JP7108117B1 - Solid polymer electrolyte, lithium ion secondary battery, method for producing lithium ion secondary battery - Google Patents
Solid polymer electrolyte, lithium ion secondary battery, method for producing lithium ion secondary battery Download PDFInfo
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- JP7108117B1 JP7108117B1 JP2021181823A JP2021181823A JP7108117B1 JP 7108117 B1 JP7108117 B1 JP 7108117B1 JP 2021181823 A JP2021181823 A JP 2021181823A JP 2021181823 A JP2021181823 A JP 2021181823A JP 7108117 B1 JP7108117 B1 JP 7108117B1
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- polymer
- solid electrolyte
- mass
- ion secondary
- secondary battery
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- 239000007787 solid Substances 0.000 title claims abstract description 53
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 101
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 65
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 49
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 description 33
- 239000011888 foil Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- -1 Cyclic sulfonic acid esters Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
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- 239000011230 binding agent Substances 0.000 description 9
- 238000007600 charging Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
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- 238000000576 coating method Methods 0.000 description 8
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 125000002091 cationic group Chemical group 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
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- 229910019142 PO4 Inorganic materials 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
【課題】イオン伝導性に優れる高分子固体電解質、その高分子固体電解質を備えたリチウムイオン二次電池、およびリチウムイオン二次電池の製造方法を提供する。【解決手段】ポリマーと、引火点が５０℃以上の有機溶媒と、リチウム塩と、を含む高分子固体電解質であって、前記高分子固体電解質の総質量に対して、前記ポリマーの含有量が２質量％以上１５質量％以下である、高分子固体電解質。【選択図】なしA solid polymer electrolyte having excellent ion conductivity, a lithium ion secondary battery comprising the solid polymer electrolyte, and a method for producing a lithium ion secondary battery are provided. A solid polymer electrolyte includes a polymer, an organic solvent having a flash point of 50° C. or higher, and a lithium salt, wherein the content of the polymer is A polymer solid electrolyte having a content of 2% by mass or more and 15% by mass or less. [Selection figure] None
Description
本発明は、高分子固体電解質、高分子固体電解質を備えたリチウムイオン二次電池、リチウムイオン二次電池の製造方法に関する。 TECHNICAL FIELD The present invention relates to a polymer solid electrolyte, a lithium ion secondary battery provided with the polymer solid electrolyte, and a method for manufacturing a lithium ion secondary battery.
一般に、リチウムイオン二次電池は、正極、負極および電解質を備える。リチウムイオン二次電池は、その発明以来、電解質として使用する有機溶媒の可燃性が懸念され、近年においてもその対策の１つとして電解質を固体化した固体電解質の開発が続けられている。 Lithium ion secondary batteries generally comprise a positive electrode, a negative electrode and an electrolyte. Since the invention of lithium-ion secondary batteries, there has been concern about the flammability of organic solvents used as electrolytes.
固体電解質としては、例えば、ポリマーと、可塑剤と、リチウム塩とを含む高分子固体電解質が挙げられる。高分子固体電解質としては、例えば、特許文献１に記載されているものが知られている。 Solid electrolytes include, for example, polymer solid electrolytes containing a polymer, a plasticizer, and a lithium salt. As a polymer solid electrolyte, for example, one described in Patent Document 1 is known.
リチウムイオン二次電池を引火し難くするために、高分子固体電解質には引火点が高い有機溶媒を用いることが望まれている。しかしながら、引火点が高い有機溶媒は粘度が高いため、高分子固体電解質に適用した場合に、高分子固体電解質のイオン伝導性が悪くなるという課題があった。 In order to make the lithium ion secondary battery less flammable, it is desired to use an organic solvent with a high flash point for the polymer solid electrolyte. However, since an organic solvent with a high flash point has a high viscosity, when applied to a polymer solid electrolyte, there is a problem that the ionic conductivity of the polymer solid electrolyte is deteriorated.
本発明は、上記事情に鑑みてなされたものであって、イオン伝導性に優れる高分子固体電解質、その高分子固体電解質を備えたリチウムイオン二次電池、およびリチウムイオン二次電池の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a solid polymer electrolyte having excellent ion conductivity, a lithium ion secondary battery comprising the solid polymer electrolyte, and a method for producing a lithium ion secondary battery. intended to provide
本発明は、以下の態様を有する。
［１］ポリマーと、引火点が５０℃以上の有機溶媒と、リチウム塩と、を含む高分子固体電解質であって、
前記高分子固体電解質の総質量に対して、前記ポリマーの含有量が２質量％以上１５質量％以下である、高分子固体電解質。
［２］前記引火点が５０℃以上の有機溶媒は２種類以上の有機溶媒を含み、そのうち少なくとも１種が環状構造をもつ有機溶媒であり、さらにそのうち少なくとも１種が直鎖状構造をもつ有機溶媒である、［１］に記載の高分子固体電解質。
［３］前記直鎖状構造を持つ有機溶媒はジニトリルである、［２］に記載の高分子固体電解質。
［４］前記ポリマーは、架橋構造を有する、［１］～［３］のいずれかに記載の高分子固体電解質。
［５］前記ポリマーは、ラジカル重合性モノマーに由来する単位と架橋性モノマーに由来する単位とを有し、
前記ラジカル重合性モノマーに由来する単位および前記架橋性モノマーに由来する単位の重量平均分子量は１０００以下である、［１］～［４］のいずれかに記載の高分子固体電解質。
［６］正極活物質を含む正極と、負極活物質を含む負極と、前記正極と前記負極の間に配される高分子固体電解質と、を備え、
前記高分子固体電解質は、［１］～［５］のいずれかに記載の高分子固体電解質である、リチウムイオン二次電池。
［７］ラジカル重合性モノマーおよび架橋性モノマー、および引火点が５０℃以上の有機溶媒、リチウム塩、および重合開始剤からなる高分子固体電解質用組成物を電池内に充填後、加熱により前記ラジカル重合性モノマーおよび前記架橋性モノマーを重合して高分子固体電解質を合成する、リチウムイオン二次電池の製造方法。
［８］前記高分子固体電解質用組成物の粘度が１ｍＰａ・ｓ以上１００ｍＰａ・ｓ以下である、［７］に記載のリチウムイオン二次電池の製造方法。
The present invention has the following aspects.
[1] A polymer solid electrolyte containing a polymer, an organic solvent having a flash point of 50° C. or higher, and a lithium salt,
A polymer solid electrolyte, wherein the content of the polymer is 2% by mass or more and 15% by mass or less with respect to the total mass of the polymer solid electrolyte.
[2] The organic solvent having a flash point of 50°C or higher contains two or more organic solvents, at least one of which is an organic solvent having a cyclic structure, and at least one of which is an organic solvent having a linear structure. The polymer solid electrolyte according to [1], which is a solvent.
[3] The solid polymer electrolyte according to [2], wherein the organic solvent having a linear structure is dinitrile.
[4] The solid polymer electrolyte according to any one of [1] to [3], wherein the polymer has a crosslinked structure.
[5] The polymer has a unit derived from a radically polymerizable monomer and a unit derived from a crosslinkable monomer,
The solid polymer electrolyte according to any one of [1] to [4], wherein the units derived from the radically polymerizable monomer and the units derived from the crosslinkable monomer have a weight average molecular weight of 1000 or less.
[6] A positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a polymer solid electrolyte disposed between the positive electrode and the negative electrode,
A lithium ion secondary battery, wherein the polymer solid electrolyte is the polymer solid electrolyte according to any one of [1] to [5].
[7] After filling a battery with a polymer solid electrolyte composition comprising a radically polymerizable monomer and a crosslinkable monomer, an organic solvent having a flash point of 50°C or higher, a lithium salt, and a polymerization initiator, the radical is heated to A method for producing a lithium ion secondary battery, comprising polymerizing a polymerizable monomer and the crosslinkable monomer to synthesize a polymer solid electrolyte.
[8] The method for producing a lithium ion secondary battery according to [7], wherein the solid polymer electrolyte composition has a viscosity of 1 mPa·s or more and 100 mPa·s or less.
本発明によれば、イオン伝導性に優れる高分子固体電解質、その高分子固体電解質を備えたリチウムイオン二次電池、およびリチウムイオン二次電池の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the solid polymer electrolyte excellent in ion conductivity, the lithium ion secondary battery provided with the polymer solid electrolyte, and the lithium ion secondary battery can be provided.
本発明の高分子固体電解質、その高分子固体電解質を備えたリチウムイオン二次電池、およびリチウムイオン二次電池の製造方法の実施の形態について説明する。
なお、本実施の形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
Embodiments of the polymer solid electrolyte of the present invention, a lithium ion secondary battery provided with the polymer solid electrolyte, and a method for manufacturing the lithium ion secondary battery will be described.
It should be noted that the present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified.
［高分子固体電解質］
本実施形態の高分子固体電解質は、ポリマーと、引火点が５０℃以上の有機溶媒と、リチウム塩と、を含む。本実施形態の高分子固体電解質は、高分子固体電解質の総質量に対して、ポリマーの含有量が２質量％以上１５質量％以下である。
本実施形態の高分子固体電解質では、ポリマーによって形成されるマトリックス内に、引火点が５０℃以上の有機溶媒が含まれる。
以下、引火点が５０℃以上の有機溶媒を高引火点溶媒と言う。
[Polymer solid electrolyte]
The polymer solid electrolyte of this embodiment contains a polymer, an organic solvent having a flash point of 50° C. or higher, and a lithium salt. The solid polymer electrolyte of the present embodiment has a polymer content of 2% by mass or more and 15% by mass or less with respect to the total mass of the solid polymer electrolyte.
In the polymer solid electrolyte of this embodiment, the matrix formed by the polymer contains an organic solvent having a flash point of 50° C. or higher.
Hereinafter, an organic solvent having a flash point of 50° C. or higher is referred to as a high flash point solvent.
ポリマーは、架橋構造を有することが好ましい。ポリマーが架橋構造を有することにより、ポリマーの流動性がなくなり、電解質の漏液を防止することができる。
ポリマーはラジカル重合および架橋反応によって架橋構造を有する高分子となるが、ラジカル重合後の構造は、下記の化学式（１）で表される。
The polymer preferably has a crosslinked structure. When the polymer has a crosslinked structure, the polymer loses fluidity, and electrolyte leakage can be prevented.
A polymer becomes a polymer having a crosslinked structure through radical polymerization and crosslinking reaction, and the structure after radical polymerization is represented by the following chemical formula (1).
上記の化学式（１）において、Ｒ１およびＲ３はＨまたは－ＣＨ３である。Ｒ２は下記の一般式（５）で表される。Ｒ４は下記の化学式（８）で表される。
上記の化学式（１）で表される構造を有する高分子（以下、化合物（１）と言う。）は、架橋反応によって架橋され、下記の化学式（２）（以下、化合物（２）と言う。）で表される構造を有する高分子となる。ここでは、Ｒ４が下記の化学式（８）で表される場合を例示するが、Ｒ４がそれ以外の場合も同様の構造を有する。
In formula (1) above, R 1 and R 3 are H or —CH 3 . R 2 is represented by the following general formula (5). R 4 is represented by the following chemical formula (8).
A polymer having a structure represented by the above chemical formula (1) (hereinafter referred to as compound (1)) is crosslinked by a cross-linking reaction to give the following chemical formula (2) (hereinafter referred to as compound (2). ), resulting in a polymer having a structure represented by Here, the case where R 4 is represented by the following chemical formula (8) is exemplified, but R 4 has the same structure in other cases.
ラジカル重合と架橋反応とは、同時に進行するため、化合物（１）は反応初期にみられるが、化合物（２）も同時に生成し、最終的に化合物（２）のみとなることが好ましい。すなわち、全てのモノマーが架橋構造を形成し、化合物（１）で表されるオリゴマーやモノマーは、重合反応終了後にはほとんど残留しないことが好ましい。 Since the radical polymerization and the cross-linking reaction proceed at the same time, compound (1) is present at the initial stage of the reaction, but compound (2) is also produced at the same time. That is, it is preferred that all monomers form a crosslinked structure and that the oligomer or monomer represented by compound (1) hardly remains after completion of the polymerization reaction.
上記の式（１）で表されるオリゴマーやモノマーの残留分は、重合反応後の高分子電解質におけるＴＨＦに溶解しない成分（以下、「ＴＨＦ不溶分」と言う。）を算出し、仕込みモノマーの全量からＴＨＦ不溶分の量を引くことにより得られる。
ＴＨＦ不溶分は、重合反応後の高分子電解質をＴＨＦに浸漬し、残存した固体の質量（Ａ）と仕込みモノマー質量（Ｂ）とから、下記の数式（１）で算出できる。
ＴＨＦ不溶分＝Ａ÷Ｂ×１００（質量％） （１）
ＴＨＦ不溶分は、９８質量％以上であることが好ましく、９９．５質量％以上であることがより好ましい。
For the remaining oligomers and monomers represented by the above formula (1), the component that does not dissolve in THF in the polymer electrolyte after the polymerization reaction (hereinafter referred to as "THF-insoluble matter") is calculated, and the amount of the charged monomer is calculated. It is obtained by subtracting the amount of THF insoluble matter from the total amount.
The THF-insoluble matter can be calculated by the following formula (1) from the mass (A) of the solid remaining after the polymerization reaction has been immersed in THF and the mass (B) of the charged monomer.
THF insoluble matter = A/B x 100 (% by mass) (1)
The THF-insoluble content is preferably 98% by mass or more, more preferably 99.5% by mass or more.
ポリマーは、ラジカル重合性モノマーに由来する単位と架橋性モノマーに由来する単位とを有する。
ラジカル重合性モノマーに由来する単位は、下記の化学式（３）で表される化合物において、ｎ＝１の場合のものである。
The polymer has units derived from radically polymerizable monomers and units derived from crosslinkable monomers.
A unit derived from a radically polymerizable monomer is a compound represented by the following chemical formula (3) where n=1.
架橋性モノマーに由来する単位は、下記の化学式（４）で表される化合物において、ｎ＝１の場合のものである。 A unit derived from a crosslinkable monomer is a compound represented by the following chemical formula (4) where n=1.
ラジカル重合性モノマーに由来する単位および架橋性モノマーに由来する単位の重量平均分子量は、１０００以下であることが好ましく、８００以下であることがより好ましく、５００以下であることがさらに好ましく、１８０未満であることが最も好ましい。ラジカル重合性モノマーに由来する単位と架橋性モノマーに由来する単位の重量平均分子量が前記上限値以下であると、分子量が小さいモノマーを高分子固体電解質用組成物に使用でき、高分子固体電解質用組成物の粘度を低減することができる。 The weight average molecular weight of the unit derived from the radically polymerizable monomer and the unit derived from the crosslinkable monomer is preferably 1000 or less, more preferably 800 or less, further preferably 500 or less, and less than 180. is most preferred. When the weight-average molecular weights of the units derived from the radically polymerizable monomer and the units derived from the crosslinkable monomer are equal to or less than the above upper limit, a monomer having a small molecular weight can be used in the solid polymer electrolyte composition. The viscosity of the composition can be reduced.
また、ラジカル重合性モノマーに由来する単位および架橋性モノマーに由来する単位の重量平均分子量は、５０以上であることが好ましく、６０以上であることが好ましく、７０以上であることがさらに好ましい。ラジカル重合性モノマーに由来する単位と架橋性モノマーに由来する単位の重量平均分子量が前記下限値以上であると、酸素、窒素原子などの極性が高い官能基を含むことになるため、Ｌｉイオンとの相互作用により電解液とポリマーとが均一な高分子固体電解質を形成することができる。 In addition, the weight average molecular weight of the unit derived from the radically polymerizable monomer and the unit derived from the crosslinkable monomer is preferably 50 or more, preferably 60 or more, and more preferably 70 or more. If the weight-average molecular weight of the unit derived from the radically polymerizable monomer and the unit derived from the crosslinkable monomer is at least the above lower limit, it will contain a highly polar functional group such as an oxygen or nitrogen atom. interaction enables the electrolytic solution and the polymer to form a uniform polymeric solid electrolyte.
本実施形態の高分子固体電解質の総質量（１００質量％）に対して、ポリマーの含有量は２質量％以上１５質量％以下であり、３質量％以上１０質量％以下であることが好ましい。ポリマーの含有量が前記下限値未満では、ポリマーによって高引火点溶媒を十分に保持することができない。したがって、電池からの電解液の漏液が発生し得る。ポリマーの含有量が前記上限値を超えると、イオン伝導性が低下し液漏れ抑制と抵抗低減が両立できなくなる。 The content of the polymer is 2% by mass or more and 15% by mass or less, preferably 3% by mass or more and 10% by mass or less, relative to the total mass (100% by mass) of the polymer solid electrolyte of the present embodiment. If the content of the polymer is less than the above lower limit, the high flash point solvent cannot be sufficiently retained by the polymer. Therefore, electrolyte leakage from the battery may occur. If the content of the polymer exceeds the above upper limit, the ionic conductivity is lowered, and it becomes impossible to achieve both liquid leakage suppression and resistance reduction.
高引火点溶媒の引火点は５０℃以上であり、５０℃以上２００℃であることが好ましく、７０℃以上１５０℃以下であることがより好ましい。引火点が５０℃未満では、高分子固体電解質を備えるリチウムイオン二次電池の引火点が一般的な電池動作温度の上限（５０℃）よりも低くなる。
高引火点溶媒は２種類以上の有機溶媒を含み、そのうち少なくとも１種が環状構造をもつ有機溶媒であり、さらにそのうち少なくとも１種が直鎖状構造をもつ有機溶媒であることが好ましい。環状構造を持つ有機溶媒と直鎖上構造を持つ有機溶媒とを混合することで、溶媒の相互作用が低減し、溶媒分子の運動の自由度が上がるため、高分子固体電解質の粘度増大に対してイオン伝導度の低減を抑制することができる。
The flash point of the high flash point solvent is 50°C or higher, preferably 50°C or higher and 200°C or lower, and more preferably 70°C or higher and 150°C or lower. If the flash point is less than 50°C, the flash point of the lithium-ion secondary battery including the polymer solid electrolyte is lower than the upper limit (50°C) of the general battery operating temperature.
It is preferable that the high flash point solvent contains two or more organic solvents, at least one of which is an organic solvent having a cyclic structure, and at least one of which is an organic solvent having a linear structure. By mixing an organic solvent with a cyclic structure and an organic solvent with a linear structure, the interaction between the solvents is reduced and the degree of freedom of movement of the solvent molecules is increased. can suppress the decrease in ionic conductivity.
環状構造を持つ有機溶媒としては、例えば、γ－ブチロラクトン、ε―カプロラクトン等のラクトン、γ―ブチロラクタム、ε－カプロラクタム等のラクタム、エチレンカーボネート、ビニレンカーボネート、プロピレンカーボネート、などの環状カーボネート、スルホラン等の環状スルホン酸エステル等が挙げられる。 Examples of organic solvents having a cyclic structure include lactones such as γ-butyrolactone and ε-caprolactone, lactams such as γ-butyrolactam and ε-caprolactam, cyclic carbonates such as ethylene carbonate, vinylene carbonate and propylene carbonate, and sulfolane. Cyclic sulfonic acid esters and the like can be mentioned.
直鎖上構造を持つ有機溶媒としては、例えば、スクシノニトリル、マロノニトリルなどのジニトリル、テトラエチレングリコールジメチルエーテル等のポリエーテル、炭酸ジフェニル等の鎖状カーボネート等が挙げられる。 Examples of the organic solvent having a linear structure include dinitriles such as succinonitrile and malononitrile, polyethers such as tetraethylene glycol dimethyl ether, and chain carbonates such as diphenyl carbonate.
高引火点溶媒の粘度は、１ｍＰａ・ｓ以上１０００ｍＰａ・ｓ以下であることが好ましく、１ｍＰａ・ｓ以上２００ｍＰａ・ｓ以下であることがより好ましく、１ｍＰａ・ｓ以上１００ｍＰａ・ｓ以下であることがさらに好ましい。高引火点溶媒の粘度が前記上限値以下であれば、高分子固体電解質におけるイオン伝導が損なわれない。 The viscosity of the high flash point solvent is preferably 1 mPa s or more and 1000 mPa s or less, more preferably 1 mPa s or more and 200 mPa s or less, and further preferably 1 mPa s or more and 100 mPa s or less. preferable. If the viscosity of the solvent with a high flash point is equal to or less than the upper limit, ionic conduction in the solid polymer electrolyte is not impaired.
高引火点溶媒の粘度を測定する方法は、音叉振動式粘度計（型式名：ＳＶ－１Ａ、株式会社エー・アンド・デイ製）を用いて、室温で粘度を測定した。 As a method for measuring the viscosity of the high flash point solvent, the viscosity was measured at room temperature using a tuning fork vibration viscometer (model name: SV-1A, manufactured by A&D Co., Ltd.).
本実施形態の高分子固体電解質の総質量（１００質量％）に対して、高引火点溶媒の含有量は２０質量％以上８０質量％以下であることが好ましく、２５質量％以上７５質量％以下であることがより好ましい。高引火点溶媒の含有量が前記下限値以上であると、高分子固体電解質はイオン伝導性に優れるものとなる。高引火点溶媒の含有量が前記上限値以下であると、相対的に塩濃度が高まるためイオン伝導が向上する。 The content of the high flash point solvent is preferably 20% by mass or more and 80% by mass or less, and 25% by mass or more and 75% by mass or less with respect to the total mass (100% by mass) of the polymer solid electrolyte of the present embodiment. is more preferable. When the content of the solvent with a high flash point is at least the lower limit, the solid polymer electrolyte will have excellent ionic conductivity. When the content of the solvent with a high flash point is equal to or less than the upper limit, the salt concentration is relatively increased, thereby improving ion conduction.
本実施形態の高分子固体電解質はリチウム塩を含む。リチウム塩としては、高引火点溶媒中におけるリチウム解離度に優れた材料であれば、特に限定されないが、例えば、六フッ化リン酸リチウム（ＬｉＰＦ６）、四フッ化ホウ素リチウム（ＬｉＢＦ４）、リチウムビスオキサレートボラート（ＬｉＣ４ＢＯ８）、ビス（トリフルオロメチルスルホニル）イミドリチウム（ＬｉＴＦＳＩ、ＬｉＮ（ＳＯ２ＣＦ３）２）等が挙げられる。 The polymer solid electrolyte of this embodiment contains a lithium salt. The lithium salt is not particularly limited as long as it is a material having excellent lithium dissociation in a solvent with a high flash point. Examples include lithium hexafluorophosphate (LiPF 6 ), lithium boron tetrafluoride (LiBF 4 ), lithium bisoxalate borate (LiC 4 BO 8 ), bis(trifluoromethylsulfonyl)imide lithium (LiTFSI, LiN(SO 2 CF 3 ) 2 ), and the like.
本実施形態の高分子固体電解質の総質量（１００質量％）に対して、リチウム塩の含有量は５質量％以上５０質量％以下であることが好ましく、１０質量％以上４０質量％以下であることがより好ましい。リチウム塩の含有量が前記下限値以上であると、高分子固体電解質はイオン伝導性に優れるものとなる。リチウム塩の含有量が前記上限値以下であると、高濃度化による高引火点溶媒との分離を防ぎ、界面抵抗上昇を抑制する。 The content of the lithium salt is preferably 5% by mass or more and 50% by mass or less, and is 10% by mass or more and 40% by mass or less with respect to the total mass (100% by mass) of the polymer solid electrolyte of the present embodiment. is more preferable. When the content of the lithium salt is at least the lower limit, the solid polymer electrolyte will have excellent ion conductivity. When the content of the lithium salt is equal to or less than the above upper limit, separation from the high flash point solvent due to high concentration is prevented, and an increase in interfacial resistance is suppressed.
本実施形態の高分子固体電解質は、イオン伝導性を損なわない範囲で、ポリマー、高引火点溶媒、リチウム塩以外の任意の成分を含んでいてもよい。
任意の成分としては、例えば、ビニレンカーボネート（ＶＣ）、フルオロエチレンカーボネート（ＦＥＣ）、リチウムジフルオロオキサラートボレート（ＬｉＤＦＯＢ）、リチウムビスオキサレートボラート（ＬｉＢＯＢ）、トリメチルボラン、リン酸トリメチル、ホウ酸トリメチル、ボロキシン等が挙げられる。
The solid polymer electrolyte of the present embodiment may contain any component other than the polymer, the high flash point solvent, and the lithium salt within a range that does not impair the ionic conductivity.
Examples of optional components include vinylene carbonate (VC), fluoroethylene carbonate (FEC), lithium difluorooxalate borate (LiDFOB), lithium bisoxalate borate (LiBOB), trimethylborane, trimethyl phosphate, and trimethyl borate. , boroxine and the like.
本実施形態の高分子固体電解質によれば、ポリマーと、引火点が５０℃以上の有機溶媒と、リチウム塩と、を含み、高分子固体電解質の総質量に対して、ポリマーの含有量が２質量％以上１５質量％以下であるため、イオン伝導性に優れる高分子固体電解質を提供することができる。 According to the solid polymer electrolyte of the present embodiment, the solid polymer electrolyte contains a polymer, an organic solvent having a flash point of 50° C. or higher, and a lithium salt, and the content of the polymer is 2 with respect to the total mass of the solid polymer electrolyte. Since it is more than mass % and 15 mass % or less, a polymer solid electrolyte excellent in ion conductivity can be provided.
［高分子固体電解質の製造方法］
本実施形態の高分子固体電解質の製造方法は、上述の実施形態の高分子固体電解質の前駆体である高分子固体電解質用組成物を調製する工程と、前記高分子固体電解質用組成物を加熱して、高分子固体電解質用組成物に含まれるモノマーを重合する工程とを有する。
[Method for producing polymer solid electrolyte]
The method for producing the solid polymer electrolyte of the present embodiment includes the steps of preparing a solid polymer electrolyte composition that is a precursor of the solid polymer electrolyte of the above-described embodiment, and heating the solid polymer electrolyte composition. and polymerizing the monomer contained in the solid polymer electrolyte composition.
高分子固体電解質用組成物を調製する工程では、少なくともラジカル重合性モノマーと、架橋性モノマーと、高引火点溶媒と、リチウム塩とを混合する。高分子固体電解質用組成物を調製する工程では、少なくともラジカル重合性モノマーと、架橋性モノマーと、高引火点溶媒と、リチウム塩とを所定の割合で配合し、これらを撹拌子や撹拌翼で混合し、高分子固体電解質用組成物を得る。 In the step of preparing the solid polymer electrolyte composition, at least a radically polymerizable monomer, a crosslinkable monomer, a high flash point solvent, and a lithium salt are mixed. In the step of preparing the solid polymer electrolyte composition, at least a radically polymerizable monomer, a crosslinkable monomer, a solvent with a high flash point, and a lithium salt are blended in predetermined proportions, and these are mixed with a stirrer or a stirring blade. Mix to obtain a polymer solid electrolyte composition.
ラジカル重合性モノマーとしては、特に限定されないが、例えば、アクリロニトリルやメタアクリロニトリル等が挙げられる。
また、ラジカル重合性モノマーとしては、下記の一般式（５）：ＣＨ２＝ＣＲ１－ＣＯＯＣＨ２Ｒ２（式中、Ｒ１は水素原子またはメチル基、Ｒ２はアルキル基またはシクロアルキル基を表す。）で表される化合物由来の単量体を重合して得られる構造単位である（メタ）アクリル酸エステル単量体単位が挙げられる。
Examples of radical polymerizable monomers include, but are not particularly limited to, acrylonitrile and methacrylonitrile.
Further, as the radically polymerizable monomer, the following general formula (5): CH 2 ═CR 1 —COOCH 2 R 2 (wherein R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group or a cycloalkyl group) and a (meth)acrylic acid ester monomer unit, which is a structural unit obtained by polymerizing a monomer derived from a compound represented by ).
上記の一般式（５）で表される単量体の具体例としては、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸ｔ－ブチル、アクリル酸ｎ－アミル、アクリル酸イソアミル、アクリル酸ｎ－ヘキシル、アクリル酸２－エチルヘキシル、アクリル酸ラウリル、アクリル酸ステアリル等のアクリレート；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸ｔ－ブチル、メタクリル酸ｎ－アミル、メタクリル酸イソアミル、メタクリル酸ｎ－ヘキシル、メタクリル酸２－エチルヘキシル、メタクリル酸ラウリル、メタクリル酸ステアリル等のメタクリレート等が挙げられる。 Specific examples of the monomer represented by the general formula (5) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic acid acrylates such as n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and stearyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylate n methacrylates such as -butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate.
エチレン性不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸等が挙げられる。 Examples of ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like.
エチレン性不飽和モノカルボン酸の誘導体としては、例えば、２－エチルアクリル酸、イソクロトン酸、α－アセトキシアクリル酸、β－ｔｒａｎｓ－アリールオキシアクリル酸、α－クロロ－β－Ｅ－メトキシアクリル酸、β－ジアミノアクリル酸等が挙げられる。 Derivatives of ethylenically unsaturated monocarboxylic acids include, for example, 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, β-diaminoacrylic acid and the like can be mentioned.
エチレン性不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸等が挙げられる。 Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
エチレン性不飽和ジカルボン酸の酸無水物としては、例えば、無水マレイン酸、アクリル酸無水物、メチル無水マレイン酸、ジメチル無水マレイン酸等が挙げられる。 Acid anhydrides of ethylenically unsaturated dicarboxylic acids include, for example, maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
エチレン性不飽和ジカルボン酸の誘導体としては、例えば、メチルマレイン酸、ジメチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸等のマレイン酸メチルアリル；並びにマレイン酸ジフェニル、マレイン酸ノニル、マレイン酸デシル、マレイン酸ドデシル、マレイン酸オクタデシル、マレイン酸フルオロアルキル等のマレイン酸エステルが挙げられる。 Derivatives of ethylenically unsaturated dicarboxylic acids include, for example, methyl allyl maleate such as methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid; , decyl maleate, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleate.
エチレン性不飽和スルホン酸単量体の具体例としては、ビニルスルホン酸、メチルビニルスルホン酸、スチレンスルホン酸、（メタ）アクリルスルホン酸、（メタ）アクリル酸－２－スルホン酸エチル、２－アクリルアミド－２－ヒドロキシプロパンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸等が挙げられる。 Specific examples of ethylenically unsaturated sulfonic acid monomers include vinylsulfonic acid, methylvinylsulfonic acid, styrenesulfonic acid, (meth)acrylsulfonic acid, ethyl (meth)acrylate-2-sulfonate, and 2-acrylamide. -2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like.
エチレン性不飽和リン酸単量体の具体例としては、（メタ）アクリル酸－３－クロロ－２－リン酸プロピル、（メタ）アクリル酸－２－リン酸エチル、３－アリロキシ－２－ヒドロキシプロパンリン酸等が挙げられる。 Specific examples of ethylenically unsaturated phosphoric acid monomers include propyl (meth)acrylate-3-chloro-2-phosphate, ethyl (meth)acrylate-2-phosphate, 3-allyloxy-2-hydroxy propane phosphate and the like.
また、上記エチレン性不飽和酸単量体のアルカリ金属塩またはアンモニウム塩も用いることができる。 Alkali metal salts or ammonium salts of the above ethylenically unsaturated acid monomers can also be used.
架橋性ポリマーのカチオン重合性官能基としては、特に限定されないが、例えば、エポキシ基（下記の化学式（６）、化学式（８）、化学式（９）で表される）、Ｎ－メチロールアミド基、オキセタニル基（下記の化学式（７）で表される）、オキサゾリン基、およびこれらの組み合わせ等が挙げられる。これらの中でも、エポキシ基が、架橋および架橋密度の調節が容易な点でより好ましい。 The cationic polymerizable functional group of the crosslinkable polymer is not particularly limited, but examples thereof include an epoxy group (represented by the following chemical formula (6), chemical formula (8), and chemical formula (9)), an N-methylolamide group, Examples thereof include an oxetanyl group (represented by the following chemical formula (7)), an oxazoline group, combinations thereof, and the like. Among these, an epoxy group is more preferable in terms of ease of cross-linking and adjustment of cross-linking density.
エポキシ基を有し、かつオレフィン性二重結合を有するカチオン重合性単量体としては、例えば、（３，４－エポキシシクロヘキシル）メチルアクリレート（Ｅａ）、ビニルグリシジルエーテル、アリルグリシジルエーテル、ブテニルグリシジルエーテル、ｏ－アリルフェニルグリシジルエーテル等の不飽和グリシジルエーテル；ブタジエンモノエポキシド、クロロプレンモノエポキシド、４，５－エポキシ－２－ペンテン、３，４－エポキシ－１－ビニルシクロヘキセン、１，２－エポキシ－５，９－シクロドデカジエン等のジエンまたはポリエンのモノエポキシド；３，４－エポキシ－１－ブテン、１，２－エポキシ－５－ヘキセン、１，２－エポキシ－９－デセン等のアルケニルエポキシド；グリシジルアクリレート、グリシジルメタクリレート、グリシジルクロトネート、グリシジル－４－ヘプテノエート、グリシジルソルベート、グリシジルリノレート、グリシジル－４－メチル－３－ペンテノエート、３－シクロヘキセンカルボン酸のグリシジルエステル、４－メチル－３－シクロヘキセンカルボン酸のグリシジルエステル等の不飽和カルボン酸のグリシジルエステル類等が挙げられる。 Examples of cationic polymerizable monomers having an epoxy group and an olefinic double bond include (3,4-epoxycyclohexyl)methyl acrylate (Ea), vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl Ethers, unsaturated glycidyl ethers such as o-allylphenyl glycidyl ether; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy- monoepoxides of dienes or polyenes such as 5,9-cyclododecadiene; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linolate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of 3-cyclohexenecarboxylic acid, 4-methyl-3-cyclohexene Examples include glycidyl esters of unsaturated carboxylic acids such as glycidyl esters of carboxylic acids.
カチオン重合性基としてＮ－メチロールアミド基を有し、かつオレフィン性二重結合を有する単量体としては、例えば、Ｎ－メチロール（メタ）アクリルアミド等のメチロール基を有する（メタ）アクリルアミド類等が挙げられる。 Examples of monomers having an N-methylolamide group as a cationic polymerizable group and an olefinic double bond include (meth)acrylamides having a methylol group such as N-methylol(meth)acrylamide. mentioned.
カチオン重合性基としてオキセタニル基を有し、かつオレフィン性二重結合を有する単量体としては、例えば、３－（（メタ）アクリロイルオキシメチル）オキセタン、３－（（メタ）アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（（メタ）アクリロイルオキシメチル）－２－フェニルオキセタン、２－（（メタ）アクリロイルオキシメチル）オキセタン、２－（（メタ）アクリロイルオキシメチル）－４－トリフロロメチルオキセタン等が挙げられる。 Monomers having an oxetanyl group as a cationic polymerizable group and an olefinic double bond include, for example, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)- 2-trifluoromethyloxetane, 3-((meth)acryloyloxymethyl)-2-phenyloxetane, 2-((meth)acryloyloxymethyl)oxetane, 2-((meth)acryloyloxymethyl)-4-trifluoro Methyloxetane and the like can be mentioned.
カチオン重合性基としてオキサゾリン基を有し、かつオレフィン性二重結合を有する単量体としては、例えば、２－ビニル－２－オキサゾリン、２－ビニル－４－メチル－２－オキサゾリン、２－ビニル－５－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、２－イソプロペニル－４－メチル－２－オキサゾリン、２－イソプロペニル－５－メチル－２－オキサゾリン、２－イソプロペニル－５－エチル－２－オキサゾリン等が挙げられる。 Monomers having an oxazoline group as a cationic polymerizable group and an olefinic double bond include, for example, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl -5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5 -ethyl-2-oxazoline and the like.
２つ以上のオレフィン性二重結合を有する多官能性単量体としては、例えば、アリル（メタ）アクリレート、エチレンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパン－トリ（メタ）アクリレート、ジプロピレングリコールジアリルエーテル、ポリグリコールジアリルエーテル、トリエチレングリコールジビニルエーテル、ヒドロキノンジアリルエーテル、テトラアリルオキシエタン、トリメチロールプロパン－ジアリルエーテル、前記以外の多官能性アルコールのアリルまたはビニルエーテル、トリアリルアミン、メチレンビスアクリルアミド、ジビニルベンゼン等が挙げられる。 Polyfunctional monomers having two or more olefinic double bonds include, for example, allyl (meth)acrylate, ethylene di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, trimethylolpropane-tri(meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl Ethers, allyl or vinyl ethers of polyfunctional alcohols other than those mentioned above, triallylamine, methylenebisacrylamide, divinylbenzene and the like can be mentioned.
ラジカル重合性モノマーに対する架橋性モノマーの配合比は、質量比で、５重量％以上４０重量％以下であることが好ましく、８重量％以上３０重量％以下であることがより好ましい。前記配合比が前記下限値以上であると、ポリマー液のゲル化を促進し、液漏れを抑制できる。前記上限値以下であると、ポリマーと液の相分離が抑制され、液がポリマーに保持できるので液漏れを抑制できる。 The mixing ratio of the crosslinkable monomer to the radically polymerizable monomer is preferably 5% by weight or more and 40% by weight or less, more preferably 8% by weight or more and 30% by weight or less. When the compounding ratio is equal to or higher than the lower limit, gelation of the polymer liquid can be promoted and liquid leakage can be suppressed. When it is at most the above upper limit, phase separation between the polymer and the liquid is suppressed, and the liquid can be retained in the polymer, so liquid leakage can be suppressed.
モノマーを重合する工程では、まず、所定の内面形状を有する固体電解質成形用の型に、高分子固体電解質用組成物を入れる。次いで、型に入れた高分子固体電解質用組成物を加熱して、前記のモノマーを重合する。これにより、所定の厚みの高分子固体電解質を得る。
なお、本実施形態の高分子固体電解質は、セパレータや正極、負極と複合化してもよい。
高分子固体電解質とセパレータとを複合化をする場合には、セパレータに高分子固体電解質用組成物を含浸させ、その後に上述の通りモノマーを重合させ、セパレータと高分子固体電解質の複合体を得る。正極または負極と複合化する場合にも同様に、高分子固体電解質用組成物を含浸させ、その後に上述の通りモノマーを重合させ、正極または負極と高分子固体電解質の複合体を得る。
In the step of polymerizing the monomer, first, the solid polymer electrolyte composition is placed in a solid electrolyte molding mold having a predetermined inner surface shape. Then, the polymer solid electrolyte composition placed in the mold is heated to polymerize the monomers. Thereby, a polymer solid electrolyte having a predetermined thickness is obtained.
Note that the polymer solid electrolyte of the present embodiment may be combined with a separator, a positive electrode, and a negative electrode.
When the solid polymer electrolyte and the separator are combined, the separator is impregnated with the solid polymer electrolyte composition, and then the monomer is polymerized as described above to obtain a composite of the separator and the solid polymer electrolyte. . Similarly, in the case of forming a composite with a positive electrode or negative electrode, the solid polymer electrolyte composition is impregnated, and then the monomer is polymerized as described above to obtain a composite of the positive electrode or negative electrode and the solid polymer electrolyte.
［リチウムイオン二次電池］
本実施形態のリチウムイオン二次電池は、正極活物質を含む正極と、負極活物質を含む負極と、正極と負極の間に配される高分子固体電解質と、を備える。本実施形態のリチウムイオン二次電池では、高分子固体電解質が上述の実施形態の高分子固体電解質である。
[Lithium ion secondary battery]
The lithium ion secondary battery of this embodiment includes a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a solid polymer electrolyte interposed between the positive electrode and the negative electrode. In the lithium ion secondary battery of this embodiment, the solid polymer electrolyte is the solid polymer electrolyte of the above-described embodiments.
「正極」
正極は、正極集電箔と、正極集電箔の少なくとも一主面に形成された正極合材層とを有する。
"positive electrode"
The positive electrode has a positive electrode current collector foil and a positive electrode mixture layer formed on at least one main surface of the positive electrode current collector foil.
正極合材層は、少なくとも正極活物質を含む。 The positive electrode mixture layer contains at least a positive electrode active material.
正極活物質としては、リチウムイオンの可逆的な進入および脱離を可能とする材料であれば、特に限定されないが、例えば、層状岩塩型酸化物、オリビン型構造のリン酸塩、ポリアニオン系化合物等が挙げられる。
層状岩塩型酸化物としては、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉｘＭｎｙＣｏｚＯ２（但し、ｘ＋ｙ＋ｚ＝１、ｘ≧０．１、ｙ≧０．１、ｚ≧０．１）等が挙げられる。
オリビン型構造のリン酸塩としては、例えば、ＬｉＭｅＰＯ４（但し、Ｍｅ＝Ｃｏ、Ｆｅ、Ｍｎ、Ｎｉ等）等が挙げられる。
ポリアニオン系化合物としては、例えば、ＬｉＭｎ（ＭｅＯ４）（但し、Ｍｅ＝Ｐ、Ｓ、Ａｓ、Ｍｏ、Ｗ、Ｓｉ等）等が挙げられる。
正極活物質は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The positive electrode active material is not particularly limited as long as it is a material that allows reversible entry and exit of lithium ions. is mentioned.
Layered rock salt oxides include, for example, LiCoO 2 , LiNiO 2 , LiNi x Mny Co z O 2 (where x+y+z=1, x≧0.1, y≧0.1, z≧0.1), etc. is mentioned.
Phosphates having an olivine structure include, for example, LiMePO 4 (where Me=Co, Fe, Mn, Ni, etc.).
Examples of polyanionic compounds include LiMn(MeO 4 ) (where Me=P, S, As, Mo, W, Si, etc.).
One type of positive electrode active material may be used alone, or two or more types may be used in combination.
正極合材層は、バインダー樹脂や導電助剤を含んでいてもよい。 The positive electrode mixture layer may contain a binder resin and a conductive aid.
バインダー樹脂としては、正極集電箔と正極合材層を接着することができる樹脂であれば、特に限定されないが、例えば、フッ素樹脂、エストラマー、セルロース誘導体、ポリエーテル、ポリビニルアルコール、アセタール樹脂等が挙げられる。
フッ素樹脂としては、例えば、ポリフッ化ビニリデンやポリフッ化ビニリデン－ヘキサフルオロプロピレン共重合体等が挙げられる。
エストラマーとしては、例えば、ブタジエンゴム、スチレンゴム、ニトリルゴム等が挙げられる。
セルロース誘導体としては、例えば、カルボキシメチルセルロース等が挙げられる。
ポリエーテルとしては、例えば、ポリエチレンオキサイド、ポリエチレングリコール等が挙げられる。
アセタール樹脂としては、例えば、ポリビニルアセタール等が挙げられる。
バインダー樹脂は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The binder resin is not particularly limited as long as it is a resin capable of bonding the positive electrode current collector foil and the positive electrode mixture layer. Examples thereof include fluororesin, elastomer, cellulose derivative, polyether, polyvinyl alcohol, and acetal resin. mentioned.
Examples of the fluororesin include polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer.
Examples of elastomers include butadiene rubber, styrene rubber, nitrile rubber and the like.
Examples of cellulose derivatives include carboxymethyl cellulose and the like.
Polyethers include, for example, polyethylene oxide and polyethylene glycol.
Examples of acetal resins include polyvinyl acetal.
Binder resin may be used individually by 1 type, and may be used in combination of 2 or more type.
導電助剤としては、例えば、アセチレンブラック、ケッチェンブラック等のカーボンブラックや、グラフェン、カーボンナノチューブ等が挙げられる。導電助剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of conductive aids include carbon black such as acetylene black and ketjen black, graphene, and carbon nanotubes. One of the conductive aids may be used alone, or two or more thereof may be used in combination.
正極集電箔としては、正極電位（２ＶｖｓＬｉ／Ｌｉ＋～５ＶｖｓＬｉ／Ｌｉ＋）で安定な金属箔であれば、特に限定されないが、例えば、アルミニウム、チタン、ニッケル、ステンレス鋼等からなる金属箔が挙げられる。 The positive electrode current collector foil is not particularly limited as long as it is a metal foil that is stable at the positive electrode potential (2 V vs Li/Li + to 5 V vs Li/Li + ). For example, metal foils made of aluminum, titanium, nickel, stainless steel, etc. mentioned.
「負極」
負極は、負極集電箔と、負極集電箔の少なくとも一主面に形成された負極合材層とを有する。
"negative electrode"
The negative electrode has a negative electrode current collector foil and a negative electrode mixture layer formed on at least one main surface of the negative electrode current collector foil.
負極合材層は、少なくとも負極活物質を含む。 The negative electrode mixture layer contains at least a negative electrode active material.
負極活物質としては、リチウムイオンの可逆的な進入および脱離を可能とする材料であれば、特に限定されないが、例えば、炭素材料、金属負極、金属酸化物、スピネル型酸化物、金属リチウム等が挙げられる。
炭素材料としては、例えば、天然黒鉛、アモルファスカーボン、グラファイト、ハードカーボン等が挙げられる。
金属負極としては、例えば、ケイ素（Ｓｉ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）等が挙げられる。
金属酸化物としては、例えば、酸化チタン（ＴｉＯ２）、酸化ケイ素（ＳｉＯｘ）等が挙げられる。
スピネル型酸化物としては、例えば、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２）等が挙げられる。
金属リチウムには、充電過程において負極集電箔上にリチウムイオンが還元されることで金属リチウムがメッキされることによって形成されるものも含まれる。
負極活物質は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The negative electrode active material is not particularly limited as long as it is a material that allows reversible entry and exit of lithium ions. Examples include carbon materials, metal negative electrodes, metal oxides, spinel-type oxides, and metallic lithium. is mentioned.
Carbon materials include, for example, natural graphite, amorphous carbon, graphite, and hard carbon.
Examples of metal negative electrodes include silicon (Si), aluminum (Al), gallium (Ga), and the like.
Examples of metal oxides include titanium oxide (TiO 2 ) and silicon oxide (SiO x ).
Examples of spinel-type oxides include lithium titanate (Li 4 Ti 5 O 12 ).
Metallic lithium also includes those formed by plating metallic lithium through reduction of lithium ions on the negative electrode current collector foil during the charging process.
One type of negative electrode active material may be used alone, or two or more types may be used in combination.
負極合材層は、バインダー樹脂や導電助剤を含んでいてもよい。 The negative electrode mixture layer may contain a binder resin and a conductive aid.
バインダー樹脂としては、正極と同様のものを用いることができる。 As the binder resin, the same one as that for the positive electrode can be used.
導電助剤としては、正極と同様のものを用いることができる。 As the conductive aid, the same materials as those used for the positive electrode can be used.
負極集電箔としては、負極電位（０ＶｖｓＬｉ／Ｌｉ＋～２ＶｖｓＬｉ／Ｌｉ＋）でリチウムと合金化しない金属箔であれば、特に限定されないが、例えば、銅、ステンレス鋼等からなる金属箔が挙げられる。 The negative electrode current collector foil is not particularly limited as long as it is a metal foil that does not alloy with lithium at the negative electrode potential (0 V vs Li/Li + to 2 V vs Li/Li + ). Examples include metal foils made of copper, stainless steel, and the like. be done.
本実施形態のリチウムイオン二次電池によれば、正極活物質を含む正極と、負極活物質を含む負極と、正極と負極に間に配される高分子固体電解質と、を備え、高分子固体電解質が上述の実施形態の高分子固体電解質であるため、サイクル特性に優れる。 According to the lithium ion secondary battery of the present embodiment, a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a polymer solid electrolyte disposed between the positive electrode and the negative electrode are provided. Since the electrolyte is the polymer solid electrolyte of the above embodiment, the cycle characteristics are excellent.
［正極の製造方法］
まず、上記の正極活物質と、必要に応じてバインダー樹脂や導電助剤と、溶媒とを混合してなる正極材料ペーストを調製する。
[Manufacturing method of positive electrode]
First, a positive electrode material paste is prepared by mixing the above positive electrode active material, a binder resin, a conductive aid, and a solvent if necessary.
正極材料ペーストに用いられる溶媒としては、Ｎ－メチル－２－ピロリドン、水、テトラヒドロフラン、アセトン、トルエン、酢酸エチル、ｎ－ヘキサン、アセトニトリル等が挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Solvents used in the positive electrode material paste include N-methyl-2-pyrrolidone, water, tetrahydrofuran, acetone, toluene, ethyl acetate, n-hexane, and acetonitrile. These solvents may be used singly or in combination of two or more.
次に、正極材料ペーストを、正極集電箔の少なくとも一主面に塗布して塗膜とし、その後、この塗膜を乾燥し、上記の正極材料ペーストからなる塗膜が少なくとも一主面に形成された正極集電箔を得る。その後、必要に応じて塗膜を加圧圧着してもよい。
以上の工程により、正極集電箔と、正極集電箔の少なくとも一主面に形成された正極合材層とを有する正極を得る。
Next, the positive electrode material paste is applied to at least one main surface of the positive current collector foil to form a coating film, and then the coating film is dried to form a coating film comprising the positive electrode material paste on at least one main surface. A positive electrode current collector foil is obtained. After that, the coating film may be pressure-bonded as needed.
Through the steps described above, a positive electrode having a positive electrode current collector foil and a positive electrode mixture layer formed on at least one main surface of the positive electrode current collector foil is obtained.
［負極の製造方法］
まず、上記の負極活物質と、必要に応じてバインダー樹脂や導電助剤と、溶媒とを混合してなる負極材料ペーストを調製する。負極材料ペーストに用いられる溶媒としては、正極材料に用いられる溶媒と同様のものが用いられる。
[Manufacturing method of negative electrode]
First, a negative electrode material paste is prepared by mixing the above negative electrode active material, a binder resin, a conductive aid, and a solvent if necessary. As the solvent used for the negative electrode material paste, the same solvent as used for the positive electrode material is used.
次に、負極材料ペーストを、負極集電箔の少なくとも一主面に塗布して塗膜とし、その後、この塗膜を乾燥し、上記の負極材料ペーストからなる塗膜が少なくとも一主面に形成された負極集電箔を得る。その後、必要に応じて塗膜を加圧圧着してもよい。
以上の工程により、負極集電箔と、負極集電箔の少なくとも一主面に形成された負極合材層とを有する負極を得る。
Next, the negative electrode material paste is applied to at least one main surface of the negative electrode current collector foil to form a coating film, and then this coating film is dried to form a coating film comprising the above negative electrode material paste on at least one main surface. to obtain a negative electrode current collector foil. After that, the coating film may be pressure-bonded as needed.
Through the steps described above, a negative electrode having a negative electrode current collector foil and a negative electrode mixture layer formed on at least one main surface of the negative electrode current collector foil is obtained.
［リチウムイオン二次電池の製造方法］
本実施形態のリチウムイオン二次電池の製造方法は、上述のようにして得られた正極と、上述のようにして得られた負極とを、高分子固体電解質と複合化した後、高分子固体電解質で絶縁できるように積層し、電池用部材を形成する工程と、前記の電池用部材をラミネートで包装し封止する工程と、を有する。
[Method for producing lithium ion secondary battery]
In the method for producing a lithium ion secondary battery of the present embodiment, the positive electrode obtained as described above and the negative electrode obtained as described above are combined with a polymer solid electrolyte, and then the polymer solid A step of forming a battery member by laminating so that it can be insulated with an electrolyte, and a step of packaging and sealing the battery member with a laminate.
電池用部材を形成する工程では、上述の高分子固体電解質用組成物を、正極と負極を有する電池内に充填後、加熱により、高分子固体電解質用組成物に含まれるラジカル重合性モノマーおよび架橋性モノマーを重合して高分子固体電解質を合成し、正極および負極と高分子固体電解質とを複合化する。 In the step of forming the battery member, after the solid polymer electrolyte composition described above is filled in a battery having a positive electrode and a negative electrode, the polymer solid electrolyte composition is heated to dissolve the radically polymerizable monomers and crosslinks contained in the solid polymer electrolyte composition. A polymer solid electrolyte is synthesized by polymerizing a polar monomer, and the positive electrode, the negative electrode, and the polymer solid electrolyte are composited.
高分子固体電解質用組成物の粘度が１ｍＰａ・ｓ以上１００ｍＰａ・ｓ以下であることが好ましく、１ｍＰａ・ｓ以上３０ｍＰａ・ｓ以下であることがより好ましい。高分子固体電解質用組成物の粘度が前記下限値以上であれば、電池内に高分子固体電解質用組成物を充填した際に、電池内から高分子固体電解質用組成物が流れ出ることを抑制できる。高分子固体電解質用組成物の粘度が前記上限値以下であれば、電池内に高分子固体電解質用組成物を容易に充填することができる。 The viscosity of the polymer solid electrolyte composition is preferably 1 mPa·s or more and 100 mPa·s or less, more preferably 1 mPa·s or more and 30 mPa·s or less. When the viscosity of the polymer solid electrolyte composition is at least the lower limit, it is possible to suppress the solid polymer electrolyte composition from flowing out of the battery when the battery is filled with the solid polymer electrolyte composition. . If the viscosity of the polymer solid electrolyte composition is equal to or less than the upper limit, the battery can be easily filled with the polymer solid electrolyte composition.
以上の工程により、本実施形態のリチウムイオン二次電池を得る。 Through the above steps, the lithium ion secondary battery of the present embodiment is obtained.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited to the following examples.
表に示す略号は以下の通りである。
ＳＮ：スクシノニトリル
ＶＣ：炭酸ビニレン
ＥＣ：炭酸エチレン
ＦＥＣ：炭酸フルオロエチレン
ＰＣ：炭酸プロピレン
ＬｉＴＦＳＩ：リチウムビス（トリフルオロメタンスルホニル）イミド
ＬｉＦＳＩ：リチウムビス（フルオロスルホニル）イミド
ＬｉＤＦＯＢ：リチウムジフルオロオキサラートボレート
ＬｉＢＯＢ：リチウムビスオキサレートボラート
Ｖ６５：２，２’－アゾビス（２，４－ジメチルバレロニトリル）
The abbreviations shown in the table are as follows.
SN: succinonitrile VC: vinylene carbonate EC: ethylene carbonate FEC: fluoroethylene carbonate PC: propylene carbonate LiTFSI: lithium bis(trifluoromethanesulfonyl)imide LiFSI: lithium bis(fluorosulfonyl)imide LiDFOB: lithium difluorooxalate borate LiBOB: Lithium bisoxalate borate V65: 2,2'-azobis(2,4-dimethylvaleronitrile)
［実施例１］
（第１液：高引火点電解液の調製）
ＳＮを４１ｇに、ＬｉＴＦＳＩを１７ｇと、ＬｉＦＳＩを３．０ｇと、ＬｉＤＦＯＢを２．０ｇと、Ｖ６５を０．４ｇとを、２５℃で溶解して、第１液（高引火点電解液）を調製した。
[Example 1]
(First liquid: preparation of high flash point electrolyte)
41 g of SN, 17 g of LiTFSI, 3.0 g of LiFSI, 2.0 g of LiDFOB, and 0.4 g of V65 are dissolved at 25 ° C., and the first solution (high flash point electrolyte) is prepared. prepared.
（第２液：ゲルポリマー前駆体の調製）
攪拌翼を備えたビーカーに、メタクリル酸メチル（ＭＭＡ）を９．０ｇと、３，４－エポキシシクロヘキシルメチルメタクリレートを１．０ｇと、ＬｉＴＦＳＩを７ｇと、ＶＣを２０ｇとを投入し、これらを攪拌、混合して、第２液（ゲルポリマー前駆体）を調製した。
(Second liquid: preparation of gel polymer precursor)
9.0 g of methyl methacrylate (MMA), 1.0 g of 3,4-epoxycyclohexylmethyl methacrylate, 7 g of LiTFSI, and 20 g of VC were added to a beaker equipped with a stirring blade and stirred. , to prepare a second liquid (gel polymer precursor).
（第１液と第２液の混合）
攪拌翼を備えたビーカーに、第１液と第２液を投入し、これらを攪拌、混合した。１０分経過し、均一に溶解し、高分子固体電解質用組成物を得た。
(Mixing of the first liquid and the second liquid)
The first liquid and the second liquid were put into a beaker equipped with a stirring blade, and they were stirred and mixed. After 10 minutes, the mixture was uniformly dissolved to obtain a solid polymer electrolyte composition.
（正極の作製）
正極活物質として平均粒子径１０μｍのＬｉＦｅＰＯ４を９２質量部と、導電助剤として一次粒子径３０ｎｍのケッチェンブラック４質量部と、結着材としてポリフッ化ビニリデン４質量部と、溶媒としてＮ－メチル－２－ピロリドン（ＮＭＰ）とを混合し、固形分６０％に調整したスラリーを得た。
このスラリーを厚み１５μｍのアルミニウム箔に両面塗布し、予備乾燥後、１２０℃で真空乾燥し、正極合材層を形成した。正極合材層を４００ｋＮ／ｍで加圧プレスし、密度３．０ｇ／ｃｃ、厚み１００μｍの正極合材層を有する正極を得た。
(Preparation of positive electrode)
92 parts by mass of LiFePO 4 having an average particle size of 10 μm as a positive electrode active material, 4 parts by mass of Ketjenblack having a primary particle size of 30 nm as a conductive agent, 4 parts by mass of polyvinylidene fluoride as a binder, and N- as a solvent. Methyl-2-pyrrolidone (NMP) was mixed to obtain a slurry adjusted to a solid content of 60%.
This slurry was coated on both sides of an aluminum foil having a thickness of 15 μm, pre-dried, and vacuum-dried at 120° C. to form a positive electrode mixture layer. The positive electrode mixture layer was pressed at 400 kN/m to obtain a positive electrode having a positive electrode mixture layer with a density of 3.0 g/cc and a thickness of 100 μm.
（負極の作製）
負極活物質として（グラファイト、平均粒子径１０μｍ）１００質量部と、結着材としてスチレンブタジエンゴム１．５質量部と、増粘材としてカルボキシメチルセルロースＮａを１．５質量部と、溶媒として水とを混合し、固形分５０％に調整したスラリーを得た。
このスラリーを厚み１２μｍ銅箔に両面塗布し、１００℃で真空乾燥し、負極合材層を形成した。負極合材層を５００ｋＮ／ｍで加圧プレスし、密度１．６ｇ／ｃｃ、厚み１００μｍの負極合材層を有する負極を得た。
(Preparation of negative electrode)
100 parts by mass of negative electrode active material (graphite, average particle size 10 μm), 1.5 parts by mass of styrene-butadiene rubber as a binder, 1.5 parts by mass of carboxymethyl cellulose Na as a thickener, and water as a solvent. were mixed to obtain a slurry adjusted to a solid content of 50%.
This slurry was applied to both sides of a copper foil having a thickness of 12 μm and dried in a vacuum at 100° C. to form a negative electrode mixture layer. The negative electrode mixture layer was pressure-pressed at 500 kN/m to obtain a negative electrode having a negative electrode mixture layer with a density of 1.6 g/cc and a thickness of 100 μm.
（積層体の製造）
セパレータとして、厚み１５μｍのポリエチレン製多孔質フィルムを用いた。
上記で得た負極と５枚、正極４枚と、セパレータ１０枚とを交互に積層し、負極、正極およびセパレータを含む積層体を作製した。
正極サイズは１１０ｍｍ×９５ｍｍ、負極サイズは１２０ｍｍ×１００ｍｍ、セパレータサイズは１４０ｍｍ×１２０ｍｍとした。
(Manufacturing of laminate)
A polyethylene porous film having a thickness of 15 μm was used as a separator.
Five sheets of the negative electrode obtained above, four sheets of the positive electrode, and 10 sheets of the separator were alternately laminated to prepare a laminate including the negative electrode, the positive electrode, and the separator.
The positive electrode size was 110 mm×95 mm, the negative electrode size was 120 mm×100 mm, and the separator size was 140 mm×120 mm.
（リチウムイオン二次電池の作製）
各正極集電体の露出部の端部を纏めて超音波溶着で接合するとともに、外部に突出する端子用タブを接合した。同様に、各負極集電体の露出部の端部を纏めて超音波融着で接合するとともに、外部に突出する端子用タブを接合した。
次いで、アルミラミネートフィルムで積層体を挟み、端子用タブを外部に突出させ、三辺をラミネート加工によって封止した。封止せずに残した一辺から、上記で得た高分子固体電解質用組成物を１０ｇ注入し、真空封止することによってラミネート型のセルを製造した。
(Production of lithium ion secondary battery)
The ends of the exposed portions of the positive electrode current collectors were collectively joined by ultrasonic welding, and a terminal tab projecting to the outside was joined. Similarly, the ends of the exposed portions of the respective negative electrode current collectors were collectively joined by ultrasonic fusion, and the terminal tabs protruding outside were joined.
Next, the laminate was sandwiched between aluminum laminate films, the terminal tab was protruded outside, and three sides were sealed by lamination. 10 g of the polymer solid electrolyte composition obtained above was poured into the left unsealed side, and vacuum-sealed to manufacture a laminate type cell.
（高分子固体電解質用組成物のゲルポリマー化）
上記セルを恒温槽に格納し、恒温槽内の温度を２５℃に保ちながら２時間待機した。その後、２５℃の恒温槽内において１回充放電を行った。まず、３．８Ｖまで０．１Ｃで電流を一定として充電し、３．８Ｖを保ちながら０．０５Ｃを終止電流値として電流を低下させながら充電した。充電終了後は１０分間待機し、その後に０．１Ｃで電流を一定として２．５Ｖまで放電した。
その後、恒温槽からセルを取り出し、ラミネートの端を切断し発生したガスを除去し、再度封止した。
その後、セルを６０℃の恒温槽に入れ、２４時間加熱した。
その後、ガス除去をもう一度行い、続いて８０℃に昇温し、８０℃到達後４時間加熱した。
８０℃加熱後の高分子固体電解質用組成物はゲル化し、高分子固体電解質となっており、セルを傾けても液がたれてくることがなかった。この状態のセルを評価用セル（リチウムイオン二次電池）とした。
(Gel polymerization of polymer solid electrolyte composition)
The cell was stored in a constant temperature bath and waited for 2 hours while maintaining the temperature in the constant temperature bath at 25°C. After that, the battery was charged and discharged once in a constant temperature bath at 25°C. First, the battery was charged with a constant current of 0.1 C up to 3.8 V, and charged while maintaining the 3.8 V and decreasing the current with a final current value of 0.05 C. After charging was completed, the battery was waited for 10 minutes, and then discharged to 2.5 V at a constant current of 0.1C.
After that, the cell was taken out from the constant temperature bath, the edge of the laminate was cut off, the generated gas was removed, and the cell was sealed again.
After that, the cell was placed in a constant temperature bath at 60° C. and heated for 24 hours.
After that, the gas was removed once more, and then the temperature was raised to 80°C, and after reaching 80°C, heating was continued for 4 hours.
After heating at 80° C., the solid polymer electrolyte composition gelled to form a solid polymer electrolyte, and the liquid did not drip even when the cell was tilted. The cell in this state was used as an evaluation cell (lithium ion secondary battery).
（０．２Ｃ放電容量の測定方法）
上記で作製した評価用セルを用い、以下の方法で充放電を行った。
恒温槽に評価用セルを格納し、恒温槽内の温度を２５℃に保ちながら２時間待機した。
その後、２５℃の恒温槽内において充放電を行った。まず、３．６Ｖまで０．１Ｃで電流を一定として充電し、３．６Ｖを保ちながら０．０５Ｃを終止電流値として電流を低下させながら充電した。
充電終了後は１分間待機し、その後、０．２Ｃで電流を一定として２．５Ｖまで放電した。
取得した放電容量を活物質の質量で割ることで活物質の質量当たりの放電容量（単位：ｍＡｈ／ｇ）を算出し、０．２Ｃ放電容量とした。
(Method for measuring 0.2C discharge capacity)
Using the evaluation cell produced above, charging and discharging were performed by the following method.
The evaluation cell was stored in a constant temperature bath and waited for 2 hours while maintaining the temperature in the constant temperature bath at 25°C.
After that, charging and discharging were performed in a constant temperature bath at 25°C. First, the battery was charged with a constant current of 0.1 C up to 3.6 V, and charged while maintaining the 3.6 V and decreasing the current with a final current value of 0.05 C.
After completion of charging, the battery was waited for 1 minute, and then discharged to 2.5 V at a constant current of 0.2C.
The obtained discharge capacity was divided by the mass of the active material to calculate the discharge capacity (unit: mAh/g) per mass of the active material, which was taken as the 0.2C discharge capacity.
（エネルギー密度）
上記で作製した評価用セルを２５℃で充放電を一度行い、放電容量を測定した。
放電容量を、（正極＋セパレータ＋負極）の厚みで割り、厚み当たりの容量（エネルギー密度）とした。
充電条件：ＣＣＣＶ充電。ＣＣ条件は、３．６Ｖ，０．２Ｃ。ＣＶ条件は、３．６Ｖ，０．０５Ｃ終止とする。
放電条件：ＣＣ放電。２．５Ｖ、０．２Ｃとする。
評価指標
Ａ：厚み当たりの容量０．９ｍＡｈ／μｍ以上
Ｂ：０．８５ｍＡｈ／μｍ以上０．９ｍＡｈ／μｍ未満
Ｃ：０．８ｍＡｈ／μｍ以上０．８５ｍＡｈ／μｍ未満
Ｄ：０．８Ａｈ／μｍ以下
(energy density)
The evaluation cell prepared above was charged and discharged once at 25° C., and the discharge capacity was measured.
The discharge capacity was divided by the thickness of (positive electrode + separator + negative electrode) to obtain the capacity per thickness (energy density).
Charging conditions: CCCV charging. CC conditions are 3.6V, 0.2C. CV conditions are 3.6V, 0.05C termination.
Discharge conditions: CC discharge. 2.5V and 0.2C.
Evaluation index A: Capacity per thickness 0.9 mAh/μm or more B: 0.85 mAh/μm or more and less than 0.9 mAh/μm C: 0.8 mAh/μm or more and less than 0.85 mAh/μm D: 0.8 Ah/μm or less
（安全性評価）
上記で作製した評価用セルについて、０．２Ｃの定電流充電を行い、次いで、４．２Ｖ到達次第、電流を減少させ０．０５Ｃとなった時点で充電完了する定電圧充電を行った。
その後、評価用セルを金属板で拘束し、評価用セルの面に対して垂直方向に釘を穿刺した。
その際の評価用セルの挙動と最高温度について評価した。
釘刺し位置：電極の中央部
釘設計：鉄製、直径３ｍｍ、先端角度３０°
穿刺速度：１０ｍｍ／ｓｅｃ
測温部：セルの再表面、かつ釘穿刺位置から１０ｍｍ以内の距離に熱電対を設置する。
評価指標
Ａ：電池は発火・発煙せず、最高到達温度１３５℃以下
Ｂ：電池は発火・発煙せず、最高到達温度１３５℃以上
Ｃ：電池は発火せず
Ｄ：電池は発火
評価用セルの発火は評価用セル自体の危険性を示し、電解液に引火したことを示す。最高到達温度は電池の持つ危険リスクを示す。
(safety evaluation)
The cell for evaluation prepared above was charged at a constant current of 0.2 C, and then, as soon as 4.2 V was reached, the current was decreased, and charging was completed at 0.05 C, followed by constant voltage charging.
After that, the evaluation cell was restrained with a metal plate, and a nail was punctured in the direction perpendicular to the surface of the evaluation cell.
The behavior and maximum temperature of the evaluation cell at that time were evaluated.
Nail penetration position: Center of electrode Nail design: Steel, diameter 3mm, tip angle 30°
Puncture speed: 10mm/sec
Temperature measuring part: A thermocouple is placed on the surface of the cell and within 10 mm from the nail puncture position.
Evaluation index A: Battery does not ignite or emit smoke, maximum temperature reached 135°C or less B: Battery does not ignite or emit smoke, maximum temperature reached 135°C or higher C: Battery does not ignite D: Battery ignites Evaluation cell Ignition indicates the danger of the evaluation cell itself and indicates that the electrolyte has caught fire. The highest temperature reached indicates the danger risk of the battery.
（サイクル特性）
上記で作製した評価用セルを２５℃、０．２Ｃの定電流充電を行い、次いで、４．２Ｖ到達次第、電流を減少させ０．０５Ｃとなった時点で充電完了する定電圧充電を行った。
その後、０．２Ｃの定電流放電を行った。
上記のサイクルを繰り返した。１００サイクル後の放電容量を１サイクル後の放電容量と比較し、容量維持率とした。
評価指標
Ａ：容量維持率５０％以上
Ｂ：容量維持率４０％以上５０％未満
Ｃ：容量維持率３０％以上４０％未満
Ｄ：容量維持率３０％未満
(Cycle characteristics)
The evaluation cell prepared above was subjected to constant current charging at 25° C. and 0.2 C, and then, as soon as 4.2 V was reached, the current was decreased and charging was completed at 0.05 C. Constant voltage charging was performed. .
After that, 0.2C constant current discharge was performed.
The above cycle was repeated. The discharge capacity after 100 cycles was compared with the discharge capacity after 1 cycle to obtain the capacity retention rate.
Evaluation index A: Capacity retention rate of 50% or more B: Capacity retention rate of 40% or more and less than 50% C: Capacity retention rate of 30% or more and less than 40% D: Capacity retention rate of less than 30%
［実施例２～実施例１４、比較例１～比較例５］
表１に示す材料を用いて、表１または表２に示す組成比としたこと以外は実施例１と同様にして、評価用セル（リチウムイオン二次電池）を作製した。
得られた評価用セルについて、実施例１と同様にして、０．２Ｃ放電容量、エネルギー密度、安全性およびサイクル特性を評価した。実施例２～実施例７については表１に、実施例８～実施例１４については表２に、比較例１～比較例５については表３に結果を示す。
[Examples 2 to 14, Comparative Examples 1 to 5]
An evaluation cell (lithium ion secondary battery) was produced in the same manner as in Example 1 except that the materials shown in Table 1 were used and the composition ratios shown in Table 1 or Table 2 were used.
The obtained evaluation cell was evaluated in the same manner as in Example 1 for 0.2C discharge capacity, energy density, safety and cycle characteristics. The results of Examples 2 to 7 are shown in Table 1, the results of Examples 8 to 14 are shown in Table 2, and the results of Comparative Examples 1 to 5 are shown in Table 3.
表１～表３の結果から、実施例１～実施例１４の高分子固体電解質を用いたリチウムイオン二次電池は、０．２Ｃ放電容量、エネルギー密度、安全性およびサイクル特性に優れることが分かった。比較例１、比較例２から、環状溶媒を含まない、または直鎖状溶媒を含まない場合には、溶媒の自由度が低下し、高分子固体電解質が高抵抗化するためにサイクル特性およびエネルギー密度が低下することが明らかである。また、比較例３から、ラジカル重合性モノマー濃度が高すぎる場合には、リチウム伝導を担う溶媒濃度が相対的に低下することから高分子固体電解質が高抵抗化するために、サイクル特性およびエネルギー密度が低下することが明らかである。ラジカル重合性モノマーに対し架橋性モノマー濃度が高すぎる場合には、溶媒とポリマーとが相分離するために、高抵抗化する、副反応が生じる、液漏れが発生すること等から放電容量、エネルギー密度、安全性およびサイクル特性が低下することが明らかである。また、比較例５から、架橋性モノマーを含まない場合には、高分子固体電解質が硬化しないことから、副反応が生じる、液漏れが発生するためにサイクル特性、安全性、ゲル化で特性が低下すること等が明らかである。
以上から、高分子固体電解質として、架橋構造を有するポリマー含有量が２質量％～１５質量％であり、直鎖状構造を持つ溶媒と環状構造を有する溶媒とからなる高分子固体電解質は優れた特性を有することが示された。
From the results in Tables 1 to 3, the lithium ion secondary batteries using the polymer solid electrolytes of Examples 1 to 14 were found to be excellent in 0.2C discharge capacity, energy density, safety and cycle characteristics. rice field. From Comparative Examples 1 and 2, when the cyclic solvent is not included or the linear solvent is not included, the degree of freedom of the solvent decreases, and the polymer solid electrolyte becomes highly resistant, resulting in poor cycle characteristics and energy consumption. A decrease in density is evident. In addition, from Comparative Example 3, when the concentration of the radically polymerizable monomer is too high, the concentration of the solvent responsible for lithium conduction is relatively decreased, so that the resistance of the polymer solid electrolyte is increased. is clearly reduced. If the concentration of the cross-linking monomer is too high relative to the radically polymerizable monomer, phase separation between the solvent and the polymer may occur, resulting in high resistance, side reactions, and liquid leakage. It is clear that the density, safety and cycling properties are degraded. In addition, from Comparative Example 5, when the crosslinkable monomer is not contained, the polymer solid electrolyte does not harden, so side reactions occur, and liquid leakage occurs, resulting in poor cycle characteristics, safety, and gelation characteristics. It is clear that the
From the above, as a polymer solid electrolyte, the content of the polymer having a crosslinked structure is 2% to 15% by mass, and the polymer solid electrolyte composed of a solvent having a linear structure and a solvent having a cyclic structure is excellent. It was shown to have properties.
本発明に係る高分子固体電解質は、イオン伝導性に優れることから、特に、リチウムイオン二次電池の分野において広く適用可能である。 INDUSTRIAL APPLICABILITY The polymer solid electrolyte according to the present invention has excellent ion conductivity, and is therefore widely applicable particularly in the field of lithium ion secondary batteries.
Claims (6)
前記高分子固体電解質の総質量に対して、前記ポリマーの含有量が２質量％以上１５質量％以下であり、
前記引火点が５０℃以上の有機溶媒は、直鎖状構造をもつ有機溶媒の少なくとも１種と、環状構造をもつ有機溶媒の少なくとも１種とを含み、
前記ポリマーは、ラジカル重合性モノマーに由来する単位と架橋性モノマーに由来する単位とを有し、
前記ラジカル重合性モノマーに由来する単位および前記架橋性モノマーに由来する単位の重量平均分子量は１０００以下であり、
前記高分子固体電解質の総質量に対する前記ラジカル重合性モノマーに由来する単位の含有量が２．８～１１．２質量％であり、
前記ラジカル重合性モノマーに対する、前記架橋性モノマーの割合は、質量比で１／１９～３／７である、高分子固体電解質。 A polymer solid electrolyte containing a polymer, an organic solvent having a flash point of 50° C. or higher, and a lithium salt,
The content of the polymer is 2% by mass or more and 15% by mass or less with respect to the total mass of the polymer solid electrolyte,
The organic solvent having a flash point of 50° C. or higher includes at least one organic solvent having a linear structure and at least one organic solvent having a cyclic structure,
The polymer has a unit derived from a radically polymerizable monomer and a unit derived from a crosslinkable monomer,
The weight average molecular weight of the unit derived from the radically polymerizable monomer and the unit derived from the crosslinkable monomer is 1000 or less,
The content of units derived from the radically polymerizable monomer is 2.8 to 11.2% by mass with respect to the total mass of the polymer solid electrolyte ,
A polymer solid electrolyte , wherein the ratio of the crosslinkable monomer to the radically polymerizable monomer is 1/19 to 3/7 in mass ratio .
前記高分子固体電解質は、請求項１～３のいずれか１項に記載の高分子固体電解質である、リチウムイオン二次電池。 A positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a polymer solid electrolyte disposed between the positive electrode and the negative electrode,
A lithium ion secondary battery, wherein the solid polymer electrolyte is the solid polymer electrolyte according to any one of claims 1 to 3.
前記高分子固体電解質用組成物は、前記ラジカル重合性モノマーおよび前記架橋性モノマー、および引火点が５０℃以上の有機溶媒、リチウム塩、および重合開始剤からなり、
前記引火点が５０℃以上の有機溶媒は、直鎖状構造をもつ有機溶媒の少なくとも１種と、環状構造をもつ有機溶媒の少なくとも１種とを含み、
前記ラジカル重合性モノマーおよび前記架橋性モノマーの重量平均分子量は１０００以下であり、
前記高分子固体電解質用組成物の総質量に対する前記ラジカル重合性モノマーの含有量が２．８～１１．２質量％であり、
前記ラジカル重合性モノマーに対する、前記架橋性モノマーの割合は、質量比で１／１９～３／７である、リチウムイオン二次電池の製造方法。 A method for producing a lithium ion secondary battery, comprising filling a battery with a solid polymer electrolyte composition and then polymerizing a radically polymerizable monomer and a crosslinkable monomer by heating to synthesize a solid polymer electrolyte,
The polymer solid electrolyte composition comprises the radically polymerizable monomer, the crosslinkable monomer, an organic solvent having a flash point of 50° C. or higher, a lithium salt, and a polymerization initiator,
The organic solvent having a flash point of 50° C. or higher includes at least one organic solvent having a linear structure and at least one organic solvent having a cyclic structure,
The weight average molecular weight of the radically polymerizable monomer and the crosslinkable monomer is 1000 or less ,
The content of the radically polymerizable monomer is 2.8 to 11.2% by mass with respect to the total mass of the polymer solid electrolyte composition ,
A method for producing a lithium ion secondary battery , wherein the ratio of the crosslinkable monomer to the radically polymerizable monomer is 1/19 to 3/7 in mass ratio .
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