WO2014080883A1 - 電気デバイス用負極、及びこれを用いた電気デバイス - Google Patents
電気デバイス用負極、及びこれを用いた電気デバイス Download PDFInfo
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- WO2014080883A1 WO2014080883A1 PCT/JP2013/081110 JP2013081110W WO2014080883A1 WO 2014080883 A1 WO2014080883 A1 WO 2014080883A1 JP 2013081110 W JP2013081110 W JP 2013081110W WO 2014080883 A1 WO2014080883 A1 WO 2014080883A1
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01G11/22—Electrodes
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- H01G11/22—Electrodes
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- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H01M4/463—Aluminium based
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large amount of expansion and contraction at the negative electrode during charge and discharge.
- the volume expansion when occluding Li ions is about 1.2 times in the case of a graphite material, while in the case of Si material, when Si and Li are alloyed, it changes from an amorphous state to a crystalline state and a large volume change
- the Si negative electrode active material there is a trade-off relationship between capacity and cycle durability, and there is a problem that it is difficult to improve high cycle durability while showing high capacity.
- a negative electrode active material for a lithium ion secondary battery which includes an amorphous alloy having the formula; Si x M y Al z .
- M is Mn, Mo, Nb, W, Ta, Fe, Cu, It is a metal consisting of at least one of Ti, V, Cr, Ni, Co, Zr, and Y.
- Patent Document 1 it is described that, in addition to the high capacity, a good cycle life is exhibited by minimizing the content of the metal M in paragraph “0018”.
- a predetermined ternary Si alloy (a ternary Si-Sn-M alloy) is used as a negative electrode active material, and a resin having an elastic modulus of a predetermined range is used as a binder. Is characterized in that it constitutes a negative electrode for an electric device.
- the lithium ion secondary battery to be a target of the present embodiment may be one using the negative electrode for a lithium ion secondary battery of the present embodiment described below, and in particular, regarding the other configuration requirements, It should not be restricted.
- the laminated battery 10 of this embodiment has a structure in which a substantially rectangular power generating element 21 in which the charge and discharge reaction actually proceeds is sealed inside a laminate sheet 29 which is an exterior body.
- Positive electrode active material for example, lithium-transition metal complex oxide, lithium-transition metal phosphate compound, lithium-transition metal sulfate compound, solid solution type, ternary system, NiMn type, NiCo type, spinel Mn type, etc. are mentioned.
- Binder is added for the purpose of binding the active materials or the active material and the current collector to maintain the electrode structure.
- a binder used for a positive electrode active material layer For example, the following materials are mentioned.
- a is preferably 0 ⁇ a ⁇ 0.5, and preferably 0 ⁇ a ⁇ 0.1.
- a method for producing the particle form of the alloy having the composition formula Si x Sn y M z A a there are a solid phase method, a liquid phase method and a gas phase method.
- a plasma melting method or the like can be used.
- a binder, a conductive auxiliary agent, and a viscosity control solvent may be added to the particles to prepare a slurry, and a slurry electrode may be formed using the slurry. Therefore, it is excellent in that it is easy to mass-produce (mass production) and easy to put to practical use as a battery electrode.
- the negative electrode active material layer may contain the other negative electrode active material.
- negative electrode active materials other than the above-mentioned predetermined alloy natural graphite, artificial graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon or carbon such as hard carbon, pure metal such as Si or Sn, or the above predetermined composition Alloy based active material out of the ratio, or TiO, Ti 2 O 3 , TiO 2 , or SiO 2 , metal oxides such as SiO 2 , SiO, SnO 2 , lithium such as Li 4/3 Ti 5/3 O 4 or Li 7 MnN And complex oxides of lithium and transition metals, Li-Pb alloys, Li-Al alloys, Li and the like.
- the content of the predetermined alloy in the total amount of 100% by mass of the negative electrode active material is preferably from the viewpoint of sufficiently exerting the effects exhibited by using the predetermined alloy as the negative electrode active material. It is 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 100% by mass.
- the value of the E elastic modulus of the binder depends on the material of the binder, the concentration of the slurry (solid-liquid ratio), the degree of crosslinking, and the heat history such as the drying temperature, the drying rate and the drying time. In this embodiment, by adjusting these, the E elastic modulus of the binder can be adjusted to the above-described desired range.
- the content of the conductive additive mixed into the active material layer is in the range of 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more based on the total amount of the active material layer.
- the content of the conductive additive mixed into the active material layer is 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less based on the total amount of the active material layer is there.
- the following effects are expressed by defining the compounding ratio (content) of the conductive aid in the active material layer in which the electron conductivity of the active material itself is low and the electrode resistance can be reduced by the amount of the conductive aid within the above range Ru. That is, without inhibiting the electrode reaction, the electron conductivity can be sufficiently ensured, the reduction of the energy density due to the reduction of the electrode density can be suppressed, and the energy density can be improved by the improvement of the electrode density. .
- a conductive binder having both the functions of the conductive aid and the binder may be used instead of the conductive aid and the binder, or one or both of the conductive aid and the binder may be used in combination.
- a commercially available TAB-2 (manufactured by Takasen Co., Ltd.) can be used as the conductive binder.
- the laminated flat lithium ion secondary battery 50 has a rectangular flat shape, and from both side portions thereof, a positive electrode current collector plate 58 for extracting electric power, a negative electrode current collector The electric plate 59 is pulled out.
- the power generation element 57 is wrapped by the battery exterior material 52 of the lithium ion secondary battery 50, and the periphery thereof is heat-fused, and the power generation element 57 draws the positive electrode current collector plate 58 and the negative electrode current collector plate 59 to the outside. It is sealed tightly.
- the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery (stacked battery) 10 shown in FIG.
- the power generation element 57 is formed by stacking a plurality of unit cell layers (single cells) 19 each including the positive electrode (positive electrode active material layer) 13, the electrolyte layer 17, and the negative electrode (negative electrode active material layer) 15.
- the said lithium ion secondary battery is not restrict
- a wound type lithium ion battery one having a cylindrical shape (coin cell) or one having a prismatic shape (square cell), or such one obtained by deforming such a cylindrical shape into a rectangular flat shape
- cylindrical cells there is no particular limitation, such as cylindrical cells.
- a laminate film may be used as the exterior material, or a conventional cylindrical can (metal can) may be used, and the like.
- the power generation element is coated with an aluminum laminate film. Weight reduction can be achieved by the form.
- the negative electrode and the lithium ion secondary battery using the negative electrode active material for a lithium ion secondary battery of the present embodiment are large in such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles. It can be suitably used as a capacitive power source. That is, it can be suitably used for a vehicle drive power supply or an auxiliary power supply where high volume energy density and high volume output density are required.
- the DC power supply 1 (Si target) is 185 W
- the DC power supply 2 (Sn target) is 35 W
- the DC power supply 1 (Si target) was 185 W
- the DC power supply 2 (Sn target) was 22 W
- the DC power supply 3 (C target) was 0 W.
- the DC power supply 1 (Si target) is 185 W
- the DC power supply 2 (Sn target) is 0 W
- the DC power supply 3 (C target) is 30 W.
- Example 2 A negative electrode and a battery were produced in the same manner as in Example 1, except that polyimide (E modulus of 2.10 GPa) was used instead of polyamideimide (E modulus of 2.00 GPa) as the binder.
- Example 5 A negative electrode and a battery were produced in the same manner as in Example 1, except that polyimide (E modulus 7.00 GPa) was used as the binder instead of polyamideimide (E modulus 2.00 GPa).
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Abstract
Description
Mは、Al、V、C、およびこれらの組み合わせからなる群から選択される少なくとも1つの金属であり、
Aは、不可避不純物であり、
x、y、z、およびaは、質量%の値を表し、この際、0<x<100、0<y<100、0<z<100、および0≦a<0.5であり、x+y+z+a=100である。)で表される合金を含む点に特徴がある。また、バインダが、1.00GPa超7.40GPa未満のE弾性率を有する樹脂を含む点にも特徴がある。
図1は、本発明の電気デバイスの代表的な一実施形態である、扁平型(積層型)のリチウムイオン二次電池(以下、単に「積層型電池」ともいう)の全体構造を模式的に表した断面概略図である。
活物質層13または15は活物質を含み、必要に応じてその他の添加剤をさらに含む。
正極活物質層13は、正極活物質を含む。
正極活物質としては、例えば、リチウム-遷移金属複合酸化物、リチウム-遷移金属リン酸化合物、リチウム-遷移金属硫酸化合物、固溶体系、3元系、NiMn系、NiCo系、スピネルMn系などが挙げられる。
バインダは、活物質同士または活物質と集電体とを結着させて電極構造を維持する目的で添加される。正極活物質層に用いられるバインダとしては、特に限定されないが、例えば、以下の材料が挙げられる。ポリエチレン、ポリプロピレン、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)、ポリアクリロニトリル、ポリイミド、ポリアミド、ポリアミドイミド、セルロース、カルボキシメチルセルロース(CMC)、エチレン-酢酸ビニル共重合体、ポリ塩化ビニル、スチレン・ブタジエンゴム(SBR)、イソプレンゴム、ブタジエンゴム、エチレン・プロピレンゴム、エチレン・プロピレン・ジエン共重合体、スチレン・ブタジエン・スチレンブロック共重合体およびその水素添加物、スチレン・イソプレン・スチレンブロック共重合体およびその水素添加物などの熱可塑性高分子、ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(FEP)、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体(PFA)、エチレン・テトラフルオロエチレン共重合体(ETFE)、ポリクロロトリフルオロエチレン(PCTFE)、エチレン・クロロトリフルオロエチレン共重合体(ECTFE)、ポリフッ化ビニル(PVF)等のフッ素樹脂、ビニリデンフルオライド-ヘキサフルオロプロピレン系フッ素ゴム(VDF-HFP系フッ素ゴム)、ビニリデンフルオライド-ヘキサフルオロプロピレン-テトラフルオロエチレン系フッ素ゴム(VDF-HFP-TFE系フッ素ゴム)、ビニリデンフルオライド-ペンタフルオロプロピレン系フッ素ゴム(VDF-PFP系フッ素ゴム)、ビニリデンフルオライド-ペンタフルオロプロピレン-テトラフルオロエチレン系フッ素ゴム(VDF-PFP-TFE系フッ素ゴム)、ビニリデンフルオライド-パーフルオロメチルビニルエーテル-テトラフルオロエチレン系フッ素ゴム(VDF-PFMVE-TFE系フッ素ゴム)、ビニリデンフルオライド-クロロトリフルオロエチレン系フッ素ゴム(VDF-CTFE系フッ素ゴム)等のビニリデンフルオライド系フッ素ゴム、エポキシ樹脂等が挙げられる。中でも、ポリフッ化ビニリデン、ポリイミド、スチレン・ブタジエンゴム、カルボキシメチルセルロース、ポリプロピレン、ポリテトラフルオロエチレン、ポリアクリロニトリル、ポリアミド、ポリアミドイミドであることがより好ましい。これらの好適なバインダは、耐熱性に優れ、さらに電位窓が非常に広く正極電位、負極電位双方に安定であり活物質層に使用が可能となる。これらのバインダは、1種単独で用いてもよいし、2種併用してもよい。
負極活物質層15は、負極活物質を含む。
負極活物質は、所定の合金を必須に含む。
上記SixSnyAlzAaは、上述のように、第1添加元素であるSnと、第2添加元素であるAlを選択したことによって、Li合金化の際に、アモルファス-結晶の相転移を抑制してサイクル寿命を向上させることができる。また、これによって、従来の負極活物質、例えば炭素系負極活物質よりも高容量のものとなる。
上記SixSnyVzAaは、上述のように、第1添加元素であるSnと、第2添加元素であるVを選択したことによって、Li合金化の際に、アモルファス-結晶の相転移を抑制してサイクル寿命を向上させることができる。また、これによって、従来の負極活物質、例えば炭素系負極活物質よりも高容量のものとなる。
上記SixSnyCzAaは、上述のように、第1添加元素であるSnと、第2添加元素であるCを選択したことによって、Li合金化の際に、アモルファス-結晶の相転移を抑制してサイクル寿命を向上させることができる。また、これによって、従来の負極活物質、例えば炭素系負極活物質よりも高容量のものとなる。
上記Si合金の平均粒子径は、既存の負極活物質層15に含まれる負極活物質の平均粒子径と同程度であればよく、特に制限されない。高出力化の観点からは、好ましくは1~20μmの範囲であればよい。ただし、上記範囲に何ら制限されるものではなく、本実施形態の作用効果を有効に発現できるものであれば、上記範囲を外れていてもよいことは言うまでもない。なお、Si合金の形状としては、特に制限はなく、球状、楕円状、円柱状、多角柱状、鱗片状、不定形などでありうる。
本形態に係る組成式SixSnyMzAaを有する合金の製造方法としては、特に制限されるものではなく、従来公知の各種の製造を利用して製造することができる。即ち、作製方法による合金状態・特性の違いはほとんどないので、ありとあらゆる作製方法が適用できる。
バインダは、1.00GPa超7.40GPa未満のE弾性率を有する樹脂を必須に含む。
以下に、正極及び負極活物質層13、15に共通する要件につき、説明する。
導電助剤とは、正極活物質層または負極活物質層の導電性を向上させるために配合される添加物をいう。導電助剤としては、アセチレンブラック等のカーボンブラック、グラファイト、気相成長炭素繊維などの炭素材料が挙げられる。活物質層が導電助剤を含むと、活物質層の内部における電子ネットワークが効果的に形成され、電池の出力特性の向上に寄与しうる。
電解質塩(リチウム塩)としては、Li(C2F5SO2)2N、LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3等が挙げられる。
イオン伝導性ポリマーとしては、例えば、ポリエチレンオキシド(PEO)系およびポリプロピレンオキシド(PPO)系のポリマーが挙げられる。
集電体11、12は導電性材料から構成される。集電体の大きさは、電池の使用用途に応じて決定される。例えば、高エネルギー密度が要求される大型の電池に用いられるのであれば、面積の大きな集電体が用いられる。
電解質層17を構成する電解質としては、液体電解質またはポリマー電解質が用いられうる。
電池外部に電流を取り出す目的で、集電板を用いてもよい。集電板は集電体やリードに電気的に接続され、電池外装材であるラミネートシートの外部に取り出される。
電池外装材29としては、公知の金属缶ケースを用いることができるほか、発電要素を覆うことができる、アルミニウムを含むラミネートフィルムを用いた袋状のケースが用いられうる。該ラミネートフィルムには、例えば、PP、アルミニウム、ナイロンをこの順に積層してなる3層構造のラミネートフィルム等を用いることができるが、これらに何ら制限されるものではない。高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが望ましい。
図2は、積層型の扁平なリチウムイオン二次電池の外観を表した斜視図である。
[1]負極の作製
スパッタ装置として、独立制御方式の3元DCマグネトロンスパッタ装置(大和機器工業株式会社製、コンビナトリアルスパッタコーティング装置、ガン-サンプル間距離:約100mm)を使用し、厚さ20μmのニッケル箔から成る基板(集電体)上に、下記の条件のもとで、各組成を有する負極活物質合金の薄膜をそれぞれ成膜することによって、都合23種の負極サンプルを得た(参考例1~14および比較参考例1~9)。
Si:50.8mm径、3mm厚さ(厚さ2mmの無酸素銅製バッキングプレート付)
Sn:50.8mm径、5mm厚さ
Al:50.8mm径、3mm厚さ。
ベース圧力:~7×10-6Pa
スパッタガス種:Ar(99.9999%以上)
スパッタガス導入量:10sccm
スパッタ圧力:30mTorr
DC電源:Si(185W)、Sn(0~40W)、Al(0~150W)
プレスパッタ時間:1min.
スパッタ時間:10min.
基板温度:室温(25℃)。
組成分析:SEM・EDX分析(JEOL社)、EPMA分析(JEOL社)
膜厚測定(スパッタレート算出のため):膜厚計(東京インスツルメンツ)
膜状態分析:ラマン分光測定(ブルカー社)。
上記により得られた各負極サンプルとリチウム箔(本城金属株式会社製、直径15mm、厚さ200μm)から成る対極とをセパレータ(セルガード社製セルガード2400)を介して対向させたのち、電解液を注入することによってCR2032型コインセルをそれぞれ作製した。
上記により得られたそれぞれの電池に対して下記の充放電試験を実施した。
[1]負極の作製
参考例1の(1)におけるターゲットの「Al:50.8mm径、3mm厚さ」を「V:50.8mm径、3mm厚さ」に変更し、(2)におけるDC電源の「Sn(0~40W)、Al(0~150W)」を「Sn(0~50W)、V(0~150W)」に変更したことを除いては、参考例1と同様の方法で、都合32種の負極サンプルを作製した(参考例15~27および比較参考例10~28)。
参考例1と同様の方法でCR2032型コインセルを作製した。
参考例1と同様の方法で電池の充放電試験を行った。この結果を表2に併せて示す。
[1]負極の作製
参考例1の(1)におけるターゲットの「Al:50.8mm径、3mm厚さ」を「C:50.8mm径、3mm厚さ(厚さ2mmの無酸素銅製バッキングプレート付)」に変更し、(2)におけるDC電源の「Al(0~150W)」を「C(0~150W)」に変更したことを除いては、参考例1と同様の方法で、都合34種の負極サンプルを作製した(参考例28~49および比較参考例29~40)。
参考例1と同様の方法でCR2032型コインセルを作製した。
参考例1と同様の方法で電池の充放電試験を行った。この結果を表3に併せて示す。
Si合金は、メカニカルアロイ法(または、アークプラズマ溶融法)により製造した。具体的には、ドイツ フリッチュ社製遊星ボールミル装置P-6を用いて、ジルコニア製粉砕ポットにジルコニア製粉砕ボールと各合金の各原料粉末を投入し、600rpm、48hかけて合金化させた。
負極活物質である上記で製造したSi合金(Si41Sn16Al43、粒子径0.3μm)80質量部と、導電助剤であるアセチレンブラック5質量部と、バインダであるポリアミドイミド(E弾性率2.00GPa)15質量部と、を混合し、N-メチルピロリドンに分散させて負極スラリーを得た。次いで、得られた負極スラリーを、銅箔よりなる負極集電体の両面にそれぞれ負極活物質層の厚さが30μmとなるように均一に塗布し、真空中で24時間乾燥させて、負極を得た。
正極活物質であるLi1.85Ni0.18Co0.10Mn0.87O3を、特開2012-185913号公報の実施例1(段落0046)に記載の手法により作製した。そして、この正極活物質90質量部と、導電助剤であるアセチレンブラック5質量部と、バインダであるポリフッ化ビニリデン5質量部と、を混合し、N-メチルピロリドンに分散させて正極スラリーを得た。次いで、得られた正極スラリーを、アルミニウム箔よりなる正極集電体の両面にそれぞれ正極活物質層の厚さが30μmとなるように均一に塗布し、乾燥させて、正極を得た。
上記で作製した正極と、負極とを対向させ、この間にセパレータ(ポリオレフィン、膜厚20μm)を配置した。次いで、負極、セパレータ、および正極の積層体をコインセル(CR2032、材質:ステンレス鋼(SUS316))の底部側に配置した。さらに、正極と負極との間の絶縁性を保つためガスケットを装着し、下記電解液をシリンジにより注入し、スプリングおよびスペーサを積層し、コインセルの上部側を重ねあわせ、かしこめることにより密閉して、リチウムイオン二次電池を得た。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリイミド(E弾性率2.10GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリイミド(E弾性率3.30GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリイミド(E弾性率3.73GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリイミド(E弾性率7.00GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリフッ化ビニリデン(PVdF)(E弾性率1.00GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
バインダとして、ポリアミドイミド(E弾性率2.00GPa)に代えてポリイミド(E弾性率7.40GPa)を用いたことを除いては、実施例1と同様の方法で負極および電池を作製した。
負極活物質として、Si合金に代えて純Siを用いたことを除いては、実施例4と同様の方法で負極および電池を作製した。
負極活物質として、Si合金に代えて純Siを用いたことを除いては、比較例1と同様の方法で負極および電池を作製した。
[サイクル特性の評価]
上記で作製した各リチウムイオン二次電池について以下の方法でサイクル特性評価を行った。各電池について、30℃の雰囲気下、定電流方式(CC、電流:0.1C)で2.0Vまで充電し、10分間休止させた後、定電流(CC、電流:0.1C)で0.01Vまで放電し、放電後10分間休止させた。この充放電過程を1サイクルとし、50サイクルの充放電試験を行い、1サイクル目の放電容量に対する50サイクル目の放電容量の割合(放電容量維持率[%])を求めた。得られた放電容量維持率の結果を、比較例1の放電容量維持率を100としたときの相対値(放電容量維持率の向上率)として、下記の表4および図18に示す。
11 正極集電体、
12 負極集電体、
13 正極活物質層、
15 負極活物質層、
17 電解質層、
19 単電池層、
21、57 発電要素、
25、58 正極集電板、
27、59 負極集電板、
29、52 電池外装材(ラミネートフィルム)。
Claims (18)
- 前記樹脂のE弾性率が2.10以上7.00以下である、請求項1に記載の電気デバイス用負極。
- 前記樹脂のE弾性率が3.30以上3.73以下である、請求項2に記載の電気デバイス用負極。
- 前記樹脂が、ポリイミド、ポリアミドイミドおよびポリアミドからなる群から選択される1種または2種以上である、請求項1~3のいずれか1項に記載の電気デバイス用負極。
- 前記MがAlであり、
前記xが12以上100未満であり、前記yが0超45以下であり、前記zが0超43以下である、請求項1~4のいずれか1項に記載の電気デバイス用負極。 - 前記xが31以上である、請求項5に記載の電気デバイス用負極。
- 前記xが50以下である、請求項6に記載の電気デバイス用負極。
- 前記yが15以上であり、前記zが18以上である、請求項7に記載の電気デバイス用負極。
- 前記MがVであり、
前記xが27以上100未満であり、前記yが0超73以下であり、前記zが0超73以下である、請求項1~4のいずれか1項に記載の電気デバイス用負極。 - 前記xが84以下であり、前記yが10以上73以下であり、前記zが6以上73以下である、請求項9に記載の電気デバイス用負極。
- 前記yが10以上63以下であり、前記zが6以上63以下である、請求項10に記載の電気デバイス用負極。
- 前記xが52以下である、請求項11に記載の電気デバイス用負極。
- 前記yが40以下であり、前記zが20以上である、請求項12に記載の電気デバイス用負極。
- 前記MがCであり、
前記xが29以上である、請求項1~4のいずれか1項に記載の電気デバイス用負極。 - 前記xが63以下であり、前記yが14以上48以下であり、前記zが11以上48以下である、請求項14に記載の電気デバイス用負極。
- 前記xが44以下である、請求項15に記載の電気デバイス用負極。
- 前記xが40以下であり、前記yが34以上である、請求項16に記載の電気デバイス用負極。
- 請求項1~17のいずれか1項に記載の電気デバイス用負極を含む、電気デバイス。
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JP6040994B2 (ja) | 2016-12-07 |
CN104813514B (zh) | 2017-10-13 |
JPWO2014080883A1 (ja) | 2017-01-05 |
EP2924775A4 (en) | 2015-12-09 |
KR101780133B1 (ko) | 2017-09-19 |
CN104813514A (zh) | 2015-07-29 |
EP2924775A1 (en) | 2015-09-30 |
KR20150082517A (ko) | 2015-07-15 |
US20150311500A1 (en) | 2015-10-29 |
EP2924775B1 (en) | 2021-03-03 |
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