JP2017188453A - Coated active material for lithium ion battery - Google Patents
Coated active material for lithium ion battery Download PDFInfo
- Publication number
- JP2017188453A JP2017188453A JP2017067084A JP2017067084A JP2017188453A JP 2017188453 A JP2017188453 A JP 2017188453A JP 2017067084 A JP2017067084 A JP 2017067084A JP 2017067084 A JP2017067084 A JP 2017067084A JP 2017188453 A JP2017188453 A JP 2017188453A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- lithium ion
- weight
- ion battery
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000004992 toluidines Chemical class 0.000 description 1
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- 229940087291 tridecyl alcohol Drugs 0.000 description 1
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
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- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- SLVHCWLFRYIBQT-UHFFFAOYSA-N tris(trichloromethyl) phosphate Chemical compound ClC(Cl)(Cl)OP(=O)(OC(Cl)(Cl)Cl)OC(Cl)(Cl)Cl SLVHCWLFRYIBQT-UHFFFAOYSA-N 0.000 description 1
- HYFGMEKIKXRBIP-UHFFFAOYSA-N tris(trifluoromethyl) phosphate Chemical compound FC(F)(F)OP(=O)(OC(F)(F)F)OC(F)(F)F HYFGMEKIKXRBIP-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウムイオン電池用被覆活物質に関する。 The present invention relates to a coated active material for a lithium ion battery.
近年、環境保護のため二酸化炭素排出量の低減が切に望まれている。自動車業界では、電気自動車(EV)やハイブリッド電気自動車(HEV)の導入による二酸化炭素排出量の低減に期待が集まっており、これらの実用化の鍵を握るモータ駆動用二次電池の開発が鋭意行われている。二次電池としては、高エネルギー密度、高出力密度が達成できるリチウムイオン二次電池に注目が集まっており、更なる高性能化をはかるために電解液及び活物質の改良が行われている。 In recent years, reduction of carbon dioxide emissions has been strongly desired for environmental protection. In the automobile industry, there are high expectations for reducing carbon dioxide emissions by introducing electric vehicles (EVs) and hybrid electric vehicles (HEVs), and we are eager to develop secondary batteries for motor drives that hold the key to their practical application. Has been done. As secondary batteries, attention has been focused on lithium ion secondary batteries that can achieve high energy density and high output density, and the electrolyte and active material have been improved in order to achieve higher performance.
なかでもサイクル特性が向上する負極活物質として、特定のヒドロキシ酸化合物が活物質の表面の少なくとも一部を被覆している非水系二次電池電極用被覆活物質が提案されている(特許文献1参照)。
また、高エネルギー密度の電池の製造を可能にした正極活物質として、活物質の表面に特定量のポリマーを備えた複合正極活物質が提案されている(特許文献2参照)。
Among these, as a negative electrode active material with improved cycle characteristics, a coating active material for a non-aqueous secondary battery electrode in which a specific hydroxy acid compound covers at least a part of the surface of the active material has been proposed (Patent Document 1). reference).
Moreover, a composite positive electrode active material having a specific amount of polymer on the surface of the active material has been proposed as a positive electrode active material capable of manufacturing a battery having a high energy density (see Patent Document 2).
しかしながら、特許文献1に記載の非水系二次電池電極用被覆負極活物質を用いた非水電解質二次電池では、充放電に伴う電極の膨張・収縮により、被覆活物質表面からの被覆層の剥がれ等が発生することにより充分なレート特性が得られない場合があるなど、リチウムイオン電池の充放電特性に課題があった。
また、特許文献2に記載の複合活物質を用いた非水電解質二次電池では、充分なレート特性が得られない場合があるなど、リチウムイオン電池の充放電特性に課題があった。
However, in the nonaqueous electrolyte secondary battery using the coated negative electrode active material for a nonaqueous secondary battery electrode described in Patent Document 1, the coating layer from the surface of the coated active material is caused by the expansion / contraction of the electrode accompanying charge / discharge. There was a problem in the charge / discharge characteristics of the lithium ion battery, for example, sufficient rate characteristics could not be obtained due to peeling.
Further, the non-aqueous electrolyte secondary battery using the composite active material described in Patent Document 2 has a problem in the charge / discharge characteristics of the lithium ion battery, such as a case where sufficient rate characteristics may not be obtained.
本発明は、上記問題点に鑑みてなされたものであり、レート特性に優れるリチウムイオン電池用被覆活物質を提供することを目的とする。 This invention is made | formed in view of the said problem, and it aims at providing the coating active material for lithium ion batteries which is excellent in a rate characteristic.
本発明者らは、上記課題を解決するために鋭意検討した結果、本発明に到達した。
すなわち、本発明は、リチウムイオン電池用活物質が有する表面の少なくとも一部を高分子化合物を含む被覆層で被覆してなるリチウムイオン電池用被覆活物質であって、以下の試験方法により測定される液滴消失時間が35秒以下であることを特徴とするリチウムイオン電池用被覆活物質である。
<液滴消失時間の測定方法>
(1)試験片の作製
エチレンカーボネートとジエチルカーボネートとの混合溶媒(重量比3:7)100重量部に対して、上記リチウムイオン電池用被覆活物質が被覆正極活物質の場合には100重量部を、上記リチウムイオン電池用被覆活物質が被覆負極活物質の場合には225重量部を加えて均一に混合して得られた活物質スラリーを厚さ20μmの銅箔上に600μmの厚さとなるようにドクターブレード法によりアルゴン雰囲気中で塗布して塗膜を形成する。塗膜表面にろ紙(No.2)を被せ、ろ紙の上から10MPa/cm2の圧力で塗膜の膜厚が400μm±100μmの厚さとなるまで押さえて試験片とする。
(2)液滴消失時間の測定
アルゴン雰囲気下、25℃で、上記試験片の中央に、上記混合溶媒を5mmの高さからマイクロシリンジで70μL滴下する。滴下終了から上記混合溶媒が試験片の内部に吸収されて、見掛け上表面から消失するまでの時間を測定し、10個の試験片について測定した時間の平均を液滴消失時間とする。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention.
That is, the present invention is a lithium ion battery coated active material obtained by coating at least part of the surface of the lithium ion battery active material with a coating layer containing a polymer compound, and is measured by the following test method. The liquid drop disappearance time is 35 seconds or less.
<Measurement method of droplet disappearance time>
(1) Preparation of test piece 100 parts by weight when the above-mentioned coated active material for lithium ion batteries is a coated positive electrode active material with respect to 100 parts by weight of a mixed solvent of ethylene carbonate and diethyl carbonate (weight ratio 3: 7). When the lithium ion battery coated active material is a coated negative electrode active material, the active material slurry obtained by adding 225 parts by weight and uniformly mixing the resultant to a thickness of 600 μm on a 20 μm thick copper foil Thus, a doctor blade method is applied in an argon atmosphere to form a coating film. A filter paper (No. 2) is put on the surface of the coating film, and pressed onto the filter paper with a pressure of 10 MPa / cm 2 until the thickness of the coating film reaches 400 μm ± 100 μm.
(2) Measurement of droplet disappearance time 70 μL of the mixed solvent is dropped from the height of 5 mm with a microsyringe to the center of the test piece at 25 ° C. in an argon atmosphere. The time from the completion of dropping until the mixed solvent is absorbed inside the test piece and apparently disappears from the surface is measured, and the average of the time measured for the 10 test pieces is taken as the liquid drop disappearance time.
本発明のリチウムイオン電池用被覆活物質を用いると、レート特性に優れるリチウムイオン電池を得ることができる。 When the coated active material for a lithium ion battery of the present invention is used, a lithium ion battery having excellent rate characteristics can be obtained.
以下、本発明を詳細に説明する。
なお、本明細書において、リチウムイオン電池と記載する場合、リチウムイオン二次電池も含む概念とする。
Hereinafter, the present invention will be described in detail.
Note that in this specification, a lithium ion battery includes a lithium ion secondary battery.
本発明は、リチウムイオン電池用活物質が有する表面の少なくとも一部を高分子化合物を含む被覆層で被覆してなるリチウムイオン電池用被覆活物質であって、以下の試験方法により測定される液滴消失時間が35秒以下であることを特徴とするリチウムイオン電池用被覆活物質である。
<液滴消失時間の測定方法>
(1)試験片の作製
エチレンカーボネートとジエチルカーボネートとの混合溶媒(重量比3:7)100重量部に対して、上記リチウムイオン電池用被覆活物質が被覆正極活物質の場合には100重量部を、上記リチウムイオン電池用被覆活物質が被覆負極活物質の場合には225重量部を加えて均一に混合して得られた活物質スラリーを厚さ20μmの銅箔上に600μmの厚さとなるようにドクターブレード法によりアルゴン雰囲気中で塗布して塗膜を形成する。塗膜表面にろ紙(No.2)を被せ、ろ紙の上から10MPa/cm2の圧力で塗膜の膜厚が400μm±100μmの厚さとなるまで押さえて試験片とする。
(2)液滴消失時間の測定
アルゴン雰囲気下、25℃で、上記試験片の中央に、上記混合溶媒を5mmの高さからマイクロシリンジで70μL滴下する。滴下終了から上記混合溶媒が試験片の内部に吸収されて、見掛け上表面から消失するまでの時間を測定し、10個の試験片について測定した時間の平均を液滴消失時間とする。
The present invention relates to a coated active material for a lithium ion battery obtained by coating at least a part of the surface of an active material for a lithium ion battery with a coating layer containing a polymer compound, which is measured by the following test method. A coating active material for a lithium ion battery, characterized in that the droplet disappearance time is 35 seconds or less.
<Measurement method of droplet disappearance time>
(1) Preparation of test piece 100 parts by weight when the above-mentioned coated active material for lithium ion batteries is a coated positive electrode active material with respect to 100 parts by weight of a mixed solvent of ethylene carbonate and diethyl carbonate (weight ratio 3: 7). When the lithium ion battery coated active material is a coated negative electrode active material, the active material slurry obtained by adding 225 parts by weight and uniformly mixing the resultant to a thickness of 600 μm on a 20 μm thick copper foil Thus, a doctor blade method is applied in an argon atmosphere to form a coating film. A filter paper (No. 2) is put on the surface of the coating film, and pressed onto the filter paper with a pressure of 10 MPa / cm 2 until the thickness of the coating film reaches 400 μm ± 100 μm.
(2) Measurement of droplet disappearance time 70 μL of the mixed solvent is dropped from the height of 5 mm with a microsyringe to the center of the test piece at 25 ° C. in an argon atmosphere. The time from the completion of dropping until the mixed solvent is absorbed inside the test piece and apparently disappears from the surface is measured, and the average of the time measured for the 10 test pieces is taken as the liquid drop disappearance time.
本発明のリチウムイオン電池用被覆活物質では、液滴消失時間が35秒以下であることから、リチウムイオン電池用被覆活物質を含む活物質層が混合溶媒に対して充分な浸透性を備えているといえ、上記活物質層への電解液の浸透性が高いことを意味する。
活物質層への電解液の浸透性が高いと活物質層中でのイオン導電性が良好となる結果、充放電特性の優れたリチウムイオン電池を与えることができる。
なお、液滴消失時間が35秒を超えると、リチウムイオン電池用被覆活物質を含む活物質層に対する浸透性が充分ではなく、活物質層の電解液保持性が不足する結果、充分なイオン導電性が得られないことがある。
また、電池容量の増加等を目的として活物質層の密度を高めた場合には、活物質層に電解液が浸透する速度が低下するが、液滴消失時間が35秒以下であると、活物質層への電解液の浸透性が良好であるため、本発明のリチウムイオン電池用被覆活物質を用いた活物質層は電解液を吸収させる工程時間を短縮できるという効果も有する。
液滴消失時間は10〜35秒が好ましく、液滴消失時間がこの範囲であるとレート特性が良好となり好ましい。また、リチウムイオン電池用活物質がリチウムイオン電池用負極活物質である場合には20〜33秒がさらに好ましい。
In the coated active material for a lithium ion battery according to the present invention, since the droplet disappearance time is 35 seconds or less, the active material layer containing the coated active material for the lithium ion battery has sufficient permeability to the mixed solvent. It can be said that the electrolyte has high permeability to the active material layer.
When the permeability of the electrolytic solution into the active material layer is high, the ionic conductivity in the active material layer becomes good, and as a result, a lithium ion battery having excellent charge / discharge characteristics can be provided.
In addition, when the droplet disappearance time exceeds 35 seconds, the permeability to the active material layer containing the coating active material for the lithium ion battery is not sufficient, and as a result, the electrolyte material retainability of the active material layer is insufficient. Sexuality may not be obtained.
Further, when the density of the active material layer is increased for the purpose of increasing the battery capacity or the like, the rate at which the electrolytic solution penetrates into the active material layer decreases, but if the droplet disappearance time is 35 seconds or less, Since the permeability of the electrolytic solution into the material layer is good, the active material layer using the coated active material for a lithium ion battery of the present invention also has an effect that the process time for absorbing the electrolytic solution can be shortened.
The droplet disappearance time is preferably 10 to 35 seconds, and if the droplet disappearance time is within this range, the rate characteristics are good, which is preferable. Moreover, when the active material for lithium ion batteries is a negative electrode active material for lithium ion batteries, 20 to 33 seconds are more preferable.
続いて、本発明のリチウムイオン電池用被覆活物質を構成する活物質について説明する。
本発明のリチウムイオン電池用被覆活物質を構成する活物質は、リチウムイオン電池用活物質であればよい。リチウムイオン電池用活物質は、正極活物質(以下、リチウムイオン電池用正極活物質ともいう)であってもよく、負極活物質(以下、リチウムイオン電池用負極活物質ともいう)であってもよい。
リチウムイオン電池用正極活物質及びリチウムイオン電池用負極活物質としては、従来公知のものを好適に使用することができ、ある電位を与えることでリチウムイオンの挿入と脱離が可能な化合物を用いることができ、リチウムイオンの挿入と脱離が起こる電位が相対的に高いものをリチウムイオン電池用正極活物質として、相対的に低いものをリチウムイオン電池用負極活物質として用いることができる。
Then, the active material which comprises the covering active material for lithium ion batteries of this invention is demonstrated.
The active material which comprises the covering active material for lithium ion batteries of this invention should just be an active material for lithium ion batteries. The active material for a lithium ion battery may be a positive electrode active material (hereinafter also referred to as a positive electrode active material for a lithium ion battery) or a negative electrode active material (hereinafter also referred to as a negative electrode active material for a lithium ion battery). Good.
As the positive electrode active material for lithium ion batteries and the negative electrode active material for lithium ion batteries, conventionally known materials can be preferably used, and compounds capable of inserting and removing lithium ions by applying a certain potential are used. A lithium ion battery positive electrode active material having a relatively high potential at which lithium ion insertion and desorption occurs and a relatively low potential as a lithium ion battery negative electrode active material can be used.
リチウムイオン電池用正極活物質としては、リチウムと遷移金属との複合酸化物{遷移金属が1種である複合酸化物(LiCoO2、LiNiO2、LiAlMnO4、LiMnO2及びLiMn2O4等)、遷移金属元素が2種である複合酸化物(例えばLiFeMnO4、LiNi1−xCoxO2、LiMn1−yCoyO2、LiNi1/3Co1/3Al1/3O2及びLiNi0.8Co0.15Al0.05O2)及び金属元素が3種類以上である複合酸化物[例えばLiMaM’bM’’cO2(M、M’及びM’’はそれぞれ異なる遷移金属元素であり、a+b+c=1を満たす。例えばLiNi1/3Mn1/3Co1/3O2)等]等}、リチウム含有遷移金属リン酸塩(例えばLiFePO4、LiCoPO4、LiMnPO4及びLiNiPO4)、遷移金属酸化物(例えばMnO2及びV2O5)、遷移金属硫化物(例えばMoS2及びTiS2)及び導電性高分子(例えばポリアニリン、ポリフッ化ビニリデン、ポリピロール、ポリチオフェン、ポリアセチレン及びポリ−p−フェニレン及びポリカルバゾール)等が挙げられ、2種以上を併用してもよい。
なお、リチウム含有遷移金属リン酸塩は、遷移金属サイトの一部を他の遷移金属で置換したものであってもよい。
The cathode active material for a lithium ion battery, a composite oxide composite oxide of lithium and transition metal {transition metal is one (LiCoO 2, LiNiO 2, LiAlMnO 4, LiMnO 2 and LiMn 2 O 4, etc.), Complex oxides having two transition metal elements (for example, LiFeMnO 4 , LiNi 1-x Co x O 2 , LiMn 1-y Co y O 2 , LiNi 1/3 Co 1/3 Al 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 ) and a composite oxide having three or more metal elements [for example, LiM a M ′ b M ″ c O 2 (M, M ′ and M ″ are respectively It is a different transition metal element and satisfies a + b + c = 1. For example, LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) etc.], lithium-containing transition metal phosphate (for example, LiF ePO 4 , LiCoPO 4 , LiMnPO 4 and LiNiPO 4 ), transition metal oxides (eg MnO 2 and V 2 O 5 ), transition metal sulfides (eg MoS 2 and TiS 2 ) and conductive polymers (eg polyaniline, polyfluoride). Vinylidene chloride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene and polycarbazole), and the like may be used in combination.
The lithium-containing transition metal phosphate may be one in which a part of the transition metal site is substituted with another transition metal.
リチウムイオン電池用正極活物質の体積平均粒子径は、電池の電気特性の観点から、0.01〜100μmであることが好ましく、0.1〜35μmであることがより好ましく、2〜30μmであることがさらに好ましい。 The volume average particle diameter of the positive electrode active material for a lithium ion battery is preferably 0.01 to 100 μm, more preferably 0.1 to 35 μm, and more preferably 2 to 30 μm from the viewpoint of the electric characteristics of the battery. More preferably.
リチウムイオン電池用負極活物質としては、炭素系材料[黒鉛、難黒鉛化性炭素、アモルファス炭素、樹脂焼成体(例えばフェノール樹脂及びフラン樹脂等を焼成し炭素化したもの等)、コークス類(例えばピッチコークス、ニードルコークス及び石油コークス等)及び炭素繊維等]、珪素系材料[珪素、酸化珪素(SiOx)、珪素−炭素複合体(炭素粒子の表面を珪素及び/又は炭化珪素で被覆したもの、珪素粒子又は酸化珪素粒子の表面を炭素及び/又は炭化珪素で被覆したもの並びに炭化珪素等)及び珪素合金(珪素−アルミニウム合金、珪素−リチウム合金、珪素−ニッケル合金、珪素−鉄合金、珪素−チタン合金、珪素−マンガン合金、珪素−銅合金及び珪素−スズ合金等)等]、導電性高分子(例えばポリアセチレン及びポリピロール等)、金属(スズ、アルミニウム、ジルコニウム及びチタン等)、金属酸化物(チタン酸化物及びリチウム・チタン酸化物等)及び金属合金(例えばリチウム−スズ合金、リチウム−アルミニウム合金及びリチウム−アルミニウム−マンガン合金等)等及びこれらと炭素系材料との混合物等が挙げられる。
上記リチウムイオン電池用負極活物質のうち、内部にリチウム又はリチウムイオンを含まないものについては、予め活物質の一部又は全部にリチウム又はリチウムイオンを含ませるプレドープ処理を施してもよい。
Examples of the negative electrode active material for lithium ion batteries include carbon materials [graphite, non-graphitizable carbon, amorphous carbon, resin fired bodies (for example, those obtained by firing and carbonizing phenol resin, furan resin, etc.), cokes (for example, Pitch coke, needle coke, petroleum coke, etc.) and carbon fiber, etc.], silicon-based materials [silicon, silicon oxide (SiOx), silicon-carbon composite (the surface of carbon particles coated with silicon and / or silicon carbide, The surface of silicon particles or silicon oxide particles coated with carbon and / or silicon carbide, silicon carbide, etc.) and silicon alloys (silicon-aluminum alloy, silicon-lithium alloy, silicon-nickel alloy, silicon-iron alloy, silicon- Titanium alloys, silicon-manganese alloys, silicon-copper alloys, silicon-tin alloys, etc.)], conductive polymers (for example, polyacetylene and poly Rolls, etc.), metals (tin, aluminum, zirconium, titanium, etc.), metal oxides (titanium oxide and lithium / titanium oxide, etc.) and metal alloys (eg lithium-tin alloys, lithium-aluminum alloys and lithium-aluminum) And a mixture of these with a carbon-based material.
Among the negative electrode active materials for lithium ion batteries described above, those that do not contain lithium or lithium ions may be subjected to a pre-doping treatment in which lithium or lithium ions are included in part or all of the active material in advance.
これらの中でも、電池容量等の観点から、炭素系材料、珪素系材料及びこれらの混合物が好ましく、炭素系材料としては、黒鉛、難黒鉛化性炭素及びアモルファス炭素がさらに好ましく、珪素系材料としては、酸化珪素及び珪素−炭素複合体がさらに好ましい。 Among these, from the viewpoint of battery capacity and the like, a carbon-based material, a silicon-based material, and a mixture thereof are preferable. As the carbon-based material, graphite, non-graphitizable carbon, and amorphous carbon are more preferable. Further, silicon oxide and silicon-carbon composite are more preferable.
リチウムイオン電池用負極活物質の体積平均粒子径は、電池の電気特性の観点から、0.01〜100μmが好ましく、0.1〜20μmであることがより好ましく、2〜10μmであることがさらに好ましい。 The volume average particle diameter of the negative electrode active material for a lithium ion battery is preferably 0.01 to 100 μm, more preferably 0.1 to 20 μm, and further preferably 2 to 10 μm, from the viewpoint of the electric characteristics of the battery. preferable.
本明細書において、リチウムイオン電池用活物質の体積平均粒子径は、マイクロトラック法(レーザー回折・散乱法)によって求めた粒度分布における積算値50%での粒径(Dv50)を意味する。マイクロトラック法とは、レーザー光を粒子に照射することによって得られる散乱光を利用して粒度分布を求める方法である。なお、体積平均粒子径の測定には、日機装(株)製のマイクロトラック等を用いることができる。 In this specification, the volume average particle diameter of the active material for a lithium ion battery means the particle diameter (Dv50) at an integrated value of 50% in the particle size distribution obtained by the microtrack method (laser diffraction / scattering method). The microtrack method is a method for obtaining a particle size distribution using scattered light obtained by irradiating particles with laser light. In addition, Nikkiso Co., Ltd. microtrack etc. can be used for the measurement of a volume average particle diameter.
続いて、本発明のリチウムイオン電池用被覆活物質を構成する被覆層について説明する。
被覆層は高分子化合物を含み、リチウムイオン電池用活物質の少なくとも一部を被覆している。
リチウムイオン電池用活物質の周囲が被覆層で被覆されていると、電極の体積変化が緩和され、電極の膨張を抑制することができる。さらに、リチウムイオン電池用被覆活物質の非水溶媒に対する濡れ性を向上させることができる。
Then, the coating layer which comprises the coating active material for lithium ion batteries of this invention is demonstrated.
The coating layer contains a polymer compound and covers at least a part of the active material for a lithium ion battery.
When the periphery of the active material for a lithium ion battery is covered with a coating layer, the volume change of the electrode is alleviated and the expansion of the electrode can be suppressed. Furthermore, the wettability with respect to the nonaqueous solvent of the coating active material for lithium ion batteries can be improved.
被覆層を構成する高分子化合物としては、電解液に浸漬した際の吸液率が10%以上であり、飽和吸液状態での引張破断伸び率が10%以上である高分子化合物が好ましい。 As the polymer compound constituting the coating layer, a polymer compound having a liquid absorption rate of 10% or more when immersed in an electrolytic solution and a tensile elongation at break in a saturated liquid absorption state of 10% or more is preferable.
電解液に浸漬した際の吸液率は、電解液に浸漬する前、浸漬した後の高分子化合物の重量を測定して、以下の式で求められる。
吸液率(%)=[(電解液浸漬後の高分子化合物の重量−電解液浸漬前の高分子化合物の重量)/電解液浸漬前の高分子化合物の重量]×100
吸液率を求めるための電解液としては、好ましくはエチレンカーボネート(EC)、ジエチルカーボネート(DEC)を体積割合でEC:DEC=3:7で混合した混合溶媒に、電解質としてLiPF6を1mol/Lの濃度になるように溶解した電解液を用いる。
吸液率を求める際の電解液への浸漬は、50℃、3日間行う。50℃、3日間の浸漬を行うことにより高分子化合物が飽和吸液状態となる。なお、飽和吸液状態とは、それ以上電解液に浸漬しても高分子化合物の重量が増えない状態をいう。
なお、リチウムイオン電池を製造する際に使用する電解液は、上記電解液に限定されるものではなく、他の電解液を使用してもよい。
The liquid absorption rate when dipped in the electrolytic solution is obtained by the following formula by measuring the weight of the polymer compound before dipping in the electrolytic solution and after dipping.
Absorption rate (%) = [(weight of polymer compound after immersion in electrolyte−weight of polymer compound before immersion in electrolyte) / weight of polymer compound before immersion in electrolyte] × 100
As an electrolytic solution for obtaining a liquid absorption rate, LiPF 6 is preferably added at a concentration of 1 mol / liter as an electrolyte in a mixed solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of EC: DEC = 3: 7. An electrolytic solution dissolved to a concentration of L is used.
The immersion in the electrolytic solution for determining the liquid absorption rate is performed at 50 ° C. for 3 days. By immersing at 50 ° C. for 3 days, the polymer compound becomes saturated. The saturated liquid absorption state refers to a state in which the weight of the polymer compound does not increase even when immersed in the electrolytic solution.
In addition, the electrolyte solution used when manufacturing a lithium ion battery is not limited to the said electrolyte solution, You may use another electrolyte solution.
吸液率が10%以上であると、リチウムイオンが高分子化合物を容易に透過することができるため、活物質層内でのイオン抵抗を低く保つことができる。吸液率が10%未満であると、リチウムイオンの伝導性が低くなり、リチウムイオン電池としての性能が充分に発揮されないことがある。
吸液率は20%以上であることが好ましく、30%以上であることがより好ましい。
また、吸液率の好ましい上限値としては、400%であり、より好ましい上限値としては300%である。
When the liquid absorption rate is 10% or more, lithium ions can easily permeate the polymer compound, so that the ionic resistance in the active material layer can be kept low. When the liquid absorption is less than 10%, the lithium ion conductivity is lowered, and the performance as a lithium ion battery may not be sufficiently exhibited.
The liquid absorption is preferably 20% or more, and more preferably 30% or more.
Moreover, as a preferable upper limit of a liquid absorption rate, it is 400%, and as a more preferable upper limit, it is 300%.
飽和吸液状態での引張破断伸び率は、高分子化合物をダンベル状に打ち抜き、上記吸液率の測定と同様に電解液への浸漬を50℃、3日間行って高分子化合物を飽和吸液状態として、ASTM D683(試験片形状TypeII)に準拠して測定することができる。引張破断伸び率は、引張試験において試験片が破断するまでの伸び率を下記式によって算出した値である。
引張破断伸び率(%)=[(破断時試験片長さ−試験前試験片長さ)/試験前試験片長さ]×100
The tensile elongation at break in the saturated liquid absorption state was determined by punching the polymer compound into a dumbbell shape and immersing it in an electrolytic solution at 50 ° C. for 3 days in the same manner as the measurement of the liquid absorption rate. The state can be measured according to ASTM D683 (test piece shape Type II). The tensile elongation at break is a value obtained by calculating the elongation until the test piece breaks in the tensile test according to the following formula.
Tensile elongation at break (%) = [(length of specimen at break−length of specimen before test) / length of specimen before test] × 100
高分子化合物の飽和吸液状態での引張破断伸び率が10%以上であると、高分子化合物が適度な柔軟性を有するため、充放電時の活物質の体積変化によって被覆層が剥離することを抑制しやすくなる。
引張破断伸び率は20%以上であることが好ましく、30%以上であることがより好ましい。
また、引張破断伸び率の好ましい上限値としては、400%であり、より好ましい上限値としては300%である。
When the tensile elongation at break in the saturated liquid absorption state of the polymer compound is 10% or more, the polymer compound has an appropriate flexibility, so that the coating layer peels off due to the volume change of the active material during charge / discharge. It becomes easy to suppress.
The tensile elongation at break is preferably 20% or more, and more preferably 30% or more.
Further, the preferable upper limit value of the tensile elongation at break is 400%, and the more preferable upper limit value is 300%.
リチウムイオン電池用活物質の重量に対する高分子化合物の重量の割合は、特に限定されるものではないが、0.1〜11重量%であることが好ましく、活物質がリチウムイオン電池用正極活物質である場合には0.1〜1重量%であることがさらに好ましく、活物質がリチウムイオン電池用負負極活物質である場合には1〜11重量%であるとさらに好ましい。 The ratio of the weight of the polymer compound to the weight of the active material for the lithium ion battery is not particularly limited, but is preferably 0.1 to 11% by weight, and the active material is the positive electrode active material for the lithium ion battery. Is more preferably 0.1 to 1% by weight, and further more preferably 1 to 11% by weight when the active material is a negative electrode active material for a lithium ion battery.
続いて、被覆層を構成する高分子化合物について具体的に説明する。
被覆層を構成する高分子化合物としては、熱可塑性樹脂や熱硬化性樹脂などが挙げられ、例えば、ビニル樹脂(A)、ウレタン樹脂(B)、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリイミド樹脂、シリコーン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、アニリン樹脂、アイオノマー樹脂、ポリカーボネート、ポリサッカロイド(アルギン酸ナトリウム等)及びこれらの混合物等が挙げられる。
これらの中では、電解液に浸漬した際の吸液率が10%以上であり、飽和吸液状態での引張破断伸び率が10%以上である高分子化合物がより好ましい。
Then, the high molecular compound which comprises a coating layer is demonstrated concretely.
Examples of the polymer compound constituting the coating layer include thermoplastic resins and thermosetting resins. For example, vinyl resin (A), urethane resin (B), polyester resin, polyamide resin, epoxy resin, polyimide resin, Examples thereof include silicone resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonates, polysaccharides (such as sodium alginate), and mixtures thereof.
Among these, a polymer compound having a liquid absorption rate of 10% or more when immersed in an electrolytic solution and a tensile elongation at break in a saturated liquid absorption state of 10% or more is more preferable.
ビニル樹脂(A)は、ビニルモノマー(a)を必須構成単量体とする重合体(A1)を含んでなる樹脂である。
特に、重合体(A1)は、ビニルモノマー(a)としてカルボキシル基又は酸無水物基を有するビニルモノマー(a1)又は下記一般式(2)で表されるビニルモノマー(a2)を含むことが好ましい。
CH2=C(R1)COOR2 (2)
[式(2)中、R1は水素原子又はメチル基であり、R2は炭素数4〜12の直鎖又は炭素数4〜36の分岐アルキル基である。]
ビニル樹脂(A)のうち、電解液に浸漬した際の吸液率が10%以上であり、飽和吸液状態での引張破断伸び率が10%以上であるものがより好ましい。
The vinyl resin (A) is a resin comprising a polymer (A1) having the vinyl monomer (a) as an essential constituent monomer.
In particular, the polymer (A1) preferably contains a vinyl monomer (a1) having a carboxyl group or an acid anhydride group as the vinyl monomer (a) or a vinyl monomer (a2) represented by the following general formula (2). .
CH 2 = C (R 1 ) COOR 2 (2)
[In Formula (2), R 1 is a hydrogen atom or a methyl group, and R 2 is a linear alkyl group having 4 to 12 carbon atoms or a branched alkyl group having 4 to 36 carbon atoms. ]
Among the vinyl resins (A), those having a liquid absorption rate of 10% or more when immersed in an electrolytic solution and a tensile elongation at break in a saturated liquid absorption state of 10% or more are more preferable.
カルボキシル基又は酸無水物基を有するビニルモノマー(a1)としては、(メタ)アクリル酸(a11)、クロトン酸、桂皮酸等の炭素数3〜15のモノカルボン酸;(無水)マレイン酸、フマル酸、(無水)イタコン酸、シトラコン酸、メサコン酸等の炭素数4〜24のジカルボン酸;アコニット酸等の炭素数6〜24の3価〜4価又はそれ以上の価数のポリカルボン酸等が挙げられる。これらの中でも(メタ)アクリル酸(a11)が好ましく、メタクリル酸がより好ましい。 Examples of the vinyl monomer (a1) having a carboxyl group or an acid anhydride group include monocarboxylic acids having 3 to 15 carbon atoms such as (meth) acrylic acid (a11), crotonic acid and cinnamic acid; (anhydrous) maleic acid, fumaric acid C4-C24 dicarboxylic acid such as acid, (anhydrous) itaconic acid, citraconic acid, mesaconic acid, etc .; C6-C24 trivalent to tetravalent or higher valent polycarboxylic acid such as aconitic acid, etc. Is mentioned. Among these, (meth) acrylic acid (a11) is preferable, and methacrylic acid is more preferable.
上記一般式(2)で表されるビニルモノマー(a2)において、R1は水素原子又はメチル基を表す。R1はメチル基であることが好ましい。
R2は、炭素数4〜12の直鎖若しくは分岐アルキル基、又は、炭素数13〜36の分岐アルキル基であることが好ましい。
In the vinyl monomer (a2) represented by the general formula (2), R 1 represents a hydrogen atom or a methyl group. R 1 is preferably a methyl group.
R 2 is preferably a linear or branched alkyl group having 4 to 12 carbon atoms or a branched alkyl group having 13 to 36 carbon atoms.
(a21)R2が炭素数4〜12の直鎖又は分岐アルキル基であるエステル化合物
炭素数4〜12の直鎖アルキル基としては、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基が挙げられる。
炭素数4〜12の分岐アルキル基としては、1−メチルプロピル基(sec−ブチル基)、2−メチルプロピル基、1,1−ジメチルエチル基(tert−ブチル基)、1−メチルブチル基、1,1−ジメチルプロピル基、1,2−ジメチルプロピル基、2,2−ジメチルプロピル基(ネオペンチル基)、1−メチルペンチル基、2−メチルペンチル基、3−メチルペンチル基、4−メチルペンチル基、1,1−ジメチルブチル基、1,2−ジメチルブチル基、1,3−ジメチルブチル基、2,2−ジメチルブチル基、2,3−ジメチルブチル基、1−エチルブチル基、2−エチルブチル基、1−メチルヘキシル基、2−メチルヘキシル基、2−メチルヘキシル基、4−メチルヘキシル基、5−メチルヘキシル基、1−エチルペンチル基、2−エチルペンチル基、3−エチルペンチル基、1,1−ジメチルペンチル基、1,2−ジメチルペンチル基、1,3−ジメチルペンチル基、2,2−ジメチルペンチル基、2,3−ジメチルペンチル基、2−エチルペンチル基、1−メチルヘプチル基、2−メチルヘプチル基、3−メチルヘプチル基、4−メチルヘプチル基、5−メチルヘプチル基、6−メチルヘプチル基、1,1−ジメチルヘキシル基、1,2−ジメチルヘキシル基、1,3−ジメチルヘキシル基、1,4−ジメチルヘキシル基、1,5−ジメチルヘキシル基、1−エチルヘキシル基、2−エチルヘキシル基、1−メチルオクチル基、2−メチルオクチル基、3−メチルオクチル基、4−メチルオクチル基、5−メチルオクチル基、6−メチルオクチル基、7−メチルオクチル基、1,1−ジメチルヘプチル基、1,2−ジメチルヘプチル基、1,3−ジメチルヘプチル基、1,4−ジメチルヘプチル基、1,5−ジメチルヘプチル基、1,6−ジメチルヘプチル基、1−エチルヘプチル基、2−エチルヘプチル基、1−メチルノニル基、2−メチルノニル基、3−メチルノニル基、4−メチルノニル基、5−メチルノニル基、6−メチルノニル基、7−メチルノニル基、8−メチルノニル基、1,1−ジメチルオクチル基、1,2−ジメチルオクチル基、1,3−ジメチルオクチル基、1,4−ジメチルオクチル基、1,5−ジメチルオクチル基、1,6−ジメチルオクチル基、1,7−ジメチルオクチル基、1−エチルオクチル基、2−エチルオクチル基、1−メチルデシル基、2−メチルデシル基、3−メチルデシル基、4−メチルデシル基、5−メチルデシル基、6−メチルデシル基、7−メチルデシル基、8−メチルデシル基、9−メチルデシル基、1,1−ジメチルノニル基、1,2−ジメチルノニル基、1,3−ジメチルノニル基、1,4−ジメチルノニル基、1,5−ジメチルノニル基、1,6−ジメチルノニル基、1,7−ジメチルノニル基、1,8−ジメチルノニル基、1−エチルノニル基、2−エチルノニル基、1−メチルウンデシル基、2−メチルウンデシル基、3−メチルウンデシル基、4−メチルウンデシル基、5−メチルウンデシル基、6−メチルウンデシル基、7−メチルウンデシル基、8−メチルウンデシル基、9−メチルウンデシル基、10−メチルウンデシル基、1,1−ジメチルデシル基、1,2−ジメチルデシル基、1,3−ジメチルデシル基、1,4−ジメチルデシル基、1,5−ジメチルデシル基、1,6−ジメチルデシル基、1,7−ジメチルデシル基、1,8−ジメチルデシル基、1,9−ジメチルデシル基、1−エチルデシル基、2−エチルデシル基等が挙げられる。
(A21) Ester compound in which R 2 is a linear or branched alkyl group having 4 to 12 carbon atoms As the linear alkyl group having 4 to 12 carbon atoms, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group can be mentioned.
Examples of the branched alkyl group having 4 to 12 carbon atoms include 1-methylpropyl group (sec-butyl group), 2-methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), 1-methylbutyl group, 1 , 1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group 1-methylhexyl group, 2-methylhexyl group, 2-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2 Ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2-ethylpentyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-methyloctyl group, 2- Methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl Group, 1,1-dimethylheptyl group, 1,2-dimethylheptyl group, 1,3-dimethylheptyl group, 1,4-dimethylheptyl group, 1,5-dimethylheptyl group, 1,6-dimethylheptyl group 1-ethylheptyl group, 2-ethylheptyl group, 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, 5-methylnonyl group, 6-methylnonyl group, 7-methylnonyl group, 8- Methylnonyl group, 1,1-dimethyloctyl group, 1,2-dimethyloctyl group, 1,3-dimethyloctyl group, 1,4-dimethyloctyl group, 1,5-dimethyloctyl group, 1,6-dimethyloctyl group 1,7-dimethyloctyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methyldecyl group, 2-methyldecyl group, 3-methyl Rudecyl group, 4-methyldecyl group, 5-methyldecyl group, 6-methyldecyl group, 7-methyldecyl group, 8-methyldecyl group, 9-methyldecyl group, 1,1-dimethylnonyl group, 1,2-dimethylnonyl group, 1 , 3-dimethylnonyl group, 1,4-dimethylnonyl group, 1,5-dimethylnonyl group, 1,6-dimethylnonyl group, 1,7-dimethylnonyl group, 1,8-dimethylnonyl group, 1-ethylnonyl Group, 2-ethylnonyl group, 1-methylundecyl group, 2-methylundecyl group, 3-methylundecyl group, 4-methylundecyl group, 5-methylundecyl group, 6-methylundecyl group, 7 -Methylundecyl group, 8-methylundecyl group, 9-methylundecyl group, 10-methylundecyl group, 1,1-dimethyldecyl group, 1,2-dimethyldecyl group Group, 1,3-dimethyldecyl group, 1,4-dimethyldecyl group, 1,5-dimethyldecyl group, 1,6-dimethyldecyl group, 1,7-dimethyldecyl group, 1,8-dimethyldecyl group 1,9-dimethyldecyl group, 1-ethyldecyl group, 2-ethyldecyl group and the like.
(a22)R2が炭素数13〜36の分岐アルキル基であるエステル化合物
炭素数13〜36の分岐アルキル基としては、1−アルキルアルキル基[1−メチルドデシル基、1−ブチルエイコシル基、1−ヘキシルオクタデシル基、1−オクチルヘキサデシル基、1−デシルテトラデシル基、1−ウンデシルトリデシル基等]、2−アルキルアルキル基[2−メチルドデシル基、2−ヘキシルオクタデシル基、2−オクチルヘキサデシル基、2−デシルテトラデシル基、2−ウンデシルトリデシル基、2−ドデシルヘキサデシル基、2−トリデシルペンタデシル基、2−デシルオクタデシル基、2−テトラデシルオクタデシル基、2−ヘキサデシルオクタデシル基、2−テトラデシルエイコシル基、2−ヘキサデシルエイコシル基等]、3〜34−アルキルアルキル基(3−アルキルアルキル基、4−アルキルアルキル基、5−アルキルアルキル基、32−アルキルアルキル基、33−アルキルアルキル基及び34−アルキルアルキル基等)、並びに、プロピレンオリゴマー(7〜11量体)、エチレン/プロピレン(モル比16/1〜1/11)オリゴマー、イソブチレンオリゴマー(7〜8量体)及びα−オレフィン(炭素数5〜20)オリゴマー(4〜8量体)等から得られるオキソアルコールから水酸基を除いた残基のような1又はそれ以上の分岐アルキル基を含有する混合アルキル基等が挙げられる。
(A22) R 2 is a branched alkyl group having 13 to 36 carbon atoms. Examples of the branched alkyl group having 13 to 36 carbon atoms include a 1-alkylalkyl group [1-methyldodecyl group, 1-butyleicosyl group, 1-hexyloctadecyl group, 1-octylhexadecyl group, 1-decyltetradecyl group, 1-undecyltridecyl group, etc.], 2-alkylalkyl group [2-methyldodecyl group, 2-hexyloctadecyl group, 2- Octylhexadecyl group, 2-decyltetradecyl group, 2-undecyltridecyl group, 2-dodecylhexadecyl group, 2-tridecylpentadecyl group, 2-decyloctadecyl group, 2-tetradecyloctadecyl group, 2- Hexadecyl octadecyl group, 2-tetradecyl eicosyl group, 2-hexadecyl eicosyl group, etc.], 3 34-alkylalkyl groups (3-alkylalkyl groups, 4-alkylalkyl groups, 5-alkylalkyl groups, 32-alkylalkyl groups, 33-alkylalkyl groups, 34-alkylalkyl groups, etc.), and propylene oligomers (7 To 11-mer), ethylene / propylene (molar ratio 16/1 to 1/11) oligomer, isobutylene oligomer (7 to 8-mer), and α-olefin (carbon number 5 to 20) oligomer (4 to 8-mer). And a mixed alkyl group containing one or more branched alkyl groups such as a residue obtained by removing a hydroxyl group from an oxo alcohol obtained from the above.
重合体(A1)は、炭素数1〜3の1価の脂肪族アルコールと(メタ)アクリル酸とのエステル化合物(a3)をさらに含んでいることが好ましい。
エステル化合物(a3)を構成する炭素数1〜3の1価の脂肪族アルコールとしては、メタノール、エタノール、1−プロパノール及び2−プロパノール等が挙げられる。
The polymer (A1) preferably further contains an ester compound (a3) of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid.
Examples of the monovalent aliphatic alcohol having 1 to 3 carbon atoms constituting the ester compound (a3) include methanol, ethanol, 1-propanol, and 2-propanol.
エステル化合物(a3)の含有量は、活物質の体積変化抑制等の観点から、重合体(A1)の合計重量に基づいて、10〜60重量%であることが好ましく、15〜55重量%であることがより好ましく、20〜50重量%であることがさらに好ましい。 The content of the ester compound (a3) is preferably 10 to 60% by weight based on the total weight of the polymer (A1) from the viewpoint of suppressing the volume change of the active material, and is preferably 15 to 55% by weight. More preferably, it is more preferably 20 to 50% by weight.
また、重合体(A1)は、さらに重合性不飽和二重結合とアニオン性基とを有するアニオン性単量体の塩(a4)を含有することが好ましい。
重合性不飽和二重結合を有する構造としてはビニル基、アリル基、スチレニル基及び(メタ)アクリロイル基等が挙げられる。
アニオン性基としては、スルホン酸基及びカルボキシル基等が挙げられる。
重合性不飽和二重結合とアニオン性基とを有するアニオン性単量体はこれらの組み合わせにより得られる化合物であり、例えばビニルスルホン酸、アリルスルホン酸、スチレンスルホン酸及び(メタ)アクリル酸が挙げられる。
なお、(メタ)アクリロイル基は、アクリロイル基及び/又はメタクリロイル基を意味する。
アニオン性単量体の塩(a4)を構成するカチオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオン及びアンモニウムイオン等が挙げられる。
The polymer (A1) preferably further contains a salt (a4) of an anionic monomer having a polymerizable unsaturated double bond and an anionic group.
Examples of the structure having a polymerizable unsaturated double bond include a vinyl group, an allyl group, a styryl group, and a (meth) acryloyl group.
Examples of the anionic group include a sulfonic acid group and a carboxyl group.
An anionic monomer having a polymerizable unsaturated double bond and an anionic group is a compound obtained by a combination thereof, such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid and (meth) acrylic acid. It is done.
The (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
Examples of the cation constituting the salt (a4) of the anionic monomer include lithium ion, sodium ion, potassium ion and ammonium ion.
アニオン性単量体の塩(a4)の含有量は、内部抵抗等の観点から、高分子化合物の合計重量に基づいて0.1〜15重量%であることが好ましく、1〜15重量%であることがより好ましく、2〜10重量%であることがさらに好ましい。 The content of the salt (a4) of the anionic monomer is preferably 0.1 to 15% by weight based on the total weight of the polymer compound from the viewpoint of internal resistance and the like, and is 1 to 15% by weight. More preferably, it is 2 to 10% by weight.
重合体(A1)は、(メタ)アクリル酸(a11)とエステル化合物(a21)とを含むことが好ましく、さらにエステル化合物(a3)を含むことがより好ましく、さらにアニオン性単量体の塩(a4)を含むことが特に好ましい。 The polymer (A1) preferably contains (meth) acrylic acid (a11) and an ester compound (a21), more preferably contains an ester compound (a3), and further contains an anionic monomer salt ( It is particularly preferred that a4) is included.
高分子化合物は、(メタ)アクリル酸(a11)、下記一般式(1)で示されるエステル化合物(a21)、炭素数1〜3の1価の脂肪族アルコールと(メタ)アクリル酸とのエステル化合物(a3)及び重合性不飽和二重結合とアニオン性基とを有するアニオン性単量体の塩(a4)を含んでなる単量体組成物を重合してなり、上記エステル化合物(a21)と上記(メタ)アクリル酸(a11)の重量比[上記エステル化合物(a21)/上記(メタ)アクリル酸(a11)]が10/90〜90/10であることが好ましい。
CH2=C(R1)COOR2 (1)
[R1は水素原子又はメチル基、R2は炭素数4〜12の直鎖又は分岐アルキル基である。]
エステル化合物(a21)と(メタ)アクリル酸(a11)の重量比が10/90〜90/10であると、これを重合してなる重合体は、活物質との接着性が良好で剥離しにくくなる。
上記重量比は、30/70〜85/15であることが好ましく、40/60〜70/30であることがさらに好ましい。
The polymer compound includes (meth) acrylic acid (a11), an ester compound (a21) represented by the following general formula (1), an ester of a monovalent aliphatic alcohol having 1 to 3 carbon atoms and (meth) acrylic acid. The ester compound (a21) obtained by polymerizing a compound (a3) and a monomer composition comprising a salt (a4) of an anionic monomer having a polymerizable unsaturated double bond and an anionic group. The weight ratio of [meth] acrylic acid (a11) [the ester compound (a21) / (meth) acrylic acid (a11)] is preferably 10/90 to 90/10.
CH 2 = C (R 1 ) COOR 2 (1)
[R 1 is a hydrogen atom or a methyl group, and R 2 is a linear or branched alkyl group having 4 to 12 carbon atoms. ]
When the weight ratio of the ester compound (a21) and (meth) acrylic acid (a11) is 10/90 to 90/10, the polymer obtained by polymerizing the ester compound (a21) has good adhesiveness to the active material and peels off. It becomes difficult.
The weight ratio is preferably 30/70 to 85/15, and more preferably 40/60 to 70/30.
また、重合体(A1)を構成する単量体には、カルボキシル基又は酸無水物基を有するビニルモノマー(a1)、上記一般式(2)で表されるビニルモノマー(a2)、炭素数1〜3の1価の脂肪族アルコールと(メタ)アクリル酸とのエステル化合物(a3)及び重合性不飽和二重結合とアニオン性基とを有するアニオン性単量体の塩(a4)の他に、活性水素を含有しない共重合性ビニルモノマー(a5)が含まれていてもよい。
活性水素を含有しない共重合性ビニルモノマー(a5)としては、下記(a51)〜(a58)が挙げられる。
(a51)炭素数13〜20の直鎖脂肪族モノオール、炭素数5〜20の脂環式モノオール又は炭素数7〜20の芳香脂肪族モノオールと(メタ)アクリル酸から形成されるハイドロカルビル(メタ)アクリレート
上記モノオールとしては、(i)直鎖脂肪族モノオール(トリデシルアルコール、ミリスチルアルコール、ペンタデシルアルコール、セチルアルコール、ヘプタデシルアルコール、ステアリルアルコール、ノナデシルアルコール、アラキジルアルコール等)、(ii)脂環式モノオール(シクロペンチルアルコール、シクロヘキシルアルコール、シクロヘプチルアルコール、シクロオクチルアルコール等)、(iii)芳香脂肪族モノオール(ベンジルアルコール等)及びこれらの2種以上の混合物が挙げられる。
The monomer constituting the polymer (A1) includes a vinyl monomer (a1) having a carboxyl group or an acid anhydride group, a vinyl monomer (a2) represented by the above general formula (2), and a carbon number of 1 In addition to the ester compound (a3) of a monovalent aliphatic alcohol of ~ 3 and (meth) acrylic acid, and a salt of an anionic monomer having a polymerizable unsaturated double bond and an anionic group (a4) The copolymerizable vinyl monomer (a5) which does not contain active hydrogen may be contained.
Examples of the copolymerizable vinyl monomer (a5) containing no active hydrogen include the following (a51) to (a58).
(A51) Hydro formed from a linear aliphatic monool having 13 to 20 carbon atoms, an alicyclic monool having 5 to 20 carbon atoms or an araliphatic monool having 7 to 20 carbon atoms and (meth) acrylic acid Carbyl (meth) acrylate As the monool, (i) linear aliphatic monool (tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol Etc.), (ii) alicyclic monools (cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol etc.), (iii) araliphatic monools (benzyl alcohol etc.) and mixtures of two or more thereof Can be mentioned.
(a52)ポリ(n=2〜30)オキシアルキレン(炭素数2〜4)アルキル(炭素数1〜18)エーテル(メタ)アクリレート[メタノールのエチレンオキサイド(以下EOと略記)10モル付加物(メタ)アクリレート、メタノールのプロピレンオキサイド(以下POと略記)10モル付加物(メタ)アクリレート等] (A52) poly (n = 2 to 30) oxyalkylene (2 to 4 carbon atoms) alkyl (1 to 18 carbon atoms) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meta ) Propylene oxide of acrylate, methanol (hereinafter abbreviated as PO), 10 mol adduct (meth) acrylate, etc.]
(a53)窒素含有ビニル化合物
(a53−1)アミド基含有ビニル化合物
(i)炭素数3〜30の(メタ)アクリルアミド化合物、例えばN,N−ジアルキル(炭素数1〜6)又はジアラルキル(炭素数7〜15)(メタ)アクリルアミド(N,N−ジメチルアクリルアミド、N,N−ジベンジルアクリルアミド等)、ジアセトンアクリルアミド
(ii)上記(メタ)アクリルアミド化合物を除く、炭素数4〜20のアミド基含有ビニル化合物、例えばN−メチル−N−ビニルアセトアミド、環状アミド[ピロリドン化合物(炭素数6〜13、例えば、N−ビニルピロリドン等)]
(A53) nitrogen-containing vinyl compound (a53-1) amide group-containing vinyl compound (i) (meth) acrylamide compound having 3 to 30 carbon atoms such as N, N-dialkyl (1 to 6 carbon atoms) or diaralkyl (carbon number) 7-15) (meth) acrylamide (N, N-dimethylacrylamide, N, N-dibenzylacrylamide, etc.), diacetone acrylamide (ii) amide group containing 4-20 carbon atoms excluding the above (meth) acrylamide compound Vinyl compounds such as N-methyl-N-vinylacetamide, cyclic amides [pyrrolidone compounds (having 6 to 13 carbon atoms, such as N-vinylpyrrolidone)]
(a53−2)(メタ)アクリレート化合物
(i)ジアルキル(炭素数1〜4)アミノアルキル(炭素数1〜4)(メタ)アクリレート[N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、t−ブチルアミノエチル(メタ)アクリレート、モルホリノエチル(メタ)アクリレート等]
(ii)4級アンモニウム基含有(メタ)アクリレート{3級アミノ基含有(メタ)アクリレート[N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート等]の4級化物(メチルクロライド、ジメチル硫酸、ベンジルクロライド、ジメチルカーボネート等の4級化剤を用いて4級化したもの)等}
(A53-2) (meth) acrylate compound (i) dialkyl (1 to 4 carbon atoms) aminoalkyl (1 to 4 carbon atoms) (meth) acrylate [N, N-dimethylaminoethyl (meth) acrylate, N, N -Diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, etc.]
(Ii) Quaternary ammonium group-containing (meth) acrylate {quaternary amino group-containing (meth) acrylate [N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, etc.] quaternary] (Quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.)}
(a53−3)複素環含有ビニル化合物
ピリジン化合物(炭素数7〜14、例えば2−又は4−ビニルピリジン)、イミダゾール化合物(炭素数5〜12、例えばN−ビニルイミダゾール)、ピロール化合物(炭素数6〜13、例えばN−ビニルピロール)、ピロリドン化合物(炭素数6〜13、例えばN−ビニル−2−ピロリドン)
(A53-3) Heterocycle-containing vinyl compound pyridine compound (carbon number 7 to 14, for example, 2- or 4-vinylpyridine), imidazole compound (carbon number 5 to 12, for example, N-vinylimidazole), pyrrole compound (carbon number) 6 to 13, for example, N-vinylpyrrole), pyrrolidone compound (6 to 13 carbon atoms, for example, N-vinyl-2-pyrrolidone)
(a53−4)ニトリル基含有ビニル化合物
炭素数3〜15のニトリル基含有ビニル化合物、例えば(メタ)アクリロニトリル、シアノスチレン、シアノアルキル(炭素数1〜4)アクリレート
(A53-4) Nitrile group-containing vinyl compound A nitrile group-containing vinyl compound having 3 to 15 carbon atoms such as (meth) acrylonitrile, cyanostyrene, cyanoalkyl (1 to 4 carbon atoms) acrylate
(a53−5)その他の窒素含有ビニル化合物
ニトロ基含有ビニル化合物(炭素数8〜16、例えばニトロスチレン)等
(A53-5) Other nitrogen-containing vinyl compounds Nitro group-containing vinyl compounds (8 to 16, for example, nitrostyrene), etc.
(a54)ビニル炭化水素
(a54−1)脂肪族ビニル炭化水素
炭素数2〜18又はそれ以上のオレフィン(エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン、オクタデセン等)、炭素数4〜10又はそれ以上のジエン(ブタジエン、イソプレン、1,4−ペンタジエン、1,5−ヘキサジエン、1,7−オクタジエン等)等
(A54) Vinyl hydrocarbon (a54-1) Aliphatic vinyl hydrocarbon olefin having 2 to 18 or more carbon atoms (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.), Diene having 4 to 10 or more carbon atoms (butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.), etc.
(a54−2)脂環式ビニル炭化水素
炭素数4〜18又はそれ以上の環状不飽和化合物、例えばシクロアルケン(例えばシクロヘキセン)、(ジ)シクロアルカジエン[例えば(ジ)シクロペンタジエン]、テルペン(例えばピネン及びリモネン)、インデン
(A54-2) Alicyclic vinyl hydrocarbon cyclic unsaturated compounds having 4 to 18 or more carbon atoms, such as cycloalkene (for example, cyclohexene), (di) cycloalkadiene [for example, (di) cyclopentadiene], terpene ( For example, pinene and limonene), indene
(a54−3)芳香族ビニル炭化水素
炭素数8〜20又はそれ以上の芳香族不飽和化合物、例えばスチレン、α−メチルスチレン、ビニルトルエン、2,4−ジメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、フェニルスチレン、シクロヘキシルスチレン、ベンジルスチレン
(A54-3) Aromatic vinyl hydrocarbon aromatic unsaturated compound having 8 to 20 or more carbon atoms, such as styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl Styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene
(a55)ビニルエステル
脂肪族ビニルエステル[炭素数4〜15、例えば脂肪族カルボン酸(モノ−又はジカルボン酸)のアルケニルエステル(例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ジアリルアジペート、イソプロペニルアセテート、ビニルメトキシアセテート)]
芳香族ビニルエステル[炭素数9〜20、例えば芳香族カルボン酸(モノ−又はジカルボン酸)のアルケニルエステル(例えばビニルベンゾエート、ジアリルフタレート、メチル−4−ビニルベンゾエート)、脂肪族カルボン酸の芳香環含有エステル(例えばアセトキシスチレン)]
(A55) vinyl ester aliphatic vinyl ester [carbon number 4-15, for example, alkenyl ester of aliphatic carboxylic acid (mono- or dicarboxylic acid) (for example, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl adipate, isopropenyl acetate, Vinyl methoxyacetate)]
Aromatic vinyl ester [carbon number 9-20, for example, alkenyl ester of aromatic carboxylic acid (mono- or dicarboxylic acid) (for example, vinyl benzoate, diallyl phthalate, methyl-4-vinyl benzoate), containing aromatic ring of aliphatic carboxylic acid Ester (eg acetoxystyrene)]
(a56)ビニルエーテル
脂肪族ビニルエーテル[炭素数3〜15、例えばビニルアルキル(炭素数1〜10)エーテル(ビニルメチルエーテル、ビニルブチルエーテル、ビニル2−エチルヘキシルエーテル等)、ビニルアルコキシ(炭素数1〜6)アルキル(炭素数1〜4)エーテル(ビニル−2−メトキシエチルエーテル、メトキシブタジエン、3,4−ジヒドロ−1,2−ピラン、2−ブトキシ−2’−ビニロキシジエチルエーテル、ビニル−2−エチルメルカプトエチルエーテル等)、ポリ(2〜4)(メタ)アリロキシアルカン(炭素数2〜6)(ジアリロキシエタン、トリアリロキシエタン、テトラアリロキシブタン、テトラメタアリロキシエタン等)]、芳香族ビニルエーテル(炭素数8〜20、例えばビニルフェニルエーテル、フェノキシスチレン)
(A56) vinyl ether aliphatic vinyl ether [carbon number 3 to 15, for example, vinyl alkyl (carbon number 1 to 10) ether (vinyl methyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, etc.), vinyl alkoxy (carbon number 1 to 6) Alkyl (C1-C4) ether (vinyl-2-methoxyethyl ether, methoxybutadiene, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl-2-ethyl Mercaptoethyl ether, etc.), poly (2-4) (meth) allyloxyalkanes (2-6 carbon atoms) (diallyloxyethane, triaryloxyethane, tetraallyloxybutane, tetrametaallyloxyethane, etc.)], Aromatic vinyl ether (carbon number 8-20, for example, vinyl phenyl ether , Phenoxystyrene)
(a57)ビニルケトン
脂肪族ビニルケトン(炭素数4〜25、例えばビニルメチルケトン、ビニルエチルケトン)、芳香族ビニルケトン(炭素数9〜21、例えばビニルフェニルケトン)
(A57) Vinyl ketone aliphatic vinyl ketone (4 to 25 carbon atoms such as vinyl methyl ketone, vinyl ethyl ketone), aromatic vinyl ketone (9 to 21 carbon atoms such as vinyl phenyl ketone)
(a58)不飽和ジカルボン酸ジエステル
炭素数4〜34の不飽和ジカルボン酸ジエステル、例えばジアルキルフマレート(2個のアルキル基は、炭素数1〜22の、直鎖、分岐鎖又は脂環式の基)、ジアルキルマレエート(2個のアルキル基は、炭素数1〜22の、直鎖、分岐鎖又は脂環式の基)
(A58) Unsaturated dicarboxylic acid diester An unsaturated dicarboxylic acid diester having 4 to 34 carbon atoms, such as a dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 1 to 22 carbon atoms) ), Dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 1 to 22 carbon atoms)
上記(a5)として例示したもののうち耐電圧の観点から好ましいのは、(a51)、(a52)及び(a53)である。 Of those exemplified as (a5) above, (a51), (a52) and (a53) are preferable from the viewpoint of withstand voltage.
重合体(A1)において、カルボキシル基又は酸無水物基を有するビニルモノマー(a1)、上記一般式(2)で表されるビニルモノマー(a2)、炭素数1〜3の1価の脂肪族アルコールと(メタ)アクリル酸とのエステル化合物(a3)、重合性不飽和二重結合とアニオン性基とを有するアニオン性単量体の塩(a4)及び活性水素を含有しない共重合性ビニルモノマー(a5)の含有量は、重合体(A1)の重量を基準として、(a1)が0.1〜80重量%、(a2)が0.1〜99.9重量%、(a3)が0〜60重量%、(a4)が0〜15重量%、(a5)が0〜99.8重量%であることが好ましい。
モノマーの含有量が上記範囲内であると、電解液への吸液性及び液滴消失時間が良好となる。
より好ましい含有量は、(a1)が15〜60重量%、(a2)が5〜60重量%、(a3)が10〜60重量%、(a4)が0.1〜15重量%、(a5)が5〜69.9重量%であり、さらに好ましい含有量は、(a1)が25〜49重量%、(a2)が15〜39重量%、(a3)が15〜39重量%、(a4)が1〜15重量%、(a5)が20〜44重量%である。
In the polymer (A1), a vinyl monomer (a1) having a carboxyl group or an acid anhydride group, a vinyl monomer (a2) represented by the above general formula (2), a monovalent aliphatic alcohol having 1 to 3 carbon atoms And (meth) acrylic acid ester compound (a3), a salt of an anionic monomer having a polymerizable unsaturated double bond and an anionic group (a4), and a copolymerizable vinyl monomer containing no active hydrogen ( The content of a5) is 0.1 to 80% by weight of (a1), 0.1 to 99.9% by weight of (a2), and 0 to (a3) based on the weight of the polymer (A1). 60% by weight, (a4) is preferably 0 to 15% by weight, and (a5) is preferably 0 to 99.8% by weight.
When the content of the monomer is within the above range, the liquid absorption property to the electrolytic solution and the droplet disappearance time are good.
More preferable contents are (a1) 15-60 wt%, (a2) 5-60 wt%, (a3) 10-60 wt%, (a4) 0.1-15 wt%, (a5 ) Is 5 to 69.9% by weight, and more preferable contents are (a1) 25 to 49% by weight, (a2) 15 to 39% by weight, (a3) 15 to 39% by weight, (a4) ) Is 1 to 15% by weight, and (a5) is 20 to 44% by weight.
重合体(A1)の数平均分子量の好ましい下限は3,000、より好ましくは50,000、さらに好ましくは100,000、特に好ましくは200,000であり、好ましい上限は2,000,000、より好ましくは1,500,000、さらに好ましくは1,000,000、特に好ましくは800,000である。 The preferable lower limit of the number average molecular weight of the polymer (A1) is 3,000, more preferably 50,000, still more preferably 100,000, particularly preferably 200,000, and the preferable upper limit is 2,000,000. It is preferably 1,500,000, more preferably 1,000,000, and particularly preferably 800,000.
重合体(A1)の数平均分子量は、以下の条件でゲルパーミエーションクロマトグラフィー(以下GPCと略記)測定により求めることができる。
装置:Alliance GPC V2000(Waters社製)
溶媒:オルトジクロロベンゼン
標準物質:ポリスチレン
検出器:RI
サンプル濃度:3mg/ml
カラム固定相:PLgel 10μm、MIXED−B 2本直列(ポリマーラボラトリーズ社製)
カラム温度:135℃
The number average molecular weight of the polymer (A1) can be determined by gel permeation chromatography (hereinafter abbreviated as GPC) measurement under the following conditions.
Apparatus: Alliance GPC V2000 (manufactured by Waters)
Solvent: Orthodichlorobenzene Reference material: Polystyrene detector: RI
Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series (manufactured by Polymer Laboratories)
Column temperature: 135 ° C
重合体(A1)の溶解度パラメータ(以下、SP値と略記する)は9.0〜20.0(cal/cm3)1/2であることが好ましい。重合体(A1)のSP値は10.0〜18.0(cal/cm3)1/2であることがより好ましく、11.5〜14.0(cal/cm3)1/2であることがさらに好ましい。重合体(A1)のSP値が9.0〜20.0(cal/cm3)1/2であると、電解液の吸液性及び液滴消失時間短縮の点で好ましい。
SP値は、Fedors法によって計算される。SP値は、次式で表せる。
SP値(δ)=(ΔH/V)1/2
但し、式中、ΔHはモル蒸発熱(cal)を、Vはモル体積(cm3)を表す。
また、ΔH及びVは、「POLYMER ENGINEERING AND SCIENCE,1974,Vol.14,No.2,ROBERT F.FEDORS.(151〜153頁)」に記載の原子団のモル蒸発熱の合計(ΔH)とモル体積の合計(V)を用いることができる。
SP値は、この数値が近いもの同士はお互いに混ざりやすく(相溶性が高い)、この数値が離れているものは混ざりにくいことを表す指標である。
The solubility parameter (hereinafter abbreviated as SP value) of the polymer (A1) is preferably 9.0 to 20.0 (cal / cm 3 ) 1/2 . The SP value of the polymer (A1) is more preferably 10.0 to 18.0 (cal / cm 3 ) 1/2 , and 11.5 to 14.0 (cal / cm 3 ) 1/2 . More preferably. When the SP value of the polymer (A1) is 9.0 to 20.0 (cal / cm 3 ) 1/2, it is preferable in terms of the liquid absorbency of the electrolytic solution and the shortening of the liquid drop disappearance time.
The SP value is calculated by the Fedors method. The SP value can be expressed by the following equation.
SP value (δ) = (ΔH / V) 1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm 3 ).
ΔH and V are the sum of the heat of molar evaporation (ΔH) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153)”. The total molar volume (V) can be used.
The SP value is an index indicating that those having a close numerical value are easily mixed with each other (high compatibility), and those having a close numerical value are difficult to mix.
また、重合体(A1)のガラス転移点[以下Tgと略記、測定法:DSC(走査型示差熱分析)法]は、電池の耐熱性の観点から好ましくは80〜200℃、より好ましくは90〜180℃、さらに好ましくは100〜150℃である。 The glass transition point of the polymer (A1) [hereinafter abbreviated as Tg, measuring method: DSC (scanning differential thermal analysis) method] is preferably 80 to 200 ° C., more preferably 90, from the viewpoint of heat resistance of the battery. It is -180 degreeC, More preferably, it is 100-150 degreeC.
重合体(A1)は、公知の重合方法(塊状重合、溶液重合、乳化重合、懸濁重合等)により製造することができる。
重合に際しては、公知の重合開始剤{アゾ系開始剤[2,2’−アゾビス(2−メチルプロピオニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル等)]、パーオキサイド系開始剤(ベンゾイルパーオキサイド、ジ−t−ブチルパーオキサイド、ラウリルパーオキサイド等)等}を使用して行なうことができる。
重合開始剤の使用量は、モノマーの全重量に基づいて好ましくは0.01〜5重量%、より好ましくは0.05〜2重量%、さらに好ましくは0.1〜1.5重量%である。
The polymer (A1) can be produced by a known polymerization method (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
In the polymerization, a known polymerization initiator {azo initiator [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile, etc.)], peroxide System initiators (benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.)} can be used.
The amount of the polymerization initiator used is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, still more preferably 0.1 to 1.5% by weight, based on the total weight of the monomers. .
溶液重合の場合に使用される溶媒としては、例えばエステル(炭素数2〜8、例えば酢酸エチル及び酢酸ブチル)、アルコール(炭素数1〜8、例えばメタノール、エタノール及びオクタノール)、炭化水素(炭素数4〜8、例えばn−ブタン、シクロヘキサン及びトルエン)及びケトン(炭素数3〜9、例えばメチルエチルケトン)が挙げられ、使用量はモノマーの合計重量に基づいて好ましくは5〜900重量%、より好ましくは10〜400重量%、さらに好ましくは30〜300重量%であり、モノマー濃度としては、好ましくは10〜95重量%、より好ましくは20〜90重量%、さらに好ましくは30〜80重量%である。 Examples of the solvent used in the solution polymerization include esters (having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate), alcohol (having 1 to 8 carbon atoms such as methanol, ethanol and octanol), and hydrocarbons (having carbon atoms). 4-8, such as n-butane, cyclohexane and toluene, and ketones (3-9 carbon atoms such as methyl ethyl ketone), preferably 5 to 900% by weight, more preferably based on the total weight of the monomers. It is 10 to 400% by weight, more preferably 30 to 300% by weight, and the monomer concentration is preferably 10 to 95% by weight, more preferably 20 to 90% by weight, and further preferably 30 to 80% by weight.
乳化重合及び懸濁重合における分散媒としては、水、アルコール(例えばエタノール)、エステル(例えばプロピオン酸エチル)、軽ナフサ等が挙げられ、乳化剤としては、高級脂肪酸(炭素数10〜24)金属塩(例えばオレイン酸ナトリウム及びステアリン酸ナトリウム)、高級アルコール(炭素数10〜24)硫酸エステル金属塩(例えばラウリル硫酸ナトリウム)、エトキシ化テトラメチルデシンジオール、メタクリル酸スルホエチルナトリウム、メタクリル酸ジメチルアミノメチル等が挙げられる。さらに安定剤としてポリビニルアルコール、ポリビニルピロリドン等を加えてもよい。
溶液又は分散液のモノマー濃度は好ましくは5〜95重量%、より好ましくは10〜90重量%、さらに好ましくは15〜85重量%であり、重合開始剤の使用量は、モノマーの全重量に基づいて好ましくは0.01〜5重量%、より好ましくは0.05〜2重量%である。
重合に際しては、公知の連鎖移動剤、例えばメルカプト化合物(ドデシルメルカプタン、n−ブチルメルカプタン等)及び/又はハロゲン化炭化水素(四塩化炭素、四臭化炭素、塩化ベンジル等)を使用することができる。使用量はモノマーの全重量に基づいて好ましくは2重量%以下、より好ましくは0.5重量%以下、さらに好ましくは0.3重量%以下である。
Examples of the dispersion medium in the emulsion polymerization and the suspension polymerization include water, alcohol (for example, ethanol), ester (for example, ethyl propionate), light naphtha and the like, and the emulsifier includes a higher fatty acid (having 10 to 24 carbon atoms) metal salt. (For example, sodium oleate and sodium stearate), higher alcohols (10 to 24 carbon atoms) sulfate metal salts (for example, sodium lauryl sulfate), ethoxylated tetramethyldecynediol, sulfoethyl sodium methacrylate, dimethylaminomethyl methacrylate, etc. Is mentioned. Furthermore, you may add polyvinyl alcohol, polyvinylpyrrolidone, etc. as a stabilizer.
The monomer concentration of the solution or dispersion is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, and still more preferably 15 to 85% by weight. The amount of the polymerization initiator used is based on the total weight of the monomers. It is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight.
In the polymerization, known chain transfer agents such as mercapto compounds (such as dodecyl mercaptan and n-butyl mercaptan) and / or halogenated hydrocarbons (such as carbon tetrachloride, carbon tetrabromide and benzyl chloride) can be used. . The amount used is preferably 2% by weight or less, more preferably 0.5% by weight or less, and still more preferably 0.3% by weight or less, based on the total weight of the monomers.
また、重合反応における系内温度は好ましくは−5〜150℃、より好ましくは30〜120℃、さらに好ましくは50〜110℃、反応時間は好ましくは0.1〜50時間、より好ましくは2〜24時間であり、反応の終点は、未反応単量体の量を使用した単量体全量の5重量%以下とすることが好ましく、より好ましくは1重量%以下、さらに好ましくは0.5重量%以下である。未反応単量体の量は、ガスクロマトグラフィー等の公知の定量手段を用いることにより確認できる。 The system temperature in the polymerization reaction is preferably -5 to 150 ° C, more preferably 30 to 120 ° C, still more preferably 50 to 110 ° C, and the reaction time is preferably 0.1 to 50 hours, more preferably 2 to 2. 24 hours, and the end point of the reaction is preferably 5% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight of the total amount of monomers using the amount of unreacted monomer. % Or less. The amount of the unreacted monomer can be confirmed by using a known quantitative means such as gas chromatography.
ビニル樹脂(A)に含まれる重合体(A1)は、重合体(A1)をポリエポキシ化合物(a’1)及び/又はポリオール化合物(a’2)で架橋してなる架橋重合体であってもよい。
架橋重合体においては、重合体(A1)中のカルボキシル基等の活性水素と反応する反応性官能基を有する架橋剤(A’)を用いて重合体(A1)を架橋することが好ましく、架橋剤(A’)としてポリエポキシ化合物(a’1)及び/又はポリオール化合物(a’2)を用いることが好ましい。
The polymer (A1) contained in the vinyl resin (A) is a crosslinked polymer obtained by crosslinking the polymer (A1) with a polyepoxy compound (a′1) and / or a polyol compound (a′2). Also good.
In the crosslinked polymer, the polymer (A1) is preferably crosslinked using a crosslinking agent (A ′) having a reactive functional group that reacts with active hydrogen such as a carboxyl group in the polymer (A1). As the agent (A ′), it is preferable to use a polyepoxy compound (a′1) and / or a polyol compound (a′2).
ポリエポキシ化合物(a’1)としては、エポキシ当量80〜2,500のもの、例えばグリシジルエーテル[ビスフェノールAジグリシジルエーテル、ビスフェノールFジグリシジルエーテル、ピロガロールトリグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテル、ポリエチレングリコール(Mw200〜2,000)ジグリシジルエーテル、ポリプロピレングリコール(Mw200〜2,000)ジグリシジルエーテル、ビスフェノールAのアルキレンオキサイド1〜20モル付加物のジグリシジルエーテル等];グリシジルエステル(フタル酸ジグリシジルエステル、トリメリット酸トリグリシジルエステル、ダイマー酸ジグリシジルエステル、アジピン酸ジグリシジルエステル等);グリシジルアミン[N,N−ジグリシジルアニリン、N,N−ジグリシジルトルイジン、N,N,N’,N’−テトラグリシジルジアミノジフェニルメタン、N,N,N’,N’−テトラグリシジルキシリレンジアミン、1,3−ビス(N,N−ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’−テトラグリシジルヘキサメチレンジアミン等];脂肪族エポキシド(エポキシ化ポリブタジエン、エポキシ化大豆油等);脂環式エポキシド(リモネンジオキサイド、ジシクロペンタジエンジオキサイド等)が挙げられる。 Examples of the polyepoxy compound (a′1) include those having an epoxy equivalent of 80 to 2,500, such as glycidyl ether [bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, pyrogallol triglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol (Mw 200-2,000) diglycidyl ether, polypropylene glycol (Mw 200-2,000) diglycidyl ether, bisphenol Diglycidyl ether of an alkylene oxide 1-20 mol adduct of A, etc.]; Diglycidyl oxalate, triglycidyl trimellitic acid, diglycidyl dimer, diglycidyl adipate, etc.); glycidyl amine [N, N-diglycidyl aniline, N, N-diglycidyl toluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidylxylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl hexamethylenediamine, etc.]; aliphatic epoxides (epoxidized polybutadiene, epoxidized soybean oil, etc.); alicyclic epoxides (limonene dioxide, dicyclopentadiene dioxide, etc.).
ポリオール化合物(a’2)としては、低分子多価アルコール{炭素数2〜20の脂肪族又は脂環式のジオール[エチレングリコール(以下EGと略記)、ジエチレングリコール(以下DEGと略記)、プロピレングリコール、1,3−ブチレングリコール、1,4−ブタンジオール(以下14BGと略記)、1,6−ヘキサンジオール、3−メチルペンタンジオール、ネオペンチルグリコール、1,9−ノナンジオール、1,4−ジヒドロキシシクロヘキサン、1,4−ビス(ヒドロキシメチル)シクロヘキサン、2,2−ビス(4,4’−ヒドロキシシクロヘキシル)プロパン等];炭素数8〜15の芳香環含有ジオール[m−又はp−キシリレングリコール、1,4−ビス(ヒドロキシエチル)ベンゼン等];炭素数3〜8のトリオール(グリセリン、トリメチロールプロパン等);4価以上の多価アルコール[ペンタエリスリトール、α−メチルグルコシド、ソルビトール、キシリット、マンニット、グルコース、フルクトース、ショ糖、ジペンタエリスリトール、ポリグリセリン(重合度2〜20)等]等}、及びこれらのアルキレン(炭素数2〜4)オキサイド付加物(重合度2〜30)等が挙げられる。 Examples of the polyol compound (a′2) include low-molecular polyhydric alcohols {aliphatic or alicyclic diols having 2 to 20 carbon atoms [ethylene glycol (hereinafter abbreviated as EG), diethylene glycol (hereinafter abbreviated as DEG), propylene glycol] 1,3-butylene glycol, 1,4-butanediol (hereinafter abbreviated as 14BG), 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol, 1,9-nonanediol, 1,4-dihydroxy Cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4,4′-hydroxycyclohexyl) propane, etc.]; aromatic ring-containing diol having 8 to 15 carbon atoms [m- or p-xylylene glycol 1,4-bis (hydroxyethyl) benzene, etc.]; a trio having 3 to 8 carbon atoms (Glycerin, trimethylolpropane, etc.); polyhydric alcohols having a valence of 4 or more [pentaerythritol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, sucrose, dipentaerythritol, polyglycerol (degree of polymerization of 2 20) etc.], etc.], and alkylene (2 to 4 carbon atoms) oxide adducts thereof (degree of polymerization 2 to 30).
架橋剤(A’)の使用量は、電解液の吸液性及び液滴消失時間短縮の観点から、重合体(A1)中の活性水素含有基と、架橋剤(A’)中の反応性官能基の当量比が好ましくは、1:0.01〜1:2、より好ましくは1:0.02〜1:1となる量である。 The amount of the cross-linking agent (A ′) used is such that the active hydrogen-containing group in the polymer (A1) and the reactivity in the cross-linking agent (A ′) are from the viewpoint of the liquid absorbency of the electrolyte and shortening the liquid drop disappearance time. The equivalent ratio of the functional groups is preferably in an amount of 1: 0.01 to 1: 2, more preferably 1: 0.02 to 1: 1.
架橋剤(A’)を用いて重合体(A1)を架橋する方法としては、リチウムイオン電池用活物質を重合体(A1)で被覆した後に架橋する方法が挙げられる。具体的には、リチウムイオン電池用活物質と重合体(A1)を含む樹脂溶液を混合し脱溶剤することにより、リチウムイオン電池用活物質が重合体(A1)で被覆された被覆活物質を製造した後に、架橋剤(A’)を含む溶液を該被覆活物質に混合して加熱することにより、脱溶剤と架橋反応を生じさせて、重合体(A1)が架橋剤(A’)によって架橋されて高分子化合物となる反応をリチウムイオン電池用活物質の表面で起こす方法が挙げられる。
加熱温度は、架橋剤としてポリエポキシ化合物(a’1)を用いる場合は70℃以上とすることが好ましく、ポリオール化合物(a’2)を用いる場合は120℃以上とすることが好ましい。
Examples of the method of crosslinking the polymer (A1) using the crosslinking agent (A ′) include a method of crosslinking after coating the lithium ion battery active material with the polymer (A1). Specifically, by mixing a resin solution containing a lithium ion battery active material and a polymer (A1) and removing the solvent, a coated active material in which the lithium ion battery active material is coated with the polymer (A1) is obtained. After the production, the solution containing the crosslinking agent (A ′) is mixed with the coated active material and heated to cause solvent removal and a crosslinking reaction, whereby the polymer (A1) is transformed with the crosslinking agent (A ′). Examples thereof include a method of causing a reaction that is crosslinked to become a polymer compound on the surface of the active material for a lithium ion battery.
The heating temperature is preferably 70 ° C. or higher when the polyepoxy compound (a′1) is used as a crosslinking agent, and is preferably 120 ° C. or higher when the polyol compound (a′2) is used.
被覆層を構成する高分子化合物としては、ウレタン樹脂(B)が好ましい。
ウレタン樹脂(B)のうち、電解液に浸漬した際の吸液率が10%以上であり、飽和吸液状態での引張破断伸び率が10%以上であるものがより好ましい。
As a high molecular compound which comprises a coating layer, a urethane resin (B) is preferable.
Among the urethane resins (B), those having a liquid absorption rate of 10% or more when immersed in an electrolytic solution and a tensile elongation at break in a saturated liquid absorption state of 10% or more are more preferable.
ウレタン樹脂(B)は、活性水素成分(b1)及びイソシアネート成分(b2)を反応させて得られる樹脂である。 The urethane resin (B) is a resin obtained by reacting the active hydrogen component (b1) and the isocyanate component (b2).
活性水素成分(b1)としては、ポリエーテルジオール、ポリカーボネートジオール及びポリエステルジオールからなる群から選ばれる少なくとも1種を含むことが好ましい。 The active hydrogen component (b1) preferably contains at least one selected from the group consisting of polyether diol, polycarbonate diol and polyester diol.
ポリエーテルジオールとしては、ポリオキシエチレングリコール(以下PEGと略記)、ポリオキシエチレンオキシプロピレンブロック共重合ジオール、ポリオキシエチレンオキシテトラメチレンブロック共重合ジオール;EG、プロピレングリコール、14BG、1,6−ヘキサメチレングリコール、ネオペンチルグリコール、ビス(ヒドロキシメチル)シクロヘキサン、4,4’−ビス(2−ヒドロキシエトキシ)−ジフェニルプロパン等の低分子グリコールのエチレンオキサイド付加物;数平均分子量2,000以下のPEGと、ジカルボン酸[炭素数4〜10の脂肪族ジカルボン酸(例えばコハク酸、アジピン酸、セバシン酸等)、炭素数8〜15の芳香族ジカルボン酸(例えばテレフタル酸、イソフタル酸等)等]の1種以上とを反応させて得られる縮合ポリエーテルエステルジオール;及びこれらの2種以上の混合物が挙げられる。
ポリエーテルジオール中にオキシエチレン単位が含まれる場合、オキシエチレン単位の含有量は好ましくは20重量%以上、より好ましくは30重量%以上、さらに好ましくは40重量%以上である。
また、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール(以下PTMGと略記)、ポリオキシプロピレンオキシテトラメチレンブロック共重合ジオール等も挙げられる。
これらのうち、好ましくはPEG、ポリオキシエチレンオキシプロピレンブロック共重合ジオール及びポリオキシエチレンオキシテトラメチレンブロック共重合ジオールであり、より好ましくはPEGである。
また、ポリエーテルジオールを1種のみ用いてもよいし、これらの2種以上の混合物を用いてもよい。
Polyether diols include polyoxyethylene glycol (hereinafter abbreviated as PEG), polyoxyethyleneoxypropylene block copolymer diol, polyoxyethyleneoxytetramethylene block copolymer diol; EG, propylene glycol, 14BG, 1,6-hexa Ethylene oxide adducts of low-molecular glycols such as methylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, 4,4′-bis (2-hydroxyethoxy) -diphenylpropane; PEG having a number average molecular weight of 2,000 or less; 1 of dicarboxylic acids [aliphatic dicarboxylic acids having 4 to 10 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, etc.), aromatic dicarboxylic acids having 8 to 15 carbon atoms (for example, terephthalic acid, isophthalic acid, etc.), etc.] More than species A condensed polyetherester diol obtained by reaction; and a mixture of two or more of these.
When the polyether diol contains an oxyethylene unit, the content of the oxyethylene unit is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight or more.
Also included are polyoxypropylene glycol, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxypropyleneoxytetramethylene block copolymer diol, and the like.
Of these, PEG, polyoxyethyleneoxypropylene block copolymer diol and polyoxyethyleneoxytetramethylene block copolymer diol are preferred, and PEG is more preferred.
Moreover, only 1 type of polyether diol may be used, and 2 or more types of these mixtures may be used.
ポリカーボネートジオールとしては、例えばポリヘキサメチレンカーボネートジオールが挙げられる。 Examples of the polycarbonate diol include polyhexamethylene carbonate diol.
ポリエステルジオールとしては、低分子ジオール及び/又は数平均分子量1,000以下のポリエーテルジオールと前述のジカルボン酸の1種以上とを反応させて得られる縮合ポリエステルジオールや、炭素数4〜12のラクトンの開環重合により得られるポリラクトンジオール等が挙げられる。上記低分子ジオールとして上記ポリエーテルジオールの項で例示した低分子グリコール等が挙げられる。上記数平均分子量1,000以下のポリエーテルジオールとしてはポリオキシプロピレングリコール、PTMG等が挙げられる。上記ラクトンとしては、例えばε−カプロラクトン、γ−バレロラクトン等が挙げられる。該ポリエステルジオールの具体例としては、ポリエチレンアジペートジオール、ポリブチレンアジペートジオール、ポリネオペンチレンアジペートジオール、ポリ(3−メチル−1,5−ペンチレンアジペート)ジオール、ポリヘキサメチレンアジペートジオール、ポリカプロラクトンジオール及びこれらの2種以上の混合物が挙げられる。 The polyester diol includes a condensed polyester diol obtained by reacting a low-molecular diol and / or a polyether diol having a number average molecular weight of 1,000 or less with one or more of the aforementioned dicarboxylic acids, or a lactone having 4 to 12 carbon atoms. And polylactone diols obtained by ring-opening polymerization. Examples of the low molecular diol include low molecular glycols exemplified in the section of the polyether diol. Examples of the polyether diol having a number average molecular weight of 1,000 or less include polyoxypropylene glycol and PTMG. Examples of the lactone include ε-caprolactone and γ-valerolactone. Specific examples of the polyester diol include polyethylene adipate diol, polybutylene adipate diol, polyneopentylene adipate diol, poly (3-methyl-1,5-pentylene adipate) diol, polyhexamethylene adipate diol, polycaprolactone diol. And mixtures of two or more thereof.
また、活性水素成分(b1)は上記ポリエーテルジオール、ポリカーボネートジオール及びポリエステルジオールのうちの2種以上の混合物であってもよい。 The active hydrogen component (b1) may be a mixture of two or more of the polyether diol, polycarbonate diol and polyester diol.
活性水素成分(b1)は数平均分子量2,500〜15,000の高分子ジオール(b11)を必須成分とすることが好ましい。高分子ジオール(b11)としては上述したポリエーテルジオール、ポリカーボネートジオール及びポリエステルジオール等が挙げられる。
高分子ジオール(b11)は、数平均分子量が2,500〜15,000であるとウレタン樹脂(B)の硬さが適度に柔らかく、また、活物質上に形成した被覆層の強度が強くなるため好ましい。
また、高分子ジオール(b11)の数平均分子量が3,000〜12,500であることがより好ましく、4,000〜10,000であることがさらに好ましい。
高分子ジオール(b11)の数平均分子量は、高分子ジオールの水酸基価から算出することができる。
また、水酸基価は、JIS K1557−1の記載に準じて測定できる。
The active hydrogen component (b1) preferably contains a polymer diol (b11) having a number average molecular weight of 2,500 to 15,000 as an essential component. Examples of the polymer diol (b11) include the polyether diol, polycarbonate diol, and polyester diol described above.
When the polymer diol (b11) has a number average molecular weight of 2,500 to 15,000, the hardness of the urethane resin (B) is moderately soft, and the strength of the coating layer formed on the active material is increased. Therefore, it is preferable.
The number average molecular weight of the polymer diol (b11) is more preferably from 3,000 to 12,500, and further preferably from 4,000 to 10,000.
The number average molecular weight of the polymer diol (b11) can be calculated from the hydroxyl value of the polymer diol.
The hydroxyl value can be measured according to the description of JIS K1557-1.
また、活性水素成分(b1)が数平均分子量2,500〜15,000の高分子ジオール(b11)を必須成分とし、上記高分子ジオール(b11)の溶解度パラメータ(SP値)が8.0〜12.0(cal/cm3)1/2であることが好ましい。高分子ジオール(b11)のSP値は8.5〜11.5(cal/cm3)1/2であることがより好ましく、9.0〜11.0(cal/cm3)1/2であることがさらに好ましい。高分子ジオール(b11)のSP値が8.0〜12.0(cal/cm3)1/2であると、ウレタン樹脂(B)の電解液の吸液性及び液滴消失時間短縮の点で好ましい。 The active hydrogen component (b1) has a polymer diol (b11) having a number average molecular weight of 2,500 to 15,000 as an essential component, and the solubility parameter (SP value) of the polymer diol (b11) is 8.0 to 8.0. It is preferably 12.0 (cal / cm 3 ) 1/2 . More preferably SP value of the polymer diol (b11) is 8.5~11.5 (cal / cm 3) 1/2 , in 9.0~11.0 (cal / cm 3) 1/2 More preferably it is. When the SP value of the polymer diol (b11) is 8.0 to 12.0 (cal / cm 3 ) 1/2 , the liquid absorbency of the electrolyte solution of the urethane resin (B) and the point of shortening the droplet disappearance time Is preferable.
また、活性水素成分(b1)が数平均分子量2,500〜15,000の高分子ジオール(b11)を必須成分とし、上記高分子ジオール(b11)の含有量が上記ウレタン樹脂(B)の重量を基準として20〜80重量%であることが好ましい。高分子ジオール(b11)の含有量は30〜70重量%であることがより好ましく、40〜65重量%であることがさらに好ましい。
高分子ジオール(b11)の含有量が20〜80重量%であると、ウレタン樹脂(B)の電解液の吸液性及び液滴消失時間短縮の点で好ましい。
The active hydrogen component (b1) has a polymer diol (b11) having a number average molecular weight of 2,500 to 15,000 as an essential component, and the content of the polymer diol (b11) is the weight of the urethane resin (B). It is preferable that it is 20 to 80 weight% on the basis of. The content of the polymer diol (b11) is more preferably 30 to 70% by weight, and further preferably 40 to 65% by weight.
When the content of the polymer diol (b11) is 20 to 80% by weight, it is preferable from the viewpoint of the liquid absorbency of the electrolyte solution of the urethane resin (B) and shortening of the droplet disappearance time.
また、活性水素成分(b1)が数平均分子量2,500〜15,000の高分子ジオール(b11)及び鎖伸長剤(b13)を必須成分とすることが好ましい。
鎖伸長剤(b13)としては、例えば炭素数2〜10の低分子ジオール(例えばEG、プロピレングリコール、14BG、DEG、1,6−ヘキサメチレングリコール等);ジアミン類[炭素数2〜6の脂肪族ジアミン(例えばエチレンジアミン、1,2−プロピレンジアミン等)、炭素数6〜15の脂環式ジアミン(例えばイソホロンジアミン、4,4’−ジアミノジシクロヘキシルメタン等)、炭素数6〜15の芳香族ジアミン(例えば4,4’−ジアミノジフェニルメタン等)等];モノアルカノールアミン(例えばモノエタノールアミン等);ヒドラジン又はその誘導体(例えばアジピン酸ジヒドラジド等)及びこれらの2種以上の混合物が挙げられる。これらのうち好ましいものは低分子ジオールであり、さらに好ましいものはEG、DEG及び14BGである。
高分子ジオール(b11)及び鎖伸長剤(b13)の組み合わせとしては、高分子ジオール(b11)としてのPEGと鎖伸長剤(b13)としてのEGの組み合わせ、又は、高分子ジオール(b11)としてのポリカーボネートジオールと鎖伸長剤(b13)としてのEGの組み合わせが好ましい。
In addition, it is preferable that the active hydrogen component (b1) includes a polymer diol (b11) having a number average molecular weight of 2,500 to 15,000 and a chain extender (b13) as essential components.
Examples of the chain extender (b13) include low-molecular diols having 2 to 10 carbon atoms (for example, EG, propylene glycol, 14BG, DEG, 1,6-hexamethylene glycol); diamines [fats having 2 to 6 carbon atoms] Group diamines (for example, ethylene diamine, 1,2-propylene diamine, etc.), alicyclic diamines having 6 to 15 carbon atoms (for example, isophorone diamine, 4,4′-diaminodicyclohexylmethane, etc.), aromatic diamines having 6 to 15 carbon atoms (For example, 4,4′-diaminodiphenylmethane and the like); monoalkanolamine (for example, monoethanolamine and the like); hydrazine or a derivative thereof (for example, adipic acid dihydrazide and the like) and a mixture of two or more of these. Of these, low molecular diols are preferred, and EG, DEG and 14BG are more preferred.
As a combination of the polymer diol (b11) and the chain extender (b13), a combination of PEG as the polymer diol (b11) and EG as the chain extender (b13), or as a polymer diol (b11) A combination of polycarbonate diol and EG as a chain extender (b13) is preferred.
また、活性水素成分(b1)が数平均分子量2,500〜15,000の高分子ジオール(b11)、上記高分子ジオール(b11)以外のジオール(b12)及び鎖伸長剤(b13)を含み、(b11)と(b12)との当量比[(b11)/(b12)]が10/1〜30/1であり、(b11)と(b12)及び(b13)の合計当量との当量比{(b11)/[(b12)+(b13)]}が0.9/1〜1.1/1であることが好ましい。
なお、(b11)と(b12)との当量比[(b11)/(b12)]はより好ましくは13/1〜25/1であり、さらに好ましくは15/1〜20/1である。
The active hydrogen component (b1) includes a polymer diol (b11) having a number average molecular weight of 2,500 to 15,000, a diol (b12) other than the polymer diol (b11), and a chain extender (b13), The equivalent ratio [(b11) / (b12)] of (b11) and (b12) is 10/1 to 30/1, and the equivalent ratio of (b11) to the total equivalent of (b12) and (b13) { (B11) / [(b12) + (b13)]} is preferably 0.9 / 1 to 1.1 / 1.
In addition, the equivalent ratio [(b11) / (b12)] of (b11) and (b12) is more preferably 13/1 to 25/1, and further preferably 15/1 to 20/1.
高分子ジオール(b11)以外のジオール(b12)としては、ジオールであって上述した高分子ジオール(b11)に含まれず、鎖伸長剤(b13)の炭素数2〜10の低分子ジオールに含まれないものであれば特に限定されるものではなく、具体的には、数平均分子量が2,500未満のジオール、及び、数平均分子量が15,000を超えるジオールが挙げられる。
ジオールの種類としては、上述したポリエーテルジオール、ポリカーボネートジオール及びポリエステルジオール等が挙げられる。
The diol (b12) other than the polymer diol (b11) is a diol and is not included in the polymer diol (b11) described above, but is included in the low molecular diol having 2 to 10 carbon atoms of the chain extender (b13). If it does not have, it will not specifically limit, Specifically, the diol whose number average molecular weight is less than 2,500, and the diol whose number average molecular weight exceeds 15,000 are mentioned.
Examples of the diol include the polyether diol, polycarbonate diol, and polyester diol described above.
イソシアネート成分(b2)としては、従来ウレタン樹脂製造に使用されているものが使用できる。このようなイソシアネートには、炭素数(NCO基中の炭素を除く、以下同様)6〜20の芳香族ジイソシアネート、炭素数2〜18の脂肪族ジイソシアネート、炭素数4〜15の脂環式ジイソシアネート、炭素数8〜15の芳香脂肪族ジイソシアネート、これらのジイソシアネートの変性体(カーボジイミド変性体、ウレタン変性体、ウレトジオン変性体等)及びこれらの2種以上の混合物が含まれる。 As an isocyanate component (b2), what is conventionally used for urethane resin manufacture can be used. Such isocyanates include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, C8-15 araliphatic diisocyanates, modified products of these diisocyanates (carbodiimide modified products, urethane modified products, uretdione modified products, etc.) and mixtures of two or more of these.
上記芳香族ジイソシアネートの具体例としては、1,3−又は1,4−フェニレンジイソシアネート、2,4−又は2,6−トリレンジイソシアネート、2,4’−又は4,4’−ジフェニルメタンジイソシアネート(以下、ジフェニルメタンジイソシアネートをMDIと略記)、4,4’−ジイソシアナトビフェニル、3,3’−ジメチル−4,4’−ジイソシアナトビフェニル、3,3’−ジメチル−4,4’−ジイソシアナトジフェニルメタン、1,5−ナフチレンジイソシアネート等が挙げられる。 Specific examples of the aromatic diisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate (hereinafter referred to as “the aromatic diisocyanate”). Diphenylmethane diisocyanate is abbreviated as MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanate Natodiphenylmethane, 1,5-naphthylene diisocyanate and the like can be mentioned.
上記脂肪族ジイソシアネートの具体例としては、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、2,6−ジイソシアナトメチルカプロエート、ビス(2−イソシアナトエチル)カーボネート、2−イソシアナトエチル−2,6−ジイソシアナトヘキサノエート等が挙げられる。 Specific examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, Examples thereof include bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
上記脂環式ジイソシアネートの具体例としては、イソホロンジイソシアネート、ジシクロヘキシルメタン−4,4’−ジイソシアネート、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート、ビス(2−イソシアナトエチル)−4−シクロヘキシレン−1,2−ジカルボキシレート、2,5−又は2,6−ノルボルナンジイソシアネート等が挙げられる。 Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2. -Dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and the like.
上記芳香脂肪族ジイソシアネートの具体例としては、m−又はp−キシリレンジイソシアネート、α,α,α’,α’−テトラメチルキシリレンジイソシアネート等が挙げられる。 Specific examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
これらのうち好ましいものは芳香族ジイソシアネート及び脂環式ジイソシアネートであり、より好ましいものは芳香族ジイソシアネートであり、さらに好ましいのはMDIである。 Among these, preferred are aromatic diisocyanates and alicyclic diisocyanates, more preferred are aromatic diisocyanates, and still more preferred is MDI.
ウレタン樹脂(B)が高分子ジオール(b11)及びイソシアネート成分(b2)を含む場合、好ましい(b2)/(b11)の当量比は10/1〜30/1であり、より好ましくは11/1〜28/1であり、さらに好ましくは15/1〜25/1である。イソシアネート成分(b2)の比率が30当量を超えると硬い被覆層となる。
また、ウレタン樹脂(B)が高分子ジオール(b11)、鎖伸長剤(b13)及びイソシアネート成分(b2)を含む場合、(b2)/[(b11)+(b13)]の当量比は好ましくは0.9/1〜1.1/1、より好ましくは0.95/1〜1.05/1である。この範囲外の場合ではウレタン樹脂が充分に高分子量にならないことがある。
When the urethane resin (B) contains the polymer diol (b11) and the isocyanate component (b2), the equivalent ratio of (b2) / (b11) is preferably 10/1 to 30/1, more preferably 11/1. It is -28/1, More preferably, it is 15/1-25/1. When the ratio of the isocyanate component (b2) exceeds 30 equivalents, a hard coating layer is obtained.
Further, when the urethane resin (B) contains the polymer diol (b11), the chain extender (b13) and the isocyanate component (b2), the equivalent ratio of (b2) / [(b11) + (b13)] is preferably 0.9 / 1 to 1.1 / 1, more preferably 0.95 / 1 to 1.05 / 1. If it is outside this range, the urethane resin may not have a sufficiently high molecular weight.
ウレタン樹脂(B)の数平均分子量は、40,000〜500,000であることが好ましく、より好ましくは50,000〜400,000であり、さらに好ましくは60,000〜300,000である。ウレタン樹脂(B)の数平均分子量が40,000未満では被覆層の強度が低くなり、500,000を超えると溶液粘度が高くなって、均一な被覆層が得られないことがある。 The number average molecular weight of the urethane resin (B) is preferably 40,000 to 500,000, more preferably 50,000 to 400,000, and further preferably 60,000 to 300,000. When the number average molecular weight of the urethane resin (B) is less than 40,000, the strength of the coating layer is lowered, and when it exceeds 500,000, the solution viscosity is increased and a uniform coating layer may not be obtained.
ウレタン樹脂(B)の数平均分子量は、ジメチルホルムアミド(以下DMFと略記)を溶剤として用い、ポリオキシプロピレングリコールを標準物質としてGPCにより測定される。サンプル濃度は0.25重量%、カラム固定相はTSKgel SuperH2000、TSKgel SuperH3000、TSKgel SuperH4000[いずれも東ソー(株)製]を各1本連結したもの、カラム温度は40℃とすればよい。 The number average molecular weight of the urethane resin (B) is measured by GPC using dimethylformamide (hereinafter abbreviated as DMF) as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration may be 0.25% by weight, the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 [both manufactured by Tosoh Corporation], and the column temperature may be 40 ° C.
ウレタン樹脂(B)は活性水素成分(b1)とイソシアネート成分(b2)を反応させて製造することができる。
例えば、活性水素成分(b1)として高分子ジオール(b11)と鎖伸長剤(b13)を用い、イソシアネート成分(b2)と高分子ジオール(b11)と鎖伸長剤(b13)とを同時に反応させるワンショット法や、高分子ジオール(b11)とイソシアネート成分(b2)とを先に反応させた後に鎖伸長剤(b13)を続けて反応させるプレポリマー法が挙げられる。
また、ウレタン樹脂(B)の製造は、イソシアネート基に対して不活性な溶媒の存在下又は非存在下で行うことができる。溶媒の存在下で行う場合の適当な溶媒としては、アミド系溶媒[DMF、ジメチルアセトアミド、N−メチル−2−ピロリドン(以下NMPと略記)等]、スルホキシド系溶媒(ジメチルスルホキシド等)、ケトン系溶媒(メチルエチルケトン、メチルイソブチルケトン等)、芳香族系溶媒(トルエン、キシレン等)、エーテル系溶媒(ジオキサン、テトラヒドロフラン等)、エステル系溶媒(酢酸エチル、酢酸ブチル等)及びこれらの2種以上の混合物が挙げられる。これらのうち好ましいものはアミド系溶媒、ケトン系溶媒、芳香族系溶媒及びこれらの2種以上の混合物である。
The urethane resin (B) can be produced by reacting the active hydrogen component (b1) and the isocyanate component (b2).
For example, the polymer diol (b11) and the chain extender (b13) are used as the active hydrogen component (b1), and the isocyanate component (b2), the polymer diol (b11), and the chain extender (b13) are reacted simultaneously. Examples thereof include a shot method and a prepolymer method in which the polymer diol (b11) and the isocyanate component (b2) are reacted first and then the chain extender (b13) is reacted continuously.
The urethane resin (B) can be produced in the presence or absence of a solvent inert to the isocyanate group. Suitable solvents when used in the presence of a solvent include amide solvents [DMF, dimethylacetamide, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), etc.], sulfoxide solvents (dimethyl sulfoxide, etc.), ketone solvents. Solvents (methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic solvents (toluene, xylene, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (ethyl acetate, butyl acetate, etc.) and mixtures of two or more of these Is mentioned. Among these, amide solvents, ketone solvents, aromatic solvents, and mixtures of two or more thereof are preferable.
ウレタン樹脂(B)の製造に際し、反応温度は公知のウレタン化反応に採用される温度と同じでよく、溶媒を使用する場合は好ましくは20〜100℃、無溶媒の場合は好ましくは20〜220℃である。 In the production of the urethane resin (B), the reaction temperature may be the same as the temperature employed in the known urethanization reaction, preferably 20 to 100 ° C. when a solvent is used, and preferably 20 to 220 when no solvent is used. ° C.
反応を促進させるために必要により、公知のウレタン化反応に使用される触媒[例えばアミン系触媒(トリエチルアミン、トリエチレンジアミン等)、錫系触媒(ジブチルチンジラウレート等)]を使用することができる。 In order to accelerate the reaction, a catalyst used in a known urethanization reaction [for example, an amine catalyst (triethylamine, triethylenediamine, etc.), a tin catalyst (dibutyltin dilaurate, etc.)] can be used.
また、必要により重合停止剤[例えば1価アルコール(エタノール、イソプロパノール、ブタノール等)、1価アミン(ジメチルアミン、ジブチルアミン等)等]を用いることもできる。 Moreover, a polymerization terminator [for example, monohydric alcohol (ethanol, isopropanol, butanol, etc.), monovalent amine (dimethylamine, dibutylamine, etc.), etc.] can also be used if necessary.
本発明のリチウムイオン電池用被覆活物質が有する被覆層は、さらに導電剤を含んでいてもよく、活物質が正極活物質である場合には導電剤を含むことが好ましい。
被覆層が導電剤を含む場合、導電剤は、導電性を有する材料から選択される。
具体的には、金属[ニッケル、アルミニウム、ステンレス(SUS)、銀、銅及びチタン等]、カーボン[グラファイト及びカーボンブラック(アセチレンブラック、ケッチェンブラック、ファーネスブラック、チャンネルブラック、サーマルランプブラック等)等]、及びこれらの混合物等が挙げられるが、これらに限定されるわけではない。
これらの導電剤は1種単独で用いてもよいし、2種以上併用してもよい。また、これらの合金又は金属酸化物を用いてもよい。電気的安定性の観点から、好ましくはアルミニウム、ステンレス、カーボン、銀、銅、チタン及びこれらの混合物であり、より好ましくは銀、アルミニウム、ステンレス及びカーボンであり、さらに好ましくはカーボンである。またこれらの導電剤としては、粒子系セラミック材料や樹脂材料の周りに導電性材料(上記した導電剤の材料のうち金属のもの)をめっき等でコーティングしたものでもよい。
The coating layer which the covering active material for lithium ion batteries of this invention has may contain the electrically conductive agent further, and when an active material is a positive electrode active material, it is preferable that an electrically conductive agent is included.
When the coating layer includes a conductive agent, the conductive agent is selected from materials having conductivity.
Specifically, metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, etc.], carbon [graphite and carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), etc. , And mixtures thereof, but are not limited thereto.
These conductive agents may be used alone or in combination of two or more. Further, these alloys or metal oxides may be used. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, copper, titanium and a mixture thereof are preferable, silver, aluminum, stainless steel and carbon are more preferable, and carbon is more preferable. Moreover, as these electrically conductive agents, what coated the electroconductive material (a metal thing among the materials of the above-mentioned electrically conductive agent) by plating etc. around the particulate ceramic material or the resin material may be used.
導電剤の平均粒子径は、特に限定されるものではないが、電池の電気特性の観点から、0.01〜10μmであることが好ましく、0.02〜5μmであることがより好ましく、0.03〜1μmであることがさらに好ましい。なお、本明細書中において、「粒子径」とは、導電剤の輪郭線上の任意の2点間の距離のうち、最大の距離Lを意味する。「平均粒子径」の値としては、走査型電子顕微鏡(SEM)や透過型電子顕微鏡(TEM)等の観察手段を用い、数〜数十視野中に観察される粒子の粒子径の平均値として算出される値を採用するものとする。 The average particle diameter of the conductive agent is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm from the viewpoint of the electric characteristics of the battery, and More preferably, it is 03-1 micrometer. In the present specification, the “particle diameter” means the maximum distance L among the distances between any two points on the contour line of the conductive agent. As the value of “average particle diameter”, the average value of the particle diameter of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
導電剤の形状(形態)は、粒子形態に限られず、粒子形態以外の形態であってもよく、カーボンナノチューブ等、いわゆるフィラー系導電性樹脂組成物として実用化されている形態であってもよい。 The shape (form) of the conductive agent is not limited to the particle form, and may be a form other than the particle form, or may be a form that is put into practical use as a so-called filler-based conductive resin composition such as a carbon nanotube. .
導電剤は、その形状が繊維状である導電性繊維であってもよい。
導電性繊維としては、PAN系炭素繊維、ピッチ系炭素繊維等の炭素繊維、合成繊維の中に導電性のよい金属や黒鉛を均一に分散させてなる導電性繊維、ステンレス鋼のような金属を繊維化した金属繊維、有機物繊維の表面を金属で被覆した導電性繊維、有機物繊維の表面を導電性物質を含む樹脂で被覆した導電性繊維等が挙げられる。これらの導電性繊維の中では炭素繊維が好ましい。また、グラフェンを練りこんだポリプロピレン樹脂も好ましい。
導電剤が導電性繊維である場合、その平均繊維径は0.1〜20μmであることが好ましい。
The conductive agent may be a conductive fiber having a fibrous shape.
Examples of conductive fibers include carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, conductive fibers obtained by uniformly dispersing highly conductive metal and graphite in synthetic fibers, and metals such as stainless steel. Examples thereof include fiberized metal fibers, conductive fibers in which the surface of organic fiber is coated with metal, and conductive fibers in which the surface of organic fiber is coated with a resin containing a conductive substance. Among these conductive fibers, carbon fibers are preferable. A polypropylene resin in which graphene is kneaded is also preferable.
When the conductive agent is a conductive fiber, the average fiber diameter is preferably 0.1 to 20 μm.
被覆層が導電剤を含む場合、リチウムイオン電池用被覆活物質の重量に対する高分子化合物と導電剤との合計重量の割合は、特に限定されるものではないが、1〜25重量%であることが好ましく、1〜20重量%がさらに好ましい。なかでも、リチウムイオン電池用活物質がリチウムイオン電池用正極活物質である場合には、1〜15重量%が特に好ましい。 When the coating layer contains a conductive agent, the ratio of the total weight of the polymer compound and the conductive agent to the weight of the coating active material for the lithium ion battery is not particularly limited, but should be 1 to 25% by weight. 1 to 20% by weight is more preferable. Especially, when the active material for lithium ion batteries is a positive electrode active material for lithium ion batteries, 1 to 15 weight% is especially preferable.
被覆層が導電剤を含む場合、被覆層が含有する導電剤の重量に対する高分子化合物の重量の割合は、特に限定されるものではないが、リチウムイオン電池用活物質がリチウムイオン電池用正極活物質の場合には、1〜4重量%であることが好ましい。また、リチウムイオン電池用活物質がリチウムイオン電池用負極活物質の場合には、13〜500重量%であることが好ましく、10〜35重量%であることがより好ましい。被覆層が含有する導電剤の重量に対する高分子化合物の重量の割合が上記範囲であると、リチウムイオン電池の内部抵抗が低くなり好ましい。 When the coating layer contains a conductive agent, the ratio of the weight of the polymer compound to the weight of the conductive agent contained in the coating layer is not particularly limited, but the lithium ion battery active material is the positive electrode active material for the lithium ion battery. In the case of a substance, it is preferably 1 to 4% by weight. Moreover, when the active material for lithium ion batteries is a negative electrode active material for lithium ion batteries, it is preferable that it is 13 to 500 weight%, and it is more preferable that it is 10 to 35 weight%. When the ratio of the weight of the polymer compound to the weight of the conductive agent contained in the coating layer is in the above range, the internal resistance of the lithium ion battery is preferably reduced.
被覆層が導電剤を含む場合、リチウムイオン電池用活物質の重量に対する導電剤の重量の割合は、特に限定されるものではないが、2〜14重量%であることが好ましい。 When the coating layer includes a conductive agent, the ratio of the weight of the conductive agent to the weight of the lithium ion battery active material is not particularly limited, but is preferably 2 to 14% by weight.
被覆層の導電率は、リチウムイオン電池用活物質がリチウムイオン電池用負極活物質の場合には、0.0001〜10mS/cmであることが好ましく、0.01〜5mS/cmであることがより好ましい。
被覆層の導電率は、四端子法によって求めることができる。
被覆層の導電率が0.0001mS/cm以上であると、リチウムイオン電池の内部抵抗が高くなりすぎず、好ましい。
The conductivity of the coating layer is preferably 0.0001 to 10 mS / cm, and preferably 0.01 to 5 mS / cm when the lithium ion battery active material is a lithium ion battery negative electrode active material. More preferred.
The conductivity of the coating layer can be determined by the four probe method.
When the electrical conductivity of the coating layer is 0.0001 mS / cm or more, the internal resistance of the lithium ion battery does not become too high, which is preferable.
被覆層の導電率は、リチウムイオン電池用活物質がリチウムイオン電池用正極活物質の場合には、0.001〜10mS/cmであることが好ましく、0.01〜5mS/cmであることがより好ましい。
被覆層の導電率が0.001mS/cm以上であると、リチウムイオン電池の内部抵抗が高くなりすぎず、好ましい。
The conductivity of the coating layer is preferably 0.001 to 10 mS / cm, and preferably 0.01 to 5 mS / cm when the active material for a lithium ion battery is a positive electrode active material for a lithium ion battery. More preferred.
It is preferable that the electrical conductivity of the coating layer is 0.001 mS / cm or more because the internal resistance of the lithium ion battery does not become too high.
以下、上述した本発明のリチウムイオン電池用被覆活物質を製造する方法について説明する。
本発明のリチウムイオン電池用活物質被覆活物質は、高分子化合物及びリチウムイオン電池用活物質並びに必要により用いる導電剤を混合することによって製造してもよく、被覆層に導電剤を用いる場合には高分子化合物と導電剤とを混合して被覆材を準備したのち、該被覆材とリチウムイオン電池用活物質とを混合することにより製造してもよく、高分子化合物、導電剤及びリチウムイオン電池用活物質を混合することによって製造してもよい。
なお、リチウムイオン電池用活物質と高分子化合物と導電剤とを混合する場合、混合順序には特に制限はないが、リチウムイオン電池用活物質と高分子化合物とを混合した後、更に導電剤を加えて更に混合することが好ましい。
上記方法により、高分子化合物と必要により用いる導電剤を含む被覆層によってリチウムイオン電池用活物質の表面の少なくとも一部が被覆される。
Hereinafter, the method for producing the above-described coated active material for a lithium ion battery of the present invention will be described.
The active material coated active material for lithium ion battery of the present invention may be produced by mixing a polymer compound, an active material for lithium ion battery, and a conductive agent used as necessary. When a conductive agent is used for the coating layer, May be prepared by mixing a polymer compound and a conductive agent to prepare a coating material, and then mixing the coating material and an active material for a lithium ion battery. You may manufacture by mixing the active material for batteries.
In addition, when mixing the active material for lithium ion batteries, the polymer compound, and the conductive agent, the mixing order is not particularly limited, but after mixing the active material for lithium ion batteries and the polymer compound, the conductive agent is further added. It is preferable to add and further mix.
By the above method, at least a part of the surface of the active material for a lithium ion battery is coated with a coating layer containing a polymer compound and a conductive agent used as necessary.
リチウムイオン電池用被覆活物質を製造する方法において用いるリチウムイオン電池用活物質、高分子化合物及び導電剤としては、それぞれ本発明のリチウムイオン電池用被覆活物質において説明したものを好適に用いることができる。 As the active material for lithium ion battery, the polymer compound and the conductive agent used in the method for producing a coated active material for lithium ion battery, those described in the coated active material for lithium ion battery of the present invention are preferably used. it can.
本発明のリチウムイオン電池用被覆活物質は、例えば、リチウムイオン電池用活物質を万能混合機に入れて30〜50rpmで撹拌した状態で、高分子化合物を含む高分子溶液を1〜90分かけて滴下混合し、さらに導電剤を混合し、撹拌したまま50〜200℃に昇温し、0.007〜0.04MPaまで減圧した後に10〜150分保持することにより得ることができる。 The coated active material for a lithium ion battery according to the present invention can be obtained, for example, by adding a polymer solution containing a polymer compound for 1 to 90 minutes in a state where the active material for a lithium ion battery is placed in a universal mixer and stirred at 30 to 50 rpm. The mixture can be mixed by dropping, further mixed with a conductive agent, heated to 50 to 200 ° C. with stirring, decompressed to 0.007 to 0.04 MPa, and held for 10 to 150 minutes.
リチウムイオン電池用活物質と高分子化合物との配合比率は特に限定されるものではないが、重量比率でリチウムイオン電池用活物質:高分子化合物=1:0.001〜0.1であることが好ましい。 The mixing ratio of the active material for the lithium ion battery and the polymer compound is not particularly limited, but the active material for the lithium ion battery: the polymer compound is 1: 0.001 to 0.1 by weight ratio. Is preferred.
本発明のリチウムイオン電池用被覆活物質を電極とする際は、リチウムイオン電池用被覆活物質及び導電材料を、分散媒(水、電解液又は溶剤)の重量に基づいて30〜60重量%の濃度で分散してスラリー化した分散液を、集電体にバーコーター等の塗工装置で塗布後、分散媒として水又は溶剤を用いた場合には乾燥することによって、分散媒として電解液を用いた場合には過剰の電解液をスポンジ等の吸収体に吸収させたり、メッシュを介して吸引することよって分散媒を除去して、必要によりプレス機でプレスすればよい。
上記分散液には、必要に応じてリチウムイオン電池用の電極に含まれる公知の電極用バインダ[ポリフッ化ビニリデン(PVdF)等]を添加してもよいが、電極用バインダは添加しないことが好ましい。電極活物質として被覆電極活物質を用いていない従来公知のリチウムイオン電池用の電極においては、電極用バインダで活物質を電極内に固定することで導電経路を維持する必要がある。しかし、本発明のリチウムイオン電池用被覆活物質を用いた場合は、被覆層の働きによって活物質を電極内に固定することなく導電経路を維持することができるため、電極用バインダを添加する必要がない。電極用バインダを添加しないことによって、活物質が電極内に固定化されないため活物質の体積変化に対する緩和能力が更に良好となる。
なお、電極の製造に用いる導電材料は、被覆層が含む導電剤とは別であり、被覆活物質が有する被覆層の外部に存在し、活物質層中において被覆活物質表面からの電子伝導性を向上する機能を有する。
When the coated active material for lithium ion batteries of the present invention is used as an electrode, the coated active material for lithium ion batteries and the conductive material are 30 to 60% by weight based on the weight of the dispersion medium (water, electrolytic solution or solvent). After applying the dispersion liquid in the form of a slurry to a current collector with a coating device such as a bar coater on the current collector, when using water or a solvent as the dispersion medium, the electrolyte is used as the dispersion medium by drying. When used, the dispersion medium is removed by absorbing an excess electrolyte solution in an absorbent body such as a sponge or sucking it through a mesh, and pressing may be performed by a press if necessary.
A known electrode binder [polyvinylidene fluoride (PVdF), etc.] contained in an electrode for a lithium ion battery may be added to the dispersion as necessary, but it is preferable not to add an electrode binder. . In a conventionally known electrode for a lithium ion battery that does not use a coated electrode active material as an electrode active material, it is necessary to maintain the conductive path by fixing the active material in the electrode with an electrode binder. However, when the coated active material for lithium ion batteries of the present invention is used, the conductive path can be maintained without fixing the active material in the electrode by the action of the coating layer, so it is necessary to add an electrode binder There is no. By not adding the electrode binder, the active material is not immobilized in the electrode, so that the ability to relax the volume change of the active material is further improved.
Note that the conductive material used for manufacturing the electrode is different from the conductive agent included in the coating layer, exists outside the coating layer of the coating active material, and conducts electrons from the surface of the coating active material in the active material layer. It has a function to improve.
分散媒のうち、水としては、イオン交換水及び超純水等が挙げられる。
分散媒のうち、電解液としては、本発明のリチウムイオン電池用被覆活物質を含む電極を用いてリチウムイオン電池を作製する際に使用する電解液(後述する)と同じものを用いることができる。
分散媒のうち、溶剤としては、本発明のリチウムイオン電池用被覆活物質を含む電極を用いてリチウムイオン電池を作製する際に使用する電解液を構成する非水溶媒と同じものを用いることができ、これらの他にも、1−メチル−2−ピロリドン、ジメチルアセトアミド及びN,N−ジメチルアミノプロピルアミン等が挙げられる。
集電体としては、銅、アルミニウム、チタン、ステンレス鋼及びニッケル等の金属箔、導電性高分子からなる樹脂集電体(特開2012−150905号公報等に記載されている)、導電性炭素シート及び導電性ガラスシート等が挙げられる。
電極用バインダとしてはデンプン、ポリフッ化ビニリデン、ポリビニルアルコール、カルボキシメチルセルロース、ポリビニルピロリドン、テトラフルオロエチレン、スチレン−ブタジエンゴム、ポリエチレン及びポリプロピレン等が挙げられる。
Among the dispersion media, examples of water include ion exchange water and ultrapure water.
Among the dispersion media, as the electrolytic solution, the same electrolytic solution (described later) used when a lithium ion battery is produced using the electrode containing the coated active material for the lithium ion battery of the present invention can be used. .
Among the dispersion media, as the solvent, the same solvent as the non-aqueous solvent that constitutes the electrolytic solution used when producing the lithium ion battery using the electrode containing the coated active material for the lithium ion battery of the present invention is used. In addition to these, 1-methyl-2-pyrrolidone, dimethylacetamide, N, N-dimethylaminopropylamine and the like can be mentioned.
Current collectors include metal foils such as copper, aluminum, titanium, stainless steel and nickel, resin current collectors made of conductive polymers (described in JP 2012-150905 A), conductive carbon Examples thereof include a sheet and a conductive glass sheet.
Examples of the binder for electrodes include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene, and polypropylene.
電極の製造時にリチウムイオン電池用被覆活物質と共に用いられる導電材料としては、被覆層に含まれる導電剤と同じものを用いることができる。 As the conductive material used together with the coating active material for a lithium ion battery at the time of manufacturing the electrode, the same conductive material as that contained in the coating layer can be used.
本発明のリチウムイオン電池用被覆活物質を含む電極を用いてリチウムイオン電池を作製する際には、対極となる電極を組み合わせて、セパレータと共にセル容器に収容し、電解液を注入し、セル容器を密封する方法等により製造することができる。
また、集電体の一方の面に正極を形成し、もう一方の面に負極を形成して双極型電極を作製し、双極型電極をセパレータと積層してセル容器に収容し、電解液を注入し、セル容器を密閉することでも得られる。
When producing a lithium ion battery using an electrode containing the coated active material for a lithium ion battery of the present invention, the electrodes serving as counter electrodes are combined, accommodated in a cell container together with a separator, an electrolyte solution is injected, and the cell container It can manufacture by the method of sealing.
In addition, a positive electrode is formed on one surface of the current collector, and a negative electrode is formed on the other surface to produce a bipolar electrode. The bipolar electrode is laminated with a separator and accommodated in a cell container. It can also be obtained by pouring and sealing the cell container.
セパレータとしては、ポリエチレン、ポリプロピレン製フィルムの微多孔膜、多孔性のポリエチレンフィルムとポリプロピレンとの多層フィルム、ポリエステル繊維、アラミド繊維、ガラス繊維等からなる不織布、及びそれらの表面にシリカ、アルミナ、チタニア等のセラミック微粒子を付着させたもの等の公知のリチウムイオン電池用セパレータが挙げられる。 As separators, polyethylene, a microporous film made of polypropylene film, a multilayer film of porous polyethylene film and polypropylene, non-woven fabric made of polyester fiber, aramid fiber, glass fiber, etc., and silica, alumina, titania etc. on their surface Known separators for lithium ion batteries, such as those having ceramic fine particles attached thereto, can be mentioned.
セル容器に注入する電解液としては、公知のリチウムイオン電池の製造に用いられる、電解質及び非水溶媒を含有する公知の電解液を使用することができる。 As the electrolytic solution to be injected into the cell container, a known electrolytic solution containing an electrolyte and a nonaqueous solvent used for manufacturing a known lithium ion battery can be used.
電解質としては、公知の電解液に用いられているもの等が使用でき、例えば、LiPF6、LiBF4、LiSbF6、LiAsF6及びLiClO4等の無機酸のリチウム塩、LiN(CF3SO2)2、LiN(C2F5SO2)2及びLiC(CF3SO2)3等の有機酸のリチウム塩等が挙げられる。これらの内、電池出力及び充放電サイクル特性の観点から好ましいのはLiPF6である。 As the electrolyte, those used in known electrolytic solutions can be used. For example, lithium salts of inorganic acids such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 and LiClO 4 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2, and lithium salts of organic acids such as LiC (CF 3 SO 2 ) 3 . Among these, LiPF 6 is preferable from the viewpoint of battery output and charge / discharge cycle characteristics.
非水溶媒としては、公知の電解液に用いられているもの等が使用でき、例えば、ラクトン化合物、環状又は鎖状炭酸エステル、鎖状カルボン酸エステル、環状又は鎖状エーテル、リン酸エステル、ニトリル化合物、アミド化合物、スルホン、スルホラン等及びこれらの混合物を用いることができる。 As the non-aqueous solvent, those used in known electrolytic solutions can be used, for example, lactone compounds, cyclic or chain carbonates, chain carboxylates, cyclic or chain ethers, phosphates, nitriles. Compounds, amide compounds, sulfones, sulfolanes and the like and mixtures thereof can be used.
ラクトン化合物としては、5員環(γ−ブチロラクトン及びγ−バレロラクトン等)及び6員環のラクトン化合物(δ−バレロラクトン等)等を挙げることができる。 Examples of the lactone compound include a 5-membered ring (γ-butyrolactone, γ-valerolactone, etc.) and a 6-membered lactone compound (δ-valerolactone, etc.).
環状炭酸エステルとしては、プロピレンカーボネート、エチレンカーボネート及びブチレンカーボネート等が挙げられる。
鎖状炭酸エステルとしては、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、メチル−n−プロピルカーボネート、エチル−n−プロピルカーボネート及びジ−n−プロピルカーボネート等が挙げられる。
Examples of the cyclic carbonate include propylene carbonate, ethylene carbonate and butylene carbonate.
Examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate.
鎖状カルボン酸エステルとしては、酢酸メチル、酢酸エチル、酢酸プロピル及びプロピオン酸メチル等が挙げられる。
環状エーテルとしては、テトラヒドロフラン、テトラヒドロピラン、1,3−ジオキソラン及び1,4−ジオキサン等が挙げられる。
鎖状エーテルとしては、ジメトキシメタン及び1,2−ジメトキシエタン等が挙げられる。
Examples of chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate.
Examples of the cyclic ether include tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,4-dioxane and the like.
Examples of the chain ether include dimethoxymethane and 1,2-dimethoxyethane.
リン酸エステルとしては、リン酸トリメチル、リン酸トリエチル、リン酸エチルジメチル、リン酸ジエチルメチル、リン酸トリプロピル、リン酸トリブチル、リン酸トリ(トリフルオロメチル)、リン酸トリ(トリクロロメチル)、リン酸トリ(トリフルオロエチル)、リン酸トリ(トリパーフルオロエチル)、2−エトキシ−1,3,2−ジオキサホスホラン−2−オン、2−トリフルオロエトキシ−1,3,2−ジオキサホスホラン−2−オン及び2−メトキシエトキシ−1,3,2−ジオキサホスホラン−2−オン等が挙げられる。
ニトリル化合物としては、アセトニトリル等が挙げられる。アミド化合物としては、DMF等が挙げられる。スルホンとしては、ジメチルスルホン及びジエチルスルホン等が挙げられる。
非水溶媒は1種を単独で用いてもよいし、2種以上を併用してもよい。
Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, tri (trifluoromethyl) phosphate, tri (trichloromethyl) phosphate, Tri (trifluoroethyl) phosphate, tri (triperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphospholan-2-one, 2-trifluoroethoxy-1,3,2- Examples include dioxaphospholan-2-one and 2-methoxyethoxy-1,3,2-dioxaphosphoran-2-one.
Examples of the nitrile compound include acetonitrile. Examples of the amide compound include DMF. Examples of the sulfone include dimethyl sulfone and diethyl sulfone.
A non-aqueous solvent may be used individually by 1 type, and may use 2 or more types together.
非水溶媒の内、電池出力及び充放電サイクル特性の観点から好ましいのは、ラクトン化合物、環状炭酸エステル、鎖状炭酸エステル及びリン酸エステルであり、更に好ましいのはラクトン化合物、環状炭酸エステル及び鎖状炭酸エステルであり、特に好ましいのは環状炭酸エステルと鎖状炭酸エステルの混合液である。最も好ましいのはエチレンカーボネート(EC)とジメチルカーボネート(DMC)の混合液、又は、エチレンカーボネート(EC)とジエチルカーボネート(DEC)の混合液である。 Of the non-aqueous solvents, lactone compounds, cyclic carbonates, chain carbonates and phosphates are preferable from the viewpoint of battery output and charge / discharge cycle characteristics, and lactone compounds, cyclic carbonates and chains are more preferable. The carbonic acid ester is particularly preferable, and a mixed solution of a cyclic carbonate and a chain carbonate is particularly preferable. Most preferred is a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) or a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC).
次に本発明を実施例によって具体的に説明するが、本発明の主旨を逸脱しない限り本発明は実施例に限定されるものではない。なお、特記しない限り部は重量部、%は重量%を意味する。 EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples without departing from the gist of the present invention. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<製造例1:被覆用高分子化合物とその溶液の作製>
撹拌機、温度計、還流冷却管、滴下ロート及び窒素ガス導入管を付した4つ口フラスコにDMF70.0部を仕込み75℃に昇温した。次いで、メタクリル酸ブチル20.0部、アクリル酸55.0部、メタクリル酸メチル22.0部、アリルスルホン酸ナトリウム3部及びDMF20部を配合したモノマー配合液と、2,2’−アゾビス(2,4−ジメチルバレロニトリル)0.4部及び2,2’−アゾビス(2−メチルブチロニトリル)0.8部をDMF10.0部に溶解した開始剤溶液とを4つ口フラスコ内に窒素を吹き込みながら、撹拌下、滴下ロートで2時間かけて連続的に滴下してラジカル重合を行った。滴下終了後、80℃に昇温し反応を5時間継続し樹脂濃度50%の共重合体溶液を得た。得られた共重合体溶液はテフロン(登録商標)製のバットに移して120℃、0.01MPaで3時間の減圧乾燥を行ってDMFを留去し、被覆用高分子化合物を得た。
<Production Example 1: Preparation of coating polymer compound and solution thereof>
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube, 70.0 parts of DMF was charged and heated to 75 ° C. Subsequently, 20.0 parts of butyl methacrylate, 55.0 parts of acrylic acid, 22.0 parts of methyl methacrylate, 3 parts of sodium allyl sulfonate and 20 parts of DMF, and 2,2′-azobis (2 , 4-dimethylvaleronitrile) and an initiator solution prepared by dissolving 0.8 part of 2,2′-azobis (2-methylbutyronitrile) in 10.0 part of DMF and nitrogen in a four-necked flask. Then, radical polymerization was carried out by continuously dropping with a dropping funnel over 2 hours under stirring. After completion of dropping, the temperature was raised to 80 ° C. and the reaction was continued for 5 hours to obtain a copolymer solution having a resin concentration of 50%. The obtained copolymer solution was transferred to a Teflon (registered trademark) vat and dried under reduced pressure at 120 ° C. and 0.01 MPa for 3 hours to distill off DMF, thereby obtaining a coating polymer compound.
<製造例2:珪素系材料の作製>
珪素粒子(シグマ・アルドリッチジャパン社製、体積平均粒子径1.5μm)を横型加熱炉中に入れ、横型加熱炉内にメタンガスを通気しながら1100℃/1000Pa、平均滞留時間約2時間の化学蒸着操作を行い、炭素量2重量%で、表面が炭素で被覆された珪素系材料(体積平均粒子径1.5μm)を得た。
<Production Example 2: Production of silicon-based material>
Chemical vapor deposition with silicon particles (Sigma Aldrich Japan, volume average particle size 1.5 μm) placed in a horizontal heating furnace and 1100 ° C / 1000 Pa, average residence time of about 2 hours while venting methane gas into the horizontal heating furnace The operation was performed to obtain a silicon-based material (volume average particle diameter of 1.5 μm) having a carbon content of 2% by weight and having a surface coated with carbon.
<実施例1>
[被覆正極活物質の作成]
正極活物質1粉末(LiNi0.8Co0.15Al0.05O2粉末、体積平均粒子径4μm)100部を万能混合機ハイスピードミキサーFS25[(株)アーステクニカ製]に入れ、室温、720rpmで撹拌した状態で、製造例1で得られた被覆用高分子化合物をイソプロパノールに1.0重量%の濃度で溶解して得られた被覆用高分子化合物溶液11.2部を2分かけて滴下し、さらに5分撹拌した。
次いで、撹拌した状態で導電剤としてアセチレンブラック[電気化学工業(株)製 デンカブラック(登録商標)]6.2部を分割しながら2分間で投入し、30分撹拌を継続した。その後、撹拌を維持したまま0.01MPaまで減圧し、次いで撹拌と減圧度を維持したまま温度を140℃まで昇温し、撹拌、減圧度及び温度を8時間維持して揮発分を留去した。得られた粉体を目開き212μmの篩いで分級し、実施例1に係る被覆正極活物質(P−1)を得た。
<Example 1>
[Creation of coated positive electrode active material]
100 parts of positive electrode active material 1 powder (LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, volume average particle diameter 4 μm) were put into a universal mixer high speed mixer FS25 [manufactured by Earth Technica Co., Ltd.] at room temperature. 11.2 parts of the coating polymer compound solution obtained by dissolving the coating polymer compound obtained in Production Example 1 in isopropanol at a concentration of 1.0% by weight with stirring at 720 rpm for 2 minutes. The mixture was added dropwise and further stirred for 5 minutes.
Next, 6.2 parts of acetylene black [Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.] as a conductive agent in a stirred state was charged in 2 minutes, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining the stirring, and then the temperature was raised to 140 ° C. while maintaining the stirring and the degree of vacuum, and the volatile matter was distilled off by maintaining the stirring, the degree of vacuum and the temperature for 8 hours. . The obtained powder was classified with a sieve having an opening of 212 μm to obtain a coated positive electrode active material (P-1) according to Example 1.
<実施例2〜4>
被覆用高分子化合物溶液の固形分濃度及び導電剤の部数のそれぞれを表1に記載したように変更したこと以外は実施例1と同様に行い、実施例2〜4に係る被覆正極活物質(P−2)〜(P−4)を得た。
なお、被覆用高分子化合物溶液の固形分濃度は、被覆用高分子化合物を溶解させるイソプロパノールの量を変更することで調整した。
<Examples 2 to 4>
The coated positive electrode active material according to Examples 2 to 4 was prepared in the same manner as in Example 1 except that the solid content concentration of the coating polymer compound solution and the number of parts of the conductive agent were changed as described in Table 1. P-2) to (P-4) were obtained.
The solid content concentration of the coating polymer compound solution was adjusted by changing the amount of isopropanol in which the coating polymer compound was dissolved.
<比較例1〜2>
正極活物質の種類、被覆用高分子化合物溶液の固形分濃度及び導電剤の部数のそれぞれを表1に記載したように変更したこと以外は実施例1と同様に行い、比較例1〜2に係る被覆正極活物質(P’−1)及び(P’−2)を得た。
<Comparative Examples 1-2>
The same procedure as in Example 1 was conducted except that the type of the positive electrode active material, the solid content concentration of the coating polymer compound solution, and the number of parts of the conductive agent were changed as described in Table 1, and Comparative Examples 1 and 2 were used. Such coated positive electrode active materials (P′-1) and (P′-2) were obtained.
表1中、正極活物質2粉末としては、体積平均粒子径8μmのLiCoO2粉末を用いた。 In Table 1, LiCoO 2 powder having a volume average particle diameter of 8 μm was used as the positive electrode active material 2 powder.
実施例1〜4及び比較例1〜2で得られた被覆正極活物質について、それぞれ下記の方法で液滴消失時間を測定し、表1に記載した。
[液滴消失時間の測定方法]
(1)試験片の作製
実施例1〜4及び比較例1〜2で得られた被覆正極活物質それぞれ225部とエチレンカーボネートとジエチルカーボネートとの混合溶媒(重量比3:7)100部とを均一に混合して活物質スラリーを作製し、厚さ20μmの銅箔上に600μmの厚さとなるようにドクターブレード法によりアルゴン雰囲気中で上記活物質スラリーを塗布して塗膜を形成した。
塗膜表面にろ紙(ADVANTEC製、定性濾紙No.2)を被せ、ろ紙の上から10MPa/cm2の圧力で塗膜の膜厚が400±100μmの厚さとなるまで押えて試験片を作製した。
(2)液滴消失時間の測定
アルゴン雰囲気下、25℃で、作製した試験片の中央に上記混合溶液を5mmの高さからマイクロシリンジで70μL滴下した。滴下終了から溶液が試験片の内部に吸収されて、見掛け上表面から消失するまでの時間を測定し、10個の試験片について測定した時間の平均を液滴消失時間として表1に記載した。
With respect to the coated positive electrode active materials obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the droplet disappearance time was measured by the following method and listed in Table 1.
[Measurement method of droplet disappearance time]
(1) Preparation of test piece 225 parts of each of the coated positive electrode active materials obtained in Examples 1 to 4 and Comparative Examples 1 to 2, and 100 parts of a mixed solvent of ethylene carbonate and diethyl carbonate (weight ratio 3: 7) An active material slurry was prepared by uniformly mixing, and the active material slurry was applied in an argon atmosphere by a doctor blade method to a thickness of 600 μm on a 20 μm thick copper foil to form a coating film.
A filter paper (manufactured by ADVANTEC, qualitative filter paper No. 2) was placed on the surface of the coating film, and a test piece was prepared by pressing from above the filter paper at a pressure of 10 MPa / cm 2 until the coating film thickness reached 400 ± 100 μm. .
(2) Measurement of droplet disappearance time In an argon atmosphere, at 25 ° C., 70 μL of the above mixed solution was dropped from the height of 5 mm with a microsyringe into the center of the prepared test piece. The time from the end of dropping until the solution was absorbed inside the test piece and apparently disappeared from the surface was measured, and the average of the time measured for 10 test pieces was shown in Table 1 as the liquid drop disappearance time.
<実施例5〜9>
[被覆負極活物質の作成]
正極活物質の種類と部数を表2に記載の負極活物質の種類と部数にし、被覆用高分子化合物溶液の固形分濃度と部数及び導電剤の部数のそれぞれを表2に記載したように変更したこと以外は実施例1と同様に行い、実施例5〜9に係る被覆負極活物質(N−1)〜(N−5)を得た。
なお、被覆用高分子化合物溶液の固形分濃度は、被覆用高分子化合物を溶解させるイソプロパノールの量を変更することで調整した。
<Examples 5-9>
[Creation of coated negative electrode active material]
Change the type and number of parts of the positive electrode active material to the type and number of parts of the negative electrode active material shown in Table 2, and change the solid content concentration and number of parts of the coating polymer compound solution and the number of parts of the conductive agent as described in Table 2. Except having carried out, it carried out similarly to Example 1 and obtained the covering negative electrode active material (N-1)-(N-5) which concerns on Examples 5-9.
The solid content concentration of the coating polymer compound solution was adjusted by changing the amount of isopropanol in which the coating polymer compound was dissolved.
<実施例10>
炭素系材料である難黒鉛化性炭素粉末1(体積平均粒子径20μm)20部と製造例2で製造した珪素系材料80部とを、万能混合機ハイスピードミキサーFS25[(株)アーステクニカ製]に入れ、室温720rpmで撹拌した状態で、製造例1で得られた被覆用高分子化合物をイソプロパノールに19.8重量%の濃度で溶解して得られた被覆用高分子化合物溶液9.2部を2分かけて滴下し、さらに5分撹拌した。
次いで、撹拌した状態で導電剤であるアセチレンブラック[電気化学工業(株)製 デンカブラック(登録商標)]11.3部を分割しながら2分間で投入し、30分撹拌を継続した。その後、撹拌を維持したまま0.01MPaまで減圧し、次いで撹拌と減圧度を維持したまま温度を140℃まで昇温し、撹拌、減圧度及び温度を8時間維持して揮発分を留去した。得られた粉体を目開き212μmの篩いで分級し、実施例10に係る被覆負極活物質(N−6)を得た。
<Example 10>
20 parts of non-graphitizable carbon powder 1 (volume average particle diameter 20 μm), which is a carbon-based material, and 80 parts of silicon-based material manufactured in Production Example 2 are combined into a universal mixer high speed mixer FS25 [manufactured by Earth Technica Co., Ltd. The coating polymer compound solution obtained in Production Example 1 was dissolved in isopropanol at a concentration of 19.8% by weight with stirring at room temperature of 720 rpm, and the coating polymer compound solution 9.2 was obtained. The portion was added dropwise over 2 minutes and further stirred for 5 minutes.
Next, 11.3 parts of acetylene black [Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.], which is a conductive agent, was added in 2 minutes while stirring, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining the stirring, and then the temperature was raised to 140 ° C. while maintaining the stirring and the degree of vacuum, and the volatile matter was distilled off by maintaining the stirring, the degree of vacuum and the temperature for 8 hours. . The obtained powder was classified with a sieve having an opening of 212 μm to obtain a coated negative electrode active material (N-6) according to Example 10.
<実施例11〜12>
炭素系材料及び珪素系材料の種類と部数、被覆用高分子化合物溶液の固形分濃度及び部数、並びに導電剤の部数のそれぞれを表2に記載したように変更したこと以外は実施例10と同様に行い、実施例11〜12に係る被覆負極活物質(N−7)〜(N−8)を得た。
<Examples 11 to 12>
The same as Example 10 except that the types and number of carbon-based materials and silicon-based materials, the solid content concentration and the number of parts of the coating polymer compound solution, and the number of parts of the conductive agent were changed as described in Table 2. The coated negative electrode active materials (N-7) to (N-8) according to Examples 11 to 12 were obtained.
<比較例3〜4>
負極活物質の種類と部数を表2に記載の負極活物質の種類と部数にし、被覆用高分子化合物溶液の固形分濃度と部数及び導電剤の部数のそれぞれを表2に記載したように変更したこと以外は実施例5と同様に行い、比較例3〜4に係る被覆負極活物質(N’−1)及び(N’−2)を得た。
<Comparative Examples 3-4>
The type and number of parts of the negative electrode active material are changed to the type and number of parts of the negative electrode active material shown in Table 2, and the solid content concentration and number of parts of the coating polymer compound solution and the number of parts of the conductive agent are changed as shown in Table 2. Except having carried out, it carried out similarly to Example 5 and obtained the coated negative electrode active material (N'-1) and (N'-2) which concern on Comparative Examples 3-4.
<比較例5〜6>
負極活物質の種類と部数を表2に記載の負極活物質の種類と部数にし、被覆用高分子化合物溶液の固形分濃度と部数及び導電剤の部数のそれぞれを表2に記載したように変更したこと以外は実施例10と同様に行い、比較例5〜6に係る被覆負極活物質(N’−3)及び(N’−4)を得た。
<Comparative Examples 5-6>
The type and number of parts of the negative electrode active material are changed to the type and number of parts of the negative electrode active material shown in Table 2, and the solid content concentration and number of parts of the coating polymer compound solution and the number of parts of the conductive agent are changed as shown in Table 2. Except having carried out, it carried out similarly to Example 10 and obtained the coated negative electrode active material (N'-3) and (N'-4) which concern on Comparative Examples 5-6.
表2中、難黒鉛化性炭素粉末1としては体積平均粒子径20μmの難黒鉛化性炭素粉末を用い、難黒鉛化性炭素粉末2としては体積平均粒子径5μmの難黒鉛化性炭素粉末を用いた。 In Table 2, a non-graphitizable carbon powder having a volume average particle diameter of 20 μm is used as the non-graphitizable carbon powder 1, and a non-graphitizable carbon powder having a volume average particle diameter of 5 μm is used as the non-graphitizable carbon powder 2. Using.
実施例5〜12及び比較例3〜6で得られた被覆負極活物質について、エチレンカーボネートとジエチルカーボネートとの混合溶媒(重量比3:7)100部に対して負極用被覆活物質100部を均一に混合して得られた活物質スラリーを用いて、被覆正極活物質と同様の方法で試験片の作製と液滴消失時間の測定を行い、表2に記載した。 About the coated negative electrode active material obtained in Examples 5-12 and Comparative Examples 3-6, 100 parts of the negative electrode coated active material was added to 100 parts of a mixed solvent of ethylene carbonate and diethyl carbonate (weight ratio 3: 7). Using the active material slurry obtained by uniformly mixing, the test piece was prepared and the droplet disappearance time was measured in the same manner as the coated positive electrode active material.
[正極評価用リチウムイオン電池の作製]
エチレンカーボネート(EC)とジエチルカーボネート(DEC)の混合溶媒(体積比率1:1)にLiPF6を1mol/Lの割合で溶解させて作製したリチウムイオン電池用電解液42部と炭素繊維[大阪ガスケミカル(株)製 ドナカーボ・ミルド S−243:平均繊維長500μm、平均繊維径13μm:電気伝導度200mS/cm]4.2部とを遊星撹拌型混合混練装置{あわとり練太郎[(株)シンキー製]}を用いて2000rpmで7分間混合し、続いて上記電解液30部と実施例1〜4又は比較例1〜2で得られた被覆正極活物質206部を追加した後、更にあわとり練太郎により2000rpmで1.5分間混合し、上記電解液20部を更に追加した後あわとり練太郎による撹拌を2000rpmで1分間行い、上記電解液2.3部を更に追加した後あわとり練太郎による撹拌を2000rpmで1.5分間混合して、正極活物質スラリーを作製した。得られた正極活物質スラリーをそれぞれ厚さ50μmのカーボンコートアルミ箔の片面に塗布し、10MPaの圧力で約10秒プレスし、厚さが約400μmの実施例1〜4及び比較例1〜2に係るリチウムイオン電池用正極(3cm×3cm)を作製した。
端子(5mm×3cm)付きカーボンコートアルミ箔(3cm×3cm)とセパレータ(セルガード2500 PP製)(5cm×5cm)1枚と端子(5mm×3cm)付き銅箔(3cm×3cm)とを、同じ方向に2つの端子が出る向きで順に積層し、それを2枚の市販の熱融着型アルミラミネートフィルム(8cm×8cm)に挟み、端子の出ている1辺を熱融着し、正極評価用ラミネートセルを作製した。
次いで、カーボンコートアルミ箔とセパレータの間に実施例1〜4又は比較例1〜2に係るリチウムイオン電池用正極(3cm×3cm)を、ラミネートセルのカーボンコートアルミ箔とリチウムイオン電池用正極のカーボンコートアルミ箔とが接する向きに挿入し、更に電極の上に電解液を70μL注液して電解液を電極に吸収させた。次いでセパレータ上にも電解液を70μL注液した。その後、セパレータと銅箔との間にリチウム箔を挿入し、先に熱融着した1辺に直交する2辺をヒートシールした。
その後、開口部から電解液を更に70μL注液し、真空シーラーを用いてセル内を真空にしながら開口部をヒートシールすることでラミネートセルを密封し、正極評価用リチウムイオン電池1〜4及び正極比較用リチウムイオン電池1〜2を得た。
得られた評価用電池について、以下の方法でレート特性、内部抵抗及びクーロン効率を測定し、結果を表3に記載した。
[Preparation of lithium ion battery for positive electrode evaluation]
42 parts of an electrolytic solution for lithium ion battery prepared by dissolving LiPF 6 in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) at a rate of 1 mol / L and carbon fiber [Osaka Gas Chemical Co., Ltd. Donakabo Mild S-243: average fiber length 500 μm, average fiber diameter 13 μm: electric conductivity 200 mS / cm] 4.2 parts and planetary agitation type mixing and kneading device {Awatori Kentaro [Corporation] After the addition of 30 parts of the electrolytic solution and 206 parts of the coated positive electrode active material obtained in Examples 1-4 or Comparative Examples 1-2, Mix for 1.5 minutes at 2000 rpm with Tori Netaro, add 20 parts of the above electrolyte, and then stir with Aritori Netaro for 1 minute at 2000 rpm. After further adding 2.3 parts of the solution, stirring by Awatori Netaro was mixed at 2000 rpm for 1.5 minutes to prepare a positive electrode active material slurry. The obtained positive electrode active material slurries were each applied to one side of a carbon-coated aluminum foil having a thickness of 50 μm, pressed at a pressure of 10 MPa for about 10 seconds, and Examples 1-4 and Comparative Examples 1-2 having a thickness of about 400 μm. The positive electrode (3 cm x 3 cm) for lithium ion batteries which concerns on this was produced.
The same carbon coated aluminum foil (3 cm × 3 cm) with terminal (5 mm × 3 cm), one separator (manufactured by Celgard 2500 PP) (5 cm × 5 cm) and copper foil (3 cm × 3 cm) with terminal (5 mm × 3 cm) Laminate in order with two terminals in the direction, sandwich it between two commercially available heat-bonded aluminum laminate films (8cm x 8cm), heat-seal one side where the terminals are protruding, and evaluate the positive electrode A laminate cell was prepared.
Next, the positive electrode for lithium ion battery (3 cm × 3 cm) according to Examples 1 to 4 or Comparative Examples 1 and 2 is used between the carbon coated aluminum foil and the separator, and the carbon coated aluminum foil of the laminate cell and the positive electrode for the lithium ion battery. The electrode was inserted in the direction in contact with the carbon-coated aluminum foil, and 70 μL of electrolyte was injected onto the electrode to absorb the electrolyte. Next, 70 μL of the electrolyte was injected onto the separator. Thereafter, a lithium foil was inserted between the separator and the copper foil, and two sides orthogonal to the one side heat-sealed first were heat sealed.
Thereafter, an additional 70 μL of electrolyte was injected from the opening, and the laminate was sealed by heat-sealing the opening while evacuating the inside of the cell using a vacuum sealer, and the lithium ion batteries 1 to 4 for positive electrode evaluation and the positive electrode Comparative lithium ion batteries 1 and 2 were obtained.
About the obtained battery for evaluation, rate characteristics, internal resistance, and coulomb efficiency were measured by the following methods, and the results are shown in Table 3.
[負極評価用リチウムイオン電池の作製]
上記正極評価用リチウムイオン電池の作製で用いたものと同じ電解液20部と炭素繊維[大阪ガスケミカル(株)製 ドナカーボ・ミルド S−243:平均繊維長500μm、平均繊維径13μm:電気伝導度200mS/cm]2部とを遊星撹拌型混合混練装置{あわとり練太郎[(株)シンキー製]}を用いて2000rpmで7分間混合し、続いて上記電解液50部と実施例5〜12又は比較例3〜6で得られた被覆負極活物質98部を追加した後、更にあわとり練太郎により2000rpmで1.5分間混合し、上記電解液25部を更に追加した後あわとり練太郎による撹拌を2000rpmで1分間行い、上記電解液50部を更に追加した後あわとり練太郎による撹拌を2000rpmで1.5分間混合して、負極活物質スラリーを作製した。
得られた負極活物質スラリーをそれぞれアラミドセパレータ[日本バイリーン(株)製]の片面に塗布し、10MPaの圧力で約10秒プレスし、厚さが約350μmのリチウムイオン電池用負極を作製した。
端子付きカーボンコートアルミ箔を端子付き銅箔に変更し、セパレータ(セルガード2500 PP製)を2枚に変更したこと以外は前記の正極評価用リチウムイオン電池の作製と同様に行い、負極評価用ラミネートセルを作製した。
次いで一方の銅箔とセパレータの間に実施例5〜12又は比較例3〜6に係るリチウムイオン電池用負極(3cm×3cm)を負極が有するアラミドセパレータとセパレータとが接する向きに挿入し、更に電極に電解液を70μL注液して電解液を電極に吸収させた。次いでセパレータ上に電解液を70μL注液した。
その後、セパレータと他方の銅箔との間にリチウム箔を挿入し、先に熱融着した1辺に直交する2辺をヒートシールした。その後、開口部から電解液を70μL注液し、真空シーラーを用いてセル内を真空にしながら開口部をヒートシールすることでラミネートセルを密封し、負極評価用リチウムイオン電池1〜8及び負極比較用リチウムイオン電池1〜4を得た。
得られた評価用電池について、以下の方法でレート特性、内部抵抗及びクーロン効率を測定し、結果を表4に記載した。
[Preparation of lithium ion battery for negative electrode evaluation]
20 parts of the same electrolytic solution and carbon fiber used in the production of the above-described positive electrode evaluation lithium ion battery [Donkerbo Mild S-243 manufactured by Osaka Gas Chemical Co., Ltd .: average fiber length 500 μm, average fiber diameter 13 μm: electrical conductivity 2 parts of 200 mS / cm] was mixed for 7 minutes at 2000 rpm using a planetary agitation type mixing and kneading apparatus {Awatori Netaro [manufactured by Shinky Co., Ltd.]}, followed by 50 parts of the above electrolyte and Examples 5 to 12 Alternatively, after adding 98 parts of the coated negative electrode active material obtained in Comparative Examples 3 to 6, the mixture was further mixed for 1.5 minutes at 2000 rpm by Nawataro Awatori, and further 25 parts of the electrolyte solution was added, and then Narotaro Atori Was added for 1 minute at 2000 rpm, 50 parts of the electrolyte solution was further added, and then the mixture was stirred for 1.5 minutes at 2000 rpm with agitator Niwataro Atori. It was manufactured.
Each of the obtained negative electrode active material slurries was applied to one side of an aramid separator [manufactured by Japan Vilene Co., Ltd.] and pressed at a pressure of 10 MPa for about 10 seconds to produce a negative electrode for a lithium ion battery having a thickness of about 350 μm.
Laminate for negative electrode evaluation was carried out in the same manner as the above-described lithium ion battery for positive electrode evaluation, except that the carbon coated aluminum foil with terminal was changed to copper foil with terminal and the separator (made of Cellguard 2500 PP) was changed to two. A cell was produced.
Next, the negative electrode for lithium ion battery (3 cm × 3 cm) according to Examples 5 to 12 or Comparative Examples 3 to 6 is inserted between one copper foil and the separator in a direction in which the aramid separator and the separator have the negative electrode, and further 70 μL of electrolyte was injected into the electrode, and the electrolyte was absorbed into the electrode. Next, 70 μL of electrolyte was injected onto the separator.
Thereafter, a lithium foil was inserted between the separator and the other copper foil, and two sides orthogonal to the one side heat-sealed first were heat sealed. Thereafter, 70 μL of electrolyte solution was injected from the opening, and the laminate cell was sealed by heat-sealing the opening while evacuating the inside of the cell using a vacuum sealer, and lithium ion batteries 1 to 8 for negative electrode evaluation and negative electrode comparison Lithium ion batteries 1 to 4 were obtained.
About the obtained battery for evaluation, rate characteristics, internal resistance, and coulomb efficiency were measured by the following methods, and the results are shown in Table 4.
<リチウムイオン電池のレート特性の測定>
45℃下、充放電測定装置「HJ−SD8」[北斗電工(株)製]を用いて以下の方法により正極評価用リチウムイオン電池1〜4、正極比較用リチウムイオン電池1〜2、負極評価用リチウムイオン電池1〜8及び負極比較用リチウムイオン電池1〜4の評価を行った。
[正極の評価]
定電流定電圧充電方式(CCCVモードともいう)で0.1Cの電流で4.2Vまで充電し、10分間の休止後、0.1Cの電流で2.6Vまで放電した。
その後、再び0.1Cの電流で4.2Vまで充電した後、10分間休止後、1.0Cの電流で2.6Vまで放電した。
その後、10分間休止した後0.5Cで2.6Vまで放電し、その後10分間休止した後に続けて0.2Cで2.6Vまで放電し、更に10分間休止した後に引き続き0.1Cの電流で2.6Vまで放電を行った。
1.0Cの電流で2.6Vまで放電した時の放電容量と最後に0.1Cの電流で2.6Vまで放電を行った時の放電容量から、以下の式でレート特性(0.1Cでの放電容量と1.0Cでの放電容量の比率)を算出した。
なお、レート特性の値が大きいほど容量の低下が少なく優れた電池特性を有することを意味する。
[レート特性(%)]=[1.0Cにおける放電容量]÷[0.1Cにおける放電容量]×100
[負極の評価]
定電流定電圧充電方式(CCCVモードともいう)で0.1Cの電流で10mVまで放電し、その後10分間の休止した後、0.1Cの電流で1.5Vまで充電した。
次いで、0.1Cの電流で10mVまで放電し、10分間の休止した後、1.0Cの電流で1.5Vまで充電する。
その後、10分間休止した後0.5Cで1.5Vまで充電し、その後10分間休止した後に続けて0.2Cで1.5Vまで充電し、更に10分間休止した後に引き続き0.1Cの電流で1.5Vまでの充電を行った。
1.0Cの電流で1.5Vまで充電した時の充電容量と最後に0.1Cの電流で1.5Vまで充電を行った時の充電容量から、以下の式でレート特性(0.1Cでの充電容量と1.0Cでの充電容量の比率)を算出した。
なお、レート特性の値が大きいほど容量の低下が少なく優れた電池特性を有することを意味する。
[レート特性(%)]=[1.0Cにおける充電容量]÷[0.1Cにおける充電容量]×100
<Measurement of rate characteristics of lithium ion battery>
The positive electrode evaluation lithium ion batteries 1 to 4, the positive electrode comparison lithium ion batteries 1 and 2, and the negative electrode evaluation were performed at 45 ° C. by the following methods using a charge / discharge measuring device “HJ-SD8” [manufactured by Hokuto Denko Corporation]. The lithium ion batteries 1 to 8 for use and the lithium ion batteries 1 to 4 for comparison with the negative electrode were evaluated.
[Evaluation of positive electrode]
The battery was charged to 4.2 V with a current of 0.1 C by a constant current constant voltage charging method (also referred to as CCCV mode), and discharged to 2.6 V with a current of 0.1 C after a pause of 10 minutes.
Thereafter, the battery was charged again to 4.2 V with a current of 0.1 C, then rested for 10 minutes, and then discharged to 2.6 V with a current of 1.0 C.
Then, after 10 minutes of rest, discharge to 2.6 V at 0.5 C, then to rest for 10 minutes, then continue to discharge to 0.2 V at 0.2 C, and then rest for another 10 minutes, followed by a current of 0.1 C. Discharge was performed to 2.6V.
From the discharge capacity when discharging to 2.6 V with a current of 1.0 C and finally the discharge capacity when discharging to 2.6 V with a current of 0.1 C, rate characteristics (at 0.1 C) The ratio of the discharge capacity to the discharge capacity at 1.0 C) was calculated.
In addition, it means that it has the battery characteristic which there are few falls of a capacity | capacitance so that the value of a rate characteristic is large.
[Rate characteristic (%)] = [Discharge capacity at 1.0 C] ÷ [Discharge capacity at 0.1 C] × 100
[Evaluation of negative electrode]
In a constant current constant voltage charging method (also referred to as CCCV mode), the battery was discharged to 10 mV with a current of 0.1 C, then rested for 10 minutes, and then charged to 1.5 V with a current of 0.1 C.
Next, the battery is discharged to 10 mV with a current of 0.1 C, paused for 10 minutes, and then charged to 1.5 V with a current of 1.0 C.
Then, after 10 minutes of rest, it was charged to 1.5V at 0.5C, then rested for 10 minutes, then charged to 1.5V at 0.2C, and then rested for another 10 minutes, followed by a current of 0.1C. Charging to 1.5V was performed.
From the charging capacity when charging to 1.5V with a current of 1.0C and the charging capacity when charging to 1.5V with a current of 0.1C at the end, rate characteristics (at 0.1C The ratio of the charging capacity to the charging capacity at 1.0 C) was calculated.
In addition, it means that it has the battery characteristic which there are few falls of a capacity | capacitance so that the value of a rate characteristic is large.
[Rate characteristic (%)] = [Charge capacity at 1.0 C] ÷ [Charge capacity at 0.1 C] × 100
<リチウムイオン電池の内部抵抗の測定>
上記のレート特性の測定と同様にして1.0Cにおける放電又は充電0秒後の電圧及び電流並びに1.0Cにおける放電又は充電10秒後の電圧及び電流を測定し、以下の式で正極及び負極の内部抵抗をそれぞれ算出した。内部抵抗が小さいほど優れた電池特性を有することを意味する。
なお、放電又は充電0秒後の電圧とは、放電又は充電したと同時に計測される電圧(放電時電圧又は充電時電圧ともいう)である。
[正極の内部抵抗(Ω)]=[(1.0Cにおける放電0秒後の電圧)−(1.0Cにおける放電10秒後の電圧)]÷[(1.0Cにおける放電0秒後の電流)−(1.0Cにおける放電10秒後の電流)]
[負極の内部抵抗(Ω)]=[(1.0Cにおける充電0秒後の電圧)−(1.0Cにおける充電10秒後の電圧)]÷[(1.0Cにおける充電0秒後の電流)−(1.0Cにおける充電10秒後の電流)]
<Measurement of internal resistance of lithium-ion battery>
In the same manner as the measurement of the rate characteristics described above, the voltage and current after 0 seconds of discharge or charge at 1.0 C and the voltage and current after 10 seconds of discharge or charge at 1.0 C were measured. The internal resistance was calculated. It means that it has the outstanding battery characteristic, so that internal resistance is small.
In addition, the voltage after discharge or charge 0 second is a voltage (it is also called the voltage at the time of discharge or the voltage at the time of charge) measured simultaneously with discharging or charging.
[Internal resistance of positive electrode (Ω)] = [(voltage after 0 second discharge at 1.0 C) − (voltage after 10 second discharge at 1.0 C)] ÷ [(current after discharge 0 second at 1.0 C) )-(Current after 10 seconds of discharge at 1.0 C)]
[Internal resistance of negative electrode (Ω)] = [(voltage after 0 second charge at 1.0 C) − (voltage after 10 second charge at 1.0 C)] ÷ [(current after 0 second charge at 1.0 C) )-(Current after 10 seconds of charging at 1.0 C)]
<リチウムイオン電池のクーロン効率の評価>
上記のレート特性の測定で得られた0.1Cにおける初回の放電又は充電容量と0.1Cにおける初回の放電又は充電容量とを用い、以下の式で正極及び負極のクーロン効率をそれぞれ算出した。クーロン効率が高いほど優れた電池特性を有することを意味する。
正極のクーロン効率(%)=(0.1Cにおける初回の放電容量)÷(0.1Cにおける初回の充電容量)×100
負極のクーロン効率(%)=(0.1Cにおける初回の充電容量)÷(0.1Cにおける初回の放電容量)×100
<Evaluation of Coulomb efficiency of lithium ion battery>
Using the initial discharge or charge capacity at 0.1 C and the initial discharge or charge capacity at 0.1 C obtained by the above-described measurement of the rate characteristics, the Coulomb efficiencies of the positive electrode and the negative electrode were respectively calculated by the following equations. Higher Coulomb efficiency means better battery characteristics.
Coulomb efficiency (%) of positive electrode = (initial discharge capacity at 0.1 C) / (initial charge capacity at 0.1 C) × 100
Coulomb efficiency (%) of negative electrode = (initial charge capacity at 0.1 C) / (initial discharge capacity at 0.1 C) × 100
本発明のリチウムイオン電池用被覆活物質を用いたリチウムイオン電池は特にレート特性に優れることがわかる。
さらに、本発明の被覆活物質を用いると、電解液の浸透性が良いため、電池の製造時において、活物質層に電解液を吸収させる工程時間を短縮できるという効果も有する。
It turns out that the lithium ion battery using the covering active material for lithium ion batteries of this invention is excellent in especially a rate characteristic.
Furthermore, when the coated active material of the present invention is used, the electrolyte solution has good permeability, and therefore, there is an effect that it is possible to shorten the process time for the electrolyte material to be absorbed in the active material layer at the time of battery production.
本発明のリチウムイオン電池用被覆活物質は、特に、携帯電話、パーソナルコンピューター、ハイブリッド自動車及び電気自動車用に用いられる双極型二次電池用及びリチウムイオン二次電池用等の活物質として有用である。 The coated active material for lithium ion batteries of the present invention is particularly useful as an active material for bipolar secondary batteries and lithium ion secondary batteries used for mobile phones, personal computers, hybrid vehicles and electric vehicles. .
Claims (9)
<液滴消失時間の測定方法>
(1)試験片の作製
エチレンカーボネートとジエチルカーボネートとの混合溶媒(重量比3:7)100重量部に対して、前記リチウムイオン電池用被覆活物質が被覆正極活物質の場合には100重量部を、前記リチウムイオン電池用被覆活物質が被覆負極活物質の場合には225重量部を加えて均一に混合して得られた活物質スラリーを厚さ20μmの銅箔上に600μmの厚さとなるようにドクターブレード法によりアルゴン雰囲気中で塗布して塗膜を形成する。塗膜表面にろ紙(No.2)を被せ、ろ紙の上から10MPa/cm2の圧力で塗膜の膜厚が400μm±100μmの厚さとなるまで押さえて試験片とする。
(2)液滴消失時間の測定
アルゴン雰囲気下、25℃で、前記試験片の中央に、前記混合溶媒を5mmの高さからマイクロシリンジで70μL滴下する。滴下終了から前記混合溶媒が試験片の内部に吸収されて、見掛け上表面から消失するまでの時間を測定し、10個の試験片について測定した時間の平均を液滴消失時間とする。 A coating active material for lithium ion batteries, wherein at least a part of the surface of the active material for lithium ion batteries is coated with a coating layer containing a polymer compound, and the droplet disappearance time measured by the following test method A coated active material for a lithium ion battery, characterized by being 35 seconds or less.
<Measurement method of droplet disappearance time>
(1) Preparation of test piece 100 parts by weight when the coated active material for lithium ion batteries is a coated positive electrode active material with respect to 100 parts by weight of a mixed solvent of ethylene carbonate and diethyl carbonate (weight ratio 3: 7). In the case where the lithium ion battery coated active material is a coated negative electrode active material, the active material slurry obtained by adding 225 parts by weight and mixing them uniformly on a copper foil having a thickness of 20 μm has a thickness of 600 μm. Thus, a doctor blade method is applied in an argon atmosphere to form a coating film. A filter paper (No. 2) is put on the surface of the coating film, and pressed onto the filter paper with a pressure of 10 MPa / cm 2 until the thickness of the coating film reaches 400 μm ± 100 μm.
(2) Measurement of droplet disappearance time In an argon atmosphere, at 25 ° C., 70 μL of the mixed solvent is dropped from the height of 5 mm with a microsyringe into the center of the test piece. The time from the completion of dropping until the mixed solvent is absorbed into the test piece and apparently disappears from the surface is measured, and the average of the time measured for 10 test pieces is defined as the drop-off time.
CH2=C(R1)COOR2 (1)
[R1は水素原子又はメチル基、R2は炭素数4〜12の直鎖又は分岐アルキル基である。] The polymer compound includes (meth) acrylic acid (a11), an ester compound (a21) represented by the following general formula (1), a monovalent aliphatic alcohol having 1 to 3 carbon atoms, and (meth) acrylic acid. An ester compound (a3) and a monomer composition containing a salt (a4) of an anionic monomer having a polymerizable unsaturated double bond and an anionic group are polymerized to obtain the ester compound (a21). The weight ratio [the ester compound (a21) / the (meth) acrylic acid (a11)] of the (meth) acrylic acid (a11) is 10/90 to 90/10. Coated active material for lithium ion batteries.
CH 2 = C (R 1 ) COOR 2 (1)
[R 1 is a hydrogen atom or a methyl group, and R 2 is a linear or branched alkyl group having 4 to 12 carbon atoms. ]
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JP2020009750A (en) * | 2018-06-29 | 2020-01-16 | 三洋化成工業株式会社 | Electrode for lithium ion battery and lithium ion battery |
JP2020009751A (en) * | 2018-06-29 | 2020-01-16 | 三洋化成工業株式会社 | Coated negative electrode active material for lithium ion battery, negative electrode slurry for lithium ion battery, negative electrode for lithium ion battery, and lithium ion battery |
JP2020068118A (en) * | 2018-10-24 | 2020-04-30 | 日産自動車株式会社 | Manufacturing method of positive electrode active material slurry for nonaqueous electrolyte secondary battery |
WO2022210741A1 (en) * | 2021-03-29 | 2022-10-06 | Apb株式会社 | Method for manufacturing lithium ion battery |
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WO2015005117A1 (en) * | 2013-07-08 | 2015-01-15 | 三洋化成工業株式会社 | Resin for coating lithium-ion-battery active material, resin composition for coating lithium-ion-battery active material, and coated active material for lithium-ion battery |
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WO2015005117A1 (en) * | 2013-07-08 | 2015-01-15 | 三洋化成工業株式会社 | Resin for coating lithium-ion-battery active material, resin composition for coating lithium-ion-battery active material, and coated active material for lithium-ion battery |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2020009750A (en) * | 2018-06-29 | 2020-01-16 | 三洋化成工業株式会社 | Electrode for lithium ion battery and lithium ion battery |
JP2020009751A (en) * | 2018-06-29 | 2020-01-16 | 三洋化成工業株式会社 | Coated negative electrode active material for lithium ion battery, negative electrode slurry for lithium ion battery, negative electrode for lithium ion battery, and lithium ion battery |
JP7297528B2 (en) | 2018-06-29 | 2023-06-26 | 三洋化成工業株式会社 | Electrodes for lithium ion batteries and lithium ion batteries |
JP7297529B2 (en) | 2018-06-29 | 2023-06-26 | 三洋化成工業株式会社 | Coated negative electrode active material for lithium ion battery, negative electrode slurry for lithium ion battery, negative electrode for lithium ion battery, and lithium ion battery |
JP2020068118A (en) * | 2018-10-24 | 2020-04-30 | 日産自動車株式会社 | Manufacturing method of positive electrode active material slurry for nonaqueous electrolyte secondary battery |
JP7285060B2 (en) | 2018-10-24 | 2023-06-01 | 日産自動車株式会社 | Method for producing positive electrode active material slurry for non-aqueous electrolyte secondary battery |
WO2022210741A1 (en) * | 2021-03-29 | 2022-10-06 | Apb株式会社 | Method for manufacturing lithium ion battery |
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