JP2016066453A - Nonaqueous electrolyte secondary battery and power storage device - Google Patents
Nonaqueous electrolyte secondary battery and power storage device Download PDFInfo
- Publication number
- JP2016066453A JP2016066453A JP2014193769A JP2014193769A JP2016066453A JP 2016066453 A JP2016066453 A JP 2016066453A JP 2014193769 A JP2014193769 A JP 2014193769A JP 2014193769 A JP2014193769 A JP 2014193769A JP 2016066453 A JP2016066453 A JP 2016066453A
- Authority
- JP
- Japan
- Prior art keywords
- group
- secondary battery
- electrolyte secondary
- aqueous electrolyte
- nonaqueous electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 94
- 238000003860 storage Methods 0.000 title claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 10
- VVFGLBKYBBUTRO-UHFFFAOYSA-N 1-[difluoromethyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C(F)F)OCC VVFGLBKYBBUTRO-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
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- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
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- 238000000034 method Methods 0.000 description 4
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- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
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- 239000006258 conductive agent Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 239000003223 protective agent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
本発明は、非水電解質二次電池、特に、非水電解質に特徴を有する非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery characterized by a non-aqueous electrolyte.
リチウム二次電池に代表される非水電解質二次電池は、その高エネルギー密度という利点を活かして、携帯電話に代表されるモバイル機器の電源として幅広く普及している。また、近年、小形機器用電源だけでなく、電力貯蔵用、電気自動車用及びハイブリッド自動車用等の中大型産業用途への展開がなされている。 Nonaqueous electrolyte secondary batteries typified by lithium secondary batteries are widely used as power sources for mobile devices typified by mobile phones, taking advantage of their high energy density. In addition, in recent years, development has been made not only for power supplies for small devices, but also for medium and large-sized industrial applications such as power storage, electric vehicles, and hybrid vehicles.
非水電解質二次電池は、一般に、正極活物質を含む正極と、負極活物質を含む負極と、セパレータと、非水溶媒及びリチウム塩を含有する非水電解質とを備えている。
非水電解質二次電池を構成する正極活物質としてはリチウム含有遷移金属酸化物が、負極活物質としてはグラファイトに代表される炭素材料が、非水電解質としては、エチレンカーボネート等の環状カーボネートとジエチルカーボネート等の鎖状カーボネートを主構成成分とする非水溶媒に六フッ化リン酸リチウム(LiPF6)等の電解質を溶解したものが広く知られている。
A nonaqueous electrolyte secondary battery generally includes a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a separator, and a nonaqueous electrolyte containing a nonaqueous solvent and a lithium salt.
The positive electrode active material constituting the nonaqueous electrolyte secondary battery is a lithium-containing transition metal oxide, the negative electrode active material is a carbon material typified by graphite, and the nonaqueous electrolyte is a cyclic carbonate such as ethylene carbonate and diethyl. A solution in which an electrolyte such as lithium hexafluorophosphate (LiPF 6 ) is dissolved in a nonaqueous solvent containing a chain carbonate such as carbonate as a main constituent is widely known.
ところで、今後の中型・大型、特に大きな需要が見込まれる産業用途への展開を考えた場合、産業用途では小型民生用では使用されないような高温環境において電池が使用される用途も存在するため、電池の安全性が非常に重要視される。
しかしながら、従来非水溶媒に用いられてきた有機溶媒は一般に揮発しやすく、引火性を有するため、可燃性物質に分類されるものである。
By the way, when considering the future expansion to medium-sized and large-sized, especially industrial applications where large demand is expected, there are applications where batteries are used in high-temperature environments that are not used in small-sized consumer applications. Safety is very important.
However, organic solvents conventionally used for non-aqueous solvents are generally volatile and flammable, and therefore are classified as flammable substances.
そこで、非水電解質二次電池の電解液の難燃性向上や、高温充放電サイクル特性及び高温保存特性向上のために、非水電解質中にリン系化合物、例えば、フッ素化ホスホン酸エステル等を添加する技術が知られている(例えば、特許文献1〜5参照)。 Therefore, in order to improve the flame retardancy of the electrolyte solution of the non-aqueous electrolyte secondary battery and to improve the high-temperature charge / discharge cycle characteristics and the high-temperature storage characteristics, a phosphorus compound such as a fluorinated phosphonate ester is added to the non-aqueous electrolyte. The technique to add is known (for example, refer patent documents 1-5).
特許文献1には、「電解質塩を有機溶媒に溶解した電解液において、該有機溶媒が下記〔化1〕の一般式(I)で表されるリン化合物の少なくとも一種を含むことを特徴とする難燃性電解液。
また、特許文献1には、この発明の目的として「電気特性に悪影響がなく、優れた難燃性を有する難燃性電解液およびこれを用いた非水電解液二次電池を提供すること」(段落[0008])が記載され、さらに、「上記リン化合物の存在割合(使用量)は、電解液を構成する有機溶媒中、5〜100重量%が好ましく、10〜100重量%が更に好ましく、特に10〜80重量%が好ましい。該割合が5重量%未満では十分な難燃化効果が得られないことがある。」(段落[0021])と記載されている。
Patent Document 1 states that “in an electrolytic solution in which an electrolyte salt is dissolved in an organic solvent, the organic solvent contains at least one phosphorus compound represented by the following general formula (I): Flame retardant electrolyte.
In addition, Patent Document 1 describes as an object of the present invention “to provide a flame retardant electrolyte solution having no adverse effect on electrical characteristics and having excellent flame retardancy and a non-aqueous electrolyte secondary battery using the same”. (Paragraph [0008]) is described, and “the abundance ratio (amount used) of the phosphorus compound is preferably 5 to 100% by weight, more preferably 10 to 100% by weight in the organic solvent constituting the electrolytic solution. In particular, 10 to 80% by weight is preferable. If the ratio is less than 5% by weight, a sufficient flame retarding effect may not be obtained ”(paragraph [0021]).
特許文献2には、「電解質及び非水溶媒を含む非水系電解液において、該非水系電解液が、下記一般式(1)で表される化合物を含有していることを特徴とする非水系電解液電池用非水系電解液。
また、特許文献2には、この発明の目的として「ガス発生が少なく、高容量で、保存特性及びサイクル特性に優れた非水系電解液電池を実現することができる非水系電解液と、この非水系電解液を用いた非水系電解液電池を提供すること」(段落[0010])が記載され、さらに、「非水系電解液中の一般式(1)で表される化合物の割合(2種以上用いる場合はその合計の割合)は、通常0.001重量%以上、好ましくは0.01重量%以上、更に好ましくは0.05重量%以上、特に好ましくは0.1重量%以上である。これより低濃度では、本発明の効果が発現しにくい場合がある。逆に濃度が高すぎると、電池の容量が低下する場合があるので、上限は、通常10重量%以下、好ましくは4重量%以下、更に好ましくは2重量%、特に好ましくは1重量%以下、最も好ましくは0.8重量%以下である。」(段落[0064])と記載されている。
Patent Document 2 states that “in a nonaqueous electrolytic solution containing an electrolyte and a nonaqueous solvent, the nonaqueous electrolytic solution contains a compound represented by the following general formula (1)”. Non-aqueous electrolyte for liquid batteries.
In addition, Patent Document 2 discloses, as an object of the present invention, “a non-aqueous electrolyte solution that can realize a non-aqueous electrolyte battery that generates less gas, has a high capacity, and has excellent storage characteristics and cycle characteristics; “Providing a non-aqueous electrolyte battery using an aqueous electrolyte” (paragraph [0010]) is further described, and “the ratio of the compound represented by the general formula (1) in the non-aqueous electrolyte (two types) When used above, the total ratio) is usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and particularly preferably 0.1% by weight or more. If the concentration is lower than this, the effect of the present invention may be difficult to be exhibited, whereas if the concentration is too high, the capacity of the battery may decrease, so the upper limit is usually 10% by weight or less, preferably 4% by weight. % Or less, more preferably 2% by weight Particularly preferably 1 wt% or less, most preferably 0.8 wt% or less. "Is described as (paragraph [0064]).
特許文献3には、上記[化2]と同様の一般式で表される化合物を含有している非水系電解液電池用非水系電解液の発明が記載され、その実施例には、トリエチルホスホノアセテート等が示されている(段落[0134]〜[0136])。
また、特許文献3には、この発明の効果として「高容量で、保存特性及びサイクル特性に優れた非水系電解液電池を提供することができ、非水系電解液電池の小型化、高性能化を達成することができる」(段落[0016])ことが記載され、さらに、「非水系電解液中のこれらの化合物の含有割合は、本願発明の効果を発現するためには、特に制限はないが、非水系電解液全体に対して、合計で、通常0.001重量%以上、好ましくは0.01重量%以上、より好ましくは0.1重量%以上である。また、上限は合計で、通常5重量%以下であり、4重量%以下が好ましく、より好ましくは3重量%以下である。これらの化合物の濃度が低すぎると改善効果が得られ難い場合があり、一方、濃度が高すぎると充放電効率の低下を招く場合がある。」(段落[0075])と記載されている。
Patent Document 3 describes an invention of a non-aqueous electrolyte solution for a non-aqueous electrolyte battery containing a compound represented by the same general formula as that in [Chemical Formula 2]. Noacetate and the like are shown (paragraphs [0134] to [0136]).
Patent document 3 describes the effect of the present invention as “a non-aqueous electrolyte battery having a high capacity and excellent storage characteristics and cycle characteristics can be provided, and the non-aqueous electrolyte battery can be reduced in size and performance. Can be achieved ”(paragraph [0016]), and further,“ the content ratio of these compounds in the non-aqueous electrolyte solution is not particularly limited in order to exhibit the effects of the present invention ”. However, the total amount is generally 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.1% by weight or more based on the total amount of the non-aqueous electrolyte. Usually 5% by weight or less, preferably 4% by weight or less, more preferably 3% by weight or less If the concentration of these compounds is too low, it may be difficult to obtain an improvement effect, while the concentration is too high. When charging and discharging efficiency is reduced There. "Is described as (paragraph [0075]).
特許文献1〜3に具体的に記載されているようなホスホン酸エステルを添加した従来の非水電解質二次電池では、難燃性、低電圧作動時の充放電サイクル性能や保存特性が改善されるものの、正極作動電位が4.3Vvs.Li/Li+以上に達する高電圧作動時に、充放電サイクル性能の低下が大きかった。そこで、本発明は、上記のような従来技術に鑑み、高電圧作動時においても、充放電サイクル性能が優れた非水電解質二次電池を提供することを課題とする。 In conventional non-aqueous electrolyte secondary batteries to which phosphonates are added as specifically described in Patent Documents 1 to 3, flame retardancy, charge / discharge cycle performance during low voltage operation, and storage characteristics are improved. However, the positive electrode operating potential is 4.3 Vvs. When operating at a high voltage exceeding Li / Li + , the charge / discharge cycle performance was greatly reduced. Accordingly, an object of the present invention is to provide a nonaqueous electrolyte secondary battery having excellent charge / discharge cycle performance even during high voltage operation, in view of the above-described conventional technology.
本発明においては、上記課題を解決するために、以下の手段を採用する。
〔1〕正極、負極、セパレータ及び非水電解質を備えた非水電解質二次電池であって、前記非水電解質は、下記一般式(1)
〔2〕前記〔1〕の非水電解質二次電池を複数個集合して構成した蓄電装置。
In the present invention, in order to solve the above problems, the following means are adopted.
[1] A nonaqueous electrolyte secondary battery including a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte, wherein the nonaqueous electrolyte is represented by the following general formula (1)
[2] A power storage device configured by assembling a plurality of the nonaqueous electrolyte secondary batteries of [1].
本発明においては、含フッ素ホスホン酸エステルを非水電解質に20質量%以下含有させることにより、含フッ素ホスホン酸エステルを含有しない場合よりも充放電サイクル性能が優れた非水電解質二次電池が得られる。 In the present invention, a non-aqueous electrolyte secondary battery having better charge / discharge cycle performance than the case where no fluorine-containing phosphonate ester is contained is obtained by containing the fluorine-containing phosphonate ester in the non-aqueous electrolyte at 20% by mass or less. It is done.
図1に、本発明に係る非水電解質二次電池の一実施形態である矩形状の非水電解質二次電池1の外観斜視図を示す。なお、同図は、容器内部を透視した図としている。図1に示す非水電解質二次電池1は、電極群2が電池容器3に収納されている。電極群2は、正極活物質を備える正極と、負極活物質を備える負極とが、セパレータを介して捲回されることにより形成されている。正極は、正極リード4’を介して正極端子4と電気的に接続され、負極は、負極リード5’を介して負極端子5と電気的に接続されている。 FIG. 1 shows an external perspective view of a rectangular nonaqueous electrolyte secondary battery 1 which is an embodiment of the nonaqueous electrolyte secondary battery according to the present invention. In the figure, the inside of the container is seen through. In the nonaqueous electrolyte secondary battery 1 shown in FIG. 1, an electrode group 2 is housed in a battery container 3. The electrode group 2 is formed by winding a positive electrode including a positive electrode active material and a negative electrode including a negative electrode active material via a separator. The positive electrode is electrically connected to the positive electrode terminal 4 via the positive electrode lead 4 ′, and the negative electrode is electrically connected to the negative electrode terminal 5 via the negative electrode lead 5 ′.
ここで、セパレータに保持されている非水電解質は、非水溶媒と該非水溶媒に溶解した電解質塩とを含むものであるが、本発明においては、さらに、特定の含フッ素ホスホン酸エステルを20質量%以下含む点に特徴を有する。 Here, the non-aqueous electrolyte retained in the separator includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent. In the present invention, the specific fluorine-containing phosphonic acid ester is further added in an amount of 20% by mass. It is characterized by the following points.
従来技術においては、特許文献1に示されているように、非水電解質二次電池の非水電解質に含フッ素ホスホン酸エステルを添加すると、難燃性は向上するが、充放電サイクル性能は低下すると考えられていた。しかし、本発明者らは、非水電解質二次電池の非水電解質に、上記一般式(1)に示されている含フッ素ホスホン酸エステルを少量添加することにより、予想外に、充放電サイクル性能が顕著に向上することを知見して、本発明に到達した。上記一般式(1)で表される含フッ素ホスホン酸エステルの含有量は、高温充放電サイクル性能を向上させるために、非水電解質の全質量に対して20質量%以下であることが好ましく、特に効果を得るためには、0.5〜10質量%であることがより好ましく、なかでも5〜10質量%であることがさらに好ましい。 In the prior art, as shown in Patent Document 1, when a fluorine-containing phosphonate is added to the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery, the flame retardancy is improved, but the charge / discharge cycle performance is decreased. It was thought to be. However, the present inventors unexpectedly added a small amount of the fluorine-containing phosphonic acid ester represented by the general formula (1) to the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery, thereby unexpectedly charging / discharging cycle. Knowing that the performance is significantly improved, the present invention has been achieved. The content of the fluorine-containing phosphonate represented by the general formula (1) is preferably 20% by mass or less with respect to the total mass of the nonaqueous electrolyte in order to improve the high-temperature charge / discharge cycle performance. In order to acquire an effect especially, it is more preferable that it is 0.5-10 mass%, and it is still more preferable that it is 5-10 mass% especially.
上記一般式(1)において、R1及びR2は、それぞれ独立して、水素原子がフッ素原子で置換されていてもよい炭素数1〜8のアルキル基を示し、R3は、少なくとも1つの水素原子がフッ素原子で置換されている炭素数1〜8のアルキル基を示す。Pに直接結合するアルキル基(R3)がフッ素原子で置換されているアルキル基である含フッ素ホスホン酸エステルを用いることにより、非水電解質中に含フッ素ホスホン酸エステルを多く(例えば10質量%)含有させた場合であっても、充放電サイクル性能を向上させる効果が充分に発揮される。従って、含フッ素ホスホン酸エステルの含有量を多くしたことに伴う難燃性向上効果を兼ね備えさせることができる。 In the general formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 8 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and R 3 represents at least one An alkyl group having 1 to 8 carbon atoms in which a hydrogen atom is substituted with a fluorine atom. By using a fluorine-containing phosphonate ester in which the alkyl group (R 3 ) directly bonded to P is an alkyl group substituted with a fluorine atom, a large amount of fluorine-containing phosphonate ester (for example, 10% by mass) is contained in the non-aqueous electrolyte. ) Even when it is contained, the effect of improving the charge / discharge cycle performance is sufficiently exhibited. Therefore, the flame retardancy improving effect accompanying the increase in the content of the fluorine-containing phosphonic acid ester can be provided.
上記一般式(1)で表される含フッ素ホスホン酸エステルが有する、炭素数1〜8の含フッ素アルキル基としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、2−フルオロエチル基、2,2−ジフルオロエチル基、2,2,2−トリフルオロエチル基、2−フルオロプロピル基、3−フルオロプロピル基、2,2−ジフルオロプロピル基、3,3−ジフルオロプロピル基、3,3,3−トリフルオロプロピル基、2,2,3,3−テトラフルオロプロピル基、2,2,3,3,3−ペンタフルオロプロピル基、2−フルオロブチル基、3−フルオロブチル基、4−フルオロブチル基、2,2−ジフルオロブチル基、3,3−ジフルオロブチル基、4,4−ジフルオロブチル基、4,4,4−トリフルオロブチル基、2,2,3,3−テトラフルオロブチル基、2,2,3,3,4,4−ヘキサフルオロブチル基、2,2,3,3,4,4,4−ヘプタフルオロブチル基、2−フルオロペンチル基、3−フルオロペンチル基、4−フルオロペンチル基、5−フルオロペンチル基、2,2−ジフルオロペンチル基、3,3−ジフルオロペンチル基、4,4−ジフルオロペンチル基、5,5−ジフルオロペンチル基、5,5,5−トリフルオロペンチル基、1H,1H,5H,5H,5H−ヘキサフルオロペンチル基、1H,1H,5H−オクタフルオロペンチル基、1H,1H−ノナフルオロペンチル基、1H,1H,7H−ドデカフルオロへプチル基、1H,1H−トリデカフルオロヘプチル基、1H,1H,8H−トリデカフルオロオクチル基、1H,1H−ペンタデカフルオロオクチル基等が挙げられる。これらのうち、フルオロメチル基、ジフルオロメチル基、2,2,2−トリフルオロエチル基、2,2,3,3−テトラフルオロプロピル基、2,2,3,3,3−ペンタフルオロプロピル基、1H,1H,5H−オクタフルオロペンチル基、1H,1H−ノナフルオロペンチル基、1H,1H,7H−ドデカフルオロへプチル基、1H,1H−トリデカフルオロヘプチル基から選択されることが好ましい。 Examples of the fluorine-containing alkyl group having 1 to 8 carbon atoms that the fluorine-containing phosphonate represented by the general formula (1) has include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-fluoropropyl group, 3-fluoropropyl group, 2,2-difluoropropyl group, 3,3-difluoropropyl group, 3,3 , 3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2-fluorobutyl group, 3-fluorobutyl group, 4- Fluorobutyl group, 2,2-difluorobutyl group, 3,3-difluorobutyl group, 4,4-difluorobutyl group, 4,4,4-trifluorobutyl group, 2 2,3,3-tetrafluorobutyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2-fluoro Pentyl group, 3-fluoropentyl group, 4-fluoropentyl group, 5-fluoropentyl group, 2,2-difluoropentyl group, 3,3-difluoropentyl group, 4,4-difluoropentyl group, 5,5-difluoro Pentyl group, 5,5,5-trifluoropentyl group, 1H, 1H, 5H, 5H, 5H-hexafluoropentyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H-nonafluoropentyl group, 1H , 1H, 7H-dodecafluoroheptyl group, 1H, 1H-tridecafluoroheptyl group, 1H, 1H, 8H-tridecafluorooctyl group, 1H, 1H Pentadecafluorooctyl group, and the like. Of these, fluoromethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group It is preferably selected from 1H, 1H, 5H-octafluoropentyl group, 1H, 1H-nonafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, and 1H, 1H-tridecafluoroheptyl group.
上記一般式(1)で表される含フッ素ホスホン酸エステルとしては、ジメチル(フルオロメチル)ホスホネート、ジメチル(ジフルオロメチル)ホスホネート、ジメチル(2,2,2−トリフルオロエチル)ホスホネート、ジメチル(2,2,3,3−テトラフルオロプロピル)ホスホネート、ジメチル(2,2,3,3,3−ペンタフルオロプロピル)ホスホネート、ジエチル(フルオロメチル)ホスホネート、ジエチル(ジフルオロメチル)ホスホネート、ジエチル(2,2,2−トリフルオロエチル)ホスホネート、ジエチル(2,2,3,3−テトラフルオロプロピル)ホスホネート、ジエチル(2,2,3,3,3−ペンタフルオロプロピル)ホスホネート等が好ましい。 Examples of the fluorine-containing phosphonate represented by the general formula (1) include dimethyl (fluoromethyl) phosphonate, dimethyl (difluoromethyl) phosphonate, dimethyl (2,2,2-trifluoroethyl) phosphonate, dimethyl (2, 2,3,3-tetrafluoropropyl) phosphonate, dimethyl (2,2,3,3,3-pentafluoropropyl) phosphonate, diethyl (fluoromethyl) phosphonate, diethyl (difluoromethyl) phosphonate, diethyl (2,2, 2-trifluoroethyl) phosphonate, diethyl (2,2,3,3-tetrafluoropropyl) phosphonate, diethyl (2,2,3,3,3-pentafluoropropyl) phosphonate and the like are preferable.
Pに直接結合するアルキル基(R3)がフッ素原子で置換されているアルキル基である含フッ素ホスホン酸エステルを用いることにより、本発明の効果が奏される作用機構については必ずしも明らかではないが、フッ素化アルキル基は、同じ炭素数のアルキル基に比べて電子供与性が低いことから、本発明の効果は、Pの電荷密度が低いことと関連していると推察される。この観点から、R3は、上記した炭素数1〜8の含フッ素アルキル基のなかでも、フルオロメチル基、ジフルオロメチル基又はトリフルオロメチル基が好ましく、フルオロメチル基又はジフルオロメチル基がより好ましく、フルオロメチル基が最も好ましい。 Although the mechanism of action in which the effect of the present invention is achieved by using a fluorine-containing phosphonic acid ester in which the alkyl group directly bonded to P (R 3 ) is an alkyl group substituted with a fluorine atom is not necessarily clear. Since the fluorinated alkyl group has a lower electron donating property than the alkyl group having the same carbon number, the effect of the present invention is presumed to be related to the low charge density of P. From this viewpoint, R 3 is preferably a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, more preferably a fluoromethyl group or a difluoromethyl group, among the above-mentioned fluorine-containing alkyl groups having 1 to 8 carbon atoms, A fluoromethyl group is most preferred.
また、後述する比較例2と比較例4の結果の対比からもわかるように、R1及びR2についても、電子供与性が低い基であることが好ましいと推察される。この観点から、上記には、一般式(1)で表される含フッ素ホスホン酸エステルの具体例として、R1及びR2がアルキル基である化合物を列挙したが、R1及びR2は、水素原子がフッ素原子で置換されている炭素数1〜8のアルキル基であるものがより好ましい。 Further, as can be seen from the comparison of the results of Comparative Example 2 and Comparative Example 4 described later, it is presumed that R 1 and R 2 are preferably groups having low electron donating properties. From this point of view, in the above, as specific examples of the fluorine-containing phosphonate represented by the general formula (1), compounds in which R 1 and R 2 are alkyl groups are listed, and R 1 and R 2 are What is a C1-C8 alkyl group by which the hydrogen atom is substituted by the fluorine atom is more preferable.
本発明において、非水電解質を構成するその他の有機溶媒は、限定されるものではなく、一般に非水電解質二次電池用非水電解質に使用される有機溶媒が使用できる。例えば、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、クロロエチレンカーボネート、スチレンカーボネート、カテコールカーボネート、1−フェニルビニレンカーボネート、1,2−ジフェニルビニレンカーボネート等の環状カーボネート、γ−ブチロラクトン、γ−バレロラクトン、プロピオラクトン等の環状カルボン酸エステル、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、ジフェニルカーボネート等の鎖状カーボネート、酢酸メチル、酪酸メチル等の鎖状カルボン酸エステル、テトラヒドロフラン若しくはその誘導体、1,3−ジオキサン、ジメトキシエタン、ジエトキシエタン、メトキシエトキシエタン、メチルジグライム等のエーテル類、アセトニトリル、ベンゾニトリル等のニトリル類、ジオキサラン若しくはその誘導体等の単独又はそれら2種以上の混合物等を挙げることができる。特に、エチレンカーボネート等の環状カーボネート及びジエチルカーボネート等の鎖状カーボネートを含有するものが好ましい。また、これらの有機溶媒は、任意の割合で混合して用いることができる。 In the present invention, other organic solvents constituting the non-aqueous electrolyte are not limited, and organic solvents generally used for non-aqueous electrolytes for non-aqueous electrolyte secondary batteries can be used. For example, cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, styrene carbonate, catechol carbonate, 1-phenyl vinylene carbonate, 1,2-diphenyl vinylene carbonate, γ-butyrolactone, γ-valerolactone, propio Cyclic carboxylic acid esters such as lactone, chain carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and diphenyl carbonate, chain carboxylic acid esters such as methyl acetate and methyl butyrate, tetrahydrofuran or derivatives thereof, 1,3-dioxane, Ethers such as dimethoxyethane, diethoxyethane, methoxyethoxyethane, methyldiglyme, acetonitrile, benzonite Examples thereof include nitriles such as ril, dioxalane or a derivative thereof alone or a mixture of two or more thereof. In particular, those containing a cyclic carbonate such as ethylene carbonate and a chain carbonate such as diethyl carbonate are preferred. Moreover, these organic solvents can be mixed and used in arbitrary ratios.
本発明の非水電解質は、上記一般式(1)で表される含フッ素ホスホン酸エステルと上記有機溶媒とを含有するものであるが、必要に応じて他の化合物を、本発明の効果を損なわない範囲で、任意の量で含有させることができる。 The non-aqueous electrolyte of the present invention contains the fluorine-containing phosphonic acid ester represented by the above general formula (1) and the above organic solvent. If necessary, other compounds can be added to the effect of the present invention. It can be contained in any amount as long as it is not impaired.
このような他の化合物としては、例えば、ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、t−ブチルベンゼン、t−アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物;2−フルオロビフェニル、o−シクロヘキシルフルオロベンゼン、p−シクロヘキシルフルオロベンゼン等の前記芳香族化合物の部分フッ素化物;2,4−ジフルオロアニソール、2,5−ジフルオロアニソール、2,6−ジフルオロアニソール、3,5−ジフルオロアニソール等の含フッ素アニソール化合物等の過充電防止剤;ビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート、ジフルオロエチレンカーボネート、トリフルオロプロピレンカーボネート、無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸、無水グルタコン酸、無水イタコン酸、シクロヘキサンジカルボン酸無水物等の負極被膜形成剤;亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、プロパンスルトン、プロペンスルトン、ブタンスルトン、メタンスルホン酸メチル、ブスルファン、トルエンスルホン酸メチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、チオアニソール、ジフェニルジスルフィド、ジピリジニウムジスルフィド等の正極保護剤等が挙げられる。 Examples of such other compounds include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; Partially fluorinated products of the above aromatic compounds such as -fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5 -Overcharge inhibitors such as fluorine-containing anisole compounds such as difluoroanisole; vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, trifluoropropylene carbonate Negative electrode film forming agents such as succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfite, propane sultone, Propene sultone, butane sultone, methyl methanesulfonate, busulfan, methyl toluenesulfonate, dimethyl sulfate, ethylene sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, thioanisole, diphenyl disulfide, Examples include positive electrode protective agents such as dipyridinium disulfide.
非水電解質中におけるこれら他の化合物の含有割合は特に限定はないが、非水電解質全体に対し、それぞれ、0.01質量%以上が好ましく、より好ましくは0.1質量%以上、さらに好ましくは0.2質量%以上であり、上限は、5質量%以下が好ましく、より好ましくは3質量%以下、さらに好ましくは2質量%以下である。これらの化合物を含有させることにより、安全性をより向上させたり、高温保存後の容量維持性能やサイクル性能を向上させたりすることができる。 The content ratio of these other compounds in the non-aqueous electrolyte is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably, with respect to the entire non-aqueous electrolyte. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less. By containing these compounds, safety can be further improved, and capacity maintenance performance and cycle performance after high-temperature storage can be improved.
本発明の非水電解質を構成する電解質塩(リチウム塩)は、限定されるものではなく、一般に非水電解質二次電池に使用される広電位領域において安定であるリチウム塩が使用できる。例えば、LiBF4、LiPF6、LiClO4、LiCF3SO3、LiN(FSO2)2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(CF3SO2)(C4F9SO2)、LiC(CF3SO2)3、LiC(C2F5SO2)3等が挙げられる。これらは単独で用いてもよく、2種以上混合して用いてもよい。 The electrolyte salt (lithium salt) constituting the nonaqueous electrolyte of the present invention is not limited, and lithium salts that are stable in a wide potential region generally used for nonaqueous electrolyte secondary batteries can be used. For example, LiBF 4 , LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2) , LiC (CF 3 SO 2) 3, LiC (C 2 F 5 SO 2) 3 and the like. These may be used alone or in combination of two or more.
非水電解質における電解質塩の濃度としては、優れた高率放電特性を有する非水電解質二次電池を確実に得るために、0.1mol/L〜5.0mol/Lが好ましく、さらに好ましくは、1.0mol/L〜2.0mol/Lである。 The concentration of the electrolyte salt in the non-aqueous electrolyte is preferably 0.1 mol / L to 5.0 mol / L, more preferably, in order to reliably obtain a non-aqueous electrolyte secondary battery having excellent high rate discharge characteristics. 1.0 mol / L to 2.0 mol / L.
本発明の非水電解質二次電池を構成する正極に使用する正極活物質としては、電気化学的にリチウムイオンを挿入・脱離可能なものであれば、特に制限はなく、一般に非水電解質二次電池用正極活物質に使用される正極活物質が使用できる。例えば、遷移金属酸化物、遷移金属硫化物、リチウム遷移金属複合酸化物、リチウム含有ポリアニオン金属複合化合物等が挙げられる。遷移金属酸化物としては、マンガン酸化物、鉄酸化物、銅酸化物、ニッケル酸化物、バナジウム酸化物、遷移金属硫化物としては、モリブデン硫化物、チタン硫化物等が挙げられる。リチウム遷移金属複合酸化物としては、リチウムマンガン複合酸化物、リチウムニッケル複合酸化物、リチウムコバルト複合酸化物、リチウムニッケルコバルト複合酸化物、リチウムニッケルマンガン複合酸化物、リチウムニッケルコバルトマンガン複合酸化物等が挙げられる。リチウム含有ポリアニオン金属複合化合物としては、リン酸鉄リチウム、リン酸コバルトリチウム等が挙げられる。さらに、ジスルフィド、ポリピロール、ポリアニリン、ポリパラスチレン、ポリアセチレン、ポリアセン系材料等の導電性高分子化合物、擬グラファイト構造炭素質材料等が挙げられる。 The positive electrode active material used for the positive electrode constituting the non-aqueous electrolyte secondary battery of the present invention is not particularly limited as long as it can electrochemically insert and desorb lithium ions. The positive electrode active material used for the positive electrode active material for secondary batteries can be used. Examples include transition metal oxides, transition metal sulfides, lithium transition metal composite oxides, lithium-containing polyanion metal composite compounds, and the like. Examples of the transition metal oxide include manganese oxide, iron oxide, copper oxide, nickel oxide, vanadium oxide, and examples of the transition metal sulfide include molybdenum sulfide and titanium sulfide. Examples of the lithium transition metal composite oxide include lithium manganese composite oxide, lithium nickel composite oxide, lithium cobalt composite oxide, lithium nickel cobalt composite oxide, lithium nickel manganese composite oxide, and lithium nickel cobalt manganese composite oxide. Can be mentioned. Examples of the lithium-containing polyanion metal composite compound include lithium iron phosphate and lithium cobalt phosphate. Further, conductive polymer compounds such as disulfide, polypyrrole, polyaniline, polyparastyrene, polyacetylene, and polyacene materials, pseudographite-structured carbonaceous materials, and the like can be given.
正極集電体の材質としては特に制限は無く、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;カーボンクロス、カーボンペーパー等の炭素質材料が挙げられる。中でも金属材料、特にアルミニウムが好ましい。
There is no restriction | limiting in particular as a material of a positive electrode electrical power collector, A well-known thing can be used arbitrarily.
Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbonaceous materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.
本発明の非水電解質二次電池を構成する負極に使用する負極活物質としては、電気化学的にリチウムイオンを挿入・脱離可能なものであれば、特に制限はなく、炭素質材料、酸化錫や酸化ケイ素等の金属酸化物、金属複合酸化物、リチウム単体やリチウムアルミニウム合金等のリチウム合金、SnやSi等のリチウムと合金形成可能な金属等が挙げられる。 炭素質材料としては、天然グラファイト、人造グラファイト、コークス類、難黒鉛化性炭素、低温焼成易黒鉛化性炭素、フラーレン、カーボンナノチューブ、カーボンブラック、活性炭等が挙げられる。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良い。中でも炭素質材料又はリチウム複合酸化物が安全性の点から好ましく用いられる。 The negative electrode active material used for the negative electrode constituting the non-aqueous electrolyte secondary battery of the present invention is not particularly limited as long as it can electrochemically insert and desorb lithium ions, and is a carbonaceous material, oxidized Examples thereof include metal oxides such as tin and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, and metals that can form alloys with lithium such as Sn and Si. Examples of the carbonaceous material include natural graphite, artificial graphite, coke, non-graphitizable carbon, low-temperature calcinable graphitizable carbon, fullerene, carbon nanotube, carbon black, activated carbon and the like. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of safety.
負極の集電体としては、公知のものを任意に用いることができる。例えば、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、中でも加工し易さとコストの点から特に銅が好ましい。 As the current collector for the negative electrode, a known one can be arbitrarily used. For example, metal materials such as copper, nickel, stainless steel, nickel-plated steel and the like can be mentioned, and copper is particularly preferable from the viewpoint of ease of processing and cost.
セパレータとして、微多孔性膜や不織布等を、単独あるいは併用することが好ましい。
セパレータを構成する材料としては、例えばポリエチレン、ポリプロピレン等に代表されるポリオレフィン系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート等に代表されるポリエステル系樹脂、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−パーフルオロビニルエーテル共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−トリフルオロエチレン共重合体、フッ化ビニリデン−フルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロアセトン共重合体、フッ化ビニリデン−エチレン共重合体、フッ化ビニリデン−プロピレン共重合体、フッ化ビニリデン−トリフルオロプロピレン共重合体、フッ化ビニリデン−テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−エチレン−テトラフルオロエチレン共重合体等を挙げることができる。中でもポリエチレン、ポリプロピレン等に代表されるポリオレフィン系樹脂を主成分とする微多孔性膜であることが好ましい。
As the separator, it is preferable to use a microporous membrane or a nonwoven fabric alone or in combination.
Examples of the material constituting the separator include polyolefin resins typified by polyethylene and polypropylene, polyester resins typified by polyethylene terephthalate and polybutylene terephthalate, polyvinylidene fluoride, and vinylidene fluoride-hexafluoropropylene copolymer. , Vinylidene fluoride-perfluorovinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-fluoroethylene copolymer, vinylidene fluoride-hexafluoro Acetone copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-propylene copolymer, vinylidene fluoride-trifluoropropylene copolymer, vinylidene fluoride-tetrafluoro Ethylene - hexafluoropropylene copolymer, vinylidene fluoride - ethylene - can be mentioned tetrafluoroethylene copolymer. Among these, a microporous film mainly composed of a polyolefin resin typified by polyethylene, polypropylene and the like is preferable.
その他の電池の構成要素としては、端子、絶縁板、電池ケース等があるが、これらの部品は従来用いられてきたものをそのまま用いて差し支えない。 Other battery components include a terminal, an insulating plate, a battery case, and the like, but these components may be used as they are.
本発明に係る非水電解質二次電池の形状については特に限定されるものではなく、円筒型電池、角型電池(矩形状の電池)、扁平型電池等が一例として挙げられる。本発明は、上記の非水電解質二次電池を複数備える蓄電装置としても実現することができる。蓄電装置の一実施形態を図2に示す。図2において、蓄電装置30は、複数の蓄電ユニット20を備えている。それぞれの蓄電ユニット20は、複数の非水電解質二次電池1を備えている。前記蓄電装置30は、電気自動車(EV)、ハイブリッド自動車(HEV)、プラグインハイブリッド自動車(PHEV)等の自動車用電源として搭載することができる。 The shape of the nonaqueous electrolyte secondary battery according to the present invention is not particularly limited, and examples thereof include a cylindrical battery, a square battery (rectangular battery), a flat battery, and the like. The present invention can also be realized as a power storage device including a plurality of the above non-aqueous electrolyte secondary batteries. One embodiment of a power storage device is shown in FIG. In FIG. 2, the power storage device 30 includes a plurality of power storage units 20. Each power storage unit 20 includes a plurality of nonaqueous electrolyte secondary batteries 1. The power storage device 30 can be mounted as a power source for vehicles such as an electric vehicle (EV), a hybrid vehicle (HEV), and a plug-in hybrid vehicle (PHEV).
以下、実施例及び比較例を用いて本発明を具体的に説明するが、本発明はその要旨を超えない限り、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example and a comparative example, this invention is not limited to these Examples, unless the summary is exceeded.
(実施例1)
実施例1においては、上記一般式(1)で表される含フッ素ホスホン酸エステルとしてジエチル(ジフルオロメチル)ホスホネートを使用した。
Example 1
In Example 1, diethyl (difluoromethyl) phosphonate was used as the fluorine-containing phosphonate represented by the above general formula (1).
(実施例1−1)
1mol/LのLiPF6を含有するエチレンカーボネート(EC):エチルメチルカーボネート(EMC)が体積比で30:70の混合溶媒に、以下の化学式を有するジエチル(ジフルオロメチル)ホスホネートを0.5質量%添加して、実施例1−1に係る非水電解質を作製した。
0.5% by mass of diethyl (difluoromethyl) phosphonate having the following chemical formula in a mixed solvent of ethylene carbonate (EC): ethyl methyl carbonate (EMC) containing 1 mol / L LiPF 6 in a volume ratio of 30:70 By adding, a nonaqueous electrolyte according to Example 1-1 was produced.
(実施例1−2〜1−4)
ジエチル(ジフルオロメチル)ホスホネートの添加量を0.5質量%から、それぞれ、1質量%、2質量%、5質量%に変更して、実施例1−2、1−3、1−4に係る非水電解質を作製した。
(Examples 1-2 to 1-4)
According to Examples 1-2, 1-3, and 1-4, the addition amount of diethyl (difluoromethyl) phosphonate was changed from 0.5% by mass to 1% by mass, 2% by mass, and 5% by mass, respectively. A non-aqueous electrolyte was produced.
(比較例2)
比較例2においては、上記一般式(1)で表される含フッ素ホスホン酸エステルとしてビス(2,2,2−トリフルオロエチル)メチルホスホネートを使用した。
(Comparative Example 2)
In Comparative Example 2, bis (2,2,2-trifluoroethyl) methylphosphonate was used as the fluorine-containing phosphonate represented by the general formula (1).
(比較例2−1)
ジエチル(ジフルオロメチル)ホスホネートの代わりに、以下の化学式を有するビス(2,2,2−トリフルオロエチル)メチルホスホネートを添加したこと以外は実施例1−1と同様にして、比較例2−1に係る非水電解質を作製した。
Comparative Example 2-1 was carried out in the same manner as Example 1-1 except that bis (2,2,2-trifluoroethyl) methylphosphonate having the following chemical formula was added instead of diethyl (difluoromethyl) phosphonate. The non-aqueous electrolyte which concerns on was produced.
(比較例2−2〜2−4)
ビス(2,2,2−トリフルオロエチル)メチルホスホネートの添加量を0.5質量%から、それぞれ、1質量%、2質量%、5質量%に変更して、比較例2−2、2−3、2−4に係る非水電解質を作製した。
(Comparative Examples 2-2 to 2-4)
The addition amount of bis (2,2,2-trifluoroethyl) methylphosphonate was changed from 0.5 mass% to 1 mass%, 2 mass%, and 5 mass%, respectively. -3 and 2-4 were produced.
(比較例3)
ジエチル(ジフルオロメチル)ホスホネートを添加しないこと以外は実施例1−1と同様にして、比較例3に係る非水電解質を作製した。
(Comparative Example 3)
A nonaqueous electrolyte according to Comparative Example 3 was produced in the same manner as in Example 1-1 except that diethyl (difluoromethyl) phosphonate was not added.
(比較例4)
ジエチル(ジフルオロメチル)ホスホネートの代わりに、以下の化学式を有するジエチルメチルホスホネートを添加したこと以外は実施例1−3と同様にして、比較例4に係る非水電解質を作製した。
A nonaqueous electrolyte according to Comparative Example 4 was produced in the same manner as in Example 1-3 except that diethylmethylphosphonate having the following chemical formula was added instead of diethyl (difluoromethyl) phosphonate.
(非水電解質二次電池の作製)
実施例1及び比較例2〜4の非水電解質を用いて、非水電解質二次電池を作製した。実施例に係る非水電解質二次電池は、正極活物質を正極集電体に塗布して得た正極と、負極活物質を負極集電体に塗布して得た負極とを、セパレータを介して積層し、扁平形状に捲回することにより形成された電極群が、電池ケースに収納されてなる。
(Preparation of non-aqueous electrolyte secondary battery)
Using the nonaqueous electrolytes of Example 1 and Comparative Examples 2 to 4, nonaqueous electrolyte secondary batteries were produced. The non-aqueous electrolyte secondary battery according to the example includes a positive electrode obtained by applying a positive electrode active material to a positive electrode current collector and a negative electrode obtained by applying a negative electrode active material to a negative electrode current collector through a separator. The electrode group formed by stacking and winding in a flat shape is housed in a battery case.
次に、上記構成の非水電解質二次電池の製造方法を説明する。
正極は次のようにして得た。まず、LiNi1/3Co1/3Mn1/3O2と、導電剤であるアセチレンブラックを混合し、さらに結着剤としてポリフッ化ビニリデンのN−メチル−2−ピロリドン溶液を混合し、この混合物(正極合剤)をアルミニウム箔からなる正極集電体の両面に塗布した後、乾燥し、正極合剤の厚さが所定の厚さとなるようにプレスした。以上の工程により正極を得た。
Next, a method for manufacturing the nonaqueous electrolyte secondary battery having the above configuration will be described.
The positive electrode was obtained as follows. First, LiNi 1/3 Co 1/3 Mn 1/3 O 2 and acetylene black as a conductive agent are mixed, and further, an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride as a binder is mixed. The mixture (positive electrode mixture) was applied to both surfaces of a positive electrode current collector made of an aluminum foil, dried, and pressed so that the thickness of the positive electrode mixture became a predetermined thickness. The positive electrode was obtained by the above process.
負極は、次のようにして得た。まず、負極活物質である黒鉛(エックス線広角回折法による(002)面の面間隔0.336nm)と、結着剤であるスチレン−ブタジエン・ゴム及びカルボキシメチルセルロースの水溶液を混合し、この混合物(負極合剤)を銅箔からなる負極集電体の両面に塗布した後、乾燥し、負極合剤の厚さが所定の厚さとなるようにプレスした。以上の工程により負極を得た。 The negative electrode was obtained as follows. First, graphite (negative electrode active material (002) plane spacing of 0.336 nm by X-ray wide angle diffraction method) and styrene-butadiene rubber and carboxymethylcellulose aqueous solution as a binder were mixed, and this mixture (negative electrode The mixture was applied to both sides of a negative electrode current collector made of copper foil, dried, and pressed so that the thickness of the negative electrode mixture became a predetermined thickness. The negative electrode was obtained by the above process.
セパレータは、ポリエチレン製微孔膜を用いた。電極群は、正極合剤と負極合剤とを対向させ、その間にセパレータを配し、正極、セパレータ、負極の順に積層して捲回することにより、構成した。次に、電極群をアルミニウム製の電池ケースに収納し、正負極端子を取り付けた。この電池ケース内部に実施例1及び比較例2〜4の非水電解質をそれぞれ注入したのちに封口した。以上のようにして、実施例1及び比較例2〜4の非水電解質二次電池をそれぞれ作製した。 As the separator, a polyethylene microporous membrane was used. The electrode group was configured by facing the positive electrode mixture and the negative electrode mixture, placing a separator therebetween, and laminating and winding the positive electrode, the separator, and the negative electrode in this order. Next, the electrode group was housed in an aluminum battery case, and positive and negative electrode terminals were attached. The battery case was sealed after injecting the nonaqueous electrolytes of Example 1 and Comparative Examples 2 to 4 respectively. As described above, the nonaqueous electrolyte secondary batteries of Example 1 and Comparative Examples 2 to 4 were produced.
(充放電試験)
これらの実施例1及び比較例2〜4の電池について、充放電試験を行った。
まず、25℃において、電流1.0CmA、終止電圧4.35Vの定電流定電圧充電と、電流1.0CmA、終止電圧2.75Vの定電流放電とを、1サイクル行った。
次に、45℃において、電流1.0CmA、終止電圧4.35Vの定電流定電圧充電と、電流1.0CmA、終止電圧2.75Vの定電流放電とを75サイクル行い、45℃における1サイクル目と75サイクル目の1.0CmA放電容量を測定した。
(Charge / discharge test)
The batteries of Example 1 and Comparative Examples 2 to 4 were subjected to a charge / discharge test.
First, at 25 ° C., a constant current and constant voltage charge with a current of 1.0 CmA and a final voltage of 4.35 V and a constant current discharge with a current of 1.0 CmA and a final voltage of 2.75 V were performed for one cycle.
Next, at 45 ° C., 75 cycles of constant current and constant voltage charging with a current of 1.0 CmA and a final voltage of 4.35 V and constant current discharge with a current of 1.0 CmA and a final voltage of 2.75 V were performed, and one cycle at 45 ° C. The 1.0 CmA discharge capacity at the first and 75th cycle was measured.
(電池厚さの測定)
上記した充放電試験において、45℃における1サイクル目の1.0CmA放電容量を測定する前及び45℃における75サイクル目の1.0CmA放電容量を測定した後の、室温における電池厚さを、ノギスを用いて測定した。
(Measurement of battery thickness)
In the charge / discharge test described above, the battery thickness at room temperature after measuring the 1.0 CmA discharge capacity at the first cycle at 45 ° C. and after measuring the 1.0 CmA discharge capacity at the 75th cycle at 45 ° C. It measured using.
以上の結果をまとめて表1及び表2に示す。なお、表1において、45℃における1サイクル目、75サイクル目の1.0CmA放電容量は、比較例3の1サイクル目の1.0CmA放電容量の値を100%として表記した。表2において、45℃における1サイクル目の1.0CmA放電容量を測定する前の電池厚さを「電池厚さ1サイクル目」、45℃における75サイクル目の1.0CmA放電容量を測定した後の電池厚さを「電池厚さ75サイクル目」とし、比較例3の45℃における1サイクル目の1.0CmA放電容量を測定する前の電池厚さの値を100%として表記した。 The above results are summarized in Table 1 and Table 2. In Table 1, the 1.0 CmA discharge capacity at the first cycle and the 75th cycle at 45 ° C. is expressed with the value of 1.0 CmA discharge capacity at the first cycle of Comparative Example 3 as 100%. In Table 2, the battery thickness before measuring the 1.0 CmA discharge capacity at the first cycle at 45 ° C. is “battery thickness first cycle”, and after measuring the 1.0 CmA discharge capacity at the 75th cycle at 45 ° C. The battery thickness was expressed as “battery thickness 75th cycle”, and the value of the battery thickness before measuring the 1.0 CmA discharge capacity in the first cycle at 45 ° C. of Comparative Example 3 was expressed as 100%.
表1及び表2に示すように、R1〜R3の水素原子の少なくとも1つがフッ素原子で置換されているアルキル基を有する含フッ素ホスホン酸エステルを5質量%以下含有した実施例1及び比較例2の非水電解質を用いた二次電池は、含フッ素ホスホン酸エステルを含有しない比較例3の非水電解質を用いた二次電池と比較して、高温充放電サイクル性能が顕著に向上し、電池厚さの増加が顕著に抑制されていることがわかる。これに対して、R1〜R53の水素原子がフッ素原子で置換されていないアルキル基を有するホスホン酸エステルを含有した比較例4の非水電解質を用いた二次電池は、比較例3の非水電解質を用いた二次電池と比較して、高温充放電サイクル性能が向上せず、電池厚さの増加が同程度であり抑制されていない。 As shown in Tables 1 and 2, Example 1 containing 5% by mass or less of a fluorinated phosphonic acid ester having an alkyl group in which at least one of the hydrogen atoms of R 1 to R 3 is substituted with a fluorine atom and comparison The secondary battery using the nonaqueous electrolyte of Example 2 has a significantly improved high-temperature charge / discharge cycle performance compared to the secondary battery using the nonaqueous electrolyte of Comparative Example 3 that does not contain a fluorinated phosphonate ester. It can be seen that the increase in battery thickness is significantly suppressed. On the other hand, the secondary battery using the nonaqueous electrolyte of Comparative Example 4 containing a phosphonic acid ester having an alkyl group in which the hydrogen atoms of R 1 to R 53 are not substituted with fluorine atoms is the same as that of Comparative Example 3. Compared with a secondary battery using a nonaqueous electrolyte, the high-temperature charge / discharge cycle performance is not improved, and the increase in battery thickness is comparable and not suppressed.
次に、含フッ素ホスホン酸エステルを5質量%添加した比較例2−5の充放電サイクル性能は、2質量%添加した比較例2−3に比べて低下する傾向が見られたのに対し、含フッ素ホスホン酸エステルを5質量%添加した実施例1−4の充放電サイクル性能は、2質量%添加した実施例1−3と同等であることに着目し、改めて実施例1で用いたものと同じ含フッ素ホスホン酸エステルを用いて、添加量の範囲を拡大した非水電解質を作製し、これらを用いた非水電解質二次電池の充放電試験を行った。 Next, the charge / discharge cycle performance of Comparative Example 2-5 in which 5% by mass of the fluorinated phosphonic acid ester was added tended to be lower than that in Comparative Example 2-3 in which 2% by mass was added. Focusing on the fact that the charge / discharge cycle performance of Example 1-4 to which 5% by mass of a fluorinated phosphonate was added was equivalent to that of Example 1-3 to which 2% by mass was added, and again used in Example 1 Using the same fluorine-containing phosphonic acid ester, a non-aqueous electrolyte with an expanded amount range was prepared, and a charge / discharge test of a non-aqueous electrolyte secondary battery using these was performed.
(実施例3)
実施例3においては、実施例1と同じく、上記一般式(1)で表される含フッ素ホスホン酸エステルとしてジエチル(ジフルオロメチル)ホスホネートを使用した。
(Example 3)
In Example 3, as in Example 1, diethyl (difluoromethyl) phosphonate was used as the fluorine-containing phosphonate represented by the general formula (1).
(実施例3−1)
1mol/LのLiPF6を含有するエチレンカーボネート(EC):エチルメチルカーボネート(EMC)が体積比で30:70の混合溶媒に、実施例1と同じく、〔化4〕の化学式を有するジエチル(ジフルオロメチル)ホスホネートを5質量%添加して、実施例3−1に係る非水電解質を作製した。
(Example 3-1)
Ethylene carbonate (EC): ethyl methyl carbonate (EMC) containing 1 mol / L LiPF 6 was mixed with 30:70 by volume in a mixed solvent of diethyl (difluoro) having the chemical formula [Chemical Formula 4] as in Example 1. A non-aqueous electrolyte according to Example 3-1 was prepared by adding 5% by mass of methyl) phosphonate.
(実施例3−2〜3−4)
ジエチル(ジフルオロメチル)ホスホネートの添加量を5質量%から、それぞれ、7.5質量%、10質量%、20質量%に変更して、実施例3−2、3−3、3−4に係る非水電解質を作製した。
(Examples 3-2 to 3-4)
According to Examples 3-2, 3-3, and 3-4, the addition amount of diethyl (difluoromethyl) phosphonate was changed from 5% by mass to 7.5% by mass, 10% by mass, and 20% by mass, respectively. A non-aqueous electrolyte was produced.
(非水電解質二次電池の作製)
実施例3及び比較例3の非水電解質を用いて、実施例1と同様にして、非水電解質二次電池を作製した。
(Preparation of non-aqueous electrolyte secondary battery)
Using the nonaqueous electrolytes of Example 3 and Comparative Example 3, a nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1.
(充放電試験)
これらの実施例3及び比較例3の電池について、充放電試験を行った。
まず、25℃において、電流1.0CmA、終止電圧4.35Vの定電流定電圧充電と、電流1.0CmA、終止電圧2.75Vの定電流放電とを、1サイクル行った。
次に、45℃において、電流1.0CmA、終止電圧4.35Vの定電流定電圧充電と、電流1.0CmA、終止電圧2.75Vの定電流放電とを100サイクル行い、45℃における1サイクル目と100サイクル目の1.0CmA放電容量を測定した。
(Charge / discharge test)
The batteries of Example 3 and Comparative Example 3 were subjected to a charge / discharge test.
First, at 25 ° C., a constant current and constant voltage charge with a current of 1.0 CmA and a final voltage of 4.35 V and a constant current discharge with a current of 1.0 CmA and a final voltage of 2.75 V were performed for one cycle.
Next, at 45 ° C., 100 cycles of constant current and constant voltage charging with a current of 1.0 CmA and a final voltage of 4.35 V and constant current discharge with a current of 1.0 CmA and a final voltage of 2.75 V were performed, and one cycle at 45 ° C. The 1.0 CmA discharge capacity at the first and 100th cycles was measured.
(電池厚さの測定)
上記した充放電試験において、45℃における1サイクル目の1.0C放電容量を測定する前及び45℃における100サイクル目の1.0CmA放電容量を測定した後の、室温における電池厚さを、ノギスを用いて測定した。
(Measurement of battery thickness)
In the above charge / discharge test, the thickness of the battery at room temperature after measuring the 1.0 C discharge capacity at the first cycle at 45 ° C. and after measuring the 1.0 C mA discharge capacity at the 100th cycle at 45 ° C. It measured using.
以上の結果をまとめて表3及び表4に示す。なお、表3において、45℃における1サイクル目、100サイクル目の1.0CmA放電容量は、比較例3の1サイクル目の1.0CmA放電容量の値を100%として表記した。表4において、45℃における1サイクル目の1.0CmA放電容量を測定する前の電池厚さを「電池厚さ1サイクル目」、45℃における100サイクル目の1.0CmA放電容量を測定した後の電池厚さを「電池厚さ100サイクル目」とし、比較例3の45℃における1サイクル目の1.0CmA放電容量を測定する前の電池厚さの値を100%として表記した。 The above results are summarized in Table 3 and Table 4. In Table 3, the 1.0 CmA discharge capacity at the first cycle and the 100th cycle at 45 ° C. is expressed as the value of 1.0 CmA discharge capacity at the first cycle of Comparative Example 3 being 100%. In Table 4, the battery thickness before measuring the 1.0 CmA discharge capacity at the first cycle at 45 ° C. is “battery thickness first cycle”, and after measuring the 1.0 CmA discharge capacity at the 100th cycle at 45 ° C. The battery thickness before the measurement of the 1.0 CmA discharge capacity in the first cycle at 45 ° C. in Comparative Example 3 was expressed as 100%.
表3及び表4に示すように、Pに直接結合するアルキル基であるR3の水素原子の少なくとも1つがフッ素原子で置換されている含フッ素ホスホン酸エステルを20質量%以下含有した実施例3の非水電解質を用いた二次電池は、含フッ素ホスホン酸エステルを含有しない比較例3の非水電解質を用いた二次電池と比較して、高温充放電サイクル性能が顕著に向上し、電池厚さの増加が顕著に抑制されていることがわかる。 As shown in Tables 3 and 4, Example 3 containing 20% by mass or less of a fluorine-containing phosphonic acid ester in which at least one hydrogen atom of R 3 which is an alkyl group directly bonded to P was substituted with a fluorine atom Compared with the secondary battery using the non-aqueous electrolyte of Comparative Example 3 that does not contain a fluorine-containing phosphonate, the secondary battery using the non-aqueous electrolyte of FIG. It can be seen that the increase in thickness is significantly suppressed.
(符号の説明)
1 非水電解質二次電池
2 電極群
3 電池容器
4 正極端子
4’ 正極リード
5 負極端子
5’ 負極リード
20 蓄電ユニット
30 蓄電装置
(Explanation of symbols)
DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte secondary battery 2 Electrode group 3 Battery container 4 Positive electrode terminal 4 'Positive electrode lead 5 Negative electrode terminal 5' Negative electrode lead 20 Power storage unit 30 Power storage device
本発明に係る非水電解質二次電池は、充放電サイクル性能が優れているので、電気自動車、ハイブリッド自動車、プラグインハイブリッド自動車等の自動車用電源として有用である。 Since the nonaqueous electrolyte secondary battery according to the present invention has excellent charge / discharge cycle performance, it is useful as a power source for vehicles such as electric vehicles, hybrid vehicles, plug-in hybrid vehicles and the like.
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