ10μmの銅箔に均一に塗布して乾燥した後、ロールプレスして負極とした。
<Production of negative electrode>
To 49 parts by mass of graphite powder, 50 parts by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose of 1% by mass) as a thickener, and an aqueous dispersion of styrene-butadiene rubber (styrene-butadiene rubber) as a binder. concentration of 49% by mass) was added and mixed with a disperser to form a slurry. The resulting slurry was uniformly applied to a copper foil having a thickness of 10 μm, dried, and roll-pressed to form a negative electrode.
<非水系電解液二次電池の製造>
上記の正極、負極、及びポリオレフィン製セパレータを、負極、セパレータ、正極の順に積層した。こうして得られた電池要素をアルミニウムラミネートフィルムで包み込み、前述の非水系電解液を注入した後で真空封止し、シート状の非水系電解液二次電池を作製した。
<Production of non-aqueous electrolyte secondary battery>
The above positive electrode, negative electrode, and polyolefin separator were laminated in the order of negative electrode, separator, and positive electrode. The thus-obtained battery element was wrapped with an aluminum laminate film, filled with the non-aqueous electrolyte, and then vacuum-sealed to produce a sheet-like non-aqueous electrolyte secondary battery.
[非水系電解液二次電池の評価]
上記の手順で作製した非水系電解液二次電池を以下のとおり評価した。
・DCR維持率の評価
25℃の恒温槽中、シート状の非水系電解液二次電池を0.025C(1時間率の放電容量による定格容量を1時間で放電する電流値を1Cとする。以下同様。)で3.6Vまで定電流充電し、次いで0.167Cで4.2Vの電圧まで定電流-定電圧充電し、その後0.167Cで2.5Vまでの定電流放電を行った。
さらに、4.1Vまで0.167Cで定電流-定電圧充電した後に、60℃で12時間保管することで非水系電解液二次電池を安定させた。その後、25℃にて2.5Vまで定電流放電し、次いで4.2Vの電圧まで0.167Cで定電流-定電圧充電を実施した。その後、0.167Cで2.5Vまでの定電流放電を行った。その後、3.7Vまで0.167Cで定電流-定電圧充電した後に、0.5C、1.0C、1.5Cで10秒間定電流放電を行い、その電圧と電流から初期DCRを求めた。次に、4.2Vの電圧まで0.2Cで定電流-定電圧充電を実施し、初期充放電を完了した。上記初期充放電後の非水系電解液二次電池を、60℃で14日間静置した。14日間の静置後、25℃で2.5Vまで定電流放電し、次いで、3.7Vまで0.167Cで定電流-定電圧充電した後に、0.5C、1.0C、1.5Cで10秒間定電流放電を行い、その電圧と電流から保存後DCRを求めた。DCR維持率は保存後DCR/初期DCRより算出した。結果を表1に示す。表1のDCR維持率は比較例1-1を100と規格化した値である。なお、DCR維持率は小さいほど好ましいといえる。
[Evaluation of non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery produced by the above procedure was evaluated as follows.
-Evaluation of DCR retention rate In a constant temperature bath at 25°C, a sheet-shaped non-aqueous electrolyte secondary battery is discharged at 0.025C (1C is the current value for discharging the rated capacity at a discharge capacity of 1 hour rate in 1 hour. The same applies below.), followed by constant-current/constant-voltage charging at 0.167C to a voltage of 4.2V, and then constant-current discharging at 0.167C to 2.5V.
Further, the non-aqueous electrolyte secondary battery was stabilized by storing at 60° C. for 12 hours after constant current-constant voltage charging at 0.167 C to 4.1 V. After that, constant current discharge to 2.5V was performed at 25° C., and then constant current-constant voltage charge was performed at 0.167C to a voltage of 4.2V. After that, constant current discharge to 2.5V was performed at 0.167C. Then, after constant-current-constant-voltage charging at 0.167 C to 3.7 V, constant-current discharging was performed at 0.5 C, 1.0 C, and 1.5 C for 10 seconds, and the initial DCR was obtained from the voltage and current. Next, constant current-constant voltage charging was performed at 0.2 C to a voltage of 4.2 V to complete initial charging and discharging. The non-aqueous electrolyte secondary battery after the initial charge/discharge was allowed to stand at 60° C. for 14 days. After standing for 14 days, constant current discharge to 2.5 V at 25 ° C., then constant current-constant voltage charge to 3.7 V at 0.167 C, then at 0.5 C, 1.0 C, 1.5 C A constant current discharge was performed for 10 seconds, and the DCR after storage was determined from the voltage and current. The DCR retention rate was calculated from post-storage DCR/initial DCR. Table 1 shows the results. The DCR retention rate in Table 1 is a value normalized to 100 for Comparative Example 1-1. Incidentally, it can be said that the smaller the DCR maintenance rate, the better.
表1より、実施例1-1~1-3と比較例1-1~1-5とを比較すると、不飽和結合を有するエステル化合物とP-F結合及びP=O結合を有するリン酸塩を非水系電解液に共に含有することにより、非水系電解液二次電池のDCR維持率が改善することが分かる。したがって、本発明の非水系電解液は、不飽和結合を有するエステル化合物とP-F結合及びP=O結合を有するリン酸塩を共に含有することにより特異的に電池性能を向上できることが分かる。特に化合物1とP-F結合及びP=O結合を有するリン酸塩の組み合わせにより。DCR増加の抑制が最も顕著であった理由としては、化合物1がP-F結合及びP=O結合を有するリン酸塩と適度に相互作用する分子の立体性を有するため、電極上での過剰な反応を抑制できるためであると考える。 From Table 1, when Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5 are compared, ester compounds having unsaturated bonds and phosphates having PF bonds and P=O bonds in the non-aqueous electrolyte improves the DCR retention rate of the non-aqueous electrolyte secondary battery. Therefore, it can be seen that the non-aqueous electrolytic solution of the present invention can specifically improve battery performance by containing both an ester compound having an unsaturated bond and a phosphate having a PF bond and a P═O bond. Especially by combining compound 1 with a phosphate having a PF bond and a P═O bond. The reason why the suppression of the DCR increase was most remarkable is that compound 1 has a steric structure of a molecule that moderately interacts with phosphate having PF bonds and P=O bonds, so excess on the electrode It is thought that this is because the reaction can be suppressed.
[実施例2-1~2-4、比較例2-1~2-2]
[非水系電解液二次電池の作製]
<非水系電解液の調製>
乾燥アルゴン雰囲気下、エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(体積比3:4:3)に、十分に乾燥させたLiPF6を1.0mol/L(12.3質量%、非水系電解液中の濃度として)溶解させた非水系電解液を基準電解液として、表2に記載の通り、エステル化合物と、併用添加剤とを溶解させて実施例2-1~2-4、比較例2-1~2-2の非水系電解液を調製した。
[Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-2]
[Preparation of non-aqueous electrolyte secondary battery]
<Preparation of non-aqueous electrolytic solution>
In a dry argon atmosphere, a mixture of ethylene carbonate, ethylmethyl carbonate and dimethyl carbonate (volume ratio 3:4:3) was added with 1.0 mol/L (12.3% by mass of non-aqueous electrolysis) of sufficiently dried LiPF6 . As the concentration in the liquid) the dissolved non-aqueous electrolytic solution is used as a reference electrolytic solution, and as shown in Table 2, the ester compound and the combined additive are dissolved Examples 2-1 to 2-4 and Comparative Examples Non-aqueous electrolytic solutions 2-1 and 2-2 were prepared.
<正極の作製>
実施例1-1~1-3、比較例1-1~1-5と同様に正極を作製し、使用した。
<Preparation of positive electrode>
Positive electrodes were prepared and used in the same manner as in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5.
<負極の作製>
実施例1-1~1-3、比較例1-1~1-5と同様に負極を作製し、使用した。
<Production of negative electrode>
Negative electrodes were prepared and used in the same manner as in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5.
<非水系電解液二次電池の製造>
上記の正極、負極、及びポリオレフィン製セパレータを、負極、セパレータ、正極の順に積層した。こうして得られた電池要素をアルミニウムラミネートフィルムで包み込み、前述の非水系電解液を注入した後で真空封止し、シート状の非水系電解液二次電池を作製した。
<Production of non-aqueous electrolyte secondary battery>
The above positive electrode, negative electrode, and polyolefin separator were laminated in the order of negative electrode, separator, and positive electrode. The thus-obtained battery element was wrapped with an aluminum laminate film, filled with the non-aqueous electrolyte, and then vacuum-sealed to produce a sheet-like non-aqueous electrolyte secondary battery.
[非水系電解液二次電池の評価]
実施例2-1~2-4、比較例2-1~2-2で作製した非水系電解液二次電池は、実施例1-1~1-3、比較例1-1~1-5と同様の評価を行った。表2に結果を示す。表2のDCR維持率は比較例1-1を100として規格化した値である。
[Evaluation of non-aqueous electrolyte secondary battery]
Non-aqueous electrolyte secondary batteries produced in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 are Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5. performed the same evaluation. Table 2 shows the results. The DCR retention rate in Table 2 is a value normalized to 100 for Comparative Example 1-1.
表1より、化合物1とP-F結合及びP=O結合を有するリン酸塩を共添加することにより顕著に電池特性が向上したことから、表2において化合物1と種々の塩との共添加を検討した。実施例2-1~2-4と比較例2-1~2-2との比較から、特定の併用添加剤を同時に含有することにより、特異的にDCR増加が抑制できることが分かる。
これらの結果から、本発明の非水系電解液は、炭素-炭素不飽和結合を有するエステル化合物と特定の併用添加剤とを含有することにより、特異的に電池性能を向上できることが分かる。
From Table 1, the co-addition of compound 1 and a phosphate having a PF bond and a P=O bond significantly improved the battery characteristics. It was investigated. From the comparison between Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2, it can be seen that the increase in DCR can be specifically suppressed by simultaneously containing a specific combined additive.
These results show that the non-aqueous electrolytic solution of the present invention can specifically improve battery performance by containing an ester compound having a carbon-carbon unsaturated bond and a specific combined additive.
Claims (7)
(式(I)中、R1~R6は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R1とR2、R1とR3、R4とR5、及びR5とR6は互いに結合し環状構造を形成していてもよい。nは0~4の整数である。) A compound (A) represented by formula (I), a phosphate having a PF bond and a P=O bond, a sulfonate having an SF bond, and a BF bond and/or an oxalate group and one or more compounds (B) selected from the group consisting of borate salts.
(In Formula (I), R 1 to R 6 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 1 and R 2 , R 1 and R 3 , R 4 and R 5 , and R 5 and R 6 may combine with each other to form a cyclic structure, and n is an integer of 0 to 4.)
(式(II)中、R7~R9は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R7とR8、R7とR9は互いに結合し環状構造を形成していてもよい。)
(式(III)中、R10~R12は、それぞれ独立に、水素原子、ハロゲン原子、又は炭化水素基であり、R10とR11、R10とR12は互いに結合し環状構造を形成していてもよい。) According to claim 1 or 2, wherein the compound (A) represented by the formula (I) is a vinyl ester compound represented by the following formula (II) and/or an allyl ester compound represented by the formula (III) The non-aqueous electrolyte described.
(In Formula (II), R 7 to R 9 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 7 and R 8 and R 7 and R 9 are bonded to each other to form a cyclic structure. may be.)
(In Formula (III), R 10 to R 12 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R 10 and R 11 and R 10 and R 12 are bonded to each other to form a cyclic structure. may be.)
る1種以上の化合物(B)を、0.01質量%以上、10質量%以下含有する、請求項1~5のいずれか1項に記載の非水系電解液。 1 selected from the group consisting of a phosphate having a PF bond and a P=O bond, a sulfonate having an SF bond, a borate having a BF bond and a borate having an oxalate group The non-aqueous electrolytic solution according to any one of claims 1 to 5, containing 0.01% by mass or more and 10% by mass or less of the compound (B) of at least one species.
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