JP7422493B2 - Lithium ion battery manufacturing method - Google Patents
Lithium ion battery manufacturing method Download PDFInfo
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- JP7422493B2 JP7422493B2 JP2019104544A JP2019104544A JP7422493B2 JP 7422493 B2 JP7422493 B2 JP 7422493B2 JP 2019104544 A JP2019104544 A JP 2019104544A JP 2019104544 A JP2019104544 A JP 2019104544A JP 7422493 B2 JP7422493 B2 JP 7422493B2
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- active material
- positive electrode
- electrode active
- negative electrode
- lithium ion
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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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
本発明は、リチウムイオン電池の製造方法に関する。 The present invention relates to a method for manufacturing 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電池に注目が集まっている。 In recent years, there has been a strong desire to reduce carbon dioxide emissions for environmental protection. In the automobile industry, expectations are high for reducing carbon dioxide emissions through the introduction of electric vehicles (EVs) and hybrid electric vehicles (HEVs), and efforts are being made to develop secondary batteries for motor drives, which hold the key to their practical application. It's being done. As a secondary battery, lithium-ion batteries that can achieve high energy density and high output density are attracting attention.
このようなリチウムイオン電池を製造する方法として、例えば、特許文献１には、正極集電体及び負極集電体上に正極活物質粒子と結着剤とを溶剤に溶解分散して得られる正極スラリーと負極活物質粒子と結着剤とを溶剤に溶解分散して得られる負極スラリーとをそれぞれ塗布して塗膜を形成した後、塗膜を乾燥、焼結等することなく、集電体に正極電極組成物又は負極電極組成物を直接配置することでリチウムイオン電池を得るリチウムイオン電池の製造方法が開示されている。 As a method for manufacturing such a lithium ion battery, for example, Patent Document 1 describes a method for producing a positive electrode obtained by dissolving and dispersing positive electrode active material particles and a binder in a solvent on a positive electrode current collector and a negative electrode current collector. After coating the slurry and a negative electrode slurry obtained by dissolving and dispersing negative electrode active material particles and a binder in a solvent to form a coating film, the current collector is coated without drying or sintering the coating film. A method for manufacturing a lithium ion battery is disclosed in which a lithium ion battery is obtained by directly disposing a positive electrode composition or a negative electrode composition on a battery.
特許文献１に記載された方法では、電極活物質スラリーを塗布して塗膜を形成した後、塗膜を乾燥、焼結等をする必要が無いので、リチウムイオン電池を効率よく製造することができる。
しかしながら、正極活物質スラリーにおいて正極活物質の比重が大きいことに起因して、正極活物質スラリーに固液分離が起こり易いことや、正極活物質スラリーにおいて導電助剤の凝集が進み易いことがあり、得られるリチウムイオン電池の電池内部抵抗や、充放電特性にバラツキが生じることがあり、改善の余地があった。
In the method described in Patent Document 1, there is no need to dry, sinter, etc. the coating film after applying the electrode active material slurry to form a coating film, and therefore it is not possible to efficiently manufacture a lithium ion battery. can.
However, due to the high specific gravity of the positive electrode active material in the positive electrode active material slurry, solid-liquid separation may easily occur in the positive electrode active material slurry, and agglomeration of the conductive additive may easily proceed in the positive electrode active material slurry. However, variations in internal resistance and charge/discharge characteristics of the resulting lithium ion batteries may occur, leaving room for improvement.
以上の状況を踏まえて、本発明は、電極活物質と電解液とを含む電極活物質スラリーを用いて電極を作製しても、電池内部抵抗を低減でき、充放電特性に優れるリチウムイオン電池を安定して製造することができるリチウムイオン電池の製造方法を提供することを目的とする。 In view of the above circumstances, the present invention provides a lithium ion battery that can reduce battery internal resistance and has excellent charge/discharge characteristics even when an electrode is made using an electrode active material slurry containing an electrode active material and an electrolyte. An object of the present invention is to provide a method for manufacturing a lithium ion battery that can be stably manufactured.
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、正極活物質スラリーの電解質濃度と、負極活物質スラリーの電解質濃度とを制御することにより、正極活物質スラリーの安定性を向上することができ、正極活物質スラリーの固液分離や導電助剤の凝集といった問題を解決でき、電池内部抵抗を低減でき、充放電特性に優れるリチウムイオン電池を安定して製造することができることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors improved the stability of the positive electrode active material slurry by controlling the electrolyte concentration of the positive electrode active material slurry and the electrolyte concentration of the negative electrode active material slurry. It is possible to solve problems such as solid-liquid separation of positive electrode active material slurry and agglomeration of conductive additives, reduce battery internal resistance, and stably produce lithium-ion batteries with excellent charge and discharge characteristics. Heading, we arrived at the present invention.
すなわち、本発明は、正極、セパレータ及び負極がこの順に積層されたリチウムイオン電池の製造方法であって、正極活物質と電解液とを含み、該電解液の電解質濃度が２．５～４ｍｏｌ／Ｌである正極活物質スラリーを正極集電体に塗工して上記正極を得る工程と、負極活物質と電解液とを含み、該電解液の電解質濃度が０．１～２ｍｏｌ／Ｌである負極活物質スラリーを負極集電体に塗工して上記負極を得る工程と、上記正極と上記負極とを、上記セパレータを介して対向して配置する工程とを有することを特徴とするリチウムイオン電池の製造方法である。 That is, the present invention is a method for manufacturing a lithium ion battery in which a positive electrode, a separator, and a negative electrode are laminated in this order, and includes a positive electrode active material and an electrolytic solution, and the electrolytic solution has an electrolyte concentration of 2.5 to 4 mol/ The method includes a step of applying a positive electrode active material slurry of L to a positive electrode current collector to obtain the positive electrode, a negative electrode active material and an electrolyte, and the electrolyte concentration of the electrolyte is 0.1 to 2 mol/L. A lithium ion characterized by comprising a step of applying a negative electrode active material slurry to a negative electrode current collector to obtain the negative electrode, and a step of arranging the positive electrode and the negative electrode to face each other with the separator interposed therebetween. This is a method for manufacturing batteries.
本発明によれば、電極活物質と電解液とを含む電極活物質スラリーを用いて電極を作製しても、電池内部抵抗を低減でき、充放電特性に優れるリチウムイオン電池を安定して製造することができる。 According to the present invention, even if an electrode is made using an electrode active material slurry containing an electrode active material and an electrolyte, the internal resistance of the battery can be reduced, and a lithium ion battery with excellent charge and discharge characteristics can be stably manufactured. be able to.
本発明のリチウムイオン電池の製造方法は、正極活物質と電解液とを含み、該電解液の電解質濃度が２．５～４ｍｏｌ／Ｌである正極活物質スラリーを正極集電体に塗工して上記正極を得る工程を有する。 The method for producing a lithium ion battery of the present invention includes coating a positive electrode current collector with a positive electrode active material slurry containing a positive electrode active material and an electrolytic solution, the electrolytic solution having an electrolyte concentration of 2.5 to 4 mol/L. and obtaining the positive electrode.
[正極活物質]
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ビニルカルバゾール）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。
[Cathode active material]
As the positive electrode active material, composite oxides of lithium and transition metals {complex oxides containing one type of transition metal (such as LiCoO 2 , LiNiO 2 , LiAlMnO 4 , LiMnO 2 and LiMn 2 O 4 ), transition metal elements Two types of composite oxides (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 containing three or more types of metal elements [for example, LiM a M' b M'' c O 2 (M, M', and M'' are each different transition metal elements) and satisfies a+b+c=1.For example, LiNi 1/3 Mn 1/3 Co 1/3 O 2 ), etc.}, lithium-containing transition metal phosphates (for example, LiFePO 4 , LiCoPO 4 , LiMnPO 4 and LiNiPO 4 ), transition metal oxides (e.g. MnO 2 and V 2 O 5 ), transition metal sulfides (e.g. MoS 2 and TiS 2 ) and conductive polymers (e.g. polyaniline, polypyrrole, polythiophene, polyacetylene and poly-p-phenylene and polyvinylcarbazole), etc., and two or more types may be used in combination.
Note that the lithium-containing transition metal phosphate may be one in which some of the transition metal sites are replaced with another transition metal.
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。
本明細書において、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。
The volume average particle diameter of the positive electrode active material is preferably 0.01 to 100 μm, more preferably 0.1 to 35 μm, and even more preferably 2 to 30 μm, from the viewpoint of battery electrical characteristics. .
In this specification, the volume average particle diameter means the particle diameter (Dv50) at 50% of the integrated value in the particle size distribution determined by the Microtrack method (laser diffraction/scattering method). The microtrack method is a method of determining particle size distribution using scattered light obtained by irradiating particles with laser light. Note that, for measuring the volume average particle diameter, a Microtrack manufactured by Nikkiso Co., Ltd., etc. can be used.
正極活物質は、導電助剤及び被覆用樹脂で被覆された被覆正極活物質であることが好ましい。
正極活物質の周囲が被覆用樹脂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。
The positive electrode active material is preferably a coated positive electrode active material coated with a conductive additive and a coating resin.
When the periphery of the positive electrode active material is coated with the coating resin, the volume change of the electrode is alleviated, and expansion of the electrode can be suppressed.
導電助剤としては、金属系導電助剤［アルミニウム、ステンレス（ＳＵＳ）、銀、金、銅及びチタン等]、炭素系導電助剤［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及び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。
これらの導電助剤は１種単独で用いられてもよいし、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として用いられてもよい。
なかでも、電気的安定性の観点から、より好ましくはアルミニウム、ステンレス、銀、金、銅、チタン、炭素系導電助剤及びこれらの混合物であり、さらに好ましくは銀、金、アルミニウム、ステンレス及び炭素系導電助剤であり、特に好ましくは炭素系導電助剤である。
またこれらの導電助剤としては、粒子系セラミック材料や樹脂材料の周りに導電性材料［好ましくは、上記した導電助剤のうち金属のもの］をめっき等でコーティングしたものでもよい。
Examples of conductive aids include metallic conductive aids [aluminum, stainless steel (SUS), silver, gold, copper, titanium, etc.], carbon-based conductive aids [graphite and carbon black (acetylene black, Ketjen black, furnace black, etc.) channel black, thermal lamp black, etc.), and mixtures thereof.
These conductive aids may be used alone or in combination of two or more. Further, alloys or metal oxides of these may be used.
Among these, from the viewpoint of electrical stability, aluminum, stainless steel, silver, gold, copper, titanium, carbon-based conductive aids, and mixtures thereof are more preferred, and even more preferred are silver, gold, aluminum, stainless steel, and carbon. A carbon-based conductive additive is particularly preferred.
Further, these conductive aids may be those in which a particulate ceramic material or a resin material is coated with a conductive material (preferably a metal among the above-mentioned conductive aids) by plating or the like.
導電助剤の形状（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、カーボンナノファイバー、カーボンナノチューブ等、いわゆるフィラー系導電助剤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 aid is not limited to the particle form, and may be in a form other than the particle form, including carbon nanofibers, carbon nanotubes, and other forms that have been put into practical use as so-called filler-based conductive aids. You can.
導電助剤の平均粒子径は、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程度であることが好ましい。なお、本明細書中において、「粒子径」とは、導電助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 additive is not particularly limited, but from the viewpoint of the electrical characteristics of the battery, it is preferably about 0.01 to 10 μm. In addition, in this specification, "particle diameter" means the maximum distance L among the distances between arbitrary two points on the contour line of a conductive support agent. The value of "average particle diameter" is the average value of the particle diameter of particles observed in several to several dozen fields of view using observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
被覆用樹脂と導電助剤の比率は特に限定されるものではないが、電池の内部抵抗等の観点から、重量比率で被覆用樹脂（樹脂固形分重量）：導電助剤が１：０．０１～１：５０であることが好ましく、１：０．２～１：３．０であることがより好ましい。 The ratio of the coating resin to the conductive aid is not particularly limited, but from the viewpoint of internal resistance of the battery, etc., the weight ratio of the coating resin (resin solid weight) to the conductive aid is 1:0.01. The ratio is preferably 1:50 to 1:50, more preferably 1:0.2 to 1:3.0.
被覆用樹脂としては、特開２０１７－０５４７０３号公報に非水系二次電池活物質被覆用樹脂として記載されたものを好適に用いることができる。 As the coating resin, those described in JP-A No. 2017-054703 as a resin for coating a non-aqueous secondary battery active material can be suitably used.
[電解液]
電解液としては、電解質及び溶媒を含む。
[Electrolyte]
The electrolytic solution includes an electrolyte and a solvent.
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、ＬｉＣｌＯ４及びＬｉＮ（ＦＳＯ２）２等の無機アニオンのリチウム塩、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２及びＬｉＣ（ＣＦ３ＳＯ２）３等の有機アニオンのリチウム塩が挙げられる。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ＬｉＮ（ＦＳＯ２）２である。 As the electrolyte, those used in known electrolytes can be used, such as lithium salts of inorganic anions such as LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 and LiN(FSO 2 ) 2 ; Examples include lithium salts of organic anions such as LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 and LiC(CF 3 SO 2 ) 3 . Among these, LiN(FSO 2 ) 2 is preferred from the viewpoint of battery output and charge/discharge cycle characteristics.
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、環状又は鎖状カーボネート、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 solvent, those used in known electrolytes can be used, such as lactone compounds, cyclic or chain carbonates, chain carboxylic acid esters, cyclic or chain ethers, phosphate esters, nitrile compounds, amides, etc. Compounds such as sulfones, sulfolanes, etc. 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 5-membered ring lactone compounds (such as γ-butyrolactone and γ-valerolactone) and 6-membered ring lactone compounds (such as δ-valerolactone).
環状カーボネートとしては、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。
鎖状カーボネートとしては、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, and 1,4-dioxane.
Examples of chain ethers 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。
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。
Phosphate esters include trimethyl phosphate, triethyl phosphate, ethyldimethyl phosphate, diethylmethyl phosphate, tripropyl phosphate, tributyl phosphate, tri(trifluoromethyl) phosphate, tri(trichloromethyl) phosphate, Tri(trifluoroethyl) phosphate, tri(triperfluoroethyl) phosphate, 2-ethoxy-1,3,2-dioxaphosphorane-2-one, 2-trifluoroethoxy-1,3,2- Examples include dioxaphosphoran-2-one and 2-methoxyethoxy-1,3,2-dioxaphosphoran-2-one.
Examples of the nitrile compound include acetonitrile and the like. Examples of the amide compound include DMF and the like. Examples of the sulfone include dimethylsulfone and diethylsulfone.
One type of solvent may be used alone, or two or more types may be used in combination.
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、環状カーボネート、鎖状カーボネート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、環状カーボネート及び鎖状カーボネートであり、特に好ましいのは環状カーボネートと鎖状カーボネートの混合液である。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。 Among the solvents, preferred from the viewpoint of battery output and charge/discharge cycle characteristics are lactone compounds, cyclic carbonates, chain carbonates, and phosphoric acid esters, and more preferred are lactone compounds, cyclic carbonates, and chain carbonates, Particularly preferred is a mixture of a cyclic carbonate and a chain carbonate. Most preferred is a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) or a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC).
また、溶媒の内、電極の耐久性を好適に付与する観点から、電解液の全溶媒に対する環状カーボネートの体積比率が、５０体積％以上であることが好ましく、７０体積％以上であることが更に好ましい。 Further, among the solvents, from the viewpoint of suitably imparting durability to the electrode, the volume ratio of cyclic carbonate to the total solvent of the electrolytic solution is preferably 50 volume% or more, and more preferably 70 volume% or more. preferable.
正極活物質スラリーにおいて、電解液の電解質濃度は２．５～４ｍｏｌ／Ｌである。
正極活物質スラリーにおいて、このような電解液を用いることにより、正極活物質スラリーが固液分離を起こしたり、導電助剤が凝集したりすることを抑制することができるので、耐久性に優れたリチウムイオン電池用正極、電池内部抵抗を低減でき、充放電特性に優れたリチウムイオン電池を安定して得ることができる。
正極活物質スラリーにおいて、電解液の電解質濃度は３．０～４．０ｍｏｌ／Ｌであることが好ましく、３．２～４．０ｍｏｌ／Ｌであることが更に好ましい。
In the positive electrode active material slurry, the electrolyte concentration of the electrolytic solution is 2.5 to 4 mol/L.
By using such an electrolyte in the positive electrode active material slurry, it is possible to suppress solid-liquid separation of the positive electrode active material slurry and agglomeration of the conductive agent, resulting in a highly durable product. A positive electrode for a lithium ion battery, which can reduce battery internal resistance and stably obtain a lithium ion battery with excellent charge and discharge characteristics.
In the positive electrode active material slurry, the electrolyte concentration of the electrolytic solution is preferably 3.0 to 4.0 mol/L, more preferably 3.2 to 4.0 mol/L.
正極活物質スラリーは、被覆正極活物質に含まれる導電助剤以外にも導電助剤を含んでもよい。
導電助剤としては、上述した被覆正極活物質に含まれる導電助剤と同様のものを好適に用いることができる。
炭素系導電助剤は、正極活物質スラリーの固液分離や導電助剤の凝集を抑制する観点及び正極の電子抵抗を低減する観点から、正極活物質スラリーの全固形分に対して、０．１～１０重量％であることが好ましく、３～７重量％であることが更に好ましい。
なお、炭素系導電助剤の含有量は、正極活物質スラリーの全固形分に対する含有量であり、被覆正極活物質に含まれる炭素系導電助剤の含有量と、被覆正極活物質以外に含まれる炭素系導電助剤の含有量を合計した含有量である。
The positive electrode active material slurry may contain a conductive additive in addition to the conductive additive contained in the coated positive electrode active material.
As the conductive aid, the same conductive aid as the one contained in the coated positive electrode active material described above can be suitably used.
From the viewpoint of suppressing solid-liquid separation of the positive electrode active material slurry and agglomeration of the conductive agent, and from the viewpoint of reducing the electronic resistance of the positive electrode, the carbon-based conductive additive is added in an amount of 0.0% to the total solid content of the positive electrode active material slurry. It is preferably 1 to 10% by weight, more preferably 3 to 7% by weight.
The content of the carbon-based conductive additive is the content based on the total solid content of the positive electrode active material slurry, and is the content of the carbon-based conductive additive contained in the coated positive electrode active material and the content other than the coated positive electrode active material. This is the total content of the carbon-based conductive additive contained in the carbon-based conductive agent.
正極活物質スラリーは、例えば、上述した材料を混合し、混錬することにより得ることができる。 The positive electrode active material slurry can be obtained, for example, by mixing and kneading the above-mentioned materials.
［正極集電体］
正極活物質スラリーは、正極集電体上に付与されることにより、正極活物質層を形成することができる。
正極集電体を構成する材料としては、銅、アルミニウム、チタン、ステンレス鋼、ニッケル及びこれらの合金等の金属材料、並びに、焼成炭素、導電性高分子材料、導電性ガラス等が挙げられる。
正極集電体としては、軽量化、耐食性の観点から、樹脂組成物を成形した樹脂集電体であって、樹脂組成物が樹脂と導電性フィラーとを含み、樹脂中に導電性フィラーが分散されていることが好ましい。
正極集電体の形状は特に限定されず、上記の材料からなるシート状の集電体、及び、上記の材料で構成された微粒子からなる堆積層であってもよい。
正極集電体の厚さは、特に限定されないが、１０～２００μｍであることが好ましい。
[Positive electrode current collector]
The positive electrode active material slurry can form a positive electrode active material layer by being applied onto the positive electrode current collector.
Examples of the material constituting the positive electrode current collector include metal materials such as copper, aluminum, titanium, stainless steel, nickel, and alloys thereof, calcined carbon, conductive polymer materials, conductive glass, and the like.
As the positive electrode current collector, from the viewpoint of weight reduction and corrosion resistance, a resin current collector molded from a resin composition is used, where the resin composition contains a resin and a conductive filler, and the conductive filler is dispersed in the resin. It is preferable that the
The shape of the positive electrode current collector is not particularly limited, and may be a sheet-like current collector made of the above-mentioned material or a deposited layer made of fine particles made of the above-mentioned material.
The thickness of the positive electrode current collector is not particularly limited, but is preferably 10 to 200 μm.
樹脂集電体を構成する樹脂としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリメチルペンテン（ＰＭＰ）、ポリシクロオレフィン（ＰＣＯ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエーテルニトリル（ＰＥＮ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレンブタジエンゴム（ＳＢＲ）、ポリアクリロニトリル（ＰＡＮ）、ポリメチルアクリレート（ＰＭＡ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリフッ化ビニリデン（ＰＶｄＦ）、エポキシ樹脂、シリコーン樹脂又はこれらの混合物等が挙げられる。
電気的安定性の観点から、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリメチルペンテン（ＰＭＰ）及びポリシクロオレフィン（ＰＣＯ）が好ましく、さらに好ましくはポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）及びポリメチルペンテン（ＰＭＰ）である。
樹脂集電体を構成する導電性フィラーとしては例えば、被覆正極活物質の任意成分である導電助剤と同様のものを好適に用いることができる。
Examples of resins constituting the resin current collector include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), polyethylene terephthalate (PET), polyethernitrile (PEN), and polytetra Fluoroethylene (PTFE), styrene butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVdF), epoxy resin, silicone resin, or mixtures thereof, etc. can be mentioned.
From the viewpoint of electrical stability, polyethylene (PE), polypropylene (PP), polymethylpentene (PMP) and polycycloolefin (PCO) are preferred, and polyethylene (PE), polypropylene (PP) and polymethylpentene are more preferred. (PMP).
As the conductive filler constituting the resin current collector, for example, the same conductive filler as an optional component of the coated positive electrode active material can be suitably used.
正極活物質スラリーを正極集電体に塗工する方法としては、例えば、正極活物質スラリーを、正極集電体上にバーコーター等の塗工装置で塗布後、必要により不織布を活物質上に静置して吸液すること等で、溶媒を除去し、必要によりプレス機でプレスする方法等が挙げられる。 As a method for applying the positive electrode active material slurry to the positive electrode current collector, for example, after applying the positive electrode active material slurry onto the positive electrode current collector using a coating device such as a bar coater, a nonwoven fabric is coated on the active material as necessary. Examples include a method in which the solvent is removed by allowing it to stand still and absorbing the liquid, and if necessary, pressing it with a press.
正極の厚みは、電池性能の観点から、１５０～６００μｍであることが好ましく、２００～４５０μｍであることがより好ましい。 From the viewpoint of battery performance, the thickness of the positive electrode is preferably 150 to 600 μm, more preferably 200 to 450 μm.
本発明のリチウムイオン電池の製造方法は、負極活物質と電解液とを含み、該電解液の電解質濃度が０．１～２ｍｏｌ／Ｌである負極活物質スラリーを負極集電体に塗工して上記負極を得る工程を有する。
なお、上述した正極を得る工程と、負極を得る工程は、何れの工程を先に行っても、同時に行ってもよい。
The method for manufacturing a lithium ion battery of the present invention includes coating a negative electrode current collector with a negative electrode active material slurry containing a negative electrode active material and an electrolytic solution, the electrolytic solution having an electrolyte concentration of 0.1 to 2 mol/L. and obtaining the negative electrode.
Note that the above-described process of obtaining the positive electrode and the process of obtaining the negative electrode may be performed either first or at the same time.
［負極活物質］
負極としては、負極活物質、導電助剤及び集電体等を含むものが挙げられる。
負極活物質としては、公知のリチウムイオン電池用負極活物質が使用でき、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。
また、負極活物質は、上述した被覆正極活物質と同様の被覆樹脂により被覆されていてもよい。
また、導電助剤は、上述した被覆正極活物質と同様の導電助剤を好適に用いることができる。
[Negative electrode active material]
Examples of the negative electrode include those containing a negative electrode active material, a conductive agent, a current collector, and the like.
As the negative electrode active material, known negative electrode active materials for lithium ion batteries can be used. cokes (e.g., pitch coke, needle coke, petroleum coke, etc.), carbon fibers, etc.], silicon-based materials [silicon, silicon oxide (SiOx), silicon-carbon composites (carbon particles whose surfaces are coated with silicon and silicon carbide, silicon particles or silicon oxide particles whose surfaces are coated with carbon and/or silicon carbide, silicon carbide, etc.) and silicon alloys (silicon-aluminum alloys, silicon-lithium alloys, silicon-nickel alloys) conductive polymers (e.g. polyacetylene and polypyrrole), metals (tin, aluminum, zirconium and titanium, etc.), metal oxides (titanium oxide and lithium titanium oxide, etc.), metal alloys (for example, lithium-tin alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy, etc.), and carbon-based materials with these. Examples include mixtures with
Further, the negative electrode active material may be coated with the same coating resin as the coated positive electrode active material described above.
Further, as the conductive aid, the same conductive aid as the coated positive electrode active material described above can be suitably used.
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、０．１～１００μｍであることが好ましく、１～５０μｍであることがより好ましく、２～２０μｍであることがさらに好ましい。
負極活物質の体積平均粒子径は、レーザー回折・散乱法（マイクロトラック法ともいう）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。レーザー回折・散乱法とは、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り、体積平均粒子径の測定には、日機装株式会社製のマイクロトラック等を用いることができる。
The volume average particle diameter of the negative electrode active material is preferably from 0.1 to 100 μm, more preferably from 1 to 50 μm, and even more preferably from 2 to 20 μm, from the viewpoint of electrical characteristics of the battery.
The volume average particle diameter of the negative electrode active material means the particle diameter (Dv50) at 50% of the integrated value in the particle size distribution determined by the laser diffraction/scattering method (also referred to as the microtrack method). The laser diffraction/scattering method is a method of determining particle size distribution using scattered light obtained by irradiating particles with laser light. To measure the volume average particle diameter, Microtrack, etc. manufactured by Nikkiso Co., Ltd. can be used.
負極活物質スラリーにおいて、電解液の電解質濃度は０．１～２ｍｏｌ／Ｌである。
負極活物質スラリーにおいて、電解液の電解質濃度は０．４～２ｍｏｌ／Ｌであることが好ましく、０．８～１．８ｍｏｌ／Ｌであることが更に好ましい。
なお、電解液としては、上述した正極活物質スラリーで記載した電解質及び溶媒と同様のものを好適に用いることができる。
In the negative electrode active material slurry, the electrolyte concentration of the electrolytic solution is 0.1 to 2 mol/L.
In the negative electrode active material slurry, the electrolyte concentration of the electrolytic solution is preferably 0.4 to 2 mol/L, more preferably 0.8 to 1.8 mol/L.
Note that as the electrolytic solution, the same electrolytes and solvents as those described in the above-mentioned positive electrode active material slurry can be suitably used.
負極活物質スラリーは、例えば、上述した材料を混合し、混錬することにより得ることができる。 The negative electrode active material slurry can be obtained, for example, by mixing and kneading the above-mentioned materials.
［負極集電体］
負極活物質スラリーは、負極集電体上に付与されることにより、負極活物質層を形成することができる。
負極集電体を構成する材料としては、銅、アルミニウム、チタン、ステンレス鋼、ニッケル及びこれらの合金等の金属材料、並びに、焼成炭素、導電性高分子及び導電性ガラス等が挙げられる。
負極集電体としては、軽量化、耐食性の観点から、樹脂組成物を成形した樹脂集電体であって、樹脂組成物が樹脂と導電性フィラーとを含み、樹脂中に導電性フィラーが分散されていることが好ましい。なお、樹脂集電体としては、上述した正極集電体で記載したものと同様のものが挙げられる。
負極集電体の厚さは、特に限定されないが、１０～２００μｍであることが好ましい。
[Negative electrode current collector]
The negative electrode active material slurry can form a negative electrode active material layer by being applied onto the negative electrode current collector.
Examples of the material constituting the negative electrode current collector include metal materials such as copper, aluminum, titanium, stainless steel, nickel, and alloys thereof, as well as fired carbon, conductive polymers, conductive glass, and the like.
From the viewpoint of weight reduction and corrosion resistance, the negative electrode current collector is a resin current collector molded from a resin composition, where the resin composition contains a resin and a conductive filler, and the conductive filler is dispersed in the resin. It is preferable that the Note that examples of the resin current collector include those similar to those described in the above-mentioned positive electrode current collector.
The thickness of the negative electrode current collector is not particularly limited, but is preferably 10 to 200 μm.
負極活物質スラリーを負極集電体に塗工する方法としては、例えば、負極活物質スラリーを、負極集電体上にバーコーター等の塗工装置で塗布後、必要により不織布を活物質上に静置して吸液すること等で、溶媒を除去し、必要によりプレス機でプレスする方法等が挙げられる。 As a method for applying the negative electrode active material slurry to the negative electrode current collector, for example, after applying the negative electrode active material slurry onto the negative electrode current collector using a coating device such as a bar coater, a nonwoven fabric is coated on the active material as necessary. Examples include a method in which the solvent is removed by allowing it to stand still and absorbing the liquid, and if necessary, pressing it with a press machine.
負極の厚みは、電池性能の観点から、１５０～６００μｍであることが好ましく、２００～４５０μｍであることがより好ましい。 From the viewpoint of battery performance, the thickness of the negative electrode is preferably 150 to 600 μm, more preferably 200 to 450 μm.
［セパレータ］
本発明のリチウムイオン電池の製造方法は、正極と負極とを、セパレータを介して対向して配置する工程を有する。
[Separator]
The method for manufacturing a lithium ion battery of the present invention includes the step of arranging a positive electrode and a negative electrode to face each other with a separator interposed therebetween.
セパレータとしては、ポリエチレン又はポリプロピレン製の多孔性フィルム、多孔性ポリエチレンフィルムと多孔性ポリプロピレンとの積層フィルム、合成繊維（ポリエステル繊維及びアラミド繊維等）又は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のセパレータが挙げられる。 As separators, porous films made of polyethylene or polypropylene, laminated films of porous polyethylene films and porous polypropylene, nonwoven fabrics made of synthetic fibers (polyester fibers, aramid fibers, etc.) or glass fibers, etc., and silica on their surfaces are used. Examples include known separators for lithium ion batteries, such as those to which ceramic fine particles of alumina, titania, etc. are attached.
［リチウムイオン電池］
本発明のリチウムイオン電池の製造方法では、正極と負極とを、セパレータを介して対向して配置し、セル容器に収納し、セル容器を密封することでリチウムイオン電池を得ることができる。なお、セルを容器に収納する際には、必要に応じて、電解液を注入してもよい。
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バイポーラ（双極）型電極を作製し、バイポーラ（双極）型電極をセパレータと積層してセル容器に収納し、電解液を注入し、セル容器を密封することでも得られる。
[Lithium ion battery]
In the method for manufacturing a lithium ion battery of the present invention, a lithium ion battery can be obtained by arranging a positive electrode and a negative electrode to face each other with a separator in between, storing them in a cell container, and sealing the cell container. Note that when storing the cell in the container, an electrolytic solution may be injected as necessary.
In addition, a positive electrode is formed on one side of the current collector and a negative electrode is formed on the other side to create a bipolar (bipolar) type electrode, and the bipolar (bipolar) type electrode is laminated with a separator to form a cell container. It can also be obtained by storing the cell, injecting electrolyte, and sealing the cell container.
本発明のリチウムイオン電池の製造方法は、電池内部抵抗を低減でき、優れた充放電特性を好適に付与する観点から、電解質濃度が１．５～３．５ｍｏｌ／Ｌの電解液を有するリチウムイオン電池の製造方法であることが好ましい。
なお、上記電解質濃度は、リチウムイオン電池を作製し、該リチウムイオン電池内の電解液の電解質濃度が均一化した後、遠心分離等で電解液を抽出し、得られた電解液をＬｉ－ＮＭＲでＬｉ塩濃度を定量することにより測定することができる。
The method for manufacturing a lithium ion battery of the present invention uses a lithium ion battery having an electrolytic solution having an electrolyte concentration of 1.5 to 3.5 mol/L from the viewpoint of reducing internal resistance of the battery and suitably imparting excellent charge/discharge characteristics. Preferably, the method is a method for manufacturing a battery.
The above electrolyte concentration is determined by producing a lithium ion battery, and after the electrolyte concentration of the electrolyte in the lithium ion battery is made uniform, the electrolyte is extracted by centrifugation, etc., and the obtained electrolyte is subjected to Li-NMR. It can be measured by quantifying the Li salt concentration.
本発明のリチウムイオン電池の製造方法において、正極集電体及び負極集電体が、樹脂組成物を成形した樹脂集電体であって、樹脂組成物が樹脂と導電性フィラーとを含むことが好ましい。
このような構成にすることにより、リチウムイオン電池を軽量化でき、耐食性を好適に付与することができる。
In the method for manufacturing a lithium ion battery of the present invention, the positive electrode current collector and the negative electrode current collector may be resin current collectors formed by molding a resin composition, and the resin composition may include a resin and a conductive filler. preferable.
With such a configuration, the weight of the lithium ion battery can be reduced and corrosion resistance can be suitably imparted.
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 explained with reference to examples, but the present invention is not limited to the examples unless it departs from the gist of the present invention. In addition, unless otherwise specified, "part" means "part by weight" and "%" means percent by weight.
以下の実施例で使用した材料は下記の通りである。 The materials used in the following examples are as follows.
［製造例１：電解液の作製］
＜電解液（Ｅ－１）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を４．０ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－１）を準備した。
[Manufacture example 1: Preparation of electrolyte]
<Preparation of electrolyte solution (E-1)>
An electrolytic solution (E-1) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 4.0 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
＜電解液（Ｅ－２）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を３．０ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－２）を準備した。
<Preparation of electrolyte solution (E-2)>
Electrolyte solution (E-2) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 3.0 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
＜電解液（Ｅ－３）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を２．０ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－３）を準備した。
<Preparation of electrolyte solution (E-3)>
An electrolytic solution (E-3) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 2.0 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
＜電解液（Ｅ－４）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を１．５ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－４）を準備した。
<Preparation of electrolyte solution (E-4)>
An electrolytic solution (E-4) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 1.5 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
＜電解液（Ｅ－５）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を１．０ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－５）を準備した。
<Preparation of electrolyte solution (E-5)>
An electrolytic solution (E-5) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 1.0 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
＜電解液（Ｅ－６）の作製＞
エチレンカーボネート（ＥＣ）とプロピレンカーボネート（ＰＣ）の混合溶媒（体積比率１：１）にＬｉＮ（ＦＳＯ２）２を０．３ｍｏｌ／Ｌの割合で溶解させて電解液（Ｅ－６）を準備した。
<Preparation of electrolyte solution (E-6)>
An electrolytic solution (E-6) was prepared by dissolving LiN(FSO 2 ) 2 at a ratio of 0.3 mol/L in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1). .
［製造例２：正極活物質スラリーの作製］
＜被覆用樹脂を構成する高分子化合物の作製＞
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ＤＭＦ１５０．０部を仕込み７５℃に昇温した。次いで、メタクリル酸メチル１０．０部、アクリル酸９０．０部及びＤＭＦ５０部を配合した単量体組成物と、２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．３部及び２，２’－アゾビス（２－メチルブチロニトリル）０．８部をＤＭＦ３０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、７５℃で反応を３時間継続した。次いで８０℃に昇温し反応を３時間継続し樹脂濃度３０％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１５０℃、０．０１ＭＰａで３時間の減圧乾燥を行いＤＭＦを留去して共重合体を得た。この共重合体をハンマーで粗粉砕した後、乳鉢にて追加粉砕して、粉末状の高分子化合物を得た。
[Production Example 2: Preparation of positive electrode active material slurry]
<Preparation of polymer compound constituting coating resin>
150.0 parts of DMF was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and the temperature was raised to 75°C. Next, a monomer composition containing 10.0 parts of methyl methacrylate, 90.0 parts of acrylic acid, and 50 parts of DMF, and 0.3 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 2 , 0.8 parts of 2'-azobis(2-methylbutyronitrile) dissolved in 30 parts of DMF were continuously added to a four-necked flask using a dropping funnel for 2 hours under stirring while blowing nitrogen into the 4-necked flask. Radical polymerization was carried out by adding the mixture dropwise. After the dropwise addition was completed, the reaction was continued at 75°C for 3 hours. Next, the temperature was raised to 80°C and the reaction was continued for 3 hours to obtain a copolymer solution with a resin concentration of 30%. The obtained copolymer solution was transferred to a Teflon (registered trademark) vat and dried under reduced pressure at 150° C. and 0.01 MPa for 3 hours to remove DMF and obtain a copolymer. This copolymer was roughly pulverized with a hammer, and then further pulverized in a mortar to obtain a powdery polymer compound.
＜被覆正極活物質の作製＞
電極活物質粉末（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［アーステクニカ製］に入れ、室温、７２０ｒｐｍで撹拌した状態で、得られた高分子化合物をＤＭＦに３．０重量％の濃度で溶解して得られた高分子化合物溶液１０．０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助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１５０℃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、被覆正極活物質を得た。
<Preparation of coated positive electrode active material>
100 parts of electrode active material powder (LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, volume average particle diameter 4 μm) was placed in a universal mixer high speed mixer FS25 [manufactured by Earth Technica] and stirred at room temperature at 720 rpm. In this state, 10.0 parts of a polymer compound solution obtained by dissolving the obtained polymer compound in DMF at a concentration of 3.0% by weight was added dropwise over 2 minutes, and the mixture was further stirred for 5 minutes.
Next, while stirring, 6.2 parts of acetylene black [Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.] as a conductive additive was added in portions over 2 minutes, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining stirring, and then the temperature was raised to 150°C while maintaining stirring and reduced pressure, and the stirring, reduced pressure, and temperature were maintained for 8 hours to distill off volatile components. . The obtained powder was classified using a sieve with an opening of 212 μm to obtain a coated positive electrode active material.
＜正極活物質スラリー１の作製＞
上記被覆正極活物質９９部と電解液（Ｅ－１）４６部と炭素繊維［昭和電工（株）製ＶＧＣＦ：平均繊維長１０μｍ、平均繊維径１５０ｎｍ］１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５分間混合して、正極活物質スラリー１を作製した。
<Preparation of positive electrode active material slurry 1>
99 parts of the above coated positive electrode active material, 46 parts of electrolyte (E-1), and 1 part of carbon fiber [VGCF manufactured by Showa Denko K.K.: average fiber length 10 μm, average fiber diameter 150 nm] were mixed in a planetary stirring type mixing and kneading device { Cathode active material slurry 1 was prepared by mixing at 2000 rpm for 5 minutes using a bubbly Rentaro [manufactured by Shinky Co., Ltd.].
＜正極活物質スラリー２の作製＞
電解液（Ｅ－２）を用いたこと以外は、正極活物質スラリー１と同様の方法により、正極活物質スラリー２を作製した。
<Preparation of positive electrode active material slurry 2>
Positive electrode active material slurry 2 was produced in the same manner as positive electrode active material slurry 1 except that electrolyte solution (E-2) was used.
＜正極活物質スラリー３の作製＞
電解液（Ｅ－３）を用いたこと以外は、正極活物質スラリー１と同様の方法により、正極活物質スラリー３を作製した。
<Preparation of positive electrode active material slurry 3>
Positive electrode active material slurry 3 was produced in the same manner as positive electrode active material slurry 1 except that electrolyte solution (E-3) was used.
＜正極活物質スラリーの貯蔵安定性＞
正極活物質スラリー１～３を作製直後にМｉｃｒоｔｒａｃ社製マイクロトラックＭＴ３０００により粒度分布測定した。正極活物質スラリー１～３作製直後の粒度分布では、粒子径２０～１００μｍ領域に存在する粒子の割合はいずれも０％以上、０．５％未満であった。
その後、正極活物質スラリー１～３を温度２５℃、露点－４５℃環境下で１２時間静置後にも粒度分布測定を実施した。静置後の粒度分布のうち、粒子径２０～１００μｍ領域に存在する粒子の割合を貯蔵安定性の指標とした。粒子径２０～１００μｍの粗大粒子は、正極活物質及び／又は導電助剤の凝集によるものと推定され、この割合が多いことは貯蔵安定性が悪いことを意味する。
◎：０％以上、０．５％未満
〇：０．５％以上、１％未満
×：１％以上
<Storage stability of positive electrode active material slurry>
Immediately after preparing the positive electrode active material slurries 1 to 3, particle size distribution was measured using Microtrac MT3000 manufactured by Microtrac. In the particle size distribution immediately after the preparation of positive electrode active material slurries 1 to 3, the proportion of particles existing in the particle diameter region of 20 to 100 μm was 0% or more and less than 0.5%.
Thereafter, particle size distribution measurements were also carried out after the positive electrode active material slurries 1 to 3 were allowed to stand for 12 hours in an environment with a temperature of 25°C and a dew point of -45°C. The proportion of particles in the particle size range of 20 to 100 μm in the particle size distribution after standing was used as an index of storage stability. Coarse particles with a particle diameter of 20 to 100 μm are presumed to be caused by aggregation of the positive electrode active material and/or conductive additive, and a high proportion means poor storage stability.
◎: 0% or more, less than 0.5% 〇: 0.5% or more, less than 1% ×: 1% or more
［製造例３：負極活物質スラリーの作製］
＜被覆負極活物質の作製＞
負極活物質として難黒鉛化性炭素［（株）クレハ・バッテリー・マテリアルズ・ジャパン製 カーボトロン（登録商標）ＰＳ（Ｆ）］１００部を万能混合機ハイスピードミキサーＦＳ２５［アーステクニカ製］に入れ、室温、７２０ｒｐｍで撹拌した状態で、高分子化合物（Ｐ－１）をＤＭＦに５．０重量％の濃度で溶解して得られた高分子化合物溶液６．０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助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）］５．１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１５０℃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、被覆負極活物質を得た。
[Production Example 3: Preparation of negative electrode active material slurry]
<Preparation of coated negative electrode active material>
100 parts of non-graphitizable carbon [Carbotron (registered trademark) PS (F) manufactured by Kureha Battery Materials Japan Co., Ltd.] as a negative electrode active material was put into a universal mixer high speed mixer FS25 [manufactured by Earth Technica]. While stirring at room temperature and 720 rpm, 6.0 parts of a polymer compound solution obtained by dissolving polymer compound (P-1) in DMF at a concentration of 5.0% by weight was added dropwise over 2 minutes. The mixture was stirred for an additional 5 minutes.
Next, while stirring, 5.1 parts of acetylene black [Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.] as a conductive additive was added in portions over 2 minutes, and stirring was continued for 30 minutes. Thereafter, the pressure was reduced to 0.01 MPa while maintaining stirring, and then the temperature was raised to 150°C while maintaining stirring and reduced pressure, and the stirring, reduced pressure, and temperature were maintained for 8 hours to distill off volatile components. . The obtained powder was classified using a sieve with an opening of 212 μm to obtain a coated negative electrode active material.
＜負極活物質スラリー１の作製＞
上記被覆負極活物質９８部と電解液（Ｅ－５）４６部と炭素繊維［昭和電工（株）製ＶＧＣＦ：平均繊維長１０μｍ、平均繊維径１５０ｎｍ］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５分間混合して、負極活物質スラリー１を作製した。
<Preparation of negative electrode active material slurry 1>
98 parts of the above coated negative electrode active material, 46 parts of electrolyte (E-5), and 2 parts of carbon fiber [VGCF manufactured by Showa Denko K.K.: average fiber length 10 μm, average fiber diameter 150 nm] were mixed in a planetary stirring type mixing and kneading device { Negative electrode active material slurry 1 was prepared by mixing at 2000 rpm for 5 minutes using a bubbly Rentaro [manufactured by Thinky Co., Ltd.].
＜負極活物質スラリー２の作製＞
電解液（Ｅ－４）を用いたこと以外は、負極活物質スラリー１と同様の方法により、負極活物質スラリー２を作製した。
<Preparation of negative electrode active material slurry 2>
Negative electrode active material slurry 2 was produced in the same manner as negative electrode active material slurry 1 except that electrolyte solution (E-4) was used.
＜負極活物質スラリー３の作製＞
電解液（Ｅ－１）を用いたこと以外は、負極活物質スラリー１と同様の方法により、負極活物質スラリー３を作製した。
<Preparation of negative electrode active material slurry 3>
Negative electrode active material slurry 3 was produced in the same manner as negative electrode active material slurry 1 except that electrolyte solution (E-1) was used.
＜負極活物質スラリー４の作製＞
電解液（Ｅ－３）を用いたこと以外は、負極活物質スラリー１と同様の方法により、負極活物質スラリー４を作製した。
<Preparation of negative electrode active material slurry 4>
Negative electrode active material slurry 4 was produced in the same manner as negative electrode active material slurry 1 except that electrolyte solution (E-3) was used.
＜負極活物質スラリー５の作製＞
電解液（Ｅ－６）を用いたこと以外は、負極活物質スラリー１と同様の方法により、負極活物質スラリー５を作製した。
<Preparation of negative electrode active material slurry 5>
Negative electrode active material slurry 5 was produced in the same manner as negative electrode active material slurry 1 except that electrolyte solution (E-6) was used.
［製造例４：樹脂集電体１の作製］
２軸押出機にて、ポリプロピレン［商品名「サンアロマーＰＬ５００Ａ」、サンアロマー（株）製］７０部、カーボンナノチューブ［商品名：「ＦｌｏＴｕｂｅ９０００」、ＣＮａｎｏ社製］２５部及び分散剤［商品名「ユーメックス１００１」、三洋化成工業（株）製］５部を２００℃、２００ｒｐｍの条件で溶融混練して樹脂混合物を得た。
得られた樹脂混合物を、Ｔダイ押出しフィルム成形機に通して、それを延伸圧延することで、厚みが２００μｍの樹脂集電体用導電性フィルムを得た。次いで、得られた樹脂集電体用導電性フィルムを６０ｍｍ×６０ｍｍとなるように切断し、樹脂集電体１を得た。
[Production Example 4: Production of resin current collector 1]
In a twin-screw extruder, 70 parts of polypropylene [trade name: "Sun Allomer PL500A", manufactured by Sun Allomer Co., Ltd.], 25 parts of carbon nanotubes [trade name: "FloTube9000", manufactured by CNano], and a dispersant [trade name: "Umex 1001"] were added. '', manufactured by Sanyo Chemical Industries, Ltd.] were melt-kneaded at 200° C. and 200 rpm to obtain a resin mixture.
The obtained resin mixture was passed through a T-die extrusion film forming machine and stretched and rolled to obtain a conductive film for a resin current collector having a thickness of 200 μm. Next, the obtained conductive film for a resin current collector was cut into a size of 60 mm x 60 mm to obtain a resin current collector 1.
（実施例１）
正極活物質スラリー１を温度２５℃、露点－４５℃環境下に１時間静置した後に、樹脂集電体１の片面に塗布し、０．９ＭＰａの圧力で約１０秒プレスし、厚みが２５０μｍの用正極（５０ｍｍ×４０ｍｍ）を作製した。
その一方で、負極活物質スラリー１を温度２５℃、露点－４５℃環境下に１時間静置した後に、樹脂集電体１の片面に塗布し、１．４ＭＰａの圧力で約１０秒プレスし、厚さが３５０μｍの負極（５２ｍｍ×４２ｍｍ）を作製した。
得られた正極及び負極を、セパレータ（セルガード製＃３５０１）を介して配置し、樹脂集電体の外周部をシール材が介した状態で真空シールした。得られた構造物を銅箔タブが付いたアルミラミネートフィルムで両面を覆い、再度、外周部を真空シールすることでリチウムイオン電池を作製した。
(Example 1)
After leaving the positive electrode active material slurry 1 in an environment with a temperature of 25° C. and a dew point of −45° C. for 1 hour, it was applied to one side of the resin current collector 1 and pressed for about 10 seconds at a pressure of 0.9 MPa to obtain a thickness of 250 μm. A positive electrode (50 mm x 40 mm) was prepared.
On the other hand, after leaving the negative electrode active material slurry 1 in an environment with a temperature of 25°C and a dew point of -45°C for 1 hour, it was applied to one side of the resin current collector 1 and pressed for about 10 seconds at a pressure of 1.4 MPa. A negative electrode (52 mm x 42 mm) with a thickness of 350 μm was produced.
The obtained positive electrode and negative electrode were placed with a separator (#3501 manufactured by Celgard) interposed therebetween, and the outer periphery of the resin current collector was vacuum-sealed with a sealing material interposed therebetween. Both sides of the resulting structure were covered with aluminum laminate films with copper foil tabs, and the outer periphery was vacuum-sealed again to produce a lithium ion battery.
（実施例２～３、比較例１～２）
正極活物質スラリー１及び／又は負極活物質スラリー１を表１に記載のものに変更したこと以外は、実施例１と同様にしてリチウムイオン電池を作製した。
(Examples 2-3, Comparative Examples 1-2)
A lithium ion battery was produced in the same manner as in Example 1, except that the positive electrode active material slurry 1 and/or the negative electrode active material slurry 1 were changed to those shown in Table 1.
＜リチウムイオン電池の電解質濃度＞
得られたリチウムイオン電池について、２５℃環境下で１２時間静置した後、遠心分離機を用いて電解液を抽出した。得られた電解液をＬｉ－ＮＭＲでＬｉ塩を定量することにより、リチウムイオン電池の電解質濃度を測定した。
<Electrolyte concentration of lithium ion batteries>
The obtained lithium ion battery was allowed to stand for 12 hours in a 25°C environment, and then the electrolyte was extracted using a centrifuge. The electrolyte concentration of the lithium ion battery was measured by quantifying Li salt in the obtained electrolyte using Li-NMR.
＜リチウムイオン電池評価＞
（電池内部抵抗の測定）
２５℃に温調した恒温槽内で、充放電測定装置「バッテリーアナライザー１４７０型」［東陽テクニカ（株）製］を用いてリチウムイオン電池の充放電を実施した。
０．１Ｃの電流で電圧４．２Ｖまで充電し、１０分間の休止後、０．１Ｃの電流で電池電圧を２．５Ｖまで放電した。
０．１Ｃ放電時における放電０秒後の電圧及び電流、並びに、０．１Ｃにおける放電１０秒後の電圧及び電流を測定し、以下の式により電池内部抵抗（Ω・ｃｍ２）を算出した。電池内部抵抗の数値が小さいほど電池性能が良好であることを示す。
［内部抵抗（Ω）］×［電極面積（ｃｍ２）］＝｛［（０．１Ｃにおける放電０秒後の電圧）－（０．１Ｃにおける放電１０秒後の電圧）］／［（０．１Ｃにおける放電０秒後の電流）－（０．１Ｃにおける放電１０秒後の電流）］｝×［電極面積（ｃｍ２）］
<Lithium ion battery evaluation>
(Measurement of battery internal resistance)
The lithium ion battery was charged and discharged using a charge and discharge measuring device "Battery Analyzer Model 1470" [manufactured by Toyo Technica Co., Ltd.] in a constant temperature bath controlled at 25°C.
The battery was charged with a current of 0.1C to a voltage of 4.2V, and after a 10-minute rest, the battery was discharged to a voltage of 2.5V with a current of 0.1C.
The voltage and current 0 seconds after discharging at 0.1C and the voltage and current 10 seconds after discharging at 0.1C were measured, and the battery internal resistance (Ω·cm 2 ) was calculated using the following formula. The smaller the battery internal resistance value, the better the battery performance.
[Internal resistance (Ω)] x [electrode area (cm 2 )] = {[(voltage after 0 seconds of discharge at 0.1C) - (voltage after 10 seconds of discharge at 0.1C)]/[(voltage after 10 seconds of discharge at 0.1C)]/[(0. Current after 0 seconds of discharge at 1C) - (Current after 10 seconds of discharge at 0.1C)] x [electrode area (cm 2 )]
（放電レート特性）
上記電気内部抵抗の測定と同様にして、リチウムイオン電池の充放電を実施した。
１サイクル目は、０．１Ｃの電流で電圧４．２Ｖまで充電し、１０分間の休止後、０．１Ｃの電流で電池電圧を２．５Ｖまで放電した。
２サイクル目は、０．１Ｃの電流で電圧４．２Ｖまで充電し、１０分間の休止後、１Ｃの電流で電池電圧を２．５Ｖまで放電し、１０分間の休止後にさらに０．１Ｃの電流値で電池電圧２．５Ｖまで放電した。２サイクル目に得られた１Ｃ放電容量と０．１Ｃ放電容量の比率[（２サイクル目１Ｃ放電容量）／（２サイクル目０．１Ｃ放電容量）×１００]から放電レート特性（％）を評価した。放電レート特性の数値が大きいほど電池性能が良好であることを示す。
なお、２サイクル目の放電は、１Ｃ放電後に０．１Ｃ放電を実施しているので、０．１Ｃ放電容量は、すでに放電している１Ｃ放電容量に追加で放電した０．１Ｃ放電容量を足した値を用いた。
(Discharge rate characteristics)
The lithium ion battery was charged and discharged in the same manner as the measurement of the electrical internal resistance described above.
In the first cycle, the battery was charged to a voltage of 4.2V with a current of 0.1C, and after a 10-minute rest, the battery was discharged to a voltage of 2.5V with a current of 0.1C.
In the second cycle, the battery voltage is charged to 4.2V with a current of 0.1C, and after a 10-minute rest, the battery voltage is discharged to 2.5V with a current of 1C, and after a rest of 10 minutes, the current is further increased to 0.1C. The battery was discharged to a voltage of 2.5V. Evaluate the discharge rate characteristics (%) from the ratio of the 1C discharge capacity and 0.1C discharge capacity obtained in the second cycle [(2nd cycle 1C discharge capacity)/(2nd cycle 0.1C discharge capacity) x 100] did. The larger the numerical value of the discharge rate characteristic is, the better the battery performance is.
In addition, in the second cycle of discharge, 0.1C discharge is performed after 1C discharge, so 0.1C discharge capacity is calculated by adding the additionally discharged 0.1C discharge capacity to the already discharged 1C discharge capacity. The value was used.
（１００サイクル容量維持率）
上記電気内部抵抗の測定と同様にして、リチウムイオン電池の充放電を実施した。
１サイクル目は、０．１Ｃの電流で電圧４．２Ｖまで充電し、１０分間の休止後、０．１Ｃの電流で電池電圧を２．５Ｖまで放電し、初回充放電容量を測定した。
その後、初回充放電と同様の条件で１００サイクル充放電を実施し、初回放電容量に対する１００サイクル目放電容量の割合[（１００サイクル目放電容量）／（初回放電容量）×１００]から１００サイクル容量維持率（％）を評価した。１００サイクル容量維持率の数値が大きいほど電池性能が良好であることを示す。
(100 cycle capacity retention rate)
The lithium ion battery was charged and discharged in the same manner as the measurement of the electrical internal resistance described above.
In the first cycle, the battery was charged to a voltage of 4.2 V with a current of 0.1 C, and after a 10-minute rest, the battery voltage was discharged to 2.5 V with a current of 0.1 C, and the initial charge/discharge capacity was measured.
Thereafter, 100 cycles of charging and discharging were carried out under the same conditions as the initial charging and discharging, and the 100th cycle capacity was determined from the ratio of the 100th cycle discharge capacity to the initial discharge capacity [(100th cycle discharge capacity)/(Initial discharge capacity) x 100]. Retention rate (%) was evaluated. The larger the value of the 100 cycle capacity retention rate, the better the battery performance.
表１より、正極活物質スラリー１及び２は、貯蔵安定性に優れることが確認された。
このような貯蔵安定性に優れる正極活物質スラリーを用い、所定の範囲に電解質濃度が制御された負極活物質スラリーを用いた実施例１～３では、電池内部抵抗を低減でき、放電レート特性及び１００サイクル容量維持率に優れたリチウムイオン電池を得ることができることが確認された。
一方で、電解質濃度が高い負極活物質スラリー３を用いた比較例１では、電池内部抵抗が高く、放電レート特性においても劣っていた。また、電解質濃度が低い正極活物質スラリー３は、貯蔵安定性に劣っており、このような正極活物質スラリーを用いた比較例２では、放電レート特性及び１００サイクル容量維持率において劣っていた。
From Table 1, it was confirmed that positive electrode active material slurries 1 and 2 had excellent storage stability.
In Examples 1 to 3, in which a positive electrode active material slurry with excellent storage stability and a negative electrode active material slurry with an electrolyte concentration controlled within a predetermined range were used, the internal resistance of the battery could be reduced, and the discharge rate characteristics and It was confirmed that a lithium ion battery with an excellent 100 cycle capacity retention rate could be obtained.
On the other hand, in Comparative Example 1 using negative electrode active material slurry 3 with a high electrolyte concentration, the battery internal resistance was high and the discharge rate characteristics were also poor. Further, the positive electrode active material slurry 3 having a low electrolyte concentration had poor storage stability, and Comparative Example 2 using such a positive electrode active material slurry had poor discharge rate characteristics and 100 cycle capacity retention rate.
本発明のリチウムイオン電池の製造方法は、特に、携帯電話、パーソナルコンピューター及びハイブリッド自動車、電気自動車用に用いられるリチウムイオン電池の製造方法として有用である。 The method for manufacturing a lithium ion battery of the present invention is particularly useful as a method for manufacturing a lithium ion battery used for mobile phones, personal computers, hybrid vehicles, and electric vehicles.
Claims (5)
正極活物質と電解液とを含み、該電解液の電解質濃度が３．０～４．０ｍｏｌ／Ｌである正極活物質スラリーを正極集電体に塗工して前記正極を得る工程と、
負極活物質と電解液とを含み、該電解液の電解質濃度が０．１～２ｍｏｌ／Ｌである負極活物質スラリーを負極集電体に塗工して前記負極を得る工程と、
前記正極と前記負極とを、前記セパレータを介して対向して配置し、セル容器に収容し、前記セル容器を密封する工程とを有し、
前記正極活物質の比重が、前記負極活物質の比重よりも大きく、
前記正極活物質が、リチウムと遷移金属との複合酸化物、リチウム含有遷移金属リン酸塩、遷移金属酸化物及び遷移金属硫化物からなる群から選択される少なくとも１種であり、
前記負極活物質が、炭素系材料、珪素系材料及び導電性高分子からなる群から選択される少なくとも１種であり、
前記珪素系材料が、珪素、酸化珪素及び珪素－炭素複合体からなる群から選択される少なくとも１種であり、
前記セル容器を密封する工程では、前記セル容器内に電解液を添加しない、ことを特徴とするリチウムイオン電池の製造方法。 A method for manufacturing a lithium ion battery in which a positive electrode, a separator, and a negative electrode are stacked in this order,
A step of applying a positive electrode active material slurry containing a positive electrode active material and an electrolytic solution and having an electrolyte concentration of 3.0 to 4.0 mol/L onto a positive electrode current collector to obtain the positive electrode;
Applying a negative electrode active material slurry containing a negative electrode active material and an electrolytic solution, the electrolytic solution having an electrolyte concentration of 0.1 to 2 mol/L to a negative electrode current collector to obtain the negative electrode;
arranging the positive electrode and the negative electrode to face each other with the separator interposed therebetween, accommodating the positive electrode and the negative electrode in a cell container, and sealing the cell container ;
The specific gravity of the positive electrode active material is greater than the specific gravity of the negative electrode active material,
The positive electrode active material is at least one selected from the group consisting of a composite oxide of lithium and a transition metal, a lithium-containing transition metal phosphate, a transition metal oxide, and a transition metal sulfide,
The negative electrode active material is at least one selected from the group consisting of carbon-based materials, silicon-based materials, and conductive polymers,
The silicon-based material is at least one selected from the group consisting of silicon, silicon oxide, and silicon-carbon composite,
A method for manufacturing a lithium ion battery , characterized in that in the step of sealing the cell container, an electrolytic solution is not added into the cell container .
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| JP2018101623A (en) | 2016-12-20 | 2018-06-28 | 三洋化成工業株式会社 | Negative electrode for lithium-ion battery and lithium-ion battery |
| CN108711636A (en) | 2018-06-01 | 2018-10-26 | 南京大学 | A kind of combination electrolyte double ion rocking chair type secondary cell and preparation method thereof |
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| JP2018101623A (en) | 2016-12-20 | 2018-06-28 | 三洋化成工業株式会社 | Negative electrode for lithium-ion battery and lithium-ion battery |
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