JP3416609B2 - Method for producing positive electrode current collector for sodium-sulfur battery - Google Patents
Method for producing positive electrode current collector for sodium-sulfur batteryInfo
- Publication number
- JP3416609B2 JP3416609B2 JP2000087939A JP2000087939A JP3416609B2 JP 3416609 B2 JP3416609 B2 JP 3416609B2 JP 2000087939 A JP2000087939 A JP 2000087939A JP 2000087939 A JP2000087939 A JP 2000087939A JP 3416609 B2 JP3416609 B2 JP 3416609B2
- Authority
- JP
- Japan
- Prior art keywords
- current collector
- positive electrode
- glass fiber
- sodium
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 67
- 239000000463 material Substances 0.000 claims description 54
- 239000011230 binding agent Substances 0.000 claims description 52
- 239000000835 fiber Substances 0.000 claims description 29
- 238000004080 punching Methods 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 20
- 238000005238 degreasing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 210000003127 knee Anatomy 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims 1
- 239000004745 nonwoven fabric Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 239000007784 solid electrolyte Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- JYGRFALVSCHYEX-UHFFFAOYSA-N [Th]=S Chemical compound [Th]=S JYGRFALVSCHYEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- RPMPQTVHEJVLCR-UHFFFAOYSA-N pentaaluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3] RPMPQTVHEJVLCR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009941 weaving 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)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】 本発明は、ナトリウム−硫
黄電池用正極集電体の製造方法に関し、詳しくは高抵抗
層の構造を精密に制御することができるナトリウム−硫
黄電池用正極集電体の製造方法に関するものである。TECHNICAL FIELD The present invention relates to sodium-sulfuric acid.
Sodium relates to a process for the preparation of the yellow battery positive electrode current collector, and there can be precisely control the structure of the high-resistance layer - vulcanized
The present invention relates to a method for manufacturing a positive electrode current collector for a yellow battery .
【０００２】[0002]
【従来の技術】 ナトリウム−硫黄電池（以下、「ＮＡ
Ｓ電池」という。）は、３００〜３５０℃の高温で作動
させる密閉型高温二次電池であって、負極活物質である
ナトリウムと正極活物質である硫黄とを、ナトリウムイ
オンを選択的に透過させる機能を有する固体電解質（例
えばβ−アルミナ、β"−アルミナ等）により隔離収納
した構造を有するものである。2. Description of the Related Art Sodium-sulfur batteries (hereinafter referred to as "NA
S battery ". ) Is a sealed high-temperature secondary battery that operates at a high temperature of 300 to 350 ° C., and is a solid having a function of selectively allowing sodium ions to permeate sodium as a negative electrode active material and sulfur as a positive electrode active material. It has a structure in which it is separated and housed by an electrolyte (for example, β-alumina, β ″ -alumina, etc.).
【０００３】 例えば図１に示すＮＡＳ電池１は、中空
円筒状の正極容器９の内部に有底円筒状の固体電解質管
１３を配置し、固体電解質管１３内部に負極活物質のナ
トリウム２を、外部には正極活物質の硫黄４を隔離収納
したものである。固体電解質管１３は、α−アルミナ等
からなる絶縁体リング３、円筒状金具５を介して正極容
器９に接合され、正極側と負極側とが電気的に絶縁され
るように構成されている。なお、図１において、符号１
０はくびれ部を、符号１１は正極集電体をそれぞれ示
す。 For example, in a NAS battery 1 shown in FIG. 1, a bottomed cylindrical solid electrolyte tube 13 is arranged inside a hollow cylindrical positive electrode container 9, and sodium 2 as a negative electrode active material is placed inside the solid electrolyte tube 13. Sulfur 4, which is a positive electrode active material, is separately stored outside. The solid electrolyte tube 13 is joined to the positive electrode container 9 via the insulator ring 3 made of α-alumina or the like and the cylindrical metal member 5 so that the positive electrode side and the negative electrode side are electrically insulated. . In FIG. 1, reference numeral 1
0 indicates a constricted portion, and 11 indicates a positive electrode current collector.
You
【０００４】 ＮＡＳ電池１は、放電時には負極活物質
のナトリウム２が外部回路に電子を放出してナトリウム
イオンとなり、固体電解質管１３内を透過して正極側に
移動し、正極活物質の硫黄４及び外部回路から供給され
る電子と反応して多硫化ソーダを生成することによっ
て、２Ｖ程度の電圧を発生させる。In the NAS battery 1, when discharging, sodium 2 of the negative electrode active material emits electrons to the external circuit to become sodium ions, permeates through the solid electrolyte tube 13 and moves to the positive electrode side, and sulfur of the positive electrode active material 4 And a voltage of about 2V is generated by reacting with electrons supplied from an external circuit to generate sodium polysulfide.
【０００５】 一方、充電時には外部回路から電圧を印
加することによって、多硫化ソーダが外部回路に電子を
放出して硫黄とナトリウムイオンを生成し、固体電解質
管１３内を透過して負極側に移動したナトリウムイオン
を、外部回路から供給する電子と反応させて電気的に中
性化することにより、電気エネルギーを化学エネルギー
に変換する。On the other hand, at the time of charging, by applying a voltage from an external circuit, sodium polysulfide releases electrons to the external circuit to generate sulfur and sodium ions, which permeate the solid electrolyte tube 13 and move to the negative electrode side. The sodium ion is reacted with an electron supplied from an external circuit to be electrically neutralized, thereby converting electric energy into chemical energy.
【０００６】 ＮＡＳ電池の正極活物質である硫黄４は
絶縁物であるため、正極と負極との間の導通を確保し、
電池の内部抵抗を低減することを目的として、正極集電
体１１を配設することが一般的である。正極集電体１１
は、導電性を有する炭素繊維又はグラファイト繊維から
なるフェルト材で構成された部材であり、正極活物質の
硫黄４を含浸させ、正極容器９内周面と固体電解質管１
３外周面の双方に当接するように配置することにより、
正極と負極との間の導通が確保され、電池の内部抵抗も
低減される。Sulfur 4, which is the positive electrode active material of the NAS battery, is an insulator, and therefore ensures continuity between the positive electrode and the negative electrode.
The positive electrode current collector 11 is generally provided for the purpose of reducing the internal resistance of the battery. Positive electrode current collector 11
Is a member composed of a felt material made of conductive carbon fiber or graphite fiber, impregnated with sulfur 4 as a positive electrode active material, and the inner peripheral surface of the positive electrode container 9 and the solid electrolyte tube 1
3 By arranging so as to contact both outer peripheral surfaces,
The conduction between the positive electrode and the negative electrode is secured, and the internal resistance of the battery is also reduced.
【０００７】 更に、上述のＮＡＳ電池１において、正
極集電体１１は、その固体電解質管１３と当接する表面
側に、絶縁性物質であるガラス繊維を、金属針のフック
部分を打ち込むニードルパンチにより打ち込んで形成さ
れた高抵抗層を有している。高抵抗層は、固体電解質管
１３と正極集電体１１との接触面近傍の導電性を低下さ
せるため、充電時に固体電解質管１３と正極集電体１１
との接触面近傍のみで電子の授受反応が行われることを
回避できる。従って、当該部分に絶縁物である硫黄が析
出し、充電反応の進行とともに電池の内部抵抗が上昇す
ることに起因する充電回復性の低下（多硫化ソーダが残
存しているにも拘わらず充電反応が進行せず、充電が完
結しない現象）を防止することが可能である。Furthermore, in the NAS battery 1 described above, the cathode current collector 11, the surface side of the solid electrolyte tube 13 of its abutting, the glass fibers is an insulating material, a metal needle hook
It has a high resistance layer formed by punching with a needle punch. Since the high resistance layer reduces the conductivity in the vicinity of the contact surface between the solid electrolyte tube 13 and the positive electrode current collector 11, the solid electrolyte tube 13 and the positive electrode current collector 11 are charged during charging.
It is possible to avoid the electron transfer reaction only in the vicinity of the contact surface with. Therefore, the sulfur, which is an insulator, is deposited in the relevant part, and the charge recovery is lowered due to the increase of the internal resistance of the battery as the charging reaction progresses. It is possible to prevent a phenomenon in which charging does not complete and charging is not completed.
【０００８】[0008]
【発明が解決しようとする課題】 ところが、高抵抗層
を有する正極集電体を配設した場合でもなお、充電回復
性が低下したり、或いは逆に電池の内部抵抗が上昇し、
放電時におけるナトリウムイオンの正極側への移動が妨
げられる場合が生じていた。これらの不具合は、高抵抗
層の構造が精密に制御されていないことに起因するもの
である。However, even when the positive electrode current collector having the high resistance layer is provided, the charge recovery property is lowered, or conversely, the internal resistance of the battery is increased,
There have been cases where the movement of sodium ions to the positive electrode side during the discharge is hindered. These defects are due to the fact that the structure of the high resistance layer is not precisely controlled.
【０００９】 具体的には、基材表面の高抵抗層による
被覆率（以下、「表面被覆率」という。）が所定の範囲
内に制御されていない場合には適切な電池の内部抵抗が
得られず、基材厚みに対するガラス繊維が打ち込まれた
深さの比率（以下、「内部到達率」という。）が所定の
範囲内に制御されていない場合には充電回復性が低下す
ることがある。Specifically, when the coverage of the high resistance layer on the surface of the base material (hereinafter referred to as “surface coverage”) is not controlled within a predetermined range, an appropriate internal resistance of the battery is obtained. is not, the ratio of the depth to which the glass fibers to substrate thickness is driven (hereinafter, referred to as "internal achievement ratio".) is sometimes charge recovery is reduced if the is not controlled within a predetermined range .
【００１０】 本発明は、このような従来技術の問題点
に鑑みてなされたものであって、その目的とするところ
は、表面被覆率や内部到達率などの高抵抗層の構造を精
密に制御することができるナトリウム−硫黄電池用正極
集電体の製造方法を提供することにある。The present invention has been made in view of the above problems of the prior art, and its object is to precisely control the structure of the high resistance layer such as surface coverage and internal reach. Another object of the present invention is to provide a method for producing a positive electrode current collector for a sodium-sulfur battery that can be manufactured.
【００１１】[0011]
【課題を解決するための手段】 本発明者らが鋭意検討
した結果、高抵抗層を形成するためのガラス繊維表面を
被覆するバインダー量及びその脱脂条件により、表面被
覆率や内部到達率などの高抵抗層の構造を精密に制御可
能であることを見出して本発明を完成した。Means for Solving the Problems The present inventors have results which was examined intensively, the binder amount and degreasing conditions to cover the glass fiber surface to form a high-resistance layer, the surface coverage and internal arrival rate, etc. The present invention has been completed by finding that the structure of the high resistance layer can be precisely controlled.
【００１２】 即ち、本発明によれば、炭素繊維又はグ
ラファイト繊維からなるフェルト状の基材の一方の表面
に、ガラス繊維からなる布状体又は綿状体を積重し、前
記布状体又は綿状体が積重された前記基材に金属針のフ
ック部分を打ち込むニードルパンチによって前記布状体
又は綿状体を前記基材に打ち込むことにより高抵抗層を
形成するナトリウム−硫黄電池用正極集電体の製造方法
であって、前記ニードルパンチの際に、前記布状体又は
綿状体を構成する前記ガラス繊維として、前記ガラス繊
維の表面に、バインダーを前記ガラス繊維の全質量に対
し０．５質量％以上、２．２質量％未満の割合で付着さ
せたものを用い、前記ニードルパンチの後に、空気中、
３００℃以上、６００℃以下の条件で前記バインダーを
脱脂することを特徴とするナトリウム−硫黄電池用正極
集電体の製造方法が提供される。[0012] That is, according to the present invention, on one surface of the felt-like substrate made of carbon fibers or graphite fibers, a cloth-like body or cotton-like material made of a glass fiber product weigh, before
A metal needle flap is attached to the base material on which a cloth-like material or a cotton-like material is stacked.
The cloth-like body is formed by needle punching into the hook portion.
Or sodium to form a high-resistance layer by implanting a flocculent body to the substrate - a process for the preparation of sulfur battery positive electrode current collector, during the needle punching, the cloth-like body or
As the glass fiber forming the cotton-like body, the glass fiber
On the surface of the fiber, a binder is added to the total mass of the glass fiber.
Attached at a rate of 0.5% by mass or more and less than 2.2% by mass.
Using a sprinkle, after the needle punch, in air,
The binder is used under the conditions of 300 ° C or higher and 600 ° C or lower.
A method for producing a positive electrode current collector for a sodium-sulfur battery, which comprises degreasing is provided.
【００１３】 本発明の製造方法においては、前記ニー
ドルパンチの際に、前記布状体又は綿状体を構成する前
記ガラス繊維として、前記基材の厚みに対し２倍以上、
１５倍未満の繊維長さを有するものを用いることが好ま
しい。 In the manufacturing method of the present invention, the knee
Before forming the above-mentioned cloth-like body or cotton-like body during dollar punching
As the glass fiber, twice or more the thickness of the base material,
It is preferable to use a fiber having a fiber length of less than 15 times.
Good
【００１４】 また、本発明の製造方法においては、前
記ニードルパンチの際に、前記金属針のフック部分を前
記基材の厚みの７０〜１００％の深さまで打ち込むこと
が好ましい。 [0014] In the production method of the present invention, prior to
When the serial needle punching, prior to the hook portion of the metal needle
It is preferable to implant up to 70% to 100% of the depth of the thickness of the serial substrate.
【００１５】[0015]
【発明の実施の形態】 本発明の製造方法は、高抵抗層
を形成するためのガラス繊維表面に付着するバインダー
量及びその脱脂条件、さらに必要に応じて、ガラス繊維
の繊維長さ及び金属針のフック部分の打ち込み深さを適
正な範囲に規定したものである。このような製造方法に
よれば、表面被覆率や内部到達率などの高抵抗層の構造
を精密に制御することが可能となる。以下、本発明のナ
トリウム−硫黄電池用正極集電体の製造方法について詳
細に説明する。Manufacturing method of the embodiment of the present invention, the binder amounts and degreasing conditions attached to the glass fiber surface to form a high resistance layer, if necessary, glass fiber
The fiber length and the driving depth of the hook portion of the metal needle are defined in an appropriate range. According to such a manufacturing method, it becomes possible to precisely control the structure of the high resistance layer such as the surface coverage and the internal reach. Below, the name of the present invention
The method for producing the positive electrode current collector for the thorium-sulfur battery will be described in detail.
【００１６】 本発明のナトリウム−硫黄電池用正極集
電体（以下、単に「集電体」という。）の製造方法は、
絶縁性に優れることに加えて、多硫化ソーダとの親和性
が高いガラス繊維を高抵抗層の材料とし、当該ガラス繊
維を、高い導電性を有し、正極活物質の硫黄に対する耐
食性に優れる炭素繊維又はグラファイト繊維をフェルト
状とした基材の一方の表面側から金属針のフック部分を
打ち込むニードルパンチにより打ち込んで高抵抗層を形
成するものである。The method for producing a positive electrode current collector for a sodium-sulfur battery (hereinafter, simply referred to as “current collector”) of the present invention comprises:
In addition to having excellent insulating properties, glass fiber having a high affinity with sodium polysulfide as a material for the high resistance layer, the glass fiber having high conductivity, carbon having excellent corrosion resistance to sulfur of the positive electrode active material From one surface side of the base material made of felt fiber or graphite fiber , hook the metal needle
The high resistance layer is formed by punching with a needle punch.
【００１７】 ニードルパンチは、不織布のフェルト加
工等に用いられるニードルパンチ機を使用して行うこと
ができる。ニードルパンチ機は、先端部や長手方向の中
途にフックを有する金属針が多数突設された針ボードを
用いて、その金属針のフック部分を加工対象物に対して
鉛直方向に打ち込み、引き抜く操作を繰り返すことが可
能な装置である。また、ニードルパンチ機には、針ボー
ドにおける金属針のフック部分の打ち込みに同期して加
工対象物を水平方向に移動可能なベルトコンベアー等の
移動手段が併設されている。Needle punching can be performed using a needle punching machine used for felting a non-woven fabric. Needle punching machines use a needle board with a large number of metal needles protruding from the tip or in the longitudinal direction.
It is a device that can be used to repeat the operation of driving the hook portion of the metal needle into the workpiece in the vertical direction and pulling it out. Further, the needle punching machine is provided with a moving means such as a belt conveyer capable of horizontally moving the workpiece in synchronization with the driving of the hook portion of the metal needle on the needle board.
【００１８】 このようなニードルパンチ機によれば、
ガラス繊維からなる布状体（例えば不織布等）や綿状体
を基材表面に積重し、ガラス繊維側から針ボードにおけ
る金属針のフック部分を打ち込むと、金属針のフック部
分に係合されたガラス繊維が金属針と共に基材の厚み方
向に打ち込まれる。更に、ベルトコンベアー等で基材を
水平方向へ移動させながら、針ボードにおける金属針の
フック部分を打ち込むことにより、基材全体に均一な間
隔でガラス繊維が打ち込まれる。According to such a needle punching machine,
Cloths made of glass fibers (for example, non-woven fabric) or cotton-like materials are stacked on the surface of the substrate, and the glass fibers are placed on the needle board .
When the hook portion of the metal needle is driven, the glass fiber engaged with the hook portion of the metal needle is driven together with the metal needle in the thickness direction of the base material. Furthermore, while moving the substrate in the horizontal direction by a belt conveyor or the like, of the metal needle in the needle board
By driving the hook portion , glass fibers are driven into the entire base material at uniform intervals.
【００１９】 上述のニードルパンチにおいて針ボード
における金属針のフック部分を継続的に打ち込むと、基
材表面のガラス繊維が基材内に打ち込まれて徐々に減少
し、基材内部と基材表面の双方にガラス繊維からなる高
抵抗層が形成される。更に打ち込みを継続すると最終的
には基材を構成する炭素繊維等の一部が表面に露出する
ようになる。In the above needle punch, a needle board
When the hook portion of the metal needle in is continuously driven, the glass fiber on the surface of the base material is driven into the base material and gradually decreases, and a high resistance layer made of glass fiber is formed both inside the base material and on the surface of the base material. It is formed. When the driving is further continued, finally, a part of the carbon fiber or the like which constitutes the base material is exposed on the surface.
【００２０】 このような方法で高抵抗層を形成した集
電体は、基材の一方の表面が高抵抗層で被覆され、当該
部分の電気抵抗が高いため、充電時に固体電解質管と集
電体との接触面近傍のみに絶縁物である硫黄が析出して
絶縁層が形成されることを防止できる。従って、充電反
応の進行とともに電池の内部抵抗が上昇することがな
く、充電回復性が高い点において好ましいものである。In the current collector in which the high resistance layer is formed by such a method, one surface of the base material is covered with the high resistance layer and the electric resistance of the portion is high. It is possible to prevent the formation of an insulating layer by depositing sulfur as an insulator only in the vicinity of the contact surface with the body. Therefore, it is preferable in that the internal resistance of the battery does not increase with the progress of the charging reaction and the charge recovery property is high.
【００２１】 また、上記方法で製造された集電体は、
ガラス繊維をニードルパンチにより打ち込んで高抵抗層
を形成しているため、ガラス繊維が基材の厚み方向に配
向している。多硫化ソーダに対する濡れ性に優れるガラ
ス繊維が基材の厚み方向に配向していると、当該ガラス
繊維に沿って多硫化ソーダが移動するため、集電体にお
ける多硫化ソーダの移動が促進される。従って、電池が
大型化し集電体の厚みが増加した場合でも、円滑な充電
が可能となり、充電回復率が高められるという効果があ
る。Further, the current collector manufactured by the above method ,
Since the glass fiber is hit by a needle punch to form the high resistance layer, the glass fiber is oriented in the thickness direction of the base material. When glass fibers having excellent wettability with respect to sodium polysulfide are oriented in the thickness direction of the base material, the sodium polysulfide moves along the glass fibers, so that the movement of the sodium polysulfide in the current collector is promoted. . Therefore, even when the battery becomes large and the thickness of the current collector increases, there is an effect that smooth charging is possible and the charge recovery rate is increased.
【００２２】[0022]
【００２３】[0023]
【００２４】[0024]
【００２５】[0025]
【００２６】[0026]
【００２７】[0027]
【００２８】[0028]
【００２９】[0029]
【００３０】[0030]
【００３１】 本発明の製造方法の実施の形態は、高抵
抗層を形成するためのガラス繊維の表面に付着するバイ
ンダー量を適正な範囲に規定するとともに、脱脂条件を
規定したものである。バインダー量を適正な範囲に規定
することにより、ニードルパンチの際にガラス繊維が破
断することなく基材内部に打ち込まれ、表面被覆率が精
密に制御された集電体を得ることができる。具体的に
は、ガラス繊維表面に付着するバインダー量をガラス繊
維質量に対し０．５質量％以上とすることにより、表面
被覆率を２０％以上に制御することが可能となる。The implementation in the form of the manufacturing method of the present invention is to define a binder quantity adsorbed to the surface of the glass fibers for forming the high-resistance layer in a proper range, the degreasing conditions
It has been prescribed . By defining the amount of the binder within an appropriate range, it is possible to obtain a current collector in which the glass fibers are driven into the base material without breaking during needle punching and the surface coverage is precisely controlled. Specifically, the surface coverage can be controlled to 20% or more by setting the amount of the binder attached to the glass fiber surface to 0.5% by mass or more with respect to the glass fiber mass.
【００３２】 バインダー量を０．５質量％未満とした
場合には、ニードルパンチの際にガラス繊維が破損して
しまい、基材とガラス繊維とが一体化できないため、表
面被覆率を２０％以上に制御することができなくなる。
なお、本明細書にいう「バインダー」とは、ガラス繊維
の破損を防止するためにガラス繊維の表面に付着せしめ
る物質を意味し、例えばコーンスターチ、澱粉類、ステ
アリン酸等の滑剤が挙げられる。When the amount of the binder is less than 0.5% by mass, the glass fiber is damaged during needle punching and the base material and the glass fiber cannot be integrated, so that the surface coverage is 20% or more. such that can not be controlled to.
The "binder" referred to in the present specification means a substance that is attached to the surface of the glass fiber in order to prevent breakage of the glass fiber, and examples thereof include lubricants such as corn starch, starches and stearic acid.
【００３３】 上述のように集電体における高抵抗層が
所定の表面被覆率を達成するためには、ガラス繊維表面
に所定量のバインダーが付着していることが必須の要件
である。但し、ガラス繊維を基材に打ち込んだ後にはバ
インダーを脱脂する必要がある点に留意しなければなら
ない。As described above, in order for the high resistance layer in the current collector to achieve a predetermined surface coverage, it is essential that a predetermined amount of binder is attached to the glass fiber surface. However, it should be noted that it is necessary to degrease the binder after driving the glass fiber into the substrate.
【００３４】 即ち、集電体を配設するＮＡＳ電池は３
００〜３５０℃の高温で作動する密閉型の電池であり、
電池内部には不活性ガスが封入されているため、有機物
であるバインダーが残存すると、高温分解により水素、
酸素、二酸化炭素等のガスが発生し電池の内圧が上昇す
る点において好ましくないからである。That is, the number of NAS batteries provided with the current collector is 3
It is a sealed battery that operates at a high temperature of 00 to 350 ° C.
Since the inert gas is sealed inside the battery, if the organic binder remains, hydrogen will decompose due to high temperature,
This is because gases such as oxygen and carbon dioxide are generated, which is not preferable in that the internal pressure of the battery rises.
【００３５】 有機物であるバインダーは、空気中のよ
うな酸素存在下における熱処理により脱脂することが可
能であるが、炭素繊維等で構成されている基材の酸化、
或いは基材への煤の付着により集電体の電子伝導性が低
下する事態は避ける必要がある。The binder, which is an organic substance, can be degreased by a heat treatment in the presence of oxygen such as in the air, but oxidation of a base material composed of carbon fiber or the like,
Alternatively, it is necessary to avoid the situation where the electron conductivity of the current collector is lowered due to the attachment of soot to the base material.
【００３６】 そこで、本発明ではガラス繊維表面に付
着せしめるバインダー量の上限及び脱脂条件についても
規定した。こうすることにより、基材の酸化等を防止で
き、かつ、バインダー成分を完全に除去することが可能
となる。具体的には、バインダー量の上限を２．２質量
％未満とし、かつ、空気中において３００℃以上、６０
０℃以下の温度でバインダーを脱脂することとしてい
る。Therefore, in the present invention, the upper limit of the amount of the binder attached to the surface of the glass fiber and the degreasing conditions are also defined. By doing so, it is possible to prevent the base material from being oxidized and to completely remove the binder component. Specifically, the upper limit of the amount of the binder is less than 2.2% by mass, and in air, the temperature is 300 ° C. or more and 60% or more.
The binder is degreased at a temperature of 0 ° C or lower.
【００３７】 バインダー量を２．２質量％未満とする
ことにより空気中、３００℃以上の条件で確実にバイン
ダーを脱脂することができ、温度を６００℃以下に制限
すれば基材が酸化されたり、基材に煤が付着することは
なく、集電体の電子伝導性が低下する事態を回避でき
る。 By making the amount of the binder less than 2.2% by mass, the binder can be surely degreased under the condition of 300 ° C. or higher in the air, and if the temperature is limited to 600 ° C. or lower, the base material may be oxidized. , Soot does not adhere to the base material, and it is possible to avoid the situation where the electron conductivity of the current collector is reduced.
It
【００３８】 本実施の形態においては、バインダー量
が所定範囲内に制御されたガラス繊維の布状体、綿状体
を用意する必要がある。ガラス繊維はガラス原料を高温
で溶融して繊維状に引き抜き、冷却固化させることによ
り得られるため、前記引き抜きの際にバインダーの希釈
溶液（水溶液など）を噴霧することにより溶媒を揮発さ
せバインダーのみをガラス繊維に付着させればよい。バ
インダー量は希釈溶液の噴霧量によって制御することが
可能である。このようにして得られたガラス繊維を、下
記の方法で不織布としたもの等を布状体、綿状体として
使用することができる。まず、原料となるガラス繊維を
所定の長さに切断して短繊維とし、機械的に解繊し、当
該短繊維を、そのまま均一に薄く綿状に積層し軽いニ
ードルパンチにより固定する方法、クロスレヤー機等
により、繊維方向を揃えた薄い網状体を作製し、当該網
状体を繊維方向が交差するように複数枚積層した後、軽
いニードルパンチにより固定する方法、溶媒に分散さ
せ、紙漉と同様の方法で不織布とする方法、等により不
織布とすることができる。 本実施の形態においては、さ
らに、高抵抗層を形成するためのガラス繊維の繊維長さ
を適正な範囲に規定することが好ましい。 ガラス繊維の
繊維長さを適正な範囲に規定することにより、表面被覆
率が精密に制御された集電体を得ることができる。具体
的には、ガラス繊維の繊維長さを基材厚みに対し２倍以
上とすることにより、表面被覆率を２０％以上に制御す
ることが可能となる。 繊維長さを基材厚みに対し２倍未
満と短くした場合には、ニードルパンチの際にガラス繊
維が基材内部に完全に埋没してしまうため、表面被覆率
が２０％未満となることがある。 表面被覆率のみに着目
すれば、ニードルパンチの際の金属針のフック部分の打
ち込さ深さを浅くすることにより、基材表面のガラス繊
維の残存量を多くする方法も考えられるが、このような
方法で製造した集電体は内部到達率が低下することに起
因して、電池の充電回復性を低下させることがある。 ま
た、ガラス繊維の繊維長さを基材厚みに対し１５倍未満
とすることにより、表面被覆率を８５％以下に制御する
ことが可能となる。 繊維長さを基材厚みに対し１５倍以
上と長くした場合には、ニードルパンチの際に基材表面
に残存するガラス繊維が多くなるため、表面被覆率を８
５％以下に制御することが困難となることがある。 表面
被覆率のみに着目すれば、ニードルパンチの際の金属針
のフック部分の打ち込み回数を多くすることにより、基
材表面のガラス繊維の残存量を減らす方法も考えられ
る。 しかしながら、このような方法で製造した集電体は
ニードルパンチ条件が過酷となることに起因して、基材
が損傷することがあるため、集電体の電子伝導性が低下
し、電池とした場合に内部抵抗の上昇を招くことがあ
る。 また、集電体は、ニードルパンチ後に所定の長さ、
幅に裁断し、金型を用いて円弧状に湾曲させ、硫黄を含
浸することにより電池部品とするため、基材が損傷した
集電体はこれらの工程で亀裂が発生する等、取扱いが著
しく困難となる点においても問題である。 In the present embodiment , it is necessary to prepare a cloth-like body or a cotton-like body made of glass fiber in which the amount of the binder is controlled within a predetermined range. The glass fiber is obtained by melting the glass raw material at a high temperature, drawing it into a fibrous shape, and cooling and solidifying it. Therefore, at the time of the drawing, the solvent is volatilized by spraying a diluted solution of the binder (such as an aqueous solution) to remove only the binder. It may be attached to glass fiber. The binder amount can be controlled by the spray amount of the diluted solution. The glass fibers thus obtained, under
A non-woven fabric obtained by the method described above can be used as a cloth-like body or a cotton-like body. First, the glass fiber as the raw material
Cut it to a specified length to make short fibers, mechanically defibrate it, and
The short fibers are laminated evenly and thinly into a cotton-like shape to create a light fiber.
-Folder punch fixing method, cross layer machine, etc.
To produce a thin net-like body with aligned fiber directions.
After stacking multiple filaments so that the fiber directions intersect,
And fix it with a needle punch.
The same as a paper strainer to make a non-woven fabric.
It can be woven. In the present embodiment,
In addition, the fiber length of the glass fiber to form the high resistance layer
Is preferably defined in an appropriate range. Glass fiber
By specifying the fiber length in an appropriate range, surface coating
It is possible to obtain a current collector whose rate is precisely controlled. Concrete
In general, the fiber length of glass fiber should be more than 2 times the substrate thickness.
By setting the above, the surface coverage is controlled to 20% or more.
It is possible to The fiber length is not twice the thickness of the base material.
When fully shortened, the glass fiber should be
Since the fibers are completely buried inside the substrate, the surface coverage
May be less than 20%. Focus only on surface coverage
The hook of the metal needle during needle punching.
By reducing the depth of penetration, the glass fiber on the substrate surface
It is possible to increase the amount of residual fiber, but
The current collector produced by this method has a low internal arrival rate.
As a result, the charge recovery of the battery may be reduced. Well
Also, the fiber length of glass fiber is less than 15 times the substrate thickness.
To control the surface coverage to 85% or less.
It becomes possible. Fiber length is 15 times or more of the substrate thickness
When lengthened to the top, the substrate surface during needle punching
Since the amount of glass fiber remaining in the
It may be difficult to control to 5% or less. surface
If you focus only on the coverage, the metal needle for needle punching
By increasing the number of times the hook part of the
A method to reduce the amount of glass fiber remaining on the material surface is also conceivable.
It However, the current collector manufactured by such a method is
Due to the severe needle punching conditions,
The electron conductivity of the current collector is reduced because the
However, when used as a battery, the internal resistance may increase.
It Further, the current collector has a predetermined length after needle punching,
Cut into width and use a mold to bend it into an arc shape,
The base material was damaged because it was made into a battery component by immersion.
The current collector is not easy to handle as cracks may occur during these steps.
It is also a problem in that it becomes difficult.
【００３９】[0039]
【００４０】 本実施の形態においては、ニードルパン
チの際に、金属針のフック部分を基材厚みの７０〜１０
０％の深さまで打ち込むことが好ましい。金属針のフッ
ク部分を打ち込む深さ（以下「打ち込み深さ」とい
う。）によりガラス繊維が基材に打ち込まれる深さを制
御することができるため、内部到達率７０〜１００％の
集電体を形成することができるからである。内部到達率
を７０％以上とすることにより、多硫化ソーダの移動が
更に促進され、充電回復性が向上する一方、内部到達率
を１００％以下とすることにより、ガラス繊維が基材の
他方の表面まで突出し、正極容器と集電体との当接面に
おける接触抵抗が高くなることを防止できる。In the present embodiment, when needle punching, the hook portion of the metal needle has a thickness of 70 to 10 of the base material.
It is preferable to drive to a depth of 0%. Since the depth at which the glass fiber is driven into the base material can be controlled by the depth at which the hook portion of the metal needle is driven (hereinafter referred to as "driving depth"), a collector having an internal arrival rate of 70 to 100% can be provided. This is because it can be formed. By setting the internal arrival rate to 70% or more, the movement of sodium polysulfide is further promoted and the charge recovery property is improved, while by setting the internal arrival rate to 100% or less, the glass fiber is not It is possible to prevent the contact resistance of the contact surface between the positive electrode container and the current collector from increasing due to the protrusion to the surface.
【００４１】 本実施の形態により製造された集電体
は、図１に示すような中空円筒状の正極容器９の内部に
有底円筒状の固体電解質管１３が配置され、固体電解質
管１３内部に負極活物質のナトリウム２、外部に正極活
物質の硫黄４が隔離収納された構造を有するＮＡＳ電池
１において、高抵抗層を有する面が固体電解質管１３の
外周面に当接するように配置することにより、充電回復
性に優れ、内部抵抗が低いＮＡＳ電池を構成することが
可能となる。In the current collector manufactured according to the present embodiment , a bottomed cylindrical solid electrolyte tube 13 is arranged inside a hollow cylindrical positive electrode container 9 as shown in FIG. In the NAS battery 1 having a structure in which sodium 2 as the negative electrode active material and sulfur 4 as the positive electrode active material are separately housed outside, the surface having the high resistance layer is arranged so as to contact the outer peripheral surface of the solid electrolyte tube 13. This makes it possible to configure a NAS battery having excellent charge recovery and low internal resistance.
【００４２】[0042]
【実施例】 以下、本発明のナトリウム−硫黄電池用正
極集電体及び本発明のナトリウム−硫黄電池用正極集電
体を用いたＮＡＳ電池を、実施例を用いて更に具体的に
説明する。但し、本発明はこれらの実施例に限定される
ものではない。なお、目付量とは、シート状材料（フェ
ルト材、布状体、綿状体など）の単位面積当たりの質量
（ｇ／ｍ2）を示すものであり、シート状材料の全質量
をその面積で除することにより算出することが可能であ
る。EXAMPLES The following sodium invention - Sodium positive <br/> electrode current collector and the present invention for sulfur battery - positive collector for sulfur battery
The NAS battery using the body will be described in more detail with reference to examples. However, the present invention is not limited to these examples. The unit weight is the mass (g / m 2 ) per unit area of a sheet material (felt material, cloth, cotton, etc.), and the total mass of the sheet material is the area. It is possible to calculate by dividing by.
【００４３】 本実施例においては、以下の方法により
ナトリウム−硫黄電池用集電体を製造した。基材として
は、直径数μｍ〜１０数μｍの炭素繊維からなり、幅５
０ｃｍ、長さ３００ｃｍ、厚さ１５ｍｍ、目付量１７０
０ｇ／ｍ2のフェルト材を使用した。基材の厚さは、厚
板直径３０ｍｍ、負荷加重２００ｇのダイヤル式シック
ネスゲージを用い、基材の幅方向、長手方向の数点につ
いて測定した厚さの平均値を使用した。In this embodiment, the following method is used.
A current collector for a sodium-sulfur battery was manufactured. The base material is made of carbon fibers having a diameter of several μm to several dozen μm and has a width of 5 μm.
0 cm, length 300 cm, thickness 15 mm, basis weight 170
A felt material of 0 g / m 2 was used. As the thickness of the base material, an average value of thicknesses measured at several points in the width direction and the longitudinal direction of the base material was used by using a dial type thickness gauge having a thick plate diameter of 30 mm and a load weight of 200 g.
【００４４】 高抵抗層の材料としては、直径１０μｍ
のガラス繊維からなる不織布を、基材と同一の幅及び長
さに切断したものを使用した。ガラス繊維は、クロスレ
ヤー機を用いて、一旦機械的に解繊し、繊維方向を揃え
た薄い網状体を作製し、当該網状体を繊維方向が交差す
るように積層する方法により目付量２５０ｇ／ｍ2の不
織布とした。The material of the high resistance layer has a diameter of 10 μm.
The non-woven fabric made of the glass fiber was cut into the same width and length as the substrate. The glass fiber is once mechanically disintegrated using a cross layer machine to prepare a thin mesh body in which the fiber directions are aligned, and the basis weight is 250 g / m 2 by laminating the mesh body so that the fiber directions intersect. 2 non-woven fabric.
【００４５】 高抵抗層の形成は、ニードルパンチ機を
使用し、前記の不織布を基材に積重し、不織布側からニ
ードルパンチすることにより行った。ニードルパンチ条
件については、金属針のフック部分の打ち込み深さを除
き、全て同一の条件で行った。即ち、針ボードの金属針
形状、金属針密度、金属針のフック位置、金属針のフッ
ク部分の打込み数（単位面積当たりの針打込み密度）等
のニードルパンチ条件については同一の条件とした。な
お、打ち込み深さは、基材厚みに対する比率（％）で表
記した。The high resistance layer was formed by using a needle punching machine, stacking the above-mentioned non-woven fabric on a substrate, and performing needle punching from the non-woven fabric side. The needle punching conditions were the same except for the driving depth of the hook portion of the metal needle. That is, the metal needle-shaped needle boards, metal needle density, the hook position of the metal needle, the metal needle fluoride
The needle punching conditions such as the number of hammered portions (needle hammering density per unit area) were the same. In addition, the driving depth was expressed as a ratio (%) to the thickness of the base material.
【００４６】[0046]
【００４７】[0047]
【００４８】[0048]
【００４９】[0049]
【００５０】[0050]
【００５１】[0051]
【００５２】[0052]
【００５３】[0053]
【００５４】[0054]
【００５５】[0055]
【００５６】[0056]
【００５７】[0057]
【００５８】（実施例１〜１０）
実施例１〜１０では、ガラス繊維表面に付着するバイン
ダー量及びその脱脂条件を制御した場合の効果について
評価した。バインダー量は、ガラス原料を高温で溶融し
て繊維状に引き抜いてガラス繊維とする際に噴霧するバ
インダー希釈溶液の噴霧量によって制御し、当該ガラス
繊維をクロスレヤー機にかけてバインダー量の異なる不
織布を得た。実施例１〜１０においては、ガラス繊維の
長さは全て６０ｍｍ（基材厚みの４倍）とした。(Examples 1 to 10 ) In Examples 1 to 10 , the effect of controlling the amount of binder adhering to the glass fiber surface and the degreasing conditions thereof was evaluated. The binder amount is controlled by the spray amount of the binder diluting solution that is sprayed when the glass raw material is melted at a high temperature and drawn into a fibrous form to form glass fibers, and the glass fibers are subjected to a cross layer machine to obtain nonwoven fabrics having different binder amounts. . In Examples 1 to 10 , all the glass fibers had a length of 60 mm (4 times the substrate thickness).
【００５９】 バインダー溶液としては、コーンスター
チの１５質量％水溶液を使用した。バインダー量０質量
％の不織布（比較例１）は、不織布を作製した後に空気
雰囲気下（酸素約２１質量％）で１０００℃、２時間の
熱処理を実施することによりバインダーを完全に除去し
たものである。As the binder solution, a 15 mass% aqueous solution of corn starch was used. The non-woven fabric with a binder amount of 0% by mass ( Comparative Example 1 ) was obtained by completely removing the binder by subjecting the non-woven fabric to heat treatment at 1000 ° C. for 2 hours in an air atmosphere (oxygen: about 21% by mass). is there.
【００６０】 評価は、実施例の各脱脂条件における残
留バインダー量、集電体の表面被覆率、抵抗比率を基準
として行った。表面被覆率、残留バインダー量、抵抗比
率については下記の方法により測定した。表面被覆
率：まず、ニードルパンチで基材にガラス繊維を打ち込
んだ集電体（試料Ａ）と、これと同一のパンチ条件でニ
ードルパンチのみ行った基材（試料Ｂ）を縦３５０ｍｍ
×横１００ｍｍの大きさに切り出した。 次いで、各試料
を表裏両面から縦４００ｍｍ×横２００ｍｍの平板状電
極で厚さ１３ｍｍまで圧縮した状態で４端子法により抵
抗値を測定し、試料Ａの抵抗値Ｒaと試料Ｂの抵抗値Ｒb
から、下記式（１）により表面被覆率を計算した。
表面被覆率［％］＝１００×（１−Ｒb／Ｒa） …（１） The evaluation was carried out on the basis of the residual binder amount, the surface coverage of the current collector, and the resistance ratio under each degreasing condition in the examples. Front surface coverage, residual amount of binder, the resistance ratio
It was measured by the following method for rate. Surface coating
Rate: First, glass fiber is driven into the base material by needle punching
Current collector (Sample A) and the same punching conditions
350 mm in length for the base material (Sample B) that was only punched
It was cut into a size of 100 mm in width. Then each sample
From the front and back sides, a plate-shaped electrode measuring 400 mm in length and 200 mm in width
With the poles compressed to a thickness of 13 mm, the
The resistance value was measured and the resistance value Ra of sample A and the resistance value Rb of sample B were measured.
From the above, the surface coverage was calculated by the following formula (1). Surface coverage [%] = 100 × (1−Rb / Ra) (1)
【００６１】 残留バインダー量ガラス繊維表面に付着
するバインダー量は、バインダーが付着した状態の不織
布の質量Ｗaと、当該不織布を空気雰囲気下において１
０００℃、２時間の熱処理を行って脱脂した後の質量Ｗ
bから、下記式（２）により計算した値を使用した。
バインダー量［質量％］＝１００×（１−Ｗb／Ｗa） …（２）[0061] Residual binder amount Attached to the glass fiber surface
The amount of binder used is the amount of non-woven fabric with the binder attached.
The mass of the fabric Wa and the non-woven fabric in an air atmosphere 1
Mass W after degreasing by heat treatment at 000 ° C for 2 hours
From b, the following formula (Two) Was used.
Binder amount [mass%] = 100 × (1-Wb / Wa) (Two)
【００６２】 残留バインダー量については、バインダ
ーが付着した状態の不織布の質量Ｗaと、当該不織布を
各実施例の脱脂条件において空気雰囲気下で熱処理を行
った後の質量Ｗcから、下記式（３）により計算した値
を使用した。
残留バインダー量［質量％］＝１００×（１−Ｗc／Ｗa） …（３）Regarding the residual binder amount, the following formula ( 3 ) is used from the mass Wa of the nonwoven fabric with the binder attached and the mass Wc of the nonwoven fabric after heat treatment under an air atmosphere under the degreasing conditions of each example. The value calculated by was used. Residual binder amount [mass%] = 100 × (1−Wc / Wa) ( 3 )
【００６３】 抵抗比率上述
の表面被覆率の測定に準じ、バインダー脱脂と同一
の条件で熱処理した後に試料Ａの抵抗値Ｒcを測定し、
試料Ａの抵抗値Ｒaと熱処理後の抵抗値Ｒcから、下記式
（４）により抵抗比率を計算した。
抵抗比率［％］＝１００×Ｒc／Ｒa …（４）[0063] Resistance ratioAbove
Same as binder degreasing according to the measurement of the surface coverage of
After the heat treatment under the conditions of, the resistance value Rc of the sample A is measured,
Resistance value Ra of sample A and resistance value R after heat treatmentcFrom the following formula
(Four) Was used to calculate the resistance ratio.
Resistance ratio [%] = 100 × Rc / Ra ... (Four)
【００６４】[0064]
【表１】 [Table 1]
【００６５】（結果）
表１に示すように、バインダー量、脱脂条件が本発明の
範囲内である場合（実施例１〜１０）は全て残留バイン
ダー量が０質量％と、完全にバインダーを除去できた。
また、バインダー量、脱脂条件が本発明の範囲内の不織
布をニードルパンチして高抵抗層を形成した集電体（実
施例１〜１０）は全て抵抗比率が１００％、即ち脱脂の
際の熱処理により基材の酸化や基材への煤の付着に伴う
抵抗の上昇は認められなかった。(Results) As shown in Table 1 , when the binder amount and the degreasing conditions were within the range of the present invention (Examples 1 to 10), the residual binder amount was 0% by mass and the binder was completely removed. did it.
Further, a non-woven fabric having a binder amount and degreasing conditions within the scope of the present invention is needle-punched to form a high-resistance layer (current collector).
In all of Examples 1 to 10), the resistance ratio was 100%, that is, no increase in resistance was observed due to oxidation of the base material or soot adhesion to the base material due to the heat treatment during degreasing.
【００６６】 一方、ガラス表面に付着するバインダー
量が０．５質量％未満の不織布を使用した場合（比較例
１〜４）、ニードルパンチの際にガラス繊維が破損して
しまい、基材とガラス繊維とが一体化できないため、表
面被覆率が２０％以上に上昇しなかった。On the other hand, when a non-woven fabric having a binder amount attached to the glass surface of less than 0.5% by mass is used ( Comparative Example
1-4 ), the glass fiber was broken during needle punching, and the base material and the glass fiber could not be integrated, so that the surface coverage was not increased to 20% or more.
【００６７】 また、バインダー量が本発明の範囲内で
も脱脂温度が３００℃未満の場合（比較例５，７）には
バインダーが残留した。また、バインダー量に拘わら
ず、脱脂温度が６００℃を超えると基材の酸化や基材へ
の煤の付着により抵抗が上昇した（比較例６，８，
９）。更に、バインダー量が本発明の範囲より高い場合
には、本発明の脱脂条件においてはバインダーを完全に
除去できなかった（比較例１０〜１４）。（実施例１１〜１９） 実施例１１〜１９では、高抵抗層を構成するガラス繊維
の繊維長さを制御した場合の効果について評価した。繊
維長さは、一旦機械的に解繊し所定長さに切断すること
により制御し、当該ガラス繊維をクロスレヤー機にかけ
て繊維長さの異なる不織布を得た。 評価は、集電体の表
面被覆率、内部到達率、破断荷重、当該集電体を組み込
んだＮＡＳ電池の内部抵抗及び充電回復率を基準として
行った。 以下、これらの測定方法を示す。表面被覆
率：実施例１〜１０の場合と同様にした。内部到達
率：まず、ニードルパンチで基材にガラス繊維を打ち込
んだ集電体を縦３５０ｍｍ×横１００ｍｍの大きさに切
り出し、試料を作製した。当該試料を有酸素雰囲気下、
１０００℃、２時間の条件で熱処理することにより基材
部分を焼失させ、残留したガラス繊維の長さの実測値Ｌ
rと熱処理前の基材厚みＬiから、下記式（５）により内
部到達率を計算した。 内部到達率［％］＝１００×Ｌr／Ｌi
…（５） ＮＡＳ電池の内部抵抗及び充電回復率については、図１
に示す構造のＮＡＳ電池１に各実施例の集電体を組み込
み、以下の方法で測定した。 正極容器９は外径９２ｍｍ
のものを、固体電解質管１３は全長４５０ｍｍ、外径６
０ｍｍ、肉厚２．５ｍｍのものを、集電体１１は厚さ１
４ｍｍ、長さ３５０ｍｍのものを使用した。内部抵
抗：電池の正極及び負極に電流、電圧端子を付けた後、
３２０℃の高温槽に入れ、定格電流による充放電を実施
した。放電、充電の各状態において充放電途中の電池電
圧と通電電流から抵抗値を換算し、放電全域、充電全域
にわたる 平均抵抗を計算し、平均放電抵抗と平均充電抵
抗を求めた。これらの平均放電抵抗、平均充電抵抗の相
加平均から平均抵抗値を算出した。 平均抵抗値が３．５
ｍΩ未満の場合は◎として評価した。充電回復率：電
池の充電時の終了条件を一定電圧とした場合の未充電容
量Ｃr（Ａｈ）と電池の設計容量Ｃf（Ａｈ）とから、下
記式（６）により充電回復率を計算した。電池の定格充
電電流での値を充電回復率１、定格の１／４の充電電流
での値を充電回復率２とし、充電回復率１が８９％以上
で、かつ、充電回復率２が９５％以上の場合は◎として
評価した。
充電回復率［％］＝１００×（１−Ｃr／Ｃf） …（６） Even when the binder amount was within the range of the present invention, the binder remained when the degreasing temperature was lower than 300 ° C. ( Comparative Examples 5 and 7 ). Further, regardless of the amount of binder, when the degreasing temperature exceeded 600 ° C., the resistance increased due to the oxidation of the base material and the attachment of soot to the base material (Comparative Examples 6, 8,
9) . Furthermore, when the amount of the binder was higher than the range of the present invention, the binder could not be completely removed under the degreasing conditions of the present invention ( Comparative Examples 10 to 14 ). (Examples 11 to 19) In Examples 11 to 19, glass fibers forming the high resistance layer were used.
The effect of controlling the fiber length was evaluated. Fiber
Weaving length is to mechanically disintegrate and cut into a predetermined length.
Control the glass fiber by the cross layer machine.
To obtain non-woven fabrics having different fiber lengths. Evaluation is the current collector table
Surface coverage, internal reach, breaking load, incorporating the current collector
Based on the internal resistance and charge recovery rate of the NAS battery
went. Hereinafter, these measuring methods will be described. Surface coating
Ratio: The same as in Examples 1 to 10. Internal reach
Rate: First, glass fiber is driven into the base material by needle punching
Cut the current collector into a size of length 350mm x width 100mm
A sample was prepared by projecting. The sample in an aerobic atmosphere,
Base material by heat treatment at 1000 ° C. for 2 hours
Measured value L of the length of the glass fiber remaining after burning away the part
From r and substrate thickness Li before heat treatment,
The part arrival rate was calculated. Internal arrival rate [%] = 100 × Lr / Li (5) The internal resistance and charge recovery rate of the NAS battery are shown in FIG.
The NAS battery 1 having the structure shown in FIG.
And measured by the following method. Positive electrode container 9 has an outer diameter of 92 mm
The solid electrolyte tube 13 has a total length of 450 mm and an outer diameter of 6
Current collector 11 with a thickness of 0 mm and a thickness of 2.5 mm has a thickness of 1
The one having a length of 4 mm and a length of 350 mm was used. Internal resistance
Anti: After attaching current and voltage terminals to the positive and negative electrodes of the battery,
Put it in a high temperature tank at 320 ℃ and charge and discharge it at the rated current.
did. The battery charge during charging / discharging is different in each state of discharging and charging.
Converts the resistance value from the pressure and the energizing current, and discharges the entire area and charges the entire area.
Calculate the average resistance over the average discharge resistance and average charge resistance.
I asked for resistance. Phase of these average discharge resistance, average charge resistance
The average resistance value was calculated from the arithmetic mean. Average resistance value is 3.5
When it was less than mΩ, it was evaluated as ⊚. Charge recovery rate: electric
Uncharged capacity when the termination condition when charging the pond is constant voltage
From the amount Cr (Ah) and the design capacity Cf (Ah) of the battery,
The charge recovery rate was calculated by the equation (6). Battery charge
Charge recovery rate is 1 and charging current is 1/4 of rated current
The charge recovery rate 1 is 89% or more.
And when the charge recovery rate 2 is 95% or more, it is marked as ◎
evaluated. Charge recovery rate [%] = 100 × (1-Cr / Cf) (6)
【表２】 （結果） 表２に示すように、繊維長さが基材の厚みの２倍以上、
１５倍未満で、打ち込み深さが基材の厚み７０〜１００
％の集電体を組み込んだＮＡＳ電池は良好な内部抵抗を
示した。 [Table 2] (Result) As shown in Table 2, the fiber length is twice or more the thickness of the substrate,
If less than 15 times, the driving depth is 70 to 100 of the thickness of the base material.
NAS battery with a current collector of 10% has a good internal resistance.
Indicated.
【００６８】[0068]
【発明の効果】 以上説明した通り、本発明のナトリウ
ム−硫黄電池用正極集電体の製造方法は、表面被覆率や
内部到達率などの高抵抗層の構造を精密に制御すること
ができる。従って、本発明の製造方法は、内部抵抗が低
く、充電回復性に優れたＮＡＳ電池の提供に資すること
ができる。As described above, the sodium of the present invention is used.
In the method for producing a positive electrode current collector for a lithium-sulfur battery, it is possible to precisely control the structure of the high resistance layer such as surface coverage and internal reach. Therefore, the manufacturing method of the present invention can contribute to the provision of a NAS battery having low internal resistance and excellent charge recovery.
【図１】 ナトリウム−硫黄電池の一般的態様を示す概
略断面図である。FIG. 1 is a schematic cross-sectional view showing a general embodiment of a sodium-sulfur battery.
１…ＮＡＳ電池、２…ナトリウム、３…絶縁体リング、
４…硫黄、５…円筒状金具、７…陰極金具、９…正極容
器、１０…くびれ部、１１…正極集電体、１３…固体電
解質管。1 ... NAS battery, 2 ... Sodium, 3 ... Insulator ring,
4 ... Sulfur, 5 ... Cylindrical metal fitting, 7 ... Cathode metal fitting, 9 ... Positive electrode container, 10 ... Constriction part, 11 ... Positive electrode collector, 13 ... Solid electrolyte tube.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平８−130032（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/30 H01M 4/64 - 4/84 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-130032 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 10/30 H01M 4/64-4 / 84
Claims (3)
フェルト状の基材の一方の表面に、ガラス繊維からなる
布状体又は綿状体を積重し、前記布状体又は綿状体が積
重された前記基材に金属針のフック部分を打ち込むニー
ドルパンチによって前記布状体又は綿状体を前記基材に
打ち込むことにより高抵抗層を形成するナトリウム−硫
黄電池用正極集電体の製造方法であって、前記ニードルパンチの際に、前記布状体又は綿状体を構
成する前記ガラス繊維として、前記ガラス繊維の表面
に、バインダーを前記ガラス繊維の全質量に対し０．５
質量％以上、２．２質量％未満の割合で付着させたもの
を用い、前記ニードルパンチの後に、 空気中、３００℃
以上、６００℃以下の条件で前記バインダーを脱脂する
ことを特徴とするナトリウム−硫黄電池用正極集電体の
製造方法。1. A cloth-like body or cotton-like body made of glass fibers is stacked on one surface of a felt-like substrate made of carbon fiber or graphite fiber, and the cloth-like body or cotton-like body is piled up.
Knee for driving the hook portion of the metal needle on the overlapped base material
Sodium to form a high-resistance layer by implanting the cloth-like body or cotton-like material to said substrate by Dorupanchi - vulcanization
A method for manufacturing a positive electrode current collector for a yellow battery , wherein the cloth-like body or the cotton-like body is formed during the needle punching.
As the glass fiber to be formed, the surface of the glass fiber
In addition, the binder is 0.5 based on the total mass of the glass fiber.
Those attached at a ratio of at least mass% and less than 2.2 mass%
Using the above, after the needle punch, in air, 300 ℃
As described above, the method for producing a positive electrode current collector for a sodium-sulfur battery, which comprises degreasing the binder under the condition of 600 ° C. or lower.
又は綿状体を構成する前記ガラス繊維として、前記基材
の厚みに対し２倍以上、１５倍未満の繊維長さを有する
ものを用いる請求項１に記載のナトリウム−硫黄電池用
正極集電体の製造方法。2. The cloth-like body during the needle punching
Alternatively, as the glass fiber constituting the cotton-like body, the base material
Has a fiber length of 2 times or more and less than 15 times the thickness of
The method for producing a positive electrode current collector for a sodium-sulfur battery according to claim 1, wherein a positive electrode current collector is used.
のフック部分を前記基材の厚みの７０〜１００％の深さ
まで打ち込む請求項１又は２に記載のナトリウム−硫黄
電池用正極集電体の製造方法。To 3. During the needlepunching sodium according hook portion of the metal needle to claim 1 or 2 implanted up 70% to 100% of the depth of thickness of the base - sulfur
A method for manufacturing a positive electrode current collector for a battery .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000087939A JP3416609B2 (en) | 2000-03-28 | 2000-03-28 | Method for producing positive electrode current collector for sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000087939A JP3416609B2 (en) | 2000-03-28 | 2000-03-28 | Method for producing positive electrode current collector for sodium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001273923A JP2001273923A (en) | 2001-10-05 |
| JP3416609B2 true JP3416609B2 (en) | 2003-06-16 |
Family
ID=18603884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000087939A Expired - Lifetime JP3416609B2 (en) | 2000-03-28 | 2000-03-28 | Method for producing positive electrode current collector for sodium-sulfur battery |
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| Country | Link |
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| JP (1) | JP3416609B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101900821B1 (en) | 2012-12-27 | 2018-09-20 | 재단법인 포항산업과학연구원 | Method and device for manufacturing felt of sodium sulfur battery and felt thereof |
| KR101516225B1 (en) * | 2013-05-03 | 2015-05-04 | 주식회사 제낙스 | Non-woven collector, method of fabricating a battery with the same and system for fabricating the same |
-
2000
- 2000-03-28 JP JP2000087939A patent/JP3416609B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001273923A (en) | 2001-10-05 |
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