JP2024079609A - Polymers for power storage devices - Google Patents
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- 238000003860 storage Methods 0.000 title claims abstract description 136
- 229920000642 polymer Polymers 0.000 title claims abstract description 108
- 230000005611 electricity Effects 0.000 claims abstract description 106
- 239000011871 silicon-based negative electrode active material Substances 0.000 claims abstract description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 47
- 239000011230 binding agent Substances 0.000 claims description 32
- 230000014759 maintenance of location Effects 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002003 electrode paste Substances 0.000 description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
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- 239000010703 silicon Substances 0.000 description 29
- 239000002131 composite material Substances 0.000 description 25
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- 229910002804 graphite Inorganic materials 0.000 description 18
- 239000010439 graphite Substances 0.000 description 18
- 239000007773 negative electrode material Substances 0.000 description 16
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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- 229920001223 polyethylene glycol Polymers 0.000 description 4
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- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
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- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- TWLBWHPWXLPSNU-UHFFFAOYSA-L [Na].[Cl-].[Cl-].[Ni++] Chemical compound [Na].[Cl-].[Cl-].[Ni++] TWLBWHPWXLPSNU-UHFFFAOYSA-L 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BSCJIBOZTKGXQP-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCO BSCJIBOZTKGXQP-UHFFFAOYSA-N 0.000 description 1
- OKPYIWASQZGASP-UHFFFAOYSA-N n-(2-hydroxypropyl)-2-methylprop-2-enamide Chemical compound CC(O)CNC(=O)C(C)=C OKPYIWASQZGASP-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
【課題】一態様において、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性および高速放電容量維持率を向上できる蓄電デバイス用重合体の提供。【解決手段】本開示は、一態様において、下記式（Ｉ）で表される構成単位を含み、下記式（Ｉ）で表される構成単位の含有量が９５質量％超の、蓄電デバイス用重合体に関する。下記式（Ｉ）中、Ｒ1は、水素原子又はメチル基であり、Ｒ2は、水素原子、炭素数１以上４以下の炭化水素基、又は、１個以上３個以下の水酸基を有する直鎖もしくは分岐鎖の炭素数１以上４以下の炭化水素基であり、Ｒ3は、１個以上３個以下の水酸基を有する直鎖又は分岐鎖の炭素数１以上４以下の炭化水素基である。【化１】TIFF2024079609000008.tif33170【選択図】なし[Problem] In one aspect, a polymer for an electricity storage device is provided that can improve the charge/discharge cycle characteristics and high-rate discharge capacity retention rate of an electricity storage device equipped with a negative electrode using a silicon-based negative electrode active material. [Solution] In one aspect, the present disclosure relates to a polymer for an electricity storage device that includes a structural unit represented by the following formula (I), and the content of the structural unit represented by the following formula (I) exceeds 95 mass %. In the following formula (I), R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a linear or branched hydrocarbon group having 1 to 4 carbon atoms and having 1 to 3 hydroxyl groups, and R3 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms and having 1 to 3 hydroxyl groups. [Chemical 1]TIFF2024079609000008.tif33170[Selected Figures]None
Description
本開示は、蓄電デバイス用重合体、バインダー組成物、蓄電デバイス負極用ペースト、蓄電デバイス用負極、及び蓄電デバイスに関する。 This disclosure relates to a polymer for an electricity storage device, a binder composition, a paste for an electricity storage device negative electrode, an electricity storage device negative electrode, and an electricity storage device.
近年のスマートフォンの普及や自動車市場でのゼロエミッション規制、さらには自然エネルギー活用の拡大等により、蓄電デバイスの需要は大きくなってきている。そのため、蓄電デバイスには、小型、軽量、大容量化が望まれ、自動車等においてはさらに高出力、高エネルギー密度を求める声が大きくなっている。このような要求において、リチウムイオン二次電池やアルカリイオン二次電池、電気二重層キャパシタやリチウムイオンキャパシタ等の蓄電デバイスの開発が進められている。 The demand for energy storage devices is growing in recent years due to the widespread use of smartphones, zero-emission regulations in the automobile market, and the expanded use of natural energy. For this reason, energy storage devices are required to be small, lightweight, and have large capacity, and there is a growing demand for higher output and higher energy density in automobiles and other applications. In response to these demands, the development of energy storage devices such as lithium-ion secondary batteries, alkaline-ion secondary batteries, electric double-layer capacitors, and lithium-ion capacitors is progressing.
このような蓄電デバイスは、一般的に金属箔上に活物質等を含む合材層が塗布された電極を備えており、合材層の剥落を防止するために蓄電デバイス電極用バインダーが合材層に添加されている。
蓄電デバイス負極用バインダーとしてもっとも広く使用されているのは、スチレン／ブタジエンラバー（ＳＢＲ）であるが、近年、蓄電デバイスの更なる性能向上を目的として、合材層の形成に用いられるバインダーの開発が進められている。
例えば、特許文献１には、ヒドロキシル基含有ビニル単量体単位を所定の割合で含有し、かつ重量平均分子量が所定の範囲内である幹重合体に対して水可溶性単量体単位を含む枝重合体が結合した構造を有するグラフト共重合体を含むバインダー組成物が提案されている。
特許文献２には、（メタ）アクリルアミド単量体単位を含有する水溶性重合体およびアミン化合物を含むバインダー組成物が提案されている。
Such an electricity storage device generally has an electrode in which a composite layer containing an active material and the like is applied onto a metal foil, and a binder for electricity storage device electrodes is added to the composite layer to prevent peeling off of the composite layer.
Styrene/butadiene rubber (SBR) is the most widely used binder for the negative electrode of an electricity storage device. However, in recent years, development of binders to be used in forming a composite layer has been progressing with the aim of further improving the performance of electricity storage devices.
For example, Patent Document 1 proposes a binder composition containing a graft copolymer having a structure in which a branch polymer containing a water-soluble monomer unit is bonded to a trunk polymer containing a predetermined ratio of hydroxyl group-containing vinyl monomer units and having a weight average molecular weight within a predetermined range.
Patent Document 2 proposes a binder composition containing a water-soluble polymer containing a (meth)acrylamide monomer unit and an amine compound.
蓄電デバイスの負極活物質には黒鉛系負極活物質が広く用いられているが、高容量化の点からシリコン系負極活物質が着目されている。
しかし、シリコン系負極活物質は充放電に伴う膨張及び収縮の体積変化が著しく大きく、従来のバインダー組成物を用いた電極（負極）では、蓄電デバイスの充放電サイクル特性を十分に高めることができないという問題が認識されている。
また、シリコン系負極活物質と従来のバインダー組成物とを用いて作製された電極（負極）では、蓄電デバイスの大電流での充電や放電時の放電容量（高速放電容量）や高速放電容量維持率（低速放電時と高速放電時の放電容量比）を十分に高めることができないという問題も認識されている。高速放電容量維持率とは、低速放電時と高速放電時の放電容量比であり、高い高速放電容量維持率は、大電流での充電や放電が必要な蓄電デバイスに求められる特性である。
すなわち、従来のバインダー組成物には、シリコン系負極活物質を用いた負極を備える蓄電デバイスに優れた充放電サイクル特性および高い高速放電容量維持率を発揮させるという点において、未だ改善の余地があった。
Graphite-based negative electrode active materials are widely used as the negative electrode active materials for power storage devices, but silicon-based negative electrode active materials have been attracting attention from the viewpoint of increasing capacity.
However, silicon-based negative electrode active materials undergo significant volumetric changes due to expansion and contraction during charging and discharging, and it has been recognized that electrodes (negative electrodes) using conventional binder compositions cannot sufficiently improve the charge-discharge cycle characteristics of electricity storage devices.
It has also been recognized that an electrode (negative electrode) made using a silicon-based negative electrode active material and a conventional binder composition cannot sufficiently increase the discharge capacity (high-rate discharge capacity) or high-rate discharge capacity retention rate (ratio of discharge capacity during low-rate discharge and high-rate discharge) during charging or discharging at a large current of an electricity storage device. The high-rate discharge capacity retention rate is the ratio of discharge capacity during low-rate discharge and high-rate discharge, and a high high-rate discharge capacity retention rate is a characteristic required for an electricity storage device that requires charging or discharging at a large current.
That is, there is still room for improvement in conventional binder compositions in terms of enabling an electricity storage device having a negative electrode using a silicon-based negative electrode active material to exhibit excellent charge-discharge cycle characteristics and a high rate discharge capacity retention rate.
そこで、本開示は、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性および高速放電容量維持率を向上できる蓄電デバイス用重合体、並びにこれを用いた蓄電デバイス用バインダー組成物、蓄電デバイス負極用スラリー組成物、蓄電デバイス用負極及び蓄電デバイスを提供する。 The present disclosure provides a polymer for an electricity storage device that can improve the charge/discharge cycle characteristics and high-rate discharge capacity retention rate of an electricity storage device having a negative electrode that uses a silicon-based negative electrode active material, as well as a binder composition for an electricity storage device, a slurry composition for a negative electrode of an electricity storage device, a negative electrode for an electricity storage device, and an electricity storage device that use the polymer.
本開示は、一態様において、下記式（Ｉ）で表される構成単位を含み、下記式（Ｉ）で表される構成単位の含有量が９５質量％超の、蓄電デバイス用重合体に関する。
本開示は、一態様において、本開示の蓄電デバイス用重合体を含む、蓄電デバイス用バインダー組成物に関する。 In one aspect, the present disclosure relates to a binder composition for an electricity storage device, comprising the polymer for an electricity storage device of the present disclosure.
本開示は、一態様において、シリコン系負極活物質、及び、本開示の蓄電デバイス用重合体、を含む、蓄電デバイス負極用ペーストに関する。 In one aspect, the present disclosure relates to a paste for a negative electrode of an electricity storage device, comprising a silicon-based negative electrode active material and a polymer for an electricity storage device of the present disclosure.
本開示は、一態様において、集電体、及び前記集電体上に形成された合材層を含む蓄電デバイス用負極であって、前記合材層が、シリコン系負極活物質、及び、本開示の蓄電デバイス用重合体、を含む、蓄電デバイス用負極に関する。 In one aspect, the present disclosure relates to a negative electrode for an electricity storage device, comprising a current collector and a composite layer formed on the current collector, the composite layer comprising a silicon-based negative electrode active material and the polymer for an electricity storage device of the present disclosure.
本開示は、本開示の蓄電デバイス用負極を備える、蓄電デバイスに関する。 This disclosure relates to an electricity storage device that includes the electricity storage device negative electrode of this disclosure.
本開示によれば、一態様において、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性および高速放電容量維持率を向上できる蓄電デバイス用重合体を提供できる。 According to one aspect of the present disclosure, it is possible to provide a polymer for an electricity storage device that can improve the charge/discharge cycle characteristics and high-rate discharge capacity retention rate of an electricity storage device having a negative electrode using a silicon-based negative electrode active material.
［蓄電デバイス用重合体］
本開示は、特定の重合体を、一又は複数の実施形態において、蓄電デバイス用バインダーとして使用すれば、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電の繰り返しに伴う負極の膨れを抑制して、蓄電デバイスの電池特性を向上できるという知見に基づく。
すなわち、本開示は、一態様において、上記式（Ｉ）で表される構成単位（以下、「構成単位Ｉ」ともいう）を含み、上記式（Ｉ）で表される構成単位の含有量が９５質量％超の、蓄電デバイス用重合体（以下、「本開示の重合体」ともいう）に関する。本開示の重合体は、一又は複数の実施形態において、構成単位Ｉを含み構成単位Ｉの含有量が９５質量％超の重合体を含む蓄電デバイス用重合体組成物である。
本開示の重合体によれば、一又は複数の実施形態において、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性を向上できる。
[Polymers for Electric Storage Devices]
The present disclosure is based on the finding that, in one or more embodiments, the use of a specific polymer as a binder for an electricity storage device can suppress swelling of the negative electrode that occurs during repeated charging and discharging of an electricity storage device that includes a negative electrode that uses a silicon-based negative electrode active material, thereby improving the battery characteristics of the electricity storage device.
That is, in one aspect, the present disclosure relates to a polymer for an electricity storage device (hereinafter also referred to as the "polymer of the present disclosure") that contains a structural unit represented by formula (I) (hereinafter also referred to as "structural unit I") and has a content of the structural unit represented by formula (I) of more than 95 mass%. In one or more embodiments, the polymer of the present disclosure is a polymer composition for an electricity storage device that contains a polymer that contains structural unit I and has a content of structural unit I of more than 95 mass%.
According to the polymer of the present disclosure, in one or a plurality of embodiments, it is possible to improve the charge/discharge cycle characteristics of an electricity storage device including a negative electrode using a silicon-based negative electrode active material.
本開示の効果発現のメカニズムについては明らかではないが、以下のように推定される。
シリコン系負極活物質は、充放電にともなって膨張・収縮し、体積変化の理論値は３００％を超える。この体積変化によって、シリコン系負極活物質の亀裂・粉砕、及びシリコン系負極活物質表面に形成される被膜（ＳＥＩ）の脱落をもたらすと考えられる。
本開示の重合体は、上記式（Ｉ）で表される構成単位Ｉを含有することで、シリコン系負極活物質への高い吸着性を発揮し、充放電にともなうシリコン系負極活物質の亀裂・粉砕、及びＳＥＩの脱落を抑制できると考えられる。
また、本開示の重合体は、負極層（合材層）と集電体との密着性、及び、シリコン系負極活物質同士の密着性を向上させ、電極（シリコン系負極）の強度を向上できると考えられる。
さらに、本開示の重合体の全構成単位中の構成単位Ｉの含有量が所定量（９５質量％）を超えることで、上述した密着性が十分に確保され、充放電サイクル試験結果も良好なものとなると考えられる。これは、構成単位Ｉが水酸基及びアミド結合を有することで、シリコン系負極活物質との親和性が高くなり、負極層（合材層）と集電体の密着性、及び、シリコン系負極活物質同士の密着性に優れることによるものであると推定される。
また、本開示の重合体を用いた蓄電デバイスでは、高速で充放電するサイクル試験においても放電容量は良好であるので高速放電容量維持率が高く、本開示の重合体は、例えば、電気自動車の急加速を可能とし、パワーツール等への適用が期待できる。これは、上記親和性の向上および密着性の向上に加え、炭化水素基や水酸基が同一分子内に存在する状態で形成されるアミド基の相互ネットワークがＬｉ+の移動を促進して内部抵抗の低下に寄与すること、によるものと推察される。
ただし、これらのメカニズムに限定して解釈されなくてもよい。
The mechanism by which the effects of the present disclosure are manifested is not clear, but is presumed to be as follows.
The silicon-based negative electrode active material expands and contracts during charging and discharging, with the theoretical volume change exceeding 300%. This volume change is believed to cause cracking and crushing of the silicon-based negative electrode active material and the detachment of the coating (SEI) formed on the surface of the silicon-based negative electrode active material.
It is believed that the polymer of the present disclosure, containing the constitutional unit I represented by the above formula (I), exhibits high adsorption properties to the silicon-based negative electrode active material, and can suppress cracking and crushing of the silicon-based negative electrode active material and falling off of the SEI that accompanies charge and discharge.
In addition, the polymer of the present disclosure is believed to improve the adhesion between the negative electrode layer (mixture layer) and the current collector, and between silicon-based negative electrode active materials, thereby improving the strength of the electrode (silicon-based negative electrode).
Furthermore, when the content of the structural unit I in all the structural units of the polymer of the present disclosure exceeds a predetermined amount (95% by mass), the above-mentioned adhesion is sufficiently ensured, and it is considered that the result of the charge-discharge cycle test is also good. This is presumably because the structural unit I has a hydroxyl group and an amide bond, which increases the affinity with the silicon-based negative electrode active material, resulting in excellent adhesion between the negative electrode layer (mixture layer) and the current collector, and between the silicon-based negative electrode active materials themselves.
Furthermore, in an electricity storage device using the polymer of the present disclosure, the discharge capacity is good even in a cycle test in which charging and discharging is performed at high speed, and therefore the high-speed discharge capacity retention rate is high, and the polymer of the present disclosure is expected to enable, for example, rapid acceleration of an electric vehicle and to be applied to power tools, etc. This is presumably due to the above-mentioned improvement in affinity and adhesion, as well as the fact that the mutual network of amide groups formed in a state in which a hydrocarbon group and a hydroxyl group exist in the same molecule promotes the movement of Li + and contributes to a decrease in internal resistance.
However, it is not necessary to interpret the present invention as being limited to these mechanisms.
＜式（Ｉ）で表される構成単位（構成単位Ｉ）＞
本開示の重合体は、下記式（Ｉ）で表される構成単位（構成単位Ｉ）を含む。構成単位Ｉは、１種でもよいし、２種以上の組合せでもよい。
The polymer of the present disclosure contains a structural unit (structural unit I) represented by the following formula (I): The structural unit I may be one type, or a combination of two or more types.
前記式（Ｉ）中、Ｒ1は、水素原子又はメチル基であり、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、水素原子が好ましい。
Ｒ2は、水素原子、炭素数１以上４以下の炭化水素基、又は、１個以上３個以下の水酸基を有する直鎖もしくは分岐鎖の炭素数１以上４以下の炭化水素基であり、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、水素原子が好ましい。
Ｒ3は、１個以上３個以下の水酸基を有する直鎖又は分岐鎖の炭素数１以上４以下の炭化水素基であり、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、１個の水酸基を有する直鎖又は分岐鎖の炭素数２以上３以下の炭化水素基が好ましく、１個の水酸基を有する直鎖の炭素数２の炭化水素基がより好ましい。
In the formula (I), R 1 is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device having a negative electrode using a silicon-based negative electrode active material.
R2 is a hydrogen atom, a hydrocarbon group having from 1 to 4 carbon atoms, or a linear or branched hydrocarbon group having from 1 to 4 carbon atoms and having from 1 to 3 hydroxyl groups. From the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device including a negative electrode using a silicon-based negative electrode active material, a hydrogen atom is preferred.
R3 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms and having 1 to 3 hydroxyl groups. From the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device including a negative electrode using a silicon-based negative electrode active material, R3 is preferably a linear or branched hydrocarbon group having 2 to 3 carbon atoms and one hydroxyl group, and more preferably a linear hydrocarbon group having 2 carbon atoms and one hydroxyl group.
本開示の重合体の全構成単位中の構成単位Ｉの含有量は、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、９５質量％を超え、９８質量％以上が好ましく、９９質量％以上がより好ましく、１００質量％が更に好ましい。 The content of structural unit I in all structural units of the polymer of the present disclosure is more than 95% by mass, preferably 98% by mass or more, more preferably 99% by mass or more, and even more preferably 100% by mass, from the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device having a negative electrode using a silicon-based negative electrode active material.
構成単位Ｉを形成するモノマーとしては、例えば、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、Ｎ－（２－ヒドロキシプロピル）アクリルアミド、Ｎ－ヒドロキシメチルメタクリルアミド、Ｎ－ヒドロキシエチルメタクリルアミド、Ｎ－（２－ヒドロキシプロピル）メタクリルアミド、及びＮ－［トリス（ヒドロキシメチル）メチル］アクリルアミドから選ばれる少なくとも１種が挙げられ、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、Ｎ－ヒドロキシエチルアクリルアミド及びＮ－（２－ヒドロキシプロピル）アクリルアミドから選ばれる少なくとも１種が好ましく、Ｎ－ヒドロキシエチルアクリルアミドがより好ましい。 Examples of monomers forming structural unit I include at least one selected from N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N-(2-hydroxypropyl)acrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-(2-hydroxypropyl)methacrylamide, and N-[tris(hydroxymethyl)methyl]acrylamide. From the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device having a negative electrode using a silicon-based negative electrode active material, at least one selected from N-hydroxyethylacrylamide and N-(2-hydroxypropyl)acrylamide is preferred, with N-hydroxyethylacrylamide being more preferred.
＜他の構成単位（構成単位ＩＩ）＞
本開示の重合体は、構成単位Ｉ以外の他の構成単位（以下、「構成単位ＩＩ」ともいう）をさらに含んでもよい。本開示の重合体の全構成単位中の構成単位ＩＩの含有量は、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性の向上の観点から、５質量％を下回り、好ましくは２質量％以下、より好ましくは１質量％以下、更に好ましくは０質量％である。
構成単位ＩＩを形成するモノマーとしては、(メタ）アクリル酸などの酸モノマー、（メタ）アクリル酸エステルのモノマー、構成単位Ｉを形成するモノマー以外の（メタ）アクリルアミドモノマー等が挙げられる。（メタ）アクリル酸エステルのモノマーとしては、例えばポリエチレングリコール（メタ）アクリレート、炭素数１２以下のアルキル（メタ）アクリレート等が挙げられる。構成単位Ｉを形成するモノマー以外の（メタ）アクリルアミドモノマーとしては、例えばジメチルアクリルアミド、ジアセトンアクリルアミド、ｔｅｒｔ－ブチルアクリルアミド等が挙げられる。
<Other structural units (structural unit II)>
The polymer of the present disclosure may further include a structural unit (hereinafter also referred to as "structural unit II") other than the structural unit I. The content of the structural unit II in all structural units of the polymer of the present disclosure is less than 5 mass%, preferably 2 mass% or less, more preferably 1 mass% or less, and even more preferably 0 mass%, from the viewpoint of improving the charge-discharge cycle characteristics of an electricity storage device including a negative electrode using a silicon-based negative electrode active material.
Examples of monomers that form the structural unit II include acid monomers such as (meth)acrylic acid, (meth)acrylic acid ester monomers, and (meth)acrylamide monomers other than the monomers that form the structural unit I. Examples of (meth)acrylic acid ester monomers include polyethylene glycol (meth)acrylate and alkyl (meth)acrylates having 12 or less carbon atoms. Examples of (meth)acrylamide monomers other than the monomers that form the structural unit I include dimethylacrylamide, diacetoneacrylamide, and tert-butylacrylamide.
本開示の重合体としては、例えば、ヒドロキシエチルアクリルアミド重合体、ヒドロキシエチルアクリルアミド／ポリエチレングリコール（メタ）アクリレート共重合体、及び、ヒドロキシエチルアクリルアミド／アクリル酸共重合体から選ばれる少なくとも１種が挙げられる。 The polymer of the present disclosure may be, for example, at least one selected from hydroxyethylacrylamide polymer, hydroxyethylacrylamide/polyethylene glycol (meth)acrylate copolymer, and hydroxyethylacrylamide/acrylic acid copolymer.
本開示の重合体は、例えば、構成単位Ｉを形成するモノマー及び必要に応じて構成単位ＩＩを形成するモノマーを重合させることによって製造できる。重合法としては、例えば、乳化重合法、溶液重合法、懸濁重合法、塊状重合法等の公知の重合法が挙げられる。 The polymer of the present disclosure can be produced, for example, by polymerizing a monomer that forms structural unit I and, if necessary, a monomer that forms structural unit II. Examples of the polymerization method include known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.
本開示の重合体の重量平均分子量は、シリコン系負極活物質と集電体との密着性の観点から、好ましくは５万以上、より好ましくは１０万以上、更に好ましくは３０万以上、更に好ましくは５０万以上であり、そして、負極ペーストのハンドリング性の観点から、好ましくは３００万以下、より好ましく２００万以下、更に好ましくは１００万以下である。本開示において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した値であり、測定条件の詳細は実施例に示すとおりである。 The weight average molecular weight of the polymer of the present disclosure is preferably 50,000 or more, more preferably 100,000 or more, even more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of adhesion between the silicon-based negative electrode active material and the current collector, and is preferably 3 million or less, more preferably 2 million or less, and even more preferably 1 million or less, from the viewpoint of handleability of the negative electrode paste. In the present disclosure, the weight average molecular weight is a value measured by gel permeation chromatography (GPC), and the details of the measurement conditions are as shown in the examples.
本開示の重合体は、一又は複数の実施形態において、蓄電デバイスの負極用バインダーとして使用することができる。すなわち、本開示は、一態様において、本開示の重合体の、蓄電デバイス負極用バインダーとしての使用に関する。 In one or more embodiments, the polymer of the present disclosure can be used as a binder for the negative electrode of an electricity storage device. That is, in one aspect, the present disclosure relates to the use of the polymer of the present disclosure as a binder for the negative electrode of an electricity storage device.
［蓄電デバイス用バインダー組成物］
本開示は、一態様において、本開示の重合体を含む、蓄電デバイス用バインダー組成物（以下、「本開示のバインダー組成物」ともいう）に関する。本開示のバインダー組成物によれば、一又は複数の実施形態において、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性を向上できる。
[Binder composition for power storage device]
In one aspect, the present disclosure relates to a binder composition for an electricity storage device (hereinafter also referred to as the "binder composition of the present disclosure") that contains the polymer of the present disclosure. In one or more embodiments, the binder composition of the present disclosure can improve the charge-discharge cycle characteristics of an electricity storage device that includes a negative electrode using a silicon-based negative electrode active material.
＜重合体＞
本開示のバインダー組成物に含まれる本開示の重合体は、１種でもよいし、２種以上の組合せでもよい。
本開示のバインダー組成物中の本開示の重合体の含有量は、電極作成時の配合性の観点から、１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上が更に好ましく、そして、粘度が増加してハンドリング性が低下するのを抑制する観点から、５０質量％以下が好ましく、４５質量以下がより好ましく、４０質量％以下が更に好ましい。本開示の重合体が２種以上の組合せである場合、本開示の重合体の含有量はそれらの合計含有量である。
<Polymer>
The polymer of the present disclosure contained in the binder composition of the present disclosure may be one type or a combination of two or more types.
The content of the polymer of the present disclosure in the binder composition of the present disclosure is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more from the viewpoint of blendability during electrode production, and is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less from the viewpoint of suppressing a decrease in handleability due to an increase in viscosity. When the polymer of the present disclosure is a combination of two or more types, the content of the polymer of the present disclosure is the total content thereof.
＜溶媒＞
本開示のバインダー組成物は、一又は複数の実施形態において、本開示の重合体を含む溶液であり、溶媒を含有する。溶媒としては、水が挙げられる。
<Solvent>
In one or more embodiments, the binder composition of the present disclosure is a solution containing the polymer of the present disclosure and contains a solvent. The solvent may be water.
＜その他の成分＞
本開示のバインダー組成物は、本開示の効果を損なわない範囲で、本開示の重合体及び溶媒以外にその他の成分を含有してもよい。その他の成分としては、例えば、界面活性剤、増粘剤、消泡剤、分散剤、防腐剤、及び中和剤から選ばれる少なくとも１種が挙げられる。
<Other ingredients>
The binder composition of the present disclosure may contain other components in addition to the polymer and solvent of the present disclosure, as long as the effects of the present disclosure are not impaired. Examples of other components include at least one selected from a surfactant, a thickener, a defoamer, a dispersant, a preservative, and a neutralizer.
本開示のバインダー組成物は、例えば、溶媒中で、本開示の重合体及び必要に応じて上述したその他の成分を、公知の方法で混合することにより調製することができる。混合方法としては、例えば、ボールミル、ビーズミル、超音波分散機等が挙げられる。 The binder composition of the present disclosure can be prepared, for example, by mixing the polymer of the present disclosure and, if necessary, the other components described above in a solvent by a known method. Examples of mixing methods include a ball mill, a bead mill, an ultrasonic disperser, etc.
［蓄電デバイス負極用ペースト］
本開示の重合体及び本開示のバインダー組成物は、蓄電デバイス負極用ペーストの調製に用いることができる。すなわち、本開示は、一態様において、シリコン系負極活物質、及び、本開示の重合体を含む、蓄電デバイス負極用ペースト（以下、「本開示の負極ペースト」ともいう）に関する。本開示の負極ペーストは、一又は複数の実施形態において、シリコン系負極活物質、及び、本開示のバインダー組成物を含むものである。本開示の負極ペーストは、一又は複数の実施形態において、蓄電池用シリコン系負極ペースト（シリコン系負極ペースト）である。本開示の負極ペーストによれば、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性を向上できる。
[Paste for negative electrodes of electricity storage devices]
The polymer of the present disclosure and the binder composition of the present disclosure can be used to prepare a paste for a negative electrode of an electric storage device. That is, in one aspect, the present disclosure relates to a paste for a negative electrode of an electric storage device (hereinafter also referred to as the "negative electrode paste of the present disclosure") that contains a silicon-based negative electrode active material and a polymer of the present disclosure. In one or more embodiments, the negative electrode paste of the present disclosure contains a silicon-based negative electrode active material and a binder composition of the present disclosure. In one or more embodiments, the negative electrode paste of the present disclosure is a silicon-based negative electrode paste for a storage battery (silicon-based negative electrode paste). According to the negative electrode paste of the present disclosure, the charge and discharge cycle characteristics of an electric storage device including a negative electrode using a silicon-based negative electrode active material can be improved.
＜シリコン系負極活物質＞
シリコン系負極活物質としては、一又は複数の実施形態において、ケイ素（Ｓｉ）、ケイ素を含む合金、ＳｉＯ、ＳｉＯx、あるいは、Ｓｉ含有材料を導電性カーボンで被覆または複合化されたＳｉ含有材料等が挙げられる。シリコン系負極活物質は、１種でもよいし、２種以上の組合せでもよい。
シリコン系負極活物質の平均粒径は、蓄電デバイスの充放電サイクル特性向上の観点から、０．０１μｍ以上が好ましく、０．１５μｍ以上がより好ましく、０．５μｍ以上が更に好ましく、そして、蓄電デバイスの充放電サイクル特性向上の観点から、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下が更に好ましい。シリコン系負極活物質の平均粒径は、レーザー回折散乱法によって測定される体積平均粒径（Ｄ50）であり、体積基準で求めた粒度分布の全体積を１００％とした累積体積分布曲線において、小粒径側からの累積体積が５０％となる点の粒子径を意味する。体積平均粒径（Ｄ50）は、レーザー回折／散乱式粒子径分布測定装置を用いて測定でき、具体的には実施例に記載の方法で測定できる。
本開示の負極ペースト中のシリコン系負極活物質の含有量は、蓄電デバイスの高容量化の観点から、０．５質量％以上が好ましく、１．５質量％以上がより好ましく、２質量％以上が更に好ましく、そして、蓄電デバイスの充放電サイクル特性向上の観点から、７０質量％以下が好ましく、４０質量％以下がより好ましく、２０質量％以下が更に好ましい。本開示のシリコン系負極活物質が２種以上の組合せである場合、本開示の負極ペースト中のシリコン系負極活物質の含有量はそれらの合計含有量である。
<Silicon-based negative electrode active material>
In one or more embodiments, the silicon-based negative electrode active material may be silicon (Si), an alloy containing silicon, SiO, SiO x , or a Si-containing material coated or composited with conductive carbon. The silicon-based negative electrode active material may be one type or a combination of two or more types.
The average particle size of the silicon-based negative electrode active material is preferably 0.01 μm or more, more preferably 0.15 μm or more, and even more preferably 0.5 μm or more from the viewpoint of improving the charge/discharge cycle characteristics of the power storage device, and is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less from the viewpoint of improving the charge/discharge cycle characteristics of the power storage device. The average particle size of the silicon-based negative electrode active material is the volume average particle size (D 50 ) measured by a laser diffraction scattering method, and means the particle size at the point where the cumulative volume from the small particle size side is 50% in the cumulative volume distribution curve where the total volume of the particle size distribution obtained on a volume basis is 100%. The volume average particle size (D 50 ) can be measured using a laser diffraction/scattering type particle size distribution measuring device, and specifically, can be measured by the method described in the examples.
The content of the silicon-based negative electrode active material in the negative electrode paste of the present disclosure is preferably 0.5 mass% or more, more preferably 1.5 mass% or more, and even more preferably 2 mass% or more from the viewpoint of increasing the capacity of the power storage device, and is preferably 70 mass% or less, more preferably 40 mass% or less, and even more preferably 20 mass% or less from the viewpoint of improving the charge/discharge cycle characteristics of the power storage device. When the silicon-based negative electrode active material of the present disclosure is a combination of two or more types, the content of the silicon-based negative electrode active material in the negative electrode paste of the present disclosure is the total content thereof.
＜重合体＞
本開示の負極ペーストに含まれる本開示の重合体は、１種でもよいし、２種以上の組合せでもよい。
本開示の負極ペースト中の本開示の重合体の含有量は、重合体と集電体との密着性の観点から、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下が更に好ましい。本開示の重合体が２種以上の組合せである場合、本開示の負極ペースト中の本開示の重合体の含有量はそれらの合計含有量である。
本開示の負極ペースト中における、シリコン系負極活物質と本開示の重合体との含有比としては、本開示の重合体の含有量が、シリコン系負極活物質１００質量部に対して、シリコン系負極活物質と集電体との密着性の観点から、０．１質量部以上が好ましく、１質量部以上がより好ましく、５質量部以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下が更に好ましい。
<Polymer>
The polymer of the present disclosure contained in the negative electrode paste of the present disclosure may be one type or a combination of two or more types.
The content of the polymer of the present disclosure in the negative electrode paste of the present disclosure is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and even more preferably 0.5 mass% or more from the viewpoint of adhesion between the polymer and the current collector, and is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less from the viewpoint of increasing the capacity of the electricity storage device. When the polymer of the present disclosure is a combination of two or more types, the content of the polymer of the present disclosure in the negative electrode paste of the present disclosure is the total content thereof.
The content ratio of the silicon-based negative electrode active material to the polymer of the present disclosure in the negative electrode paste of the present disclosure is, from the viewpoint of adhesion between the silicon-based negative electrode active material and the current collector, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the silicon-based negative electrode active material, and from the viewpoint of increasing the capacity of the electricity storage device, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less.
＜分散媒＞
本開示の負極ペーストは、一又は複数の実施形態において、分散媒を含む。分散媒としては、例えば、水が挙げられる。
<Dispersion medium>
In one or more embodiments, the negative electrode paste of the present disclosure includes a dispersion medium. Examples of the dispersion medium include water.
＜その他の成分＞
本開示の負極ペーストは、上述した成分以外のその他の成分を含有してもよい。その他の成分としては、一又は複数の実施形態において、シリコン系負極活物質以外の負極活物質、導電材、増粘剤等が挙げられる。
シリコン系負極活物質以外の負極活物質としては、グラファイト等の黒鉛系負極活物質が挙げられる。本開示の負極ペーストが黒鉛系負極活物質を含む場合、本開示の負極ペースト中の黒鉛系負極活物質の含有量は、蓄電デバイスの充放電サイクル特性向上の観点から、０．５質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、７０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下が更に好ましい。黒鉛系負極活物質が２種以上の組合せである場合、本開示の負極ペースト中の黒鉛系負極活物質の含有量はそれらの合計含有量である。
導電材としては、蓄電デバイスに使用可能な公知の導電材であればよく、例えば、アセチレンブラック、ケッチェンブラック、黒鉛、カーボンナノチューブ等の炭素材料が挙げられる。本開示の負極ペーストが導電材を含む場合、本開示の負極ペースト中の導電材の含有量は、蓄電デバイスの抵抗性の観点から、０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．２質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、２質量％以下が好ましく、１．５質量％以下がより好ましく、１質量％以下が更に好ましい。導電材が２種以上の組合せである場合、本開示の負極ペースト中の導電材の含有量はそれらの合計含有量である。
増粘剤としては、例えば、カルボキシメチルセルロース（ＣＭＣ）等が挙げられる。本開示の負極ペーストが増粘剤を含む場合、本開示の負極ペースト中の増粘剤の含有量は、負極ペーストの塗工性の観点から、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、２質量％以下が好ましく、１．５質量％以下がより好ましく、１質量％以下が更に好ましい。増粘剤が２種以上の組合せである場合、本開示の負極ペースト中の増粘剤の含有量はそれらの合計含有量である。
<Other ingredients>
The negative electrode paste of the present disclosure may contain other components in addition to the above-mentioned components. In one or more embodiments, the other components may include a negative electrode active material other than a silicon-based negative electrode active material, a conductive material, a thickener, and the like.
Examples of the negative electrode active material other than the silicon-based negative electrode active material include graphite-based negative electrode active materials such as graphite. When the negative electrode paste of the present disclosure contains a graphite-based negative electrode active material, the content of the graphite-based negative electrode active material in the negative electrode paste of the present disclosure is preferably 0.5 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more from the viewpoint of improving the charge-discharge cycle characteristics of the power storage device, and is preferably 70 mass% or less, more preferably 60 mass% or less, and even more preferably 50 mass% or less from the viewpoint of increasing the capacity of the power storage device. When the graphite-based negative electrode active material is a combination of two or more types, the content of the graphite-based negative electrode active material in the negative electrode paste of the present disclosure is the total content thereof.
The conductive material may be any known conductive material that can be used in an electricity storage device, such as acetylene black, ketjen black, graphite, carbon materials such as carbon nanotubes, etc. When the negative electrode paste of the present disclosure contains a conductive material, the content of the conductive material in the negative electrode paste of the present disclosure is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more from the viewpoint of the resistance of the electricity storage device, and is preferably 2 mass% or less, more preferably 1.5 mass% or less, and even more preferably 1 mass% or less from the viewpoint of increasing the capacity of the electricity storage device. When the conductive material is a combination of two or more types, the content of the conductive material in the negative electrode paste of the present disclosure is the total content thereof.
Examples of thickeners include carboxymethyl cellulose (CMC). When the negative electrode paste of the present disclosure contains a thickener, the content of the thickener in the negative electrode paste of the present disclosure is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more from the viewpoint of the coatability of the negative electrode paste, and is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less from the viewpoint of increasing the capacity of the power storage device. When the thickener is a combination of two or more types, the content of the thickener in the negative electrode paste of the present disclosure is the total content thereof.
本開示の負極ペースト中の固形分濃度は、蓄電デバイスの生産性の観点から、２０質量％以上が好ましく、３０質量％以上がより好ましく、３５質量％以上が更に好ましく、そして、負極ペーストのハンドリング性の観点から、８０質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下が更に好ましい。 From the viewpoint of productivity of the electric storage device, the solids concentration in the negative electrode paste of the present disclosure is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, and from the viewpoint of the handleability of the negative electrode paste, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
＜本開示の負極ペーストの調製方法＞
本開示の負極ペーストは、シリコン系負極活物質、本開示の重合体、分散媒、及び必要に応じてその他の成分を混合することにより調製できる。混合方法としては、例えば、ボールミル、ビーズミル、超音波分散機等を用いる方法が挙げられる。
<Method of preparing negative electrode paste according to the present disclosure>
The negative electrode paste of the present disclosure can be prepared by mixing a silicon-based negative electrode active material, a polymer of the present disclosure, a dispersion medium, and other components as necessary. Examples of the mixing method include a method using a ball mill, a bead mill, an ultrasonic disperser, etc.
［蓄電デバイス用負極］
本開示の重合体、本開示のバインダー組成物、及び本開示の負極ペーストは、蓄電デバイス用電極（負極）の合材層の作製に使用することができる。
すなわち、本開示は、一態様において、集電体、及び前記集電体上に形成された合材層を含む蓄電デバイス用負極であって、前記合材層が、シリコン系負極活物質及び本開示の重合体を含む、蓄電デバイス用負極（以下、「本開示の負極」ともいう）に関する。本開示の負極における前記合材層は、一又は複数の実施形態において、シリコン系負極活物質及び本開示のバインダー組成物を含むものである。本開示の負極によれば、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性を向上できる。
[Negative electrode for electricity storage device]
The polymer of the present disclosure, the binder composition of the present disclosure, and the negative electrode paste of the present disclosure can be used to produce a composite layer of an electrode (negative electrode) for an electricity storage device.
That is, in one aspect, the present disclosure relates to a negative electrode for an electricity storage device (hereinafter also referred to as the "negative electrode of the present disclosure") that includes a current collector and a composite layer formed on the current collector, the composite layer including a silicon-based negative electrode active material and a polymer of the present disclosure. In one or more embodiments, the composite layer in the negative electrode of the present disclosure includes a silicon-based negative electrode active material and a binder composition of the present disclosure. The negative electrode of the present disclosure can improve the charge and discharge cycle characteristics of an electricity storage device that includes a negative electrode using a silicon-based negative electrode active material.
＜集電体＞
前記集電体としては、導電性を有する材料から選ぶことができ、例えば、銅箔、ニッケル箔、アルミニウム箔、ステンレス箔等の金属箔が挙げられる。
<Current collector>
The current collector can be selected from materials having electrical conductivity, and examples thereof include metal foils such as copper foil, nickel foil, aluminum foil, and stainless steel foil.
＜合材層＞
前記合材層は、例えば、シリコン系負極活物質及び本開示の重合体を含む本開示の負極ペーストを集電体上に塗布し、前記負極ペースト中の溶媒を乾燥除去することにより得ることができる。
負極ペースト（スラリー）を集電体に塗布する方法としては、公知の塗布方法を用いることができ、例えば、グラビア法、リバースロール法、ダイレクトロール法、ドクターブレード法等が挙げられる。
負極ペーストは集電体の片面だけに塗布してもよいし、両面に塗布してもよい。塗膜の厚みは、乾燥後に得られる合材層の厚みに応じて適宜設定できる。
負極ペーストを乾燥する方法としては、公知の乾燥方法を用いることができ、例えば、温風等による乾燥法、真空乾燥法、赤外線照射等による乾燥法が挙げられる。
前記合材層は、一又は複数の実施形態において、シリコン系負極活物質、本開示の重合体、必要に応じてその他の成分を含む。その他の成分としては、上述した本開示の負極ペーストのその他の成分と同じものが挙げられる。
（シリコン系負極活物質）
前記合材層中のシリコン系負極活物質の含有量は、電池エネルギー密度の確保の観点から、１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上が更に好ましく、そして、シリコン系負極活物質の膨張収縮による負極の劣化抑制の観点から、９９．８質量％以下が好ましく、８０質量％以下がより好ましく、５０質量％以下が更に好ましく、３０質量％以下が更に好ましい。シリコン系負極活物質が２種以上の組合せである場合、合材層中のシリコン系負極活物質の含有量はそれらの合計含有量である。
（重合体）
前記合材層中の本開示の重合体の含有量は、シリコン系負極活物質と集電体との密着性の観点から、０．２質量％以上が好ましく、０．５質量％以上がより好ましく、１質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、２０質量％以下が好ましく、１０質量％以下がより好ましく、５質量％以下が更に好ましい。本開示の重合体が２種以上の組合せである場合、合材層中の本開示の重合体の含有量はそれらの合計含有量である。
前記合材層中におけるシリコン系負極活物質と本開示の重合体の含有比としては、本開示の重合体の含有量が、シリコン系負極活物質１００質量部に対して、シリコン系負極活物質同士の密着性の観点から、好ましくは０．１質量部以上、より好ましくは１質量部以上、更に好ましくは１０質量部以上、そして、蓄電デバイスの高容量化の観点から、好ましくは２００質量部以下、より好ましくは１００質量部以下、更に好ましくは５０質量部以下である。
（その他の成分）
本開示の合材層が黒鉛系負極活物質を含む場合、前記合材層中の黒鉛系負極活物質の含有量は、蓄電デバイスの充放電サイクル特性向上の観点から、１質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、９８．８質量％以下が好ましく、９７質量％以下がより好ましく、９５質量％以下が更に好ましい。本開示の黒鉛系負極活物質が２種以上の組合せである場合、合材層中の黒鉛系負極活物質の含有量はそれらの合計含有量である。
本開示の合材層が導電材を含む場合、前記合材層中の導電材の含有量は、蓄電デバイスの抵抗性の観点から、０．０２質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、３質量％以下が好ましく、２．５質量％以下がより好ましく、２質量％以下が更に好ましい。本開示の黒鉛系負極活物質が２種以上の組合せである場合、合材層中の導電材の含有量はそれらの合計含有量である。
本開示の合材層が増粘剤を含む場合、前記合材層中の増粘剤の含有量は、負極ペーストの塗工性の観点から、０．２質量％以上が好ましく、０．５質量％以上がより好ましく、１質量％以上が更に好ましく、そして、蓄電デバイスの高容量化の観点から、５質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましい。本開示の増粘剤が２種以上の組合せである場合、合材層中の増粘剤の含有量はそれらの合計含有量である。
<Composite layer>
The mixture layer can be obtained, for example, by applying the negative electrode paste of the present disclosure containing a silicon-based negative electrode active material and the polymer of the present disclosure onto a current collector, and then drying and removing the solvent in the negative electrode paste.
The method for applying the negative electrode paste (slurry) to the current collector can be a known application method, such as a gravure method, a reverse roll method, a direct roll method, or a doctor blade method.
The negative electrode paste may be applied to only one side of the current collector or to both sides of the current collector. The thickness of the coating film can be appropriately set depending on the thickness of the mixture layer obtained after drying.
The negative electrode paste can be dried by a known drying method, for example, drying using hot air or the like, vacuum drying, drying using infrared radiation or the like.
In one or more embodiments, the composite layer contains a silicon-based negative electrode active material, a polymer according to the present disclosure, and other components as necessary. Examples of the other components include the same components as those of the negative electrode paste according to the present disclosure described above.
(Silicon-based negative electrode active material)
The content of the silicon-based negative electrode active material in the composite layer is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more from the viewpoint of ensuring the battery energy density, and is preferably 99.8% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less, and even more preferably 30% by mass or less from the viewpoint of suppressing deterioration of the negative electrode due to expansion and contraction of the silicon-based negative electrode active material. When the silicon-based negative electrode active material is a combination of two or more types, the content of the silicon-based negative electrode active material in the composite layer is the total content thereof.
(Polymer)
The content of the polymer of the present disclosure in the mixture layer is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more from the viewpoint of adhesion between the silicon-based negative electrode active material and the current collector, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less from the viewpoint of increasing the capacity of the power storage device. When the polymer of the present disclosure is a combination of two or more types, the content of the polymer of the present disclosure in the mixture layer is the total content thereof.
Regarding the content ratio of the silicon-based negative electrode active material and the polymer of the present disclosure in the composite layer, the content of the polymer of the present disclosure is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the silicon-based negative electrode active material, from the viewpoint of adhesion between silicon-based negative electrode active materials, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, from the viewpoint of increasing the capacity of the electricity storage device.
(Other ingredients)
When the composite layer of the present disclosure contains a graphite-based negative electrode active material, the content of the graphite-based negative electrode active material in the composite layer is preferably 1 mass% or more, more preferably 10 mass% or more, and even more preferably 20 mass% or more from the viewpoint of improving the charge/discharge cycle characteristics of the power storage device, and is preferably 98.8 mass% or less, more preferably 97 mass% or less, and even more preferably 95 mass% or less from the viewpoint of increasing the capacity of the power storage device. When the graphite-based negative electrode active material of the present disclosure is a combination of two or more types, the content of the graphite-based negative electrode active material in the composite layer is the total content thereof.
When the composite layer of the present disclosure contains a conductive material, the content of the conductive material in the composite layer is preferably 0.02 mass% or more, more preferably 0.2 mass% or more, and even more preferably 0.5 mass% or more from the viewpoint of the resistance of the power storage device, and is preferably 3 mass% or less, more preferably 2.5 mass% or less, and even more preferably 2 mass% or less from the viewpoint of increasing the capacity of the power storage device. When the graphite-based negative electrode active material of the present disclosure is a combination of two or more types, the content of the conductive material in the composite layer is the total content thereof.
When the mixture layer of the present disclosure contains a thickener, the content of the thickener in the mixture layer is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more from the viewpoint of coatability of the negative electrode paste, and is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less from the viewpoint of increasing the capacity of the power storage device. When the thickener of the present disclosure is a combination of two or more types, the content of the thickener in the mixture layer is the total content thereof.
［蓄電デバイス］
本開示は、一態様において、本開示の負極を備える蓄電デバイス（以下、「本開示の蓄電デバイス」ともいう）に関する。本開示によれば、優れた充放電サイクル特性を有する蓄電デバイスを提供できる。
本開示の蓄電デバイスとしては、一又は複数の実施形態において、リチウムイオン二次電池、リチウム空気二次電池、リチウム－硫黄二次電池、ナトリウムイオン二次電池、ナトリウム－硫黄二次電池、ナトリウム－塩化ニッケル二次電池、有機ラジカル電池、亜鉛－空気二次電池、全固体電池等が挙げられる。
[Electricity storage device]
According to one aspect, the present disclosure relates to an electricity storage device including a negative electrode of the present disclosure (hereinafter also referred to as an "electricity storage device of the present disclosure"). According to the present disclosure, it is possible to provide an electricity storage device having excellent charge-discharge cycle characteristics.
In one or a plurality of embodiments, the power storage device of the present disclosure may include a lithium ion secondary battery, a lithium-air secondary battery, a lithium-sulfur secondary battery, a sodium ion secondary battery, a sodium-sulfur secondary battery, a sodium-nickel chloride secondary battery, an organic radical battery, a zinc-air secondary battery, and an all-solid-state battery.
本開示の蓄電デバイスは、一又は複数の実施形態は、本開示の負極、及び、電解液を含む蓄電デバイスである。電解液としては、溶媒と電解質を含むものが挙げられ、溶媒として、例えば、水、イオン液体、あるいは、エチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）等のカーボネート類が挙げられ、電解質としては、金属塩が挙げられ、例えば、ＬｉＰＦ6などのリチウム塩が挙げられる。
本開示の蓄電デバイスは、例えば、公知の蓄電デバイス製造方法により製造できる。蓄電デバイスの製造方法としては、例えば、２つの電極（正極及び負極）を、セパレータを介して重ね合わせ、電池形状に捲回あるいは積層させて、電池容器あるいはラミネート容器に入れ、容器に電解液を注入して封口する方法が挙げられる。
One or more embodiments of the power storage device of the present disclosure are power storage devices including the negative electrode of the present disclosure and an electrolyte solution. The electrolyte solution may include a solvent and an electrolyte, and examples of the solvent include water, an ionic liquid, or carbonates such as ethylene carbonate (EC) and diethyl carbonate (DEC), and examples of the electrolyte include metal salts, such as lithium salts such as LiPF6 .
The electricity storage device of the present disclosure can be manufactured by, for example, a known method for manufacturing an electricity storage device, for example, a method in which two electrodes (a positive electrode and a negative electrode) are stacked with a separator interposed therebetween, wound or laminated into a battery shape, placed in a battery container or a laminate container, and an electrolyte is poured into the container and sealed.
本願は、さらに以下の蓄電デバイス用重合体、蓄電デバイス用バインダー組成物、および蓄電デバイス負極用ペースト等を開示する。 This application further discloses the following polymers for electricity storage devices, binder compositions for electricity storage devices, and pastes for negative electrodes of electricity storage devices.
［１］ 下記式（Ｉ）で表される構成単位を含み、
下記式（Ｉ）で表される構成単位の含有量が９５質量％超の、蓄電デバイス用重合体。
［２］ Ｒ1が、水素原子である、前記［１］に記載の蓄電デバイス用重合体。
［３］ Ｒ2が、水素原子である、前記［１］又は［２］に記載の蓄電デバイス用重合体。
［４］ Ｒ3が、１個の水酸基を有する直鎖の炭素数２の炭化水素基である、前記［１］から［３］のいずれかに記載の蓄電デバイス用重合体。
［５］ 重量平均分子量が、５万以上３００万以上である、前記［１］から［４］のいずれかに記載の蓄電デバイス用重合体。
［６］ 前記（Ｉ）で表される構成単位の含有量が１００質量％である、前記［１］から［５］のいずれかに記載の蓄電デバイス用重合体。
［７］ 前記［１］から［６］のいずれかに記載の蓄電デバイス用重合体と溶媒とを含む、蓄電デバイス用バインダー組成物。
［８］ シリコン系負極活物質と、前記［１］から［６］のいずれかに記載の蓄電デバイス用重合体とを含む、蓄電デバイス負極用ペースト。
［９］ 集電体と、前記集電体上に形成された合材層とを含む蓄電デバイス用負極であって、
前記合材層が、シリコン系負極活物質、及び、前記［１］から［６］のいずれかに記載の蓄電デバイス用重合体を含む、蓄電デバイス用負極。
［10］ 前記［９］に記載の蓄電デバイス用負極を備える、蓄電デバイス。
［11］ 蓄電デバイス用バインダー組成物の製造のための前記［１］から［６］のいずれか１つに記載の蓄電デバイス用重合体の使用。
［12］ 蓄電デバイス負極用ペーストの製造のための前記［１］から［６］のいずれか１つに記載の蓄電デバイス用重合体の使用。
［13］ 蓄電デバイス用負極の製造のための前記［１］から［６］のいずれか１つに記載の蓄電デバイス用重合体の使用。
[1] Contains a structural unit represented by the following formula (I):
A polymer for an electricity storage device, comprising a structural unit represented by the following formula (I) in an amount of more than 95 mass %:
[2] The polymer for an electricity storage device according to the above [1], wherein R 1 is a hydrogen atom.
[3] The polymer for an electricity storage device according to the above [1] or [2], wherein R 2 is a hydrogen atom.
[4] The polymer for an electricity storage device according to any one of the above [1] to [3], wherein R 3 is a linear hydrocarbon group having 2 carbon atoms and one hydroxyl group.
[5] The polymer for an electricity storage device according to any one of [1] to [4] above, having a weight average molecular weight of 50,000 or more and 3,000,000 or more.
[6] The polymer for an electricity storage device according to any one of [1] to [5] above, wherein the content of the structural unit represented by (I) is 100 mass %.
[7] A binder composition for an electricity storage device, comprising the polymer for an electricity storage device according to any one of [1] to [6] above and a solvent.
[8] A paste for a negative electrode of an electricity storage device, comprising a silicon-based negative electrode active material and the polymer for a electricity storage device according to any one of [1] to [6] above.
[9] A negative electrode for an electricity storage device, comprising: a current collector; and a mixture layer formed on the current collector,
The negative electrode for an electricity storage device, wherein the mixture layer contains a silicon-based negative electrode active material and the polymer for an electricity storage device according to any one of [1] to [6].
[10] An electricity storage device comprising the electricity storage device negative electrode according to [9].
[11] Use of the polymer for an electrical storage device according to any one of the above [1] to [6] for producing a binder composition for an electrical storage device.
[12] Use of the polymer for an electricity storage device according to any one of the above [1] to [6] for producing a paste for a negative electrode of an electricity storage device.
[13] Use of the polymer for an electricity storage device according to any one of the above [1] to [6] for producing a negative electrode for an electricity storage device.
以下に、実施例により本開示を具体的に説明するが、本開示はこれらの実施例によって何ら限定されるものではない。 The present disclosure will be explained in detail below with reference to examples, but the present disclosure is not limited to these examples.
１．蓄電デバイス用重合体Ａ１～Ａ３の合成
［製造例１：重合体Ａ１の合成］
内容量１Ｌのガラス製４つ口セパラブルフラスコに、イオン交換水３６３ｇを仕込み、窒素雰囲気下で０．５時間攪拌した。フラスコ内の溶液を７５℃に昇温し、フラスコ内にＮ－ヒドロキシエチルアクリルアミド(ＫＪケミカルス社製)５０．０ｇの６０質量％水溶液８３ｇ、および２，２'－アゾビス（２－メチルプロピオンアミジン）二塩酸塩（富士フイルム和光純薬社製）０．６ｇの１質量％水溶液６０ｇを１時間かけて滴下した。その後、フラスコ内の溶液を７５℃でさらに４時間保持することで、製造例１のポリマー溶液（重合体Ａ１）を得た。ポリマー溶液中の重合体濃度は、１０質量％であった。重合体1の重量平均分子量は７５万であった（表１）。
［製造例２～３：重合体Ａ２～Ａ３の合成］
製造例１の方法に従って、一般式（１）の構成単位を形成する重合性単量体と、表１に記載の残りの構成単位ＩＩを形成する重合性単量体（ＰＥＧ10－Ａ：ポリエチレングリコールアクリレート、ＥＯ付加モル数１０、日油社製の"ＡＥ－４００"）とを共重合して、製造例２～３のポリマー溶液（重合体Ａ２～Ａ３）を得た。ポリマー溶液中の重合体Ａ２～Ａ３の濃度はそれぞれ、１０質量％であった。重合体Ａ２～Ａ３の重量平均分子量は表１に示した。
1. Synthesis of Polymers A1 to A3 for Electric Storage Devices [Production Example 1: Synthesis of Polymer A1]
363 g of ion-exchanged water was charged into a 1 L four-neck glass separable flask and stirred under a nitrogen atmosphere for 0.5 hours. The solution in the flask was heated to 75°C, and 83 g of a 60% by mass aqueous solution of 50.0 g of N-hydroxyethylacrylamide (KJ Chemicals) and 60 g of a 1% by mass aqueous solution of 0.6 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (FUJIFILM Wako Pure Chemical Industries, Ltd.) were dropped into the flask over 1 hour. The solution in the flask was then kept at 75°C for another 4 hours to obtain a polymer solution (polymer A1) of Production Example 1. The polymer concentration in the polymer solution was 10% by mass. The weight average molecular weight of polymer 1 was 750,000 (Table 1).
[Production Examples 2 to 3: Synthesis of Polymers A2 to A3]
According to the method of Production Example 1, the polymerizable monomer forming the structural unit of general formula (1) and the polymerizable monomer forming the remaining structural unit II shown in Table 1 (PEG 10 -A: polyethylene glycol acrylate, EO addition mole number 10, "AE-400" manufactured by NOF Corporation) were copolymerized to obtain polymer solutions (polymers A2 to A3) of Production Examples 2 to 3. The concentrations of polymers A2 to A3 in the polymer solutions were each 10 mass %. The weight average molecular weights of polymers A2 to A3 are shown in Table 1.
［重量平均分子量の測定］
蓄電デバイス用重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した。詳細な条件を下記に示す。
＜測定条件＞
測定装置：ＨＬＣ－８３２０ＧＰＣ（東ソー社製、検出器一体型）
カラム：ＧＭＰＷＸＬ＋ＧＭＰＷＸＬ（アニオン、東ソー社製）
溶離液：０．２モル濃度のリン酸バッファー／アセトニトリル（＝９／１）
流量：０．５ｍＬ／分
カラム温度：４０℃
検出器：ＲＩ 検出器
標準物質：ポリエチレンオキサイド
[Measurement of weight average molecular weight]
The weight-average molecular weight of the polymer for use in an electricity storage device was measured by gel permeation chromatography (GPC) under the following detailed conditions.
<Measurement conditions>
Measuring device: HLC-8320GPC (Tosoh Corporation, detector integrated type)
Column: GMPWXL + GMPWXL (anion, manufactured by Tosoh Corporation)
Eluent: 0.2 molar phosphate buffer/acetonitrile (=9/1)
Flow rate: 0.5 mL/min Column temperature: 40° C.
Detector: RI Detector standard material: polyethylene oxide
２．シリコン系負極ペーストの調製
（実施例１）
導電材（アセチレンブラック、デンカ社製、「Ｌｉ－１００」） ０．１６ｇと１．５質量％の増粘剤（カルボキシメチルセルロースナトリウム、富士フイルム和光純薬社製）水溶液 ５．５ｇと黒鉛系負極活物質（グラファイト、昭和電工社製「ＭＣＭＧ－ＣＦ－Ｃ」）７．８８ｇとシリコン系負極活物質（一酸化シリコン、富士フイルム和光純薬社製）０．８８ｇを混合して、スラリー［１］を調製した。
次いで、スラリー［１］に、１．５質量％の増粘剤（カルボキシメチルセルロースナトリウム、富士フイルム和光純薬社製）水溶液 ３．７３ｇおよびイオン交換水 ０．５３ｇ入れて混合して、スラリー［２］を調製した。
次に、調製した製造例１の１０質量％の重合体Ａ１水溶液１．８５ｇを添加し、実施例１のシリコン系負極ペーストの調製を行った。各成分の混合には、「あわとり練太郎（ＡＲＶ－３１０）」を用いた。シリコン系負極ペースト中の各成分の含有量は、重合体：０.９質量％、シリコン系負極活物質：４．３質量％、黒鉛系負極活物質：３８．４質量％、導電材：０．８質量％、増粘剤：０．６７質量％であった。シリコン系負極ペースト中の重合体の含有量は、シリコン系負極活物質１００質量部に対して２１質量部であった。シリコン系負極ペーストの固形分濃度は４５質量％であった。
（比較例１～２）
実施例１のシリコン系負極ペーストの調製方法と同様にして、比較例１～２のシリコン系負極ペーストを調製した。配合組成は実施例１と同じで、使用した重合体の種類のみを変更した。
2. Preparation of silicon-based negative electrode paste (Example 1)
A slurry [1] was prepared by mixing 0.16 g of a conductive material (acetylene black, manufactured by Denka Co., Ltd., "Li-100"), 5.5 g of a 1.5 mass % aqueous solution of a thickener (sodium carboxymethylcellulose, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 7.88 g of a graphite-based negative electrode active material (graphite, manufactured by Showa Denko K.K., "MCMG-CF-C"), and 0.88 g of a silicon-based negative electrode active material (silicon monoxide, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
Next, 3.73 g of a 1.5% by mass aqueous solution of a thickener (sodium carboxymethylcellulose, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.53 g of ion-exchanged water were added to and mixed with the slurry [1] to prepare a slurry [2].
Next, 1.85 g of the 10 mass % aqueous solution of polymer A1 prepared in Production Example 1 was added to prepare the silicon-based negative electrode paste of Example 1. The components were mixed using a "Thin Mixer (ARV-310)". The contents of the components in the silicon-based negative electrode paste were: polymer: 0.9 mass %, silicon-based negative electrode active material: 4.3 mass %, graphite-based negative electrode active material: 38.4 mass %, conductive material: 0.8 mass %, and thickener: 0.67 mass %. The content of the polymer in the silicon-based negative electrode paste was 21 parts by mass relative to 100 parts by mass of the silicon-based negative electrode active material. The solid content of the silicon-based negative electrode paste was 45 mass %.
(Comparative Examples 1 to 2)
Silicon-based negative electrode pastes of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1. The blended compositions were the same as in Example 1, and only the type of polymer used was changed.
３．シリコン系負極の作製１
厚さ２０μｍの銅箔上に、負極容量密度が６ｍＡｈ/ｃｍ2となるように、シリコン系負極ペーストを塗工し、塗膜（厚さ３８０μｍ）を、真空乾燥器を用いて１００℃で１２時間乾燥した。これにより、集電体上に合材層（厚さ１２０μｍ）が形成されたシリコン系負極（負極合剤層を有するシリコン系負極）を作製した。これをプレス機でプレスして、集電体上に合材層（１００μｍ）が形成されたシリコン系負極（負極合剤層を有するシリコン系負極）とした。電極（負極）組成としては、グラファイト８５．３質量％、ＳｉＯ(平均粒径：１μｍ)９．５質量％、導電材:１．７質量％、増粘剤:１．５質量％、重合体：２．０質量％となるように作製した。
［シリコン系負極活物質の平均粒径の測定］
レーザー回折/散乱式粒子径分布測定装置ＬＡ－９２０（堀場製作所製）を用いて体積平均粒径（Ｄ50）を測定した。
3. Preparation of silicon-based negative electrode 1
A silicon-based negative electrode paste was applied onto a copper foil having a thickness of 20 μm so that the negative electrode capacity density was 6 mAh/cm 2 , and the coating film (thickness 380 μm) was dried at 100 ° C. for 12 hours using a vacuum dryer. This produced a silicon-based negative electrode (silicon-based negative electrode having a negative electrode mixture layer) in which a composite layer (thickness 120 μm) was formed on the current collector. This was pressed with a press machine to produce a silicon-based negative electrode (silicon-based negative electrode having a negative electrode mixture layer) in which a composite layer (100 μm) was formed on the current collector. The electrode (negative electrode) composition was prepared to be 85.3% by mass of graphite, 9.5% by mass of SiO (average particle size: 1 μm), 1.7% by mass of conductive material, 1.5% by mass of thickener, and 2.0% by mass of polymer.
[Measurement of average particle size of silicon-based negative electrode active material]
The volume average particle size (D 50 ) was measured using a laser diffraction/scattering type particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.).
４．負極性能の評価
実施例１及び比較例１～２のシリコン系負極を用い下記のようにして作製した蓄電デバイスの充放電特性を、下記充放電サイクル試験により負極性能を評価した。
［コインセル（蓄電デバイス）の作製］
シリコン系負極をそれぞれ直径１４ｍｍに打ち抜きプレスした。そして、プレスしたシリコン系負極上に、直径１９ｍｍのセパレータ［宝泉社製］、直径１５ｍｍ、厚さ０．５ｍｍのコイン状の金属リチウム箔を対極として配置し、２０３２型コインハーフセルを作製した。電解液には、１Ｍ ＬｉＰＦ6 ＥＣ/ＤＥＣ（体積比）＝３／７を用いた。
［充放電サイクル試験］
作製したコインセルを、エレクトロフィールド社製充放電試験機（ABE1024）を用いて、４５℃の環境下、充放電サイクル試験を行った。充電は、ＯＣＶから０Ｖまで０．１Ｃで定電流充電をした後、１０分間定電圧充電することとした。放電は、１．２Ｖまで０．１Ｃで定電流放電することとした。この充放電を５０サイクル繰り返した。尚、本セルの充電とは、リチウム金属からシリコン系負極へのリチウムイオン挿入過程をいい、放電はその逆反応をいう。
［容量維持率］
作製したコインセル（蓄電デバイス）を用いて上記充放電サイクル試験を行い、下記式により容量維持率を求めた。結果を表２に示す。
容量維持率＝（５０サイクル目の放電容量）／（１サイクル目の放電容量）
4. Evaluation of Negative Electrode Performance The charge/discharge characteristics of the electricity storage devices prepared as described below using the silicon-based negative electrodes of Example 1 and Comparative Examples 1 and 2 were evaluated for negative electrode performance by the following charge/discharge cycle test.
[Fabrication of coin cells (electricity storage devices)]
Each silicon-based negative electrode was punched out to a diameter of 14 mm and pressed. A separator with a diameter of 19 mm [manufactured by Hosen Co., Ltd.] and a coin-shaped lithium foil with a diameter of 15 mm and a thickness of 0.5 mm were placed on the pressed silicon-based negative electrode to prepare a 2032-type coin half cell. 1M LiPF 6 EC/DEC (volume ratio) = 3/7 was used as the electrolyte.
[Charge-discharge cycle test]
The prepared coin cell was subjected to a charge-discharge cycle test in an environment of 45°C using an Electrofield charge-discharge tester (ABE1024). Charging was performed by constant current charging at 0.1C from OCV to 0V, followed by constant voltage charging for 10 minutes. Discharging was performed by constant current discharging at 0.1C to 1.2V. This charging and discharging was repeated 50 cycles. Note that charging of this cell refers to the process of lithium ions being inserted from lithium metal to the silicon-based negative electrode, and discharging refers to the reverse reaction.
[Capacity retention rate]
The above-mentioned charge/discharge cycle test was carried out using the produced coin cell (electricity storage device), and the capacity retention rate was calculated by the following formula. The results are shown in Table 2.
Capacity retention rate=(discharge capacity at 50th cycle)/(discharge capacity at 1st cycle)
表２に示されるように、構成単位Ｉの含有量が９５質量％超の重合体Ａ１を用いた実施例１では、構成単位Ｉの含有量が９５質量％以下である重合体Ａ２及びＡ３を用いた比較例１～２に比べて、充放電サイクルでの容量維持率が高く、シリコン系負極活物質を用いた負極を備える蓄電デバイスの充放電サイクル特性が向上できることがわかった。 As shown in Table 2, in Example 1, which used polymer A1 with a content of structural unit I exceeding 95% by mass, the capacity retention rate during charge-discharge cycles was higher than in Comparative Examples 1 and 2, which used polymers A2 and A3 with a content of structural unit I of 95% by mass or less, and it was found that the charge-discharge cycle characteristics of an electricity storage device having a negative electrode using a silicon-based negative electrode active material can be improved.
５．シリコン系負極の作製２（フルセル用負極）
厚さ２０μｍの銅箔上に、負極容量密度が２．１ｍＡｈ/ｃｍ2となるように、シリコン系負極ペーストを塗工し、塗膜（厚さ１３０μｍ）を、真空乾燥器を用いて１００℃で１２時間乾燥した。これにより、集電体上に合材層（厚さ４５μｍ）が形成されたシリコン系負極（負極合剤層を有するシリコン系負極）を作製した。これをプレス機でプレスして、集電体上に合材層（３５μｍ）が形成されたシリコン系負極（負極合剤層を有するシリコン系負極）とした。電極（負極）組成としては、グラファイト８５．３質量％、ＳｉＯ(平均粒径：１μｍ)９．５質量％、導電材:１．７質量％、増粘剤:１．５質量％、重合体
：２．０質量％となるように作製した。
5. Preparation of silicon-based negative electrode 2 (negative electrode for full cell)
A silicon-based negative electrode paste was applied onto a copper foil having a thickness of 20 μm so that the negative electrode capacity density was 2.1 mAh/cm 2 , and the coating film (thickness 130 μm) was dried at 100 ° C. for 12 hours using a vacuum dryer. This produced a silicon-based negative electrode (silicon-based negative electrode having a negative electrode mixture layer) in which a composite layer (thickness 45 μm) was formed on the current collector. This was pressed with a press machine to produce a silicon-based negative electrode (silicon-based negative electrode having a negative electrode mixture layer) in which a composite layer (35 μm) was formed on the current collector. The electrode (negative electrode) composition was prepared to be 85.3% by mass of graphite, 9.5% by mass of SiO (average particle size: 1 μm), 1.7% by mass of conductive material, 1.5% by mass of thickener, and 2.0% by mass of polymer.
６．フルセル用正極の作製
正極活物質（日本化学工業社製、NCM523）１５ｇ、ポリビニリデンフルオライド（ＰＶＤＦ）のn-メチルピロリドン（ＮＭＰ）溶液（固形分８％ ＫＦポリマーＬ＃７２０８、株式会社クレハ製、バインダー溶液）５．９８ｇ、導電材（アセチレンブラック、デンカ社製、「Ｌｉ－１００」） ０．４８ｇと溶媒（ＮＭＰ）１２．９７ｇを自転公転ミキサー（ＡＲ－１００ 株式会社 シンキー製）にて、１０分間混合して、固形分４６質量％の正極ペーストを作製した。これを厚さ２０μｍのアルミホイルに塗布して、１００℃で乾燥させることによって正極容量密度が２．０ｍＡｈ/ｃｍ2正極を製造した。
6. Preparation of a positive electrode for full cells 15 g of positive electrode active material (manufactured by Nippon Chemical Industry Co., Ltd., NCM523), 5.98 g of n-methylpyrrolidone (NMP) solution of polyvinylidene fluoride (PVDF) (solid content 8% KF polymer L#7208, manufactured by Kureha Corporation, binder solution), 0.48 g of conductive material (acetylene black, manufactured by Denka Co., Ltd., "Li-100") and 12.97 g of solvent (NMP) were mixed for 10 minutes in a rotation and revolution mixer (AR-100 manufactured by Thinky Corporation) to prepare a positive electrode paste with a solid content of 46% by mass. This was applied to an aluminum foil with a thickness of 20 μm and dried at 100 ° C. to produce a positive electrode with a positive electrode capacity density of 2.0 mAh / cm 2 .
［コインセル（蓄電デバイス）の作製（フルセル）］
正極を直径１３ｍｍ、シリコン系負極を直径１４ｍｍに打ち抜き、正極上に、直径１９ｍｍのセパレータ［宝泉社製］、その後にシリコン系負極を対極として配置し、２０３２型コインセル（フルセル）を作製した。電解液には、１Ｍ ＬｉＰＦ6 ＥＣ/ＤＥＣ（体積比）＝３／７を用いた。
[Fabrication of coin cells (electricity storage devices) (full cells)]
The positive electrode was punched out to a diameter of 13 mm, and the silicon-based negative electrode was punched out to a diameter of 14 mm. A separator with a diameter of 19 mm [manufactured by Hosen Co., Ltd.] was placed on the positive electrode, followed by the silicon-based negative electrode as a counter electrode to prepare a 2032-type coin cell (full cell). 1M LiPF6 EC/DEC (volume ratio) = 3/7 was used as the electrolyte.
［フルセルの評価］
得られたフルセルを用いて、電池特性（レート特性５Ｃ）を測定した。具体的には、電池を２５℃の環境下で下記の条件に従い０．１Ｃで４．２Ｖまで充電し、その後０．１Ｃで３Ｖになるまで放電し放電容量を求めた。次いで５Ｃの放電容量を同様にして求め、０．１Ｃの放電容量を基準に５Ｃの放電容量維持率を求めた。
（充電条件） ０．１Ｃ ＣＣ―ＣＶ４．２Ｖ（０．０２Ｃ Ｃｕｔ ｏｆｆ)
（放電条件） ０．１Ｃもしくは５Ｃ ＣＣ（３Ｖ Ｃｕｔ ｏｆｆ）
高速放電容量維持率（％）＝（５Ｃの放電容量／０．１Ｃの放電容量）×１００
[Full cell evaluation]
The resulting full cell was used to measure the battery characteristics (rate characteristics 5C). Specifically, the battery was charged to 4.2 V at 0.1 C under the following conditions in an environment of 25° C., and then discharged to 3 V at 0.1 C to determine the discharge capacity. The 5C discharge capacity was then determined in the same manner, and the 5C discharge capacity retention rate was calculated based on the 0.1C discharge capacity.
(Charging conditions) 0.1C CC-CV4.2V (0.02C Cut off)
(Discharge conditions) 0.1C or 5C CC (3V Cut off)
High-speed discharge capacity retention rate (%)=(5 C discharge capacity/0.1 C discharge capacity)×100
表３に示されるように、構成単位Ｉの含有量が９５質量％超の重合体Ａ１を用いた実施例１では、構成単位Ｉの含有量が９５質量％以下である重合体Ａ２及びＡ３を用いた比較例１～２に比べて高速放電容量維持率が高く、シリコン系負極活物質を用いた負極を備える蓄電デバイスの高速放電容量維持率の特性が向上できることがわかった。 As shown in Table 3, in Example 1, which used polymer A1 with a content of structural unit I exceeding 95% by mass, the high-rate discharge capacity retention rate was higher than in Comparative Examples 1 and 2, which used polymers A2 and A3 with a content of structural unit I of 95% by mass or less, and it was found that the high-rate discharge capacity retention rate characteristics of an electricity storage device having a negative electrode using a silicon-based negative electrode active material can be improved.
本開示に係る蓄電デバイス用重合体は、例えば、様々な蓄電デバイスに利用できる。 The polymer for electricity storage devices according to the present disclosure can be used, for example, in various electricity storage devices.
Claims (6)
下記式（Ｉ）で表される構成単位の含有量が９５質量％超の、蓄電デバイス用重合体。
A polymer for an electricity storage device, comprising a structural unit represented by the following formula (I) in an amount of more than 95 mass %:
前記合材層が、シリコン系負極活物質、及び、請求項１又は２に記載の蓄電デバイス用重合体を含む、蓄電デバイス用負極。 A negative electrode for an electricity storage device comprising a current collector and a mixture layer formed on the current collector,
3. A negative electrode for an electricity storage device, wherein the mixture layer comprises a silicon-based negative electrode active material and the polymer for an electricity storage device according to claim 1.
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