JP2019140126A - Manufacturing method of current collector for lithium ion secondary battery - Google Patents
Manufacturing method of current collector for lithium ion secondary battery Download PDFInfo
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- JP2019140126A JP2019140126A JP2019101169A JP2019101169A JP2019140126A JP 2019140126 A JP2019140126 A JP 2019140126A JP 2019101169 A JP2019101169 A JP 2019101169A JP 2019101169 A JP2019101169 A JP 2019101169A JP 2019140126 A JP2019140126 A JP 2019140126A
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- active material
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 30
- 239000010935 stainless steel Substances 0.000 claims abstract description 17
- 239000011149 active material Substances 0.000 claims abstract description 14
- 238000009941 weaving Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 3
- 238000010248 power generation Methods 0.000 description 26
- 239000011888 foil Substances 0.000 description 21
- 239000007773 negative electrode material Substances 0.000 description 20
- 239000007774 positive electrode material Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000007599 discharging Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
本発明は、リチウムイオン二次電池用の集電体の製造方法に関する。 The present invention relates to a method for producing a current collector for a lithium ion secondary battery.
携帯電話やノート型パソコンに代表されるモバイル電子機器用途の蓄電池としては、リチウムイオン二次電池が広く普及している。近年は、ハイブリッド自動車や電気自動車の駆動用電源に使用できる程度の比較的大型の蓄電池としてもリチウムイオン二次電池が普及している。また、環境にやさしい太陽光発電や風力発電といった自然エネルギーを利用した発電方法が普及しつつあるが、自然エネルギーを利用した発電手法は天候の影響を受けやすく、出力が不安定となりやすい。そこで、将来的には自然エネルギーの蓄電にも比較的大型の蓄電池として、リチウムイオン二次電池の適用が考えられる。 Lithium ion secondary batteries are widely used as storage batteries for mobile electronic devices such as mobile phones and laptop computers. In recent years, lithium ion secondary batteries have become widespread as relatively large storage batteries that can be used as power sources for driving hybrid vehicles and electric vehicles. In addition, power generation methods using natural energy, such as environmentally friendly solar power generation and wind power generation, are becoming widespread, but power generation methods using natural energy are easily affected by the weather and output is likely to be unstable. Therefore, in the future, a lithium ion secondary battery can be considered as a relatively large storage battery for storing natural energy.
リチウムイオン二次電池の電極の構造としては、集電体の表面に活物質が塗布されており、集電体には金属箔が用いられている。（特許文献１） As the electrode structure of the lithium ion secondary battery, an active material is applied to the surface of the current collector, and a metal foil is used for the current collector. (Patent Document 1)
しかしながら、金属箔は、強度が低いため、金属箔に活物質を塗布する製造ラインにおいて金属箔の変形が生じやすく、形状精度の高い電極を得るためには高度な管理が要求される。管理が不十分である場合には、製造ライン内で金属箔の帯が破断することもある。また、電極が大型化した際、金属箔の自重で破断しやすくなったりするなど、強度が問題である。 However, since the strength of the metal foil is low, the metal foil is likely to be deformed in a production line for applying an active material to the metal foil, and high management is required to obtain an electrode with high shape accuracy. If the management is insufficient, the metal foil strip may break in the production line. In addition, when the electrode is enlarged, the strength is a problem such that the metal foil is easily broken by its own weight.
本発明は、上記の課題を解決するためになされたものであって、実用的なリチウムイオン二次電池用の集電体の製造方法を提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a practical method for producing a current collector for a lithium ion secondary battery.
本発明の要旨は以下のとおりである。
[１] リチウムイオン二次電池用の集電体の製造方法であって、
前記集電体が、少なくとも活物質層と接触する表面において、ステンレス製ワイヤを縦方向および横方向に織り込むことにより形成され、前記活物質層の少なくとも一部が内部に埋め込まれるメッシュ構造を有しており、前記集電体の前記縦方向の初期弾性率と前記集電体の前記横方向の初期弾性率の比が０．８以上、１．２以下となるように、縦方向および横方向に織り込まれた前記ステンレス製ワイヤに対してカレンダー加工を行うことを特徴とするリチウムイオン二次電池用の集電体の製造方法。
[２] 前記ステンレス製ワイヤの径が２０μｍ以下であり、かつ前記集電体のメッシュ数が２９０以上であることを特徴とする[１]に記載のリチウムイオン二次電池用の集電体の製造方法。
[３] 前記集電体の厚さが５μｍ以上２５μｍ以下であることを特徴とする[１]または[２]に記載のリチウムイオン二次電池用の集電体の製造方法。
The gist of the present invention is as follows.
[1] A method for producing a current collector for a lithium ion secondary battery, comprising:
The current collector is formed by weaving stainless steel wires in the vertical and horizontal directions at least on the surface in contact with the active material layer, and has a mesh structure in which at least a part of the active material layer is embedded inside And the longitudinal direction and the transverse direction so that the ratio between the initial elastic modulus in the longitudinal direction of the current collector and the initial elastic modulus in the transverse direction of the current collector is 0.8 or more and 1.2 or less. A method for producing a current collector for a lithium ion secondary battery, wherein calendar processing is performed on the stainless steel wire woven into the battery.
[2] The current collector for a lithium ion secondary battery according to [1], wherein a diameter of the stainless steel wire is 20 μm or less and a mesh number of the current collector is 290 or more. Production method.
[3] The method for producing a current collector for a lithium ion secondary battery according to [1] or [2], wherein the current collector has a thickness of 5 μm or more and 25 μm or less.
本発明によれば、破断し難いことに加えて、リチウムイオン二次電池の性能（特に、満充電容量）が低下することを抑制できるリチウムイオン二次電池用の集電体を提供することが可能となる。 According to the present invention, in addition to being hard to break, it is possible to provide a current collector for a lithium ion secondary battery that can suppress a decrease in performance (particularly, a full charge capacity) of the lithium ion secondary battery. It becomes possible.
以下に、本発明の実施形態であるリチウムイオン二次電池用の集電体について詳細に説明する。 Below, the collector for lithium ion secondary batteries which is embodiment of this invention is demonstrated in detail.
図１は、リチウムイオン二次電池の発電要素の構造を示す概略図である。発電要素１とは、充放電を行う要素であり、発電要素１は、電池ケース（図示せず）に収容される。 FIG. 1 is a schematic diagram showing the structure of a power generation element of a lithium ion secondary battery. The power generation element 1 is an element that charges and discharges, and the power generation element 1 is accommodated in a battery case (not shown).
発電要素１は、正極板１０と、負極板２０と、正極板１０および負極板２０の間に配置されるセパレータ３０とを有する。正極板１０は、集電体１１と、集電体１１に付着した正極活物質層１２とを有する。正極活物質層１２の表面は、セパレータ３０と接触している。正極活物質層１２には、正極活物質、バインダおよび導電助剤が含まれる。正極活物質としては、例えば、コバルト酸リチウム、マンガン酸リチウム、コバルト・ニッケル・マンガン酸リチウム、ニッケル酸リチウム、リン酸鉄リチウムを用いることができる。 The power generation element 1 includes a positive electrode plate 10, a negative electrode plate 20, and a separator 30 disposed between the positive electrode plate 10 and the negative electrode plate 20. The positive electrode plate 10 includes a current collector 11 and a positive electrode active material layer 12 attached to the current collector 11. The surface of the positive electrode active material layer 12 is in contact with the separator 30. The positive electrode active material layer 12 includes a positive electrode active material, a binder, and a conductive additive. As the positive electrode active material, for example, lithium cobaltate, lithium manganate, cobalt / nickel / lithium manganate, lithium nickelate, or lithium iron phosphate can be used.
負極板２０は、集電体２１と、集電体２１に付着した負極活物質層２２とを有する。負極活物質層２２の表面は、セパレータ３０と接触している。負極活物質層２２には、負極活物質、バインダおよび導電助剤が含まれる。負極活物質としては、例えば、シリコンやカーボンを用いることができる。 The negative electrode plate 20 includes a current collector 21 and a negative electrode active material layer 22 attached to the current collector 21. The surface of the negative electrode active material layer 22 is in contact with the separator 30. The negative electrode active material layer 22 includes a negative electrode active material, a binder, and a conductive additive. As the negative electrode active material, for example, silicon or carbon can be used.
正極活物質層１２、負極活物質層２２およびセパレータ３０には、電解液が染み込んでいる。なお、電解液が染み込んだセパレータ３０の代わりに、固体電解質を用いることができる。 The positive electrode active material layer 12, the negative electrode active material layer 22, and the separator 30 are infiltrated with an electrolytic solution. A solid electrolyte can be used in place of the separator 30 soaked with the electrolytic solution.
集電体１１，２１は、ステンレスによって形成されたワイヤ（ステンレス製ワイヤ）を織り上げることによって形成されており、メッシュ構造を有する。具体的には、各集電体１１，２１は、縦方向に延び、横方向に並んで配置された複数のステンレス製ワイヤ（縦方向のステンレス製ワイヤという）と、横方向に延び、縦方向に並んで配置された複数のステンレス製ワイヤ（横方向のステンレス製ワイヤという）とによって構成されている。 The current collectors 11 and 21 are formed by weaving wires made of stainless steel (stainless steel wires) and have a mesh structure. Specifically, each of the current collectors 11 and 21 extends in the vertical direction, and extends in the horizontal direction and a plurality of stainless steel wires arranged in the horizontal direction (referred to as a vertical stainless steel wire). And a plurality of stainless steel wires (referred to as lateral stainless steel wires) arranged side by side.
集電体１１のメッシュ構造の内部には、正極活物質層１２の一部が埋め込まれており、集電体２１のメッシュ構造の内部には、負極活物質層２２の一部が埋め込まれている。なお、本実施形態では、集電体１１，２１の両方がメッシュ構造を有しているが、集電体１１，２１の一方だけがメッシュ構造を有していてもよい。この場合、集電体１１，２１の他方は、平板状に形成された金属箔を用いることができる。 A part of the positive electrode active material layer 12 is embedded inside the mesh structure of the current collector 11, and a part of the negative electrode active material layer 22 is embedded inside the mesh structure of the current collector 21. Yes. In this embodiment, both the current collectors 11 and 21 have a mesh structure, but only one of the current collectors 11 and 21 may have a mesh structure. In this case, the other of the current collectors 11 and 21 can be a metal foil formed in a flat plate shape.
本実施形態では、集電体１１の表面および、集電体１１のメッシュ構造の内部に、正極活物質層１２が設けられているが、これに限るものではない。具体的には、図２に示すように、集電体１１のメッシュ構造の内部だけに、正極活物質層１２を設けることができる。また、本実施形態では、集電体２１の表面および、集電体２１のメッシュ構造の内部に、負極活物質層２２が設けられているが、これに限るものではない。具体的には、図２に示す構造と同様に、集電体２１のメッシュ構造の内部だけに、負極活物質層２２を設けることができる。 In the present embodiment, the positive electrode active material layer 12 is provided on the surface of the current collector 11 and the mesh structure of the current collector 11. However, the present invention is not limited to this. Specifically, as shown in FIG. 2, the positive electrode active material layer 12 can be provided only inside the mesh structure of the current collector 11. In the present embodiment, the negative electrode active material layer 22 is provided on the surface of the current collector 21 and the mesh structure of the current collector 21, but is not limited thereto. Specifically, similarly to the structure shown in FIG. 2, the negative electrode active material layer 22 can be provided only inside the mesh structure of the current collector 21.
集電体１１，２１をステンレス製ワイヤによって構成することにより、集電体１１，２１の強度を確保しやすくなり、集電体１１，２１の破断を抑制できる。集電体１１，２１として金属箔を用いると、金属箔の端部の破断によって、金属箔の内部まで破断してしまうおそれがある。本実施形態のように、ステンレス製ワイヤによって集電体１１，２１を構成することにより、集電体１１，２１の端部が破断してしまっても、集電体１１，２１の内部まで破断が進行してしまうことを抑制できる。 By configuring the current collectors 11 and 21 with stainless steel wires, the strength of the current collectors 11 and 21 can be easily secured, and breakage of the current collectors 11 and 21 can be suppressed. When a metal foil is used as the current collectors 11 and 21, there is a possibility that the metal foil may be broken to the inside due to breakage of the end of the metal foil. By configuring the current collectors 11 and 21 with stainless steel wires as in this embodiment, even if the ends of the current collectors 11 and 21 are broken, the current collectors 11 and 21 are broken. Can be suppressed.
集電体１１，２１は、メッシュ構造を有しているため、電気伝導を担うリチウムイオンが集電体１１，２１の内部を通過することが可能である。このような集電体１１，２１を備えた発電要素１では、発電要素１に対してリチウムイオンを容易に補充することができる。 Since the current collectors 11 and 21 have a mesh structure, lithium ions responsible for electrical conduction can pass through the current collectors 11 and 21. In the power generation element 1 including such current collectors 11 and 21, lithium ions can be easily supplemented to the power generation element 1.
リチウムイオンを補充するとき、図３に示すように、発電要素１の集電体１１に、セパレータ４０を介してリチウム箔５０を配置する。リチウム箔５０および負極板２０の集電体２１に電源６０を接続して電流を流すと、リチウム箔５０から脱離したリチウムイオンが、セパレータ４０、正極板１０およびセパレータ３０を通過して、負極活物質層２２に挿入される。これにより、発電要素１にリチウムイオンを補充することができる。例えば、金属リチウムの析出によって、発電要素１の充放電に関与するリチウムイオンが減少しても、リチウムイオンの補充によって、発電要素１の電池性能（満充電容量）が低下することを抑制できる。 When replenishing lithium ions, as shown in FIG. 3, a lithium foil 50 is disposed on the current collector 11 of the power generation element 1 via the separator 40. When a power source 60 is connected to the current collector 21 of the lithium foil 50 and the negative electrode plate 20 and current is passed, lithium ions desorbed from the lithium foil 50 pass through the separator 40, the positive electrode plate 10, and the separator 30, and the negative electrode It is inserted into the active material layer 22. Thereby, lithium ion can be replenished to the power generation element 1. For example, even if the lithium ions involved in charging / discharging of the power generation element 1 decrease due to the deposition of metallic lithium, it is possible to suppress the battery performance (full charge capacity) of the power generation element 1 from decreasing due to the replenishment of lithium ions.
集電体として多く用いられている金属箔の場合、電気伝導を担うリチウムイオンは、集電体を通過することはできないため、集電体としての金属箔に、リチウムイオンを通過させるための貫通孔を形成する必要がある。しかし、金属箔に貫通孔を設けると、金属箔の強度が低下しやすくなる。特に、貫通孔を形成した部分から金属箔が破断しやすくなってしまう。本実施形態のように、ステンレス製ワイヤを織り上げて集電体１１，２１を形成すれば、集電体１１，２１に貫通孔（すなわち、メッシュ構造の開口部）を形成しながら、集電体１１，２１の強度を確保しやすくなる。 In the case of a metal foil often used as a current collector, lithium ions responsible for electrical conduction cannot pass through the current collector. It is necessary to form holes. However, when a through-hole is provided in the metal foil, the strength of the metal foil is likely to decrease. In particular, the metal foil easily breaks from the portion where the through hole is formed. If the current collectors 11 and 21 are formed by weaving stainless steel wires as in this embodiment, the current collectors 11 and 21 are formed with through holes (that is, openings having a mesh structure) while the current collectors are formed. It becomes easy to ensure the strength of 11 and 21.
本実施形態の集電体１１，２１では、縦方向の初期弾性率（Ｅ１）と横方向の初期弾性率（Ｅ２）の比が０．８以上、１．２以下である。ここで、縦方向の初期弾性率（Ｅ１）と横方向の初期弾性率（Ｅ２）の比とは、縦方向の初期弾性率（Ｅ１）に対する横方向の初期弾性率（Ｅ２）の比（Ｅ２／Ｅ１）または、横方向の初期弾性率（Ｅ２）に対する縦方向の初期弾性率（Ｅ１）の比（Ｅ１／Ｅ２）のことである。初期弾性率とは、後述するように、集電体１１，２１の強伸度曲線において、伸長の初期の傾きから算出される弾性率である。これにより、発電要素１の充放電を繰り返しても、集電体１１，２１のメッシュ構造の内部に活物質層１２，２２を留めておくことができ、活物質層１２，２２の一部が集電体１１，２１から剥離することを抑制できる。縦方向の初期弾性率と横方向の初期弾性率の比が０．８以上、１．２以下とする加工方法は、適宜選択できるが、カレンダー加工を用いることが好ましい。 In the current collectors 11 and 21 of the present embodiment, the ratio between the initial elastic modulus (E1) in the longitudinal direction and the initial elastic modulus (E2) in the horizontal direction is 0.8 or more and 1.2 or less. Here, the ratio between the initial elastic modulus (E1) in the longitudinal direction and the initial elastic modulus (E2) in the transverse direction is the ratio of the initial elastic modulus (E2) in the transverse direction to the initial elastic modulus (E1) in the longitudinal direction (E2 / E1) or the ratio (E1 / E2) of the initial elastic modulus (E1) in the longitudinal direction to the initial elastic modulus (E2) in the transverse direction. As will be described later, the initial elastic modulus is an elastic modulus calculated from an initial inclination of elongation in the strong elongation curves of the current collectors 11 and 21. Thereby, even if charging / discharging of the electric power generation element 1 is repeated, the active material layers 12 and 22 can be kept inside the mesh structure of the current collectors 11 and 21, and a part of the active material layers 12 and 22 can be retained. Peeling from the current collectors 11 and 21 can be suppressed. A processing method in which the ratio between the initial elastic modulus in the vertical direction and the initial elastic modulus in the horizontal direction is 0.8 or more and 1.2 or less can be selected as appropriate, but calendering is preferably used.
正極板１０において、充電の際は、リチウムイオンが正極活物質から脱離することにより、正極活物質が収縮し、放電の際は、リチウムイオンが正極活物質に挿入することにより、正極活物質が膨張する。このように、発電要素１の充放電を繰り返すことにより、正極活物質が膨張および収縮を繰り返す。ここで、正極板１０の集電体１１において、縦方向の初期弾性率と横方向の初期弾性率の比が０．８未満あるいは１．２よりも大きいと、正極活物質の膨張および収縮によって、正極活物質層１２の一部が集電体１１から剥離しやすくなり、集電体１１から剥離した正極活物質層１２は、発電要素１の充放電に関与しなくなる。正極活物質層１２の一部が発電要素１の充放電に関与しなくなると、発電要素１の電池性能（特に、満充電容量）が低下してしまう。 In the positive electrode plate 10, when lithium ions are desorbed from the positive electrode active material during charging, the positive electrode active material contracts, and during discharge, lithium ions are inserted into the positive electrode active material, thereby positive electrode active material. Expands. Thus, by repeating charging / discharging of the power generation element 1, the positive electrode active material repeatedly expands and contracts. Here, in the current collector 11 of the positive electrode plate 10, when the ratio of the initial elastic modulus in the longitudinal direction to the initial elastic modulus in the horizontal direction is less than 0.8 or greater than 1.2, the positive electrode active material expands and contracts. Part of the positive electrode active material layer 12 is easily peeled off from the current collector 11, and the positive electrode active material layer 12 peeled off from the current collector 11 does not participate in charging / discharging of the power generation element 1. When a part of the positive electrode active material layer 12 is not involved in charging / discharging of the power generation element 1, the battery performance (particularly, the full charge capacity) of the power generation element 1 is reduced.
負極板２０において、充電の際は、リチウムイオンが負極活物質に挿入することにより、負極活物質が膨張し、放電の際は、リチウムイオンが負極活物質から脱離することにより、負極活物質が収縮する。このように、発電要素１の充放電を繰り返すことにより、負極活物質が膨張および収縮を繰り返す。ここで、負極板２０の集電体２１において、縦方向の初期弾性率と横方向の初期弾性率の比が０．８未満あるいは１．２よりも大きいと、負極活物質の膨張および収縮によって、負極活物質層２２の一部が集電体２１から剥離しやすくなり、集電体１１から剥離した負極活物質層２２は、発電要素１の充放電に関与しなくなる。負極活物質層２２の一部が発電要素１の充放電に関与しなくなると、発電要素１の電池性能（特に、満充電容量）が低下してしまう。 In the negative electrode plate 20, when the lithium ion is inserted into the negative electrode active material during charging, the negative electrode active material expands, and during the discharge, the lithium ion is desorbed from the negative electrode active material. Contracts. Thus, by repeating charging / discharging of the power generation element 1, the negative electrode active material repeatedly expands and contracts. Here, in the current collector 21 of the negative electrode plate 20, if the ratio of the initial elastic modulus in the vertical direction to the initial elastic modulus in the horizontal direction is less than 0.8 or greater than 1.2, the negative electrode active material expands and contracts. A part of the negative electrode active material layer 22 is easily peeled off from the current collector 21, and the negative electrode active material layer 22 peeled off from the current collector 11 does not participate in charging / discharging of the power generation element 1. When a part of the negative electrode active material layer 22 is not involved in charging / discharging of the power generation element 1, the battery performance (particularly, the full charge capacity) of the power generation element 1 is reduced.
本実施形態の集電体１１のメッシュ数は、２９０以上であることが好ましい。メッシュ数が２９０未満である場合、上述したようにリチウムイオンを補充するとき、リチウムイオンが集電体１１を通過し難くなる。また、メッシュ数が２９０以上であればいいというものではなく、メッシュ（開口部）の大きさも考慮する必要がある。例えば、メッシュ数を固定値としたとき、ステンレス製ワイヤの径が大きいほど、開口部の面積は小さくなり、ステンレス製ワイヤの径が小さいほど、開口部の面積は大きくなる。そこで、本実施形態のステンレス製ワイヤの径は、２０μｍ以下であることが好ましい。ステンレス製ワイヤの径が２０μｍより大きくなると、開口部の面積が小さくなりやすく、リチウムイオンが集電体１１を通過し難くなる。 The number of meshes of the current collector 11 of the present embodiment is preferably 290 or more. When the number of meshes is less than 290, it becomes difficult for lithium ions to pass through the current collector 11 when replenishing lithium ions as described above. In addition, the number of meshes is not limited to 290 or more, and the size of the mesh (opening) needs to be considered. For example, when the number of meshes is a fixed value, the larger the diameter of the stainless steel wire, the smaller the area of the opening, and the smaller the diameter of the stainless steel wire, the larger the area of the opening. Therefore, the diameter of the stainless steel wire of this embodiment is preferably 20 μm or less. When the diameter of the stainless steel wire is larger than 20 μm, the area of the opening is likely to be small, and lithium ions are difficult to pass through the current collector 11.
本実施形態の集電体１１，２１では、上述したように、縦方向の初期弾性率と横方向の初期弾性率の比を１．２以下とするために、カレンダー加工によって集電体１１，２１を形成することが好ましい。カレンダー加工を行う上では、集電体１１，２１の厚さが５μｍ以上、２５μｍ以下であることが好ましい。集電体１１，２１の厚さが２５μｍを超える場合、カレンダー加工の効果が小さく、縦方向の初期弾性率と横方向の初期弾性率の比が１．２以下になりにくい。 In the current collectors 11 and 21 of the present embodiment, as described above, the current collectors 11 and 21 are formed by calendering so that the ratio between the initial elastic modulus in the vertical direction and the initial elastic modulus in the horizontal direction is 1.2 or less. 21 is preferably formed. In performing the calendar process, it is preferable that the current collectors 11 and 21 have a thickness of 5 μm or more and 25 μm or less. When the thickness of the current collectors 11 and 21 exceeds 25 μm, the effect of calendering is small, and the ratio between the initial elastic modulus in the vertical direction and the initial elastic modulus in the horizontal direction is less than 1.2.
また、集電体１１の厚さが５μｍ未満である場合、メッシュ（開口部）が小さくなりやすく、上述したようにリチウムイオンを補充するとき、リチウムイオンが集電体１１を通過し難くなる。リチウムイオンの補充時にリチウムイオンの通過を確保する上では、集電体１１の厚さを５μｍ以上にすればよいが、集電体１１，２１を共用するときには、集電体１１の厚さと同様に、集電体２１の厚さも５μｍ以上にすることができる。 Further, when the thickness of the current collector 11 is less than 5 μm, the mesh (opening) is likely to be small, and when lithium ions are replenished as described above, the lithium ions are difficult to pass through the current collector 11. In order to ensure the passage of lithium ions during replenishment of lithium ions, the thickness of the current collector 11 may be set to 5 μm or more. However, when the current collectors 11 and 21 are shared, the thickness is similar to that of the current collector 11. In addition, the thickness of the current collector 21 can also be 5 μm or more.
なお、本実施形態では、集電体１１，２１の全体を、ステンレス製ワイヤによって構成しているが、これに限るものではない。具体的には、集電体１１，２１の表面だけを、ステンレス製ワイヤによって構成することができる。すなわち、金属箔の表面に、縦方向および横方向のステンレス製ワイヤを配置することにより、集電体１１，２１を構成することができる。ここで、ステンレス製ワイヤは、活物質層１２，２２と接触する面に設ければよい。金属箔およびステンレス製ワイヤを組み合わせて、集電体１１，２１を構成することにより、集電体１１，２１の強度を確保しやすくなる。 In the present embodiment, the entire current collectors 11 and 21 are made of stainless steel wires, but are not limited thereto. Specifically, only the surfaces of the current collectors 11 and 21 can be formed of stainless steel wires. That is, the current collectors 11 and 21 can be configured by disposing stainless steel wires in the vertical and horizontal directions on the surface of the metal foil. Here, the stainless steel wire may be provided on the surface in contact with the active material layers 12 and 22. By configuring the current collectors 11 and 21 by combining the metal foil and the stainless steel wire, the strength of the current collectors 11 and 21 can be easily secured.
次に実施例を挙げて本発明をより具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.
（実施例１）
ステンレス製ワイヤの径が１９μm、メッシュ数が４００であるステンレスメッシュにカレンダー加工を施し、厚さを２１μmに加工した。このステンレスメッシュを集電体２１として用い、リチウムイオン二次電池の作製を行った。リチウムイオン二次電池の作製は、以下の通りに実施した。
Example 1
A stainless steel mesh having a diameter of 19 μm and a mesh number of 400 was calendered to a thickness of 21 μm. Using this stainless steel mesh as the current collector 21, a lithium ion secondary battery was produced. The production of the lithium ion secondary battery was performed as follows.
負極活物質粉末としてのシリコン（Ｓｉ）、バインダとしてのポリイミド(ＰＩ)、導電助剤としてのアセチレンブラック（ＡＢ）を、負極活物質粉末：バインダ：導電助剤＝８０：２：１８（重量比）の割合となるように秤量し、Ｎ−メチルピロリドン(ＮＭＰ)に分散した後、自転・公転ミキサーで十分に撹拌してスラリー化した。得られたスラリーを、上述したように加工した集電体（ステンレスメッシュ）２１上に塗布し、８０℃で乾燥後，３６０℃で１．５ｈ熱処理し負極シートを作製した。この負極シートを電極打ち抜き機で直径１１ｍｍの円板状に打ち抜き、負極板２０を得た。このようにして得た負極板２０と、対極としてのＬｉ箔と、セパレータ３０としてのガラスフィルターを用いて、「ＣＲ２０３２」と呼ばれるコイン型のリチウムイオン二次電池を作製した。電解液としては、ＥＣ(エチレンカーボネート)およびＤＥＣ(ジエチルカーボネート)が１:１(ｖｏｌ％)である溶媒にＬｉＰＦ６（１Ｍ）を混合したものを用いた。なお、コイン型のリチウムイオン二次電池の作製は露点温度−６０℃以下の環境で行った。 Silicon (Si) as a negative electrode active material powder, polyimide (PI) as a binder, and acetylene black (AB) as a conductive auxiliary agent, negative electrode active material powder: binder: conductive auxiliary agent = 80: 2: 18 (weight ratio) ) And was dispersed in N-methylpyrrolidone (NMP), and then sufficiently stirred with a rotation / revolution mixer to form a slurry. The obtained slurry was applied onto a current collector (stainless mesh) 21 processed as described above, dried at 80 ° C., and then heat-treated at 360 ° C. for 1.5 h to prepare a negative electrode sheet. This negative electrode sheet was punched into a disk shape having a diameter of 11 mm with an electrode punching machine, whereby a negative electrode plate 20 was obtained. A coin-type lithium ion secondary battery called “CR2032” was manufactured using the negative electrode plate 20 thus obtained, the Li foil as the counter electrode, and the glass filter as the separator 30. As the electrolytic solution, a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) in 1: 1 (vol%) and LiPF 6 (1M) was used. The coin-type lithium ion secondary battery was manufactured in an environment with a dew point temperature of −60 ° C. or lower.
（実施例２）
ステンレス製ワイヤの径が２０μm、メッシュ数が２９０であるステンレスメッシュ（厚さ２５μｍ）を集電体２１として用いた以外は実施例１と同様にリチウムイオン二次電池の作製を行った。
(Example 2)
A lithium ion secondary battery was produced in the same manner as in Example 1 except that a stainless mesh (thickness 25 μm) having a diameter of stainless steel wire of 20 μm and a mesh number of 290 was used as the current collector 21.
（比較例１）
ステンレス製ワイヤの径が１９μm、メッシュ数が４００であるステンレスメッシュ（厚さ３９μｍ）を集電体２１として用いた以外は実施例１と同様にリチウムイオン二次電池の作製を行った。
（評価）
(Comparative Example 1)
A lithium ion secondary battery was fabricated in the same manner as in Example 1 except that a stainless steel mesh (thickness: 39 μm) having a diameter of 19 μm and a mesh number of 400 was used as the current collector 21.
(Evaluation)
（強伸度評価）
各集電体２１の縦方向及び横方向における引張試験を実施し、強伸度曲線（強度［ｇ／ｄ］および伸長［％］の関係を示す曲線）を得た。強伸度曲線において、伸長の初期の傾きから初期弾性率を算出し、集電体２１の縦方向の初期弾性率に対する集電体２１の横方向の初期弾性率の比を算出した。下記表１に示すように、実施例１、２の集電体２１においては、縦方向の初期弾性率に対する横方向の初期弾性率の比はそれぞれ、１．０及び８．３ x １０−１であった。また、実施例１，２の集電体２１において、横方向の初期弾性率に対する縦方向の初期弾性率の比はそれぞれ、１．０及び１．２となる。
(Strong elongation evaluation)
Tensile tests in the longitudinal direction and the transverse direction of each current collector 21 were carried out to obtain a strong elongation curve (curve showing the relationship between strength [g / d] and elongation [%]). In the strong elongation curve, the initial elastic modulus was calculated from the initial slope of elongation, and the ratio of the initial elastic modulus in the lateral direction of the current collector 21 to the initial initial elastic modulus of the current collector 21 was calculated. As shown in Table 1 below, in the current collectors 21 of Examples 1 and 2, the ratio of the initial elastic modulus in the transverse direction to the initial elastic modulus in the longitudinal direction is 1.0 and 8.3 × 10 −1 , respectively. Met. In the current collectors 21 of Examples 1 and 2, the ratios of the initial elastic modulus in the longitudinal direction to the initial elastic modulus in the horizontal direction are 1.0 and 1.2, respectively.
一方で、比較例１の集電体２１においては、縦方向の初期弾性率に対する横方向の初期弾性率の比は２．９であった。また、比較例１の集電体２１において、横方向の初期弾性率に対する縦方向の初期弾性率の比は０．３となる。 On the other hand, in the current collector 21 of Comparative Example 1, the ratio of the initial elastic modulus in the transverse direction to the initial elastic modulus in the longitudinal direction was 2.9. In the current collector 21 of Comparative Example 1, the ratio of the initial elastic modulus in the longitudinal direction to the initial elastic modulus in the horizontal direction is 0.3.
（充放電挙動評価）
実施例１、２および比較例１であるリチウムイオン二次電池に対して、充放電のサイクル試験を行い、電池容量の評価を行った。サイクル試験では、充放電レートを０．１Ｃ、カットオフ電圧を０．００１−１．０Ｖとして、充放電を繰り返した。
(Evaluation of charge / discharge behavior)
The lithium ion secondary batteries of Examples 1 and 2 and Comparative Example 1 were subjected to a charge / discharge cycle test, and the battery capacity was evaluated. In the cycle test, charging / discharging was repeated at a charge / discharge rate of 0.1 C and a cut-off voltage of 0.001-1.0 V.
下記表２には、実施例１、２において作製したリチウムイオン二次電池について、サイクル試験の結果を示す。下記表２は、サイクル数と、各サイクル数の後の電池容量（単位質量当たりの容量［ｍＡｈ／ｇ］）との関係を示す。一方で、比較例１においては、サイクル試験後の電池容量を測定できなかった。これは、縦方向と横方向における集電体２１の初期弾性率が大きく異なる場合、充放電時に生じる活物質の体積変化による集電体（ステンレスメッシュ）２１の変形が一様にならず、集電体２１からの活物質の剥離が生じたためと考えられる。 Table 2 below shows the results of the cycle test for the lithium ion secondary batteries produced in Examples 1 and 2. Table 2 below shows the relationship between the number of cycles and the battery capacity (capacity per unit mass [mAh / g]) after each number of cycles. On the other hand, in Comparative Example 1, the battery capacity after the cycle test could not be measured. This is because when the initial elastic modulus of the current collector 21 in the vertical direction and the horizontal direction is greatly different, the deformation of the current collector (stainless mesh) 21 due to the volume change of the active material that occurs during charging and discharging is not uniform. It is considered that the active material was peeled off from the electric body 21.
１：発電要素、１０：正極板、１１：集電体、１２：正極活物質層、２０：負極板、
２１：集電体、２２：負極活物質層、３０：セパレータ、４０：セパレータ、
５０：リチウム箔、６０：電源
1: power generation element, 10: positive electrode plate, 11: current collector, 12: positive electrode active material layer, 20: negative electrode plate,
21: current collector, 22: negative electrode active material layer, 30: separator, 40: separator
50: Lithium foil, 60: Power supply
Claims (3)
前記集電体が、少なくとも活物質層と接触する表面において、ステンレス製ワイヤを縦方向および横方向に織り込むことにより形成され、前記活物質層の少なくとも一部が内部に埋め込まれるメッシュ構造を有しており、
前記集電体の前記縦方向の初期弾性率と前記集電体の前記横方向の初期弾性率の比が０．８以上、１．２以下となるように、縦方向および横方向に織り込まれた前記ステンレス製ワイヤに対してカレンダー加工を行うことを特徴とするリチウムイオン二次電池用の集電体の製造方法。 A method for producing a current collector for a lithium ion secondary battery, comprising:
The current collector is formed by weaving stainless steel wires in the vertical and horizontal directions at least on the surface in contact with the active material layer, and has a mesh structure in which at least a part of the active material layer is embedded inside And
It is woven in the longitudinal direction and the lateral direction so that the ratio between the initial elastic modulus in the longitudinal direction of the current collector and the initial elastic modulus in the lateral direction of the current collector is 0.8 or more and 1.2 or less. A method of manufacturing a current collector for a lithium ion secondary battery, wherein calendar processing is performed on the stainless steel wire.
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