JP2020181810A - Composition for forming microbial fuel cell anode, anode, and microbial fuel cell - Google Patents
Composition for forming microbial fuel cell anode, anode, and microbial fuel cell Download PDFInfo
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- JP2020181810A JP2020181810A JP2020066947A JP2020066947A JP2020181810A JP 2020181810 A JP2020181810 A JP 2020181810A JP 2020066947 A JP2020066947 A JP 2020066947A JP 2020066947 A JP2020066947 A JP 2020066947A JP 2020181810 A JP2020181810 A JP 2020181810A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Inert Electrodes (AREA)
Abstract
Description
本発明は、微生物燃料電池アノード形成用組成物に関する。 The present invention relates to a composition for forming a microbial fuel cell anode.
近年、生体触媒の酵素を用いたバイオ燃料電池、微生物を用いた微生物燃料電池などの生物燃料電池の開発が進められている。微生物燃料電池は、発電菌と呼ばれる微生物により有機物を分解する際に生じる電子を回収し、電気エネルギーとして利用する発電方法である。例えば、生活廃水や産業廃水などの浄化に用いた場合、廃水中の有機物の分解処理と発電が並行して行えるため、消費エネルギーを低減できる水処理方法としても期待されている（非特許文献１）。また、微生物燃料電池は、水や底泥、土壌などに含まれる有機物で発電出来るため、廃水や土壌における電源としての利用も期待出来る。 In recent years, the development of biofuel cells such as biofuel cells using biocatalytic enzymes and microbial fuel cells using microorganisms has been promoted. Microbial fuel cells are a power generation method that collects electrons generated when organic matter is decomposed by microorganisms called power generation bacteria and uses them as electrical energy. For example, when it is used for purifying domestic wastewater or industrial wastewater, it is expected as a water treatment method that can reduce energy consumption because it can decompose organic matter in the wastewater and generate electricity in parallel (Non-Patent Document 1). ). In addition, since the microbial fuel cell can generate electricity from organic substances contained in water, bottom mud, soil, etc., it can be expected to be used as a power source in wastewater and soil.
このような微生物燃料電池の構成には、二槽型と一槽型が知られている（特許文献１、非特許文献２）。アノードでの微生物による分解反応から生じた電子が外部回路を経由し、カソードにて還元反応で消費される点は共通している。二槽型はイオン交換膜などの隔壁で両極を分け、酸素やフェリシアン化カリウムなどの酸化剤をカソードで反応させている。一方、一槽型は隔壁が無く、一つの槽内にカソードおよびアノードを配置する。 Two-tank type and one-tank type are known as configurations of such a microbial fuel cell (Patent Document 1 and Non-Patent Document 2). It is common that electrons generated from the decomposition reaction by microorganisms at the anode pass through an external circuit and are consumed in the reduction reaction at the cathode. In the two-tank type, both poles are separated by a partition wall such as an ion exchange membrane, and an oxidizing agent such as oxygen or potassium ferricyanide is reacted at the cathode. On the other hand, the one-tank type has no partition wall, and the cathode and anode are arranged in one tank.
微生物燃料電池に用いられるカソードおよびアノードの材料においては電極反応において導電性が必要であり、導電性の多孔質材料を使用するのが一般的である（特許文献１〜３）。カソードでは電極上で酸素を還元する必要があるため、カーボンペーパー、カーボンフェルト、カーボンクロス、または活性炭シートなどのカーボン材料や、アルミニウム、銅、ステンレス、ニッケル、またはチタンなどの金属材料が使われる。さらに、それら材料に白金などの酸素還元触媒を担持させて使用することも知られている。一方、アノードでは有機物を分解して電子を取り出す発電菌を多くコンタクトさせるために、カーボンペーパー、カーボンフェルト、カーボンクロス、または活性炭シートなどのカーボン材料や、アルミニウム、銅、ステンレス、ニッケル、またはチタンなどの金属材料が使われることが知られている（特許文献２、３）。それらの電極反応の効率はいまだ不十分であり、発電特性の向上が課題となっている。 In the materials of the cathode and the anode used in the microbial fuel cell, conductivity is required in the electrode reaction, and it is common to use a conductive porous material (Patent Documents 1 to 3). Since the cathode needs to reduce oxygen on the electrodes, carbon materials such as carbon paper, carbon felt, carbon cloth, or activated carbon sheets and metal materials such as aluminum, copper, stainless steel, nickel, or titanium are used. Further, it is also known that these materials are used by supporting an oxygen reduction catalyst such as platinum. On the other hand, at the anode, carbon materials such as carbon paper, carbon felt, carbon cloth, or activated carbon sheet, aluminum, copper, stainless steel, nickel, or titanium, etc., are used to contact many power-generating bacteria that decompose organic substances and extract electrons. It is known that the metal material of (Patent Documents 2 and 3) is used. The efficiency of these electrode reactions is still insufficient, and improvement of power generation characteristics has become an issue.
これらの課題解決のために、アノード反応効率を改善する必要があり、微生物の担持量や活性を高めることが望ましい。また、微生物反応を妨げることのない電極部材、特に樹脂を選択する必要があり、かつ樹脂総量は少ない方が望ましい。例えば、特許文献４では、導電性カーボン材料と樹脂とを含む導電部で非導電性基材を被覆する積層体が開示されている。しかしながら、さらなる発電効率の向上は課題として残っており、さらには安定した発電効率を維持出来る耐久性まで両立出来るような技術が求められている。 In order to solve these problems, it is necessary to improve the anodic reaction efficiency, and it is desirable to increase the amount and activity of microorganisms carried. Further, it is necessary to select an electrode member that does not interfere with the microbial reaction, particularly a resin, and it is desirable that the total amount of the resin is small. For example, Patent Document 4 discloses a laminate in which a non-conductive base material is coated with a conductive portion containing a conductive carbon material and a resin. However, further improvement of power generation efficiency remains an issue, and there is a demand for a technology that can achieve both durability that can maintain stable power generation efficiency.
本発明の目的は、発電量に優れたアノード用組成物、電極を提供し、発電特性や耐久性に優れる電池を提供することである。 An object of the present invention is to provide an anode composition and electrodes having excellent power generation amount, and to provide a battery having excellent power generation characteristics and durability.
本発明者らは、前記の諸問題を解決するために鋭意研究を重ねた結果、本発明に至った。 The present inventors have arrived at the present invention as a result of repeated diligent studies to solve the above-mentioned problems.
即ち本発明は、導電材と、水溶性樹脂とを含有する微生物燃料電池アノード形成用組成物に関する。 That is, the present invention relates to a composition for forming a microbial fuel cell anode containing a conductive material and a water-soluble resin.
また、本発明は、さらに、水性樹脂微粒子を含有する前記の微生物燃料電池アノード形成用組成物に関する。 The present invention further relates to the above-mentioned composition for forming a microbial fuel cell anode, which contains aqueous resin fine particles.
また、本発明は、水性液状媒体を含有する前記の微生物燃料電池アノード形成用組成物に関する。 The present invention also relates to the above-mentioned composition for forming a microbial fuel cell anode, which contains an aqueous liquid medium.
また、本発明は、前記導電材の含有量が、アノード形成用組成物の全固形分の合計１００質量％に対して８０〜９９質量％であることを特徴とする前記の微生物燃料電池アノード形成用組成物に関する。 Further, the present invention is characterized in that the content of the conductive material is 80 to 99% by mass with respect to the total 100% by mass of the total solid content of the composition for forming the anode. Regarding the composition for use.
また、本発明は、前記導電材がカーボン材料を含み、前記カーボン材料が、グラファイト（Ａ−ａ）とグラファイト以外のカーボン材料（Ａ−ｂ）とを含むことを特徴とする前記の微生物燃料電池アノード形成用組成物に関する。 Further, the present invention is characterized in that the conductive material contains a carbon material, and the carbon material contains graphite (Aa) and a carbon material other than graphite (Ab). Regarding the composition for forming an anode.
また、本発明は、前記の微生物燃料電池アノード形成用組成物を用いることを特徴とする微生物燃料電池用アノードに関する。 The present invention also relates to an anode for a microbial fuel cell, which comprises using the above-mentioned composition for forming an anode of a microbial fuel cell.
また、本発明は、前記の微生物燃料電池用アノードを用いることを特徴とする微生物燃料電池に関する。 The present invention also relates to a microbial fuel cell, which comprises using the above-mentioned anode for a microbial fuel cell.
本発明によれば、発電量に優れたアノード用組成物、電極を提供し、発電特性や耐久性に優れる微生物電池を提供することができる。 According to the present invention, it is possible to provide an anode composition and an electrode having an excellent power generation amount, and to provide a microbial battery having excellent power generation characteristics and durability.
以下、詳細にわたって本発明の実施形態を説明する。なお、本発明において、（メタ）アクリル酸とはアクリル酸および／またはメタクリル酸を意味し、（メタ）アクリレートとはアクリレートおよび／またはメタクリレートを意味し、（メタ）アクリルアミドとはアクリルアミドおよび／またはメタクリルアミドを意味し、（メタ）アクリロイル基とはアクリロイル基および／またはメタクリロイル基を意味し、（メタ）アクリル系エマルションとはアクリル系エマルションおよび／またはメタクリル系エマルションを意味し、（メタ）アクリル系乳化重合物とはアクリル系乳化重合物および／またはメタクリル系乳化重合物を意味する。 Hereinafter, embodiments of the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and / or methacrylic acid, (meth) acrylate means acrylate and / or methacrylate, and (meth) acrylamide means acrylamide and / or methacrylic acid. Meaning amide, (meth) acryloyl group means acryloyl group and / or methacryloyl group, (meth) acrylic emulsion means acrylic emulsion and / or methacrylic emulsion, and (meth) acrylic emulsification. The polymer means an acrylic emulsified polymer and / or a methacrylic emulsified polymer.
＜微生物燃料電池アノード形成用組成物＞
本発明の微生物燃料電池アノード形成用組成物（以下、アノード形成用組成物）は、少なくとも導電材と、水溶性樹脂とを含有するものである。本発明によれば、水溶性樹脂が導電材と共に含まれた微生物燃料電池アノード形成用組成物は、塗膜形成された後、水溶性樹脂の微生物との高い親和性により、アノードへの微生物の付着や育成が促進されるため、多くの微生物を担持できる。また、微生物と導電材や基材との結着が強化される。さらに、例えば水中に浸漬した場合に、水溶性樹脂の水との高い親和性による電極の電解液に対する濡れ性の向上とともに、水溶性樹脂の膨潤、あるいは水溶性樹脂の溶出による流路の形成により、微生物燃料電池の発電に必要なプロトンの拡散に優れた電極を提供できる。これらの効果により、本発明によれば、微生物燃料電池の発電特性に加えて耐久性をも向上することができる。
<Composition for forming microbial fuel cell anode>
The composition for forming an anode of a microbial fuel cell of the present invention (hereinafter referred to as a composition for forming an anode) contains at least a conductive material and a water-soluble resin. According to the present invention, a composition for forming a microbial fuel cell anode containing a water-soluble resin together with a conductive material has a high affinity of the water-soluble resin with microorganisms after the coating film is formed. Since adhesion and growth are promoted, many microorganisms can be carried. In addition, the binding between the microorganism and the conductive material or the base material is strengthened. Further, for example, when immersed in water, the wettability of the electrode to the electrolytic solution is improved due to the high affinity of the water-soluble resin with water, and the swelling of the water-soluble resin or the formation of a flow path due to the elution of the water-soluble resin. , It is possible to provide an electrode having excellent diffusion of protons required for power generation of a microbial fuel cell. Due to these effects, according to the present invention, not only the power generation characteristics of the microbial fuel cell but also the durability can be improved.
＜導電材＞
導電材について説明する。導電材は電極での電子伝導性を高め酸化還元反応を進めやすくするために含有される。本発明の導電材としては、カーボン材料や金属材料等が挙げられるが、これに限るものではない。また、２種類以上を併せて使用することもできる。
<Conductive material>
The conductive material will be described. The conductive material is contained to enhance the electron conductivity at the electrode and facilitate the redox reaction. Examples of the conductive material of the present invention include, but are not limited to, carbon materials and metal materials. Further, two or more types can be used together.
カーボン材料としては、導電性を有するカーボン材料であれば特に限定されるものではないが、グラファイト、カーボンブラック、活性炭、導電性炭素繊維（カーボンナノチューブ、カーボンナノファイバー、カーボンファイバー）、グラフェン、フラーレン等を単独で、もしくは２種類以上併せて使用することができる。また、カーボン材料には、ヘテロ元素や卑金属元素がドープされていてもよい。 The carbon material is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, activated carbon, conductive carbon fibers (carbon nanotubes, carbon nanofibers, carbon fibers), graphene, fullerene, etc. Can be used alone or in combination of two or more. Further, the carbon material may be doped with a hetero element or a base metal element.
カーボン材料としては、グラファイト（Ａ−ａ）とグラファイト以外の炭素材料（Ａ−ｂ）とを併用することが好ましい。グラファイト以外の炭素材料（Ａ−ｂ）は、単独で、もしくは２種類以上併せて使用することが出来る。グラファイト（Ａ−ａ）とグラファイト以外の炭素材料（Ａ−ｂ）とを併用することにより、電極内部の電子パスが密になり、好適な表面形態により物質拡散性も高まるため、高い発電特性が得られる。 As the carbon material, it is preferable to use graphite (Aa) and a carbon material other than graphite (Ab) in combination. The carbon material (Ab) other than graphite can be used alone or in combination of two or more. By using graphite (Aa) and a carbon material (Ab) other than graphite in combination, the electron paths inside the electrodes become dense, and the material diffusivity is enhanced by the suitable surface morphology, resulting in high power generation characteristics. can get.
カーボン材料に含まれるグラファイト（Ａ−ａ）の含有率［（Ａ−ａ）／｛（Ａ−ａ）＋（Ａ−ｂ）｝×１００］は、好ましくは５〜９９質量％であり、より好ましくは１０〜９０質量％、さらに好ましくは１５〜８５％である。 The content of graphite (A-a) contained in the carbon material [(A-a) / {(A-a) + (A-b)} x 100] is preferably 5 to 99% by mass, and more. It is preferably 10 to 90% by mass, more preferably 15 to 85%.
グラファイトとしては、例えば人造黒鉛や天然黒鉛等を使用することが出来る。人造黒鉛としては、無定形炭素の熱処理により、不規則な配列の微小黒鉛結晶の配向を人工的に行わせたものであり、一般的には石油コークスや石炭系ピッチコークスを主原料として製造される。天然黒鉛としては、鱗片状黒鉛、塊状黒鉛、土状黒鉛等を使用することが出来る。また、鱗片状黒鉛を化学処理等した膨張黒鉛（膨張性黒鉛ともいう）や、膨張黒鉛を熱処理して膨張化させた後、微細化やプレスにより得られた膨張化黒鉛等を使用することも出来る。 As the graphite, for example, artificial graphite, natural graphite, or the like can be used. Artificial graphite is made by artificially orienting irregularly arranged micrographite crystals by heat treatment of amorphous carbon, and is generally manufactured using petroleum coke or coal-based pitch coke as the main raw material. To. As the natural graphite, scaly graphite, lump graphite, earth graphite and the like can be used. It is also possible to use expanded graphite (also referred to as expansive graphite) obtained by chemically treating scaly graphite, or expanded graphite obtained by heat-treating expanded graphite to expand it and then refining it or pressing it. You can.
これら黒鉛の表面は、本発明の特性を損なわない限りにおいてバインダー樹脂との親和性を増すために、表面処理、例えばエポキシ処理、ウレタン処理、シランカップリング処理、および酸化処理等が施されていてもよい。
これらの黒鉛の中でも、導電性の観点から、天然黒鉛が好ましく、球状黒
鉛、鱗状黒鉛、および膨張化黒鉛等の薄片状黒鉛が好ましい。
The surface of these graphites is subjected to surface treatments such as epoxy treatment, urethane treatment, silane coupling treatment, oxidation treatment and the like in order to increase the affinity with the binder resin as long as the characteristics of the present invention are not impaired. May be good.
Among these graphites, natural graphite is preferable from the viewpoint of conductivity, and flaky graphite such as spheroidal graphite, scaly graphite, and expanded graphite is preferable.
また、用いるグラファイトの平均粒径は、０．５〜５００μｍが好ましく、特に、２〜１００μｍが好ましい。 The average particle size of the graphite used is preferably 0.5 to 500 μm, and particularly preferably 2 to 100 μm.
本発明でいう平均粒径とは、体積粒度分布において、粒子径の細かいものからその粒子の体積割合を積算していったときに、５０％となるところの粒子径（Ｄ５０）であり、一般的な粒度分布計、例えば、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）等で測定される。 The average particle size referred to in the present invention is a particle size (D50) that becomes 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution. It is measured with a standard particle size distribution meter, for example, a dynamic light scattering type particle size distribution meter (“Microtrack UPA” manufactured by Nikkiso Co., Ltd.).
市販のグラファイトとしては、例えば、薄片状黒鉛として、日本黒鉛工業社製のＣＭＸ、ＵＰ−５、ＵＰ−１０、ＵＰ−２０、ＵＰ−３５Ｎ、ＣＳＳＰ、ＣＳＰＥ、ＣＳＰ、ＣＰ、ＣＢ−１５０、ＣＢ−１００、ＡＣＰ、ＡＣＰ−１０００、ＡＣＢ−５０、ＡＣＢ−１００、ＡＣＢ−１５０、ＳＰ−１０、ＳＰ−２０、Ｊ−ＳＰ、ＳＰ−２７０、ＨＯＰ、ＧＲ−６０、ＬＥＰ、Ｆ＃１、Ｆ＃２、Ｆ＃３、中越黒鉛社製のＣＸ−３０００、ＦＢＦ、ＢＦ、ＣＢＲ、ＳＳＣ−３０００、ＳＳＣ−６００、ＳＳＣ−３、ＳＳＣ、ＣＸ−６００、ＣＰＦ−８、ＣＰＦ−３、ＣＰＢ−６Ｓ、ＣＰＢ、９６Ｅ、９６Ｌ、９６Ｌ−３、９０Ｌ−３、ＣＰＣ、Ｓ−８７、Ｋ−３、ＣＦ−８０、ＣＦ−４８、ＣＦ−３２、ＣＰ−１５０、ＣＰ−１００、ＣＰ、ＨＦ−８０、ＨＦ−４８、ＨＦ−３２、ＳＣ−１２０、ＳＣ−８０、ＳＣ−６０、ＳＣ−３２、伊藤黒鉛工業社製のＥＣ１５００、ＥＣ１０００、ＥＣ５００、ＥＣ３００、ＥＣ１００、ＥＣ５０、西村黒鉛社製の１００９９Ｍ、ＰＢ−９９等が挙げられる。球状天然黒鉛としては、日本黒鉛工業社製のＣＧＣ−２０、ＣＧＣ−５０、ＣＧＢ−２０、ＣＧＢ−５０が挙げられる。土状黒鉛としては、日本黒鉛工業社製の青Ｐ、ＡＰ、ＡＯＰ、Ｐ＃１、中越黒鉛社製のＡＰＲ、Ｓ−３、ＡＰ−６、３００Ｆが挙げられる。人造黒鉛としては、日本黒鉛工業社製のＰＡＧ−６０、ＰＡＧ−８０、ＰＡＧ−１２０、ＰＡＧ−５、ＨＡＧ−１０Ｗ、ＨＡＧ−１５０、中越黒鉛社製のＲＡ−３０００、ＲＡ−１５、ＲＡ−４４、ＧＸ−６００、Ｇ−６Ｓ、Ｇ−３、Ｇ−１５０、Ｇ−１００、Ｇ−４８、Ｇ−３０、Ｇ−５０、ＳＥＣカーボン社製のＳＧＰ−１００、ＳＧＰ−５０、ＳＧＰ−２５、ＳＧＰ−１５、ＳＧＰ−５、ＳＧＰ−１、ＳＧＯ−１００、ＳＧＯ−５０、ＳＧＯ−２５、ＳＧＯ−１５、ＳＧＯ−５、ＳＧＯ−１、ＳＧＸ−１００、ＳＧＸ−５０、ＳＧＸ−２５、ＳＧＸ−１５、ＳＧＸ−５、ＳＧＸ−１が挙げられる。 As commercially available graphite, for example, as flaky graphite, CMX, UP-5, UP-10, UP-20, UP-35N, CSSP, CSPE, CSP, CP, CB-150, CB manufactured by Nippon Graphite Industry Co., Ltd. -100, ACP, ACP-1000, ACB-50, ACB-100, ACB-150, SP-10, SP-20, J-SP, SP-270, HOP, GR-60, LEP, F # 1, F # 2, F # 3, CX-3000, FBF, BF, CBR, SSC-3000, SSC-600, SSC-3, SSC, CX-600, CPF-8, CPF-3, CPB- manufactured by Chuetsu Graphite Co., Ltd. 6S, CPB, 96E, 96L, 96L-3, 90L-3, CPC, S-87, K-3, CF-80, CF-48, CF-32, CP-150, CP-100, CP, HF- 80, HF-48, HF-32, SC-120, SC-80, SC-60, SC-32, EC1500, EC1000, EC500, EC300, EC100, EC50 manufactured by Ito Graphite Industry, 10099M manufactured by Nishimura Graphite Co., Ltd. , PB-99 and the like. Examples of spherical natural graphite include CGC-20, CGC-50, CGB-20, and CGB-50 manufactured by Nippon Graphite Industry Co., Ltd. Examples of earth-like graphite include blue P, AP, AOP, P # 1 manufactured by Nippon Graphite Industry Co., Ltd., and APR, S-3, AP-6, 300F manufactured by Chuetsu Graphite Co., Ltd. As artificial graphite, PAG-60, PAG-80, PAG-120, PAG-5, HAG-10W, HAG-150 manufactured by Nippon Graphite Industry Co., Ltd., RA-3000, RA-15, RA- of Chuetsu Graphite Co., Ltd. 44, GX-600, G-6S, G-3, G-150, G-100, G-48, G-30, G-50, SGP-100, SGP-50, SGP-25 manufactured by SEC Carbon Co., Ltd. , SGP-15, SGP-5, SGP-1, SGO-100, SGO-50, SGO-25, SGO-15, SGO-5, SGO-1, SGX-100, SGX-50, SGX-25, SGX -15, SGX-5, SGX-1 can be mentioned.
カーボンブラックとしては、気体もしくは液体の原料を反応炉中で連続的に熱分解し製造するファーネスブラック、特にエチレン重油を原料としたケッチェンブラック、原料ガスを燃焼させて、その炎をチャンネル鋼底面にあて急冷し析出させたチャンネルブラック、ガスを原料とし燃焼と熱分解を周期的に繰り返すことにより得られるサーマルブラック、特にアセチレンガスを原料とするアセチレンブラックなどの各種のものを単独で、もしくは２種類以上併せて使用することができる。また、通常行われている酸化処理されたカーボンブラックや、中空カーボン等も使用できる。 Carbon black includes furnace black, which is produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially acetylene black, which is made from ethylene heavy oil, and the raw material gas is burned to burn the flame to the bottom of the channel steel. Various types such as channel black that has been rapidly cooled and precipitated, thermal black that is obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and acetylene black that uses acetylene gas as a raw material, alone or 2 More than one type can be used together. In addition, normally oxidized carbon black, hollow carbon, and the like can also be used.
カーボンの酸化処理は、カーボンを空気中で高温処理したり、硝酸や二酸化窒素、オゾン等で二次的に処理したりすることより、例えばフェノール基、キノン基、カルボキシル基、カルボニル基の様な酸素含有極性官能基をカーボン表面に直接導入（共有結合）する処理であり、カーボンの分散性を向上させるために一般的に行われている。しかしながら、官能基の導入量が多くなる程カーボンの導電性が低下することが一般的であるため、酸化処理をしていないカーボンの使用が好ましい。 Oxidation treatment of carbon is performed by treating carbon at a high temperature in air or secondary treatment with nitrate, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group, etc. It is a process of directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since the conductivity of carbon generally decreases as the amount of functional groups introduced increases, it is preferable to use carbon that has not been oxidized.
用いるカーボンブラックの比表面積は、値が大きいほど、カーボンブラック粒子どうしの接触点が増えるため、電極の内部抵抗を下げるのに有利となるが、カーボンブラックの分散性が低くなるため、具体的には、比表面積で、１０ｍ２／ｇ以上、３０００ｍ２／ｇ以下、好ましくは２０ｍ２／ｇ以上、１５００ｍ２／ｇ以下のものを使用することが望ましい。なお、比表面積は、窒素ガスを吸着質としたＢＥＴ法（ＪＩＳ Ｚ ８８０３：２０１３）により測定できる。 As the specific surface area of the carbon black used increases, the contact points between the carbon black particles increase, which is advantageous for lowering the internal resistance of the electrode, but the dispersibility of the carbon black decreases. It is desirable to use a specific surface area of 10 m 2 / g or more and 3000 m 2 / g or less, preferably 20 m 2 / g or more and 1500 m 2 / g or less. The specific surface area can be measured by the BET method (JIS Z 8803: 2013) using nitrogen gas as an adsorbent.
また、用いるカーボンブラックの粒径は、一次粒子径で０．００５〜１μｍが好ましく、特に、０．０１〜０．２μｍが好ましい。ただし、ここでいう一次粒子径とは、電子顕微鏡などで測定された粒子径を平均したものである。 The particle size of the carbon black used is preferably 0.005 to 1 μm in primary particle size, and particularly preferably 0.01 to 0.2 μm. However, the primary particle size referred to here is an average of the particle size measured by an electron microscope or the like.
市販のカーボンブラックとしては、例えば、東海カーボン社製のトーカブラック＃４３００、＃４４００、＃４５００、＃５５００、デグサ社製のプリンテックスＬ、コロンビヤン社製のＲａｖｅｎ７０００、５７５０、５２５０、５０００ＵＬＴＲＡIII、５０００ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ＳＣ ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ９７５ ＵＬＴＲＡ、ＰＵＥＲ ＢＬＡＣＫ１００、１１５、２０５、三菱化学社製の＃２３５０、＃２４００Ｂ、＃２６００Ｂ、＃３０５０Ｂ、＃３０３０Ｂ、＃３２３０Ｂ、＃３３５０Ｂ、＃３４００Ｂ、＃５４００Ｂ、キャボット社製のＭＯＮＡＲＣＨ１４００、１３００、９００、ＶｕｌｃａｎＸＣ−７２Ｒ、ＢｌａｃｋＰｅａｒｌｓ２０００、ＴＩＭＣＡＬ社製のＥｎｓａｃｏ２５０Ｇ、Ｅｎｓａｃｏ２６０Ｇ、Ｅｎｓａｃｏ３５０Ｇ、ＳｕｐｅｒＰ−Ｌｉ等のファーネスブラック）、ライオン社製のＥＣ−３００Ｊ、ＥＣ−６００ＪＤ等のケッチェンブラック、デンカ社製のデンカブラック、デンカブラックＨＳ−１００、ＦＸ−３５等のアセチレンブラックが挙げられるが、これらに限定されるものではなく、２種以上を組み合わせて用いても良い。 Examples of commercially available carbon black include Tokai Carbon's Talker Black # 4300, # 4400, # 4500, # 5500, Degussa's Printex L, Colombian's Raven 7000, 5750, 5250, 5000 ULTRAIII, 5000 ULTRA, etc. Conductex SC ULTRA, Conductex 975 ULTRA, PUER BLACK100, 115, 205, Mitsubishi Chemical # 2350, # 2400B, # 2600B, # 3050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B, Cabot MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, Ensaco250G, Ensaco260G, Ensaco350G, SuperP-Li, etc. Furness Black manufactured by TIMCAL), EC-300J, EC-600JD, etc. Examples thereof include acetylene blacks such as Denka Black, Denka Black HS-100, and FX-35 manufactured by the same company, but the present invention is not limited to these, and two or more types may be used in combination.
活性炭としては、具体的にはフェノール系、ヤシガラ系、レーヨン系、アクリル系、石炭−石油系ピッチコークス、メソカーボンマイクロビーズ（ＭＣＭＢ）等を賦活した活性炭を挙げることができる。同じ質量でもより広い面積の界面を形成することが可能な、比表面積の大きいものが好ましい。具体的には、比表面積が３０ｍ2／ｇ以上が好ましく、より好ましくは５００〜５０００ｍ2／ｇ、さらに好ましくは１０００〜３０００ｍ2／ｇである。 Specific examples of the activated carbon include activated carbons activated by phenol-based, coconut husk-based, rayon-based, acrylic-based, coal-petroleum-based pitch coke, mesocarbon microbeads (MCMB) and the like. Those having a large specific surface area, which can form an interface having a wider area even with the same mass, are preferable. Specifically, the specific surface area is preferably 30 m 2 / g or more, more preferably 500 to 5000 m 2 / g, and further preferably 1000 to 3000 m 2 / g.
導電性炭素繊維としては石油由来の原料から焼成して得られるものが良いが、植物由来の原料からも焼成して得られるものも用いることが出来る。また、カーボンナノチューブには、グラフェンシートが一層でナノメートル領域の直径を有するチューブを形成する単層カーボンナノチューブと、グラフェンシートが多層である多層カーボンナノチューブがある。そのため、多層カーボンナノチューブの直径は、典型的な単層カーボンナノチューブの０．７−２．０ｎｍに対して、３０ｎｍと大きい値を示す。 As the conductive carbon fiber, those obtained by firing from a raw material derived from petroleum are preferable, but those obtained by firing from a raw material derived from a plant can also be used. Further, the carbon nanotubes include a single-walled carbon nanotube in which a graphene sheet forms a tube having a diameter in a nanometer region, and a multi-walled carbon nanotube in which the graphene sheet is a multi-walled layer. Therefore, the diameter of the multi-walled carbon nanotube shows a large value of 30 nm with respect to 0.7-2.0 nm of a typical single-walled carbon nanotube.
市販の導電性炭素繊維やカーボンナノチューブとしては、昭和電工社製のＶＧＣＦ等の気相法炭素繊維、名城ナノカーボン社製のＥＣ１．０，ＥＣ１．５，ＥＣ２．０，ＥＣ１．５−Ｐ等の単層カーボンナノチューブ、ＣＮａｎｏ社製のＦｌｏＴｕｂｅ９０００、ＦｌｏＴｕｂｅ９１００、ＦｌｏＴｕｂｅ９１１０、ＦｌｏＴｕｂｅ９２００、Ｎａｎｏｃｙｌ社製のＮＣ７０００、Ｋｎａｎｏ社製の１００Ｔ等が挙げられる。 Examples of commercially available conductive carbon fibers and carbon nanotubes include vapor-phase carbon fibers such as VGCF manufactured by Showa Denko, EC1.0, EC1.5, EC2.0, and EC1.5-P manufactured by Meijo Nanocarbon. Examples thereof include single-walled carbon nanotubes manufactured by CNano, FloTube9100, FloTube9100, FloTube9110, FloTube9200, NC7000 manufactured by Nanocyl, and 100T manufactured by Knano.
金属材料としては、導電性を有する金属材料であれば特に限定されるものではないが、アルミニウム、チタン、ニッケル、鉄、スズ、銅等の卑金属や、銀、金、白金等の貴金属、ステンレス、真鍮、ジュラルミン等の合金等を単独で、もしくは２種類以上併せて使用することができる。用いる金属材料は、粉末状であることが好ましい。用いる金属材料の粒径は、一次粒子径で０．００５μｍ〜１ｍｍが好ましく、特に、０．０１〜１００μｍが好ましい。 The metal material is not particularly limited as long as it is a conductive metal material, but base metals such as aluminum, titanium, nickel, iron, tin and copper, precious metals such as silver, gold and platinum, stainless steel, etc. Alloys such as brass and duralmin can be used alone or in combination of two or more. The metal material used is preferably in the form of powder. The particle size of the metal material used is preferably 0.005 μm to 1 mm in primary particle size, and particularly preferably 0.01 to 100 μm.
導電材であるカーボン材料や金属材料のアノード形成用組成物中の分散粒径は、０．０１μｍ以上、１０μｍ以下に微細化することが望ましい。 It is desirable that the dispersed particle size of the conductive carbon material or metal material in the anode forming composition be made finer to 0.01 μm or more and 10 μm or less.
導電材の平均比表面積は、５〜３００ｍ２／ｇが好ましく、２０〜１００ｍ２／ｇはさらに好ましい。ここで、導電材の平均比表面積とは、アノード形成用組成物中に含まれる導電材の比表面積の相加平均をいう。例として、導電材として２種の導電材Ｃ１及びＣ２を使用する場合を示す。導電材Ｃ１の比表面積がＡ１ ｍ２／ｇ、導電材Ｃ１の組成物中の添加量がＢ１ ｇ、導電材Ｃ２の比表面積がＡ２ ｍ２／ｇ、添加量がＢ２ ｇであった場合、導電材の平均比表面積は、以下の式１で表される。
（Ａ１×Ｂ１＋Ａ２×Ｂ２）／（Ｂ１＋Ｂ２） …式１
Average specific surface area of the conductive material is preferably 5~300m 2 / g, 20~100m 2 / g is more preferred. Here, the average specific surface area of the conductive material means the arithmetic mean of the specific surface areas of the conductive material contained in the composition for forming an anode. As an example, a case where two kinds of conductive materials C1 and C2 are used as the conductive material is shown. When the specific surface area of the conductive material C1 is A1 m 2 / g, the amount of the conductive material C1 added to the composition is B1 g, the specific surface area of the conductive material C2 is A2 m 2 / g, and the amount of addition is B2 g. The average specific surface area of the conductive material is represented by the following formula 1.
(A1 x B1 + A2 x B2) / (B1 + B2) ... Equation 1
導電材の平均比表面積が５ｍ２／ｇ以上である場合、アノードの表面積が大きくなり、微生物の吸着性が向上する。また、導電材の平均比表面積が３００ｍ２／ｇ以下であると、アノードの表面粗さが大きくなり、微生物の吸着性が向上する。 When the average specific surface area of the conductive material is 5 m 2 / g or more, the surface area of the anode becomes large and the adsorptivity of microorganisms is improved. Further, when the average specific surface area of the conductive material is 300 m 2 / g or less, the surface roughness of the anode becomes large and the adsorptivity of microorganisms is improved.
＜水溶性樹脂＞
本発明の水溶性樹脂とは、２５℃の水９９ｇ中に樹脂１ｇを入れて撹拌し、２５℃で２４時間放置した後、分離・析出せずに水中で樹脂が完全に溶解可能なものである。上述のように、水溶性樹脂には、微生物担持量やプロトン拡散を向上する効果がある。
<Water-soluble resin>
The water-soluble resin of the present invention is a resin in which 1 g of the resin is put in 99 g of water at 25 ° C., stirred, left at 25 ° C. for 24 hours, and then the resin can be completely dissolved in water without separation and precipitation. is there. As described above, the water-soluble resin has an effect of improving the amount of microorganisms supported and the diffusion of protons.
水溶性樹脂としては、アニオン性樹脂、カチオン性樹脂、アニオン性とカチオン性の性質を併せ持つ両性樹脂、またそれ以外のノニオン性樹脂に大別され、更にその樹脂が複数の単量体から構成されてもよい。また、水溶性樹脂は１種単独で用いても良いし、２種以上併用しても良い。 Water-soluble resins are roughly classified into anionic resins, cationic resins, amphoteric resins having both anionic and cationic properties, and other nonionic resins, and the resins are further composed of a plurality of monomers. You may. Further, the water-soluble resin may be used alone or in combination of two or more.
アニオン性樹脂としては、カルボキシル基、スルホ基、リン酸基およびそれらを一部あるいは全てを中和した骨格を含有する樹脂が挙げられる。例示すると、（メタ）アクリル酸、イタコン酸、フマル酸、マレイン酸、２−スルホエチルメタクリレート、２−メタクリロイルオキシエチルアシッドホスフェートなどの重合性単量体の単独重合物、または他の重合性単量体との共重合物およびそれらのアルカリ中和物等が挙げられる。 Examples of the anionic resin include a resin containing a carboxyl group, a sulfo group, a phosphoric acid group, and a skeleton in which some or all of them are neutralized. For example, homopolymers of polymerizable monomers such as (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, 2-sulfoethyl methacrylate, 2-methacryloyloxyethyl acid phosphate, or other polymerizable single amounts. Examples thereof include copolymers with the body and alkali-neutralized products thereof.
カチオン性樹脂としては、環状を含むアミノ基およびアミノ基の一部あるいは全て中和
した骨格や4級アンモニウム塩を含有する樹脂等が挙げられる。例示すると、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチル（メタ）アクリレート、ビニルピリジンなどの重合性単量体の単独重合物、または他の重合性単量体との共重合物およびそれらの酸中和物が挙げられる。
Examples of the cationic resin include an amino group containing a cyclic compound, a skeleton in which a part or all of the amino group is neutralized, a resin containing a quaternary ammonium salt, and the like. For example, homopolymers of polymerizable monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethyl (meth) acrylate, vinylpyridine, or co-polymerization with other polymerizable monomers. Examples include polymers and their acid neutralized products.
両性樹脂としては、前記アニオン性骨格と前記カチオン性骨格を共に含有する樹脂が挙
げられる。例示すると、スチレン−マレイン酸−Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレートの共重合物などが挙げられる。
Examples of the amphoteric resin include a resin containing both the anionic skeleton and the cationic skeleton. Examples thereof include a copolymer of styrene-maleic acid-N, N-dimethylaminoethyl (meth) acrylate.
ノニオン性樹脂は、前記アニオン性、カチオン性および両性樹脂以外の樹脂である。例
示すると、ポリビニルピロリドン、ポリビニルアルコール、ポリアクリルアミド、ポリ−Ｎ−ビニルアセトアミド、ポリアルキレングリコールなどが挙げられる。
The nonionic resin is a resin other than the anionic, cationic and amphoteric resins. Examples thereof include polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, poly-N-vinylacetamide, polyalkylene glycol and the like.
また、水溶性樹脂は、前記以外にも次に例示する単量体を複数含む共重合体でも良い。 In addition to the above, the water-soluble resin may be a copolymer containing a plurality of the following monomers.
芳香環を有する単量体としては、スチレン、α−メチルスチレンもしくはベンジル（メタ）アクリレートを例示出来る。 Examples of the monomer having an aromatic ring include styrene, α-methylstyrene or benzyl (meth) acrylate.
鎖式飽和炭化水素基を有する単量体としては、具体的に例示すると、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート等の炭素数１〜２２のアルキル（メタ）アクリレートがあり、好ましくは炭素数２〜１２、さらに好ましくは炭素数２〜８のアルキル基を有するアルキル基含有アクリレートまたは対応するメタクリレートが挙げられる。これらのアルキル基は分岐してもよく、具体例としては、イソプロピル（メタ）アクリレート、イソブチル（メタ）アクリレート、ターシャリーブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、２−ブチルヘキシル（メタ）アクリレート等が挙げられる。
また、酢酸ビニル、酪酸ビニル、プロピオン酸ビニル、ヘキサン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル等、脂肪酸ビニル化合物が挙げられる。
更に、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン等、α−オレフィン化合物が挙げられる。
Specific examples of the monomer having a chain saturated hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like having 1 to 22 carbon atoms. Alkyl (meth) acrylates, preferably alkyl group-containing acrylates having an alkyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, or corresponding methacrylates. These alkyl groups may be branched, and specific examples thereof include isopropyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-butylhexyl (meth). ) Acrylate and the like can be mentioned.
Examples thereof include fatty acid vinyl compounds such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate and vinyl stearate.
Further, α-olefin compounds such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene can be mentioned.
環状飽和炭化水素基を有する単量体としては、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、トリメチルシクロヘキシル（メタ）アクリレート、１−アダマンチル（メタ）アクリレート等が挙げられる。 Examples of the monomer having a cyclic saturated hydrocarbon group include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and 1-adamantyl (meth) acrylate. Can be mentioned.
ポリオキシアルキレン構造を有する単量体としては、ジエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等、末端に水酸基を有し、ポリオキシアルキレン鎖を有するモノアクリレートまたはモノメタアクリレート等、メトキシエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート等、末端にアルコキシ基を有し、ポリオキシアルキレン鎖を有するモノアクリレートまたは対応するモノメタアクリレートがある。また、アルキルビニルエーテル化合物としては、ブチルビニルエーテル、エチルビニルエーテル等が挙げられる。
また、グリシジル（メタ）クリレート、テトラヒドロフルフリル（メタ）アクリレート等のように環式化合物を用いても良い。
Examples of the monomer having a polyoxyalkylene structure include diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate, which have a hydroxyl group at the terminal and have a polyoxyalkylene chain. Polyoxyalkylene having an alkoxy group at the terminal such as methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etc. such as acrylate or monomethacrylate. There are monoacrylates with chains or corresponding monomethacrylates. Further, examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.
Further, a cyclic compound such as glycidyl (meth) clearate and tetrahydrofurfuryl (meth) acrylate may be used.
水酸基を有する単量体としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、４−ヒドロキシスチレン、ビニルアルコール、アリルアルコール等が挙げられる。
また、ビニルアルコールの誘導体である単量体としては、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル等のビニルエステルが例示できる。これらのビニルエステルを共重合し、得られた共重合体を水酸化ナトリウムなどにより鹸化することで、水酸基を形成できる。
Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxystyrene, and vinyl alcohol. , Allyl alcohol and the like.
Examples of the monomer that is a derivative of vinyl alcohol include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl versatic acid. Hydroxyl groups can be formed by copolymerizing these vinyl esters and saponifying the obtained copolymer with sodium hydroxide or the like.
窒素含有の単量体としては、Ｎ−ビニル−２−ピロリドン、（メタ）アクリルアミド、Ｎ−ビニルアセトアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル−（メタ）アクリルアミド等のモノアルキロール（メタ）アクリルアミド、Ｎ，Ｎ−ジ（メチロール）アクリルアミド、Ｎ−メチロール−Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジ（メトキシメチル）アクリルアミド等を例示できる。 Examples of the nitrogen-containing monomer include monoalkyrroles such as N-vinyl-2-pyrrolidone, (meth) acrylamide, N-vinylacetamide, N-methylol (meth) acrylamide, and N-methoxymethyl- (meth) acrylamide. Examples thereof include meta) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide and the like.
更にその他の単量体としては、パーフルオロメチルメチル（メタ）アクリレート、パーフルオロエチルメチル（メタ）アクリレート、２−パーフルオロブチルエチル（メタ）アクリレート、２−パーフルオロヘキシルエチル（メタ）アクリレート等の炭素数１〜２０のパーフルオロアルキル基を有するパーフルオロアルキルアルキル（メタ）アクリレート類；
パーフルオロブチルエチレン、パーフルオロヘキシルエチレン、パーフルオロオクチルエチレン、パーフルオロデシルエチレン等のパーフルオロアルキル、アルキレン類等のパーフルオロアルキル基含有ビニルモノマー、ビニルトリクロルシラン、ビニルトリス（βメトキシエトキシ）シラン、ビニルトリエトキシシラン、γ-（メタ）アクリロキシプロピルトリメトキシシラン等のシラノール基含有ビニル化合物及びその誘導体などを挙げることができ、これらの群から複数用いることができる。
Still other monomers include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate and the like. Perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms;
Perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, perfluoroalkyl group-containing vinyl monomer such as alkylenes, vinyl trichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyl Examples thereof include silanol group-containing vinyl compounds such as triethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof, and a plurality of them can be used from these groups.
エチニル化合物としては、アセチレン、エチニルベンゼン、エチニルトルエン、１−エチニル−１−シクロヘキサノール等が挙げられる。これらは単独もしくは２種類以上を併用して使用することもできる。 Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyl toluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.
水溶性樹脂の分子量は特に限定されないが、好ましくは質量平均分子量が５，０００〜２，５００，０００である。質量平均分子量（Ｍｗ）とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）におけるポリエチレンオキサイド換算分子量を示す。 The molecular weight of the water-soluble resin is not particularly limited, but the mass average molecular weight is preferably 5,000 to 2,500,000. The mass average molecular weight (Mw) indicates the polyethylene oxide-equivalent molecular weight in gel permeation chromatography (GPC).
＜水性樹脂微粒子＞
本発明のアノード形成用組成物には、さらに、バインダー樹脂として水性樹脂微粒子を含むことが好ましい。水性樹脂微粒子は、樹脂が水中で溶解せずに微粒子の状態で存在するもので、その水分散体は一般的に水性エマルションとも呼ばれる。
<Aqueous resin fine particles>
The composition for forming an anode of the present invention preferably further contains aqueous resin fine particles as a binder resin. Aqueous resin fine particles are those in which the resin does not dissolve in water and exists in the form of fine particles, and the aqueous dispersion is also generally called an aqueous emulsion.
水性樹脂微粒子が導電材及び水溶性樹脂と共に分散されたアノード形成用組成物は、塗膜形成された場合、粒子間及び基材との密着性に優れ、強度の高い微生物燃料電池用アノードを提供できる。 The composition for forming an anode in which water-based resin fine particles are dispersed together with a conductive material and a water-soluble resin provides an anode for a microbial fuel cell having excellent adhesion between particles and a base material when a coating film is formed. it can.
また、水性樹脂微粒子と導電材の結着は点接触によるため、微生物が付着しやすい表面形態を形成することができる。また、界面を反応場とする反応を阻害しにくい。更に、密着性に優れることから必要な樹脂は少量で済むため、結果、樹脂による抵抗が低減できる。即ち、導電材と水性樹脂微粒子とを含有するアノード形成用組成物を使用することで、発電性能に優れた微生物燃料電池を提供できる。 Further, since the water-based resin fine particles and the conductive material are bound by point contact, it is possible to form a surface morphology to which microorganisms easily adhere. In addition, it is difficult to inhibit the reaction using the interface as the reaction field. Further, since the adhesiveness is excellent, a small amount of resin is required, and as a result, the resistance due to the resin can be reduced. That is, by using the anode forming composition containing the conductive material and the aqueous resin fine particles, it is possible to provide a microbial fuel cell having excellent power generation performance.
更に、水性樹脂微粒子は構成する単量体によっては安価に製造することも可能なため、微生物燃料電池用アノードの製造費を低減できる。 Further, since the aqueous resin fine particles can be produced at low cost depending on the constituent monomers, the production cost of the anode for a microbial fuel cell can be reduced.
水性樹脂微粒子としては、（メタ）アクリル系エマルション、ニトリル系エマルション、ウレタン系エマルション、ジエン系エマルション（スチレン・ブタジエンゴム（ＳＢＲ）など）、フッ素系エマルション（ポリフッ化ビニリデン（ＰＶＤＦ）やポリテトラフルオロエチレン（ＰＴＦＥ）など）等が挙げられる。水溶性高分子と異なり、エマルションは粒子間の結着性と柔軟性（膜の可とう性）に優れるものが好ましい。 Aqueous resin fine particles include (meth) acrylic emulsion, nitrile emulsion, urethane emulsion, diene emulsion (styrene-butadiene rubber (SBR), etc.), fluorine emulsion (polyvinylidene fluoride (PVDF), polytetrafluoroethylene). (PTFE), etc.) and the like. Unlike the water-soluble polymer, the emulsion preferably has excellent bondability and flexibility (flexibility of the film) between particles.
また、本発明に用いる水性樹脂微粒子の粒子構造は、多層構造、いわゆるコアシェル粒子にすることもできる。例えば、コア部、またはシェル部に官能基を有する単量体を主に重合させた樹脂を局在化させたり、コアとシェルによってＴｇや組成に差を設けたりすることにより、硬化性、乾燥性、成膜性、バインダーの機械強度を向上させることができる。 Further, the particle structure of the aqueous resin fine particles used in the present invention may be a multilayer structure, so-called core-shell particles. For example, by localizing a resin in which a monomer having a functional group is mainly polymerized in the core portion or the shell portion, or by providing a difference in Tg and composition between the core and the shell, curability and drying are performed. It is possible to improve the property, film forming property, and mechanical strength of the binder.
本発明に用いる水性樹脂微粒子の平均粒子径は、結着性や粒子の安定性の点から、１０〜５００ｎｍであることが好ましく、１０〜３００ｎｍであることがより好ましい。また、１μｍを超えるような粗大粒子が多く含有されるようになると粒子の安定性が損なわれるので、１μｍを超える粗大粒子は多くとも５％以下であることが好ましい。なお、本発明における平均粒子径とは、体積平均粒子径のことを表し、動的光散乱法により測定できる。 The average particle size of the aqueous resin fine particles used in the present invention is preferably 10 to 500 nm, more preferably 10 to 300 nm, from the viewpoint of binding properties and particle stability. Further, if a large amount of coarse particles exceeding 1 μm is contained, the stability of the particles is impaired, so that the amount of coarse particles exceeding 1 μm is preferably 5% or less at most. The average particle size in the present invention represents the volume average particle size and can be measured by a dynamic light scattering method.
動的光散乱法による平均粒子径の測定は、以下のようにして行うことができる。架橋型樹脂微粒子分散液は固形分に応じて２００〜１０００倍に水希釈しておく。該希釈液約５ｍｌを測定装置［（株）日機装社製マイクロトラック］のセルに注入し、サンプルに応じた溶剤（本発明では水）および樹脂の屈折率条件を入力後、測定を行う。この時得られた体積粒子径分布データ（ヒストグラム）のピークを本発明の平均粒子径とする。 The average particle size can be measured by the dynamic light scattering method as follows. The crosslinked resin fine particle dispersion is diluted 200 to 1000 times with water depending on the solid content. Approximately 5 ml of the diluted solution is injected into a cell of a measuring device [Microtrac manufactured by Nikkiso Co., Ltd.], and the measurement is performed after inputting the refractive index conditions of the solvent (water in the present invention) and the resin according to the sample. The peak of the volumetric particle size distribution data (histogram) obtained at this time is taken as the average particle size of the present invention.
＜その他の樹脂＞
本発明のアノード形成用組成物には、前述の水溶性樹脂や水性樹脂微粒子に当てはまらない、その他の樹脂をバインダー樹脂として含んでもよい。このような樹脂としては、有機溶剤に溶解させて使用する溶剤系樹脂などを使用することが出来る。本発明のアノード形成用組成物には、その他の樹脂を使用することで、導電材同士、あるいは導電材と基材を強く結着させることが出来るため、良好な発電特性や耐久性を向上させることが出来る。
<Other resins>
The composition for forming an anode of the present invention may contain other resins that do not apply to the above-mentioned water-soluble resin and water-based resin fine particles as a binder resin. As such a resin, a solvent-based resin or the like which is used by dissolving it in an organic solvent can be used. By using another resin in the composition for forming an anode of the present invention, the conductive materials or the conductive material and the base material can be strongly bonded to each other, so that good power generation characteristics and durability are improved. Can be done.
その他の樹脂としては、ポリウレタン系樹脂、ポリアミド系樹脂、アクリロニトリル系樹脂、アクリル系樹脂、ブタジエン系樹脂、ポリビニルブチラール系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂、ＥＶＡ系樹脂、ポリフッ化ビニリデン系樹脂、及びシリコン系樹脂等からなる群から選ばれる１ 種以上を含むことができる。ただし、これらの樹脂に限定されるわけではなく、１種単独で用いても良いし、２ 種以上併用しても良い。 Other resins include polyurethane resin, polyamide resin, acrylonitrile resin, acrylic resin, butadiene resin, polyvinyl butyral resin, polyolefin resin, polyester resin, polystyrene resin, EVA resin, polyvinylidene fluoride. It can contain one or more kinds selected from the group consisting of based resins, silicon based resins and the like. However, the resin is not limited to these resins, and one type may be used alone, or two or more types may be used in combination.
次に、溶媒について説明する。アノード形成用組成物の材料を均一に混合する場合、溶媒を適宜用いることが出来る。そのような溶媒としては、水性液状媒体が好ましい。本発明に使用する水性液状媒体としては、水を使用することが好ましいが、必要に応じて、例えば、導電性基材への塗工性向上のために、水と相溶する液状媒体を使用しても良い。
水と相溶する液状媒体としては、アルコール類、グリコール類、セロソルブ類、アミノアルコール類、アミン類、ケトン類、カルボン酸アミド類、リン酸アミド類、スルホキシド類、カルボン酸エステル類、リン酸エステル類、エーテル類、ニトリル類等が挙げられ、水と相溶する範囲で使用しても良い。
Next, the solvent will be described. When the materials of the composition for forming the anode are uniformly mixed, a solvent can be appropriately used. As such a solvent, an aqueous liquid medium is preferable. Water is preferably used as the aqueous liquid medium used in the present invention, but if necessary, for example, a liquid medium compatible with water is used in order to improve the coatability on the conductive substrate. You may.
Liquid media compatible with water include alcohols, glycols, cellosolves, aminoalcohols, amines, ketones, carboxylic acid amides, phosphate amides, sulfoxides, carboxylic acid esters, and phosphate esters. , Ethers, nitriles and the like, and may be used as long as they are compatible with water.
更に、アノード形成用組成物には、増粘剤、分散剤、成膜助剤、消泡剤、レベリング剤、防腐剤、ｐＨ調整剤などを必要に応じて配合できる。 Further, a thickener, a dispersant, a film forming aid, a defoaming agent, a leveling agent, a preservative, a pH adjusting agent and the like can be added to the anode forming composition as needed.
＜アノード形成用組成物の調製方法＞
アノード形成用組成物の調製方法に特に制限はない。調製方法は、
（１）各成分を同時に分散してもよく、
（２）導電材を溶媒中に分散後、他の材料を添加してもよく、
（３）導電材と水溶性樹脂を溶媒中に分散後、他の材料を添加してもよく、
使用する導電材、水溶性樹脂により最適化することができる。
<Method of preparing composition for forming anode>
There is no particular limitation on the method for preparing the composition for forming the anode. The preparation method is
(1) Each component may be dispersed at the same time.
(2) After dispersing the conductive material in the solvent, another material may be added.
(3) After dispersing the conductive material and the water-soluble resin in the solvent, another material may be added.
It can be optimized depending on the conductive material and water-soluble resin used.
水性樹脂微粒子を添加する場合、導電材と水溶性樹脂とを水性液状媒体中に分散した後に、水性樹脂微粒子を添加してアノード形成用組成物を作製すると、分散時間の短縮などコストダウンに大きく貢献することができる。 When adding the aqueous resin fine particles, if the conductive material and the water-soluble resin are dispersed in the aqueous liquid medium and then the aqueous resin fine particles are added to prepare a composition for forming an anode, the dispersion time is shortened and the cost is greatly reduced. Can contribute.
本発明のアノード形成用組成物において、導電材の含有量は、導電性や基材への密着性等から、アノード形成用組成物の全固形分の合計１００質量％に対して、好ましくは５０〜９９．９質量％、さらに好ましくは８０〜９９質量％、特に好ましくは８５〜９９質量％である。導電材の含有量が５０質量％以上であると、アノード内部での電子パスが発達し、十分な導電性が得られる。導電材の含有量が８０質量％以上であると、表面に導電材が露出することによって導電材と微生物の間の電子パスが増加し、アノード反応が促進されるため、電池の発電特性が向上する。 In the composition for forming an anode of the present invention, the content of the conductive material is preferably 50 with respect to 100% by mass of the total solid content of the composition for forming an anode from the viewpoint of conductivity, adhesion to a substrate, and the like. It is ~ 99.9% by mass, more preferably 80 to 99% by mass, and particularly preferably 85 to 99% by mass. When the content of the conductive material is 50% by mass or more, the electron path inside the anode develops and sufficient conductivity can be obtained. When the content of the conductive material is 80% by mass or more, the electron path between the conductive material and the microorganism is increased by exposing the conductive material on the surface, and the anode reaction is promoted, so that the power generation characteristics of the battery are improved. To do.
水溶性樹脂の含有量は、アノード形成用組成物の全固形分の合計１００質量％に対して、好ましくは０．５〜２０質量％、さらに好ましくは１〜１５質量％である。水溶性樹脂の含有量が０．５質量％以上であると、前述の通り、微生物をより多く担持でき、プロトン拡散性が良好なアノードが得られる。また、水溶性樹脂の含有量が２０質量％以下であると、電解液中での耐久性が良好なアノードが得られる。 The content of the water-soluble resin is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on 100% by mass of the total solid content of the composition for forming the anode. When the content of the water-soluble resin is 0.5% by mass or more, as described above, an anode capable of supporting more microorganisms and having good proton diffusivity can be obtained. Further, when the content of the water-soluble resin is 20% by mass or less, an anode having good durability in the electrolytic solution can be obtained.
水性樹脂微粒子を含む場合、その含有量は、電極用組成物の全固形分の合計１００質量％に対して、好ましくは１〜４０質量％、さらに好ましくは１〜１８質量％、特に好ましくは１〜８質量％である。水性樹脂微粒子の含有量が１質量％以上であると、アノードの強度が改善する。また、水性樹脂微粒子の含有量が４０質量％以下の場合、良好な導電性を有するアノードが得られる。さらに、水性樹脂微粒子の含有量が２０質量％以下である場合、水性樹脂微粒子と導電材との点結着により、微生物の吸着に適した表面形態が形成される。さらに、水性樹脂微粒子の含有量が５質量％以下である場合、塗膜表面において導電材がより多く露出するため、微生物と導電材とが接触しやすくなり、アノード反応が促進される。 When the aqueous resin fine particles are contained, the content thereof is preferably 1 to 40% by mass, more preferably 1 to 18% by mass, and particularly preferably 1 with respect to 100% by mass of the total solid content of the electrode composition. ~ 8% by mass. When the content of the aqueous resin fine particles is 1% by mass or more, the strength of the anode is improved. Further, when the content of the aqueous resin fine particles is 40% by mass or less, an anode having good conductivity can be obtained. Further, when the content of the aqueous resin fine particles is 20% by mass or less, the surface morphology suitable for the adsorption of microorganisms is formed by the point binding between the aqueous resin fine particles and the conductive material. Further, when the content of the aqueous resin fine particles is 5% by mass or less, the conductive material is more exposed on the surface of the coating film, so that the microorganisms and the conductive material are likely to come into contact with each other, and the anodic reaction is promoted.
また、アノード形成用組成物の適正粘度は、組成物の塗工方法によるが、一般には、１０ｍＰａ・ｓ以上、３０，０００ｍＰａ・ｓ以下とするのが好ましい。
＜分散機・混合機＞
アノード形成用組成物を得る際に用いられる装置としては、顔料分散等に通常用いられている分散機、混合機が使用できる。
The appropriate viscosity of the anode forming composition depends on the coating method of the composition, but is generally preferably 10 mPa · s or more and 30,000 mPa · s or less.
<Disperser / Mixer>
As an apparatus used for obtaining the composition for forming an anode, a disperser or a mixer usually used for pigment dispersion or the like can be used.
例えば、ディスパー、ホモミキサー、若しくはプラネタリーミキサー等のミキサー類；エム・テクニック社製「クレアミックス」、若しくはＰＲＩＭＩＸ社「フィルミックス」等のホモジナイザー類；ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、若しくはコボールミル等のメディア型分散機；湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ−５」、若しくは奈良機械社製「ＭＩＣＲＯＳ」等のメディアレス分散機；または、その他ロールミル等が挙げられるが、これらに限定されるものではない。 For example, mixers such as disperser, homomixer, or planetary mixer; homogenizers such as "Clearmix" manufactured by M-Technique or "Philmix" manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill. (Symmal Enterprises "Dyno Mill" etc.), Atreiter, Pearl Mill (Eirich "DCP Mill" etc.), or media type disperser such as Coball Mill; Wet Jet Mill (Genus "Genus PY", Sugino) Medialess dispersers such as Machine's "Star Burst", Nanomizer's "Nanomizer"), M-Technique's "Claire SS-5", or Nara Machinery's "MICROS"; or other roll mills, etc. However, it is not limited to these.
例えば、メディア型分散機を使用する場合は、アジテーター及びベッセルがセラミック製又は樹脂製の分散機を使用する方法や、金属製アジテーター及びベッセル表面をタングステンカーバイド溶射や樹脂コーティング等の処理をした分散機を用いることが好ましい。そして、メディアとしては、ガラスビーズ、または、ジルコニアビーズ、若しくはアルミナビーズ等のセラミックビーズを用いることが好ましい。また、ロールミルを使用する場合についても、セラミック製ロールを用いることが好ましい。分散装置は、１種のみを使用しても良いし、複数種の装置を組み合わせて使用しても良い。また、強い衝撃で導電材が割れやすいあるいは潰れやすい場合は、メディア型分散機よりは、ロールミルやホモジナイザー等のメディアレス分散機が好ましい。 For example, when using a media type disperser, a method in which the agitator and vessel use a disperser made of ceramic or resin, or a disperser in which the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. As the medium, it is preferable to use glass beads, zirconia beads, or ceramic beads such as alumina beads. Also, when a roll mill is used, it is preferable to use a ceramic roll. As the dispersive device, only one type may be used, or a plurality of types of devices may be used in combination. Further, when the conductive material is easily cracked or crushed by a strong impact, a medialess disperser such as a roll mill or a homogenizer is preferable to a media type disperser.
＜微生物燃料電池用アノード＞
本発明の微生物燃料電池用アノードは、導電材と水溶性樹脂とを含有する。
本発明の微生物燃料電池用アノードは、種々の方法で得ることができる。アノードの構成としては、特に限定されるものではないが、例えば、あらかじめ微生物を導電材やアノード用組成物などへ混合してからアノードを作製しても良いし、あらかじめ電極を作製しておき、その後に微生物の植種を行っても良い。また、電極を電解液中へ設置した後に電解液中の微生物の吸着によりアノードとして機能させることも出来る。
アノード形成用組成物から電極を作製する場合、特に限定されるものではないが、例えば、
（１）導電材と水溶性樹脂とを混合したアノード形成用組成物を導電性基材へ塗工することにより作製した電極や、
（２）導電材と水溶性樹脂と水性樹脂微粒子とを混合したアノード形成用組成物を導電性基材へ塗工することにより作製した電極や、
（３）導電材と水溶性樹脂と水性液状媒体とを混合したアノード形成用組成物を導電性基材へ塗工することにより作製した電極や、
（４）導電材と水溶性樹脂と水性樹脂微粒子と水性液状媒体とを混合したアノード形成用組成物を導電性基材へ塗工することにより作製した電極、
等が挙げられる。
<Anode for microbial fuel cell>
The anode for a microbial fuel cell of the present invention contains a conductive material and a water-soluble resin.
The anode for a microbial fuel cell of the present invention can be obtained by various methods. The configuration of the anode is not particularly limited, but for example, the anode may be prepared after mixing the microorganism with the conductive material or the composition for the anode in advance, or the electrode may be prepared in advance. After that, the seeding of the microorganism may be carried out. Further, after the electrode is placed in the electrolytic solution, it can function as an anode by adsorbing microorganisms in the electrolytic solution.
When the electrode is prepared from the composition for forming an anode, the electrode is not particularly limited, but for example,
(1) Electrodes produced by applying a composition for forming an anode, which is a mixture of a conductive material and a water-soluble resin, to a conductive base material, or
(2) Electrodes produced by applying a composition for forming an anode, which is a mixture of a conductive material, a water-soluble resin, and water-based resin fine particles, to a conductive base material.
(3) Electrodes produced by applying a composition for forming an anode, which is a mixture of a conductive material, a water-soluble resin, and an aqueous liquid medium, to a conductive base material.
(4) An electrode prepared by applying a composition for forming an anode, which is a mixture of a conductive material, a water-soluble resin, water-based resin fine particles, and an water-based liquid medium, to a conductive base material.
And so on.
＜導電性基材＞
本発明の電極で使用する導電性基材としては、耐腐食性、電気伝導性に優れ、表面積が大きく、反応物及び生成物の拡散に優れるものが良く、材質や形状は特に限定されない。例えばグラファイトペーパー（カーボンペーパー）、グラファイトクロス（カーボンクロス）及びグラファイトフェルト（カーボンフェルト）等のカーボン材料の他、ステンレスメッシュ、銅メッシュや白金メッシュ等の金属材料を用いることができるが、この限りではない。電極に用いる導電性基材には、予め撥水処理しても良い。例えば、ＰＴＦＥの分散液をカソードに含浸させ、乾燥後４００℃前後で加熱することで撥水性が発現する。また、ＰＴＦＥ分散液には導電材を分散させても良い。なお、撥水処理はこれらに限定されるものではない。
<Conductive base material>
The conductive base material used in the electrode of the present invention is preferably one having excellent corrosion resistance and electrical conductivity, a large surface area, and excellent diffusion of reactants and products, and the material and shape are not particularly limited. For example, in addition to carbon materials such as graphite paper (carbon paper), graphite cloth (carbon cloth) and graphite felt (carbon felt), metal materials such as stainless mesh, copper mesh and platinum mesh can be used, but this is not the case. Absent. The conductive base material used for the electrode may be water-repellent in advance. For example, the cathode is impregnated with a dispersion of PTFE, dried, and then heated at around 400 ° C. to develop water repellency. Further, the conductive material may be dispersed in the PTFE dispersion liquid. The water repellent treatment is not limited to these.
＜塗工方法＞
本発明のアノード形成用組成物を導電性基材に塗布する方法は、特に制限はなく公知の方法を用いることができる。例示すると、グラビアコーティング法、スプレーコーティング法、スクリーン印刷法、ディップコーティング法、ダイコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スクリーン印刷法または静電塗装法等を挙げることができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機等が使用できるが、特にこれらに限定されるものではない。
<Coating method>
The method for applying the anode-forming composition of the present invention to the conductive substrate is not particularly limited, and a known method can be used. Examples include a gravure coating method, a spray coating method, a screen printing method, a dip coating method, a die coating method, a roll coating method, a doctor coating method, a knife coating method, a screen printing method or an electrostatic coating method. As the drying method, a stand-alone drying, a blower dryer, a warm air dryer, an infrared heater, a far infrared heater and the like can be used, but the drying method is not particularly limited thereto.
本発明の微生物燃料電池用アノードの体積抵抗率は、５×１０１Ω・ｃｍ未満であることが好ましく、さらに好ましくは５×１００Ω・ｃｍ未満、さらに好ましくは１×１０−１Ω・ｃｍ未満である。導電性が良好な電極ほど電池の電力を有効に取り出すことが可能となる。 The volume resistivity of the anode microbial fuel cell of the present invention is preferably less than 5 × 10 1 Ω · cm, more preferably less than 5 × 10 0 Ω · cm, more preferably 1 × 10 -1 Ω · It is less than cm. The better the conductivity of the electrode, the more effectively the battery power can be taken out.
＜微生物燃料電池＞
本発明の微生物燃料電池には、アノードのほかに、カソード、電解液、外部抵抗などが用いられる。アノードは微生物を含んでおり、カソードは還元触媒を含んでいる。アノードとカソードとは、電解液を介して接しており、カソードは酸化剤と触れることができる位置に配置されている。酸化剤としては、大気中に存在する酸素を用いることが好ましい。また、アノードとカソードとは、外部抵抗を経由して電気的に接続されている。ここで、外部抵抗とは、電気回路における電気抵抗を示す。
<Microbial fuel cell>
In the microbial fuel cell of the present invention, in addition to the anode, a cathode, an electrolytic solution, an external resistor and the like are used. The anode contains microorganisms and the cathode contains a reduction catalyst. The anode and the cathode are in contact with each other via an electrolytic solution, and the cathode is arranged at a position where it can come into contact with the oxidizing agent. As the oxidizing agent, it is preferable to use oxygen existing in the atmosphere. Further, the anode and the cathode are electrically connected via an external resistor. Here, the external resistance indicates an electric resistance in an electric circuit.
アノードでは、微生物の代謝によって有機物が酸化分解されると同時に、電子とプロトンが発生する。発生した電子はアノードに取り込まれ外部抵抗を経由してカソードへと移動する。発生したプロトンは、電解液中を通過して、カソード側へと移動する。また、カソードでは、還元触媒の作用によって、アノード側から移動してきた電子とプロトン、及びカソード付近の酸化剤が反応する。そして、上記の反応が繰り返されることで、カソードとアノードとの間に起電力が発生する。 At the anode, organic matter is oxidatively decomposed by the metabolism of microorganisms, and at the same time, electrons and protons are generated. The generated electrons are taken into the anode and move to the cathode via an external resistor. The generated protons pass through the electrolytic solution and move to the cathode side. Further, at the cathode, the electrons and protons that have moved from the anode side react with the oxidizing agent near the cathode due to the action of the reduction catalyst. Then, by repeating the above reaction, an electromotive force is generated between the cathode and the anode.
微生物燃料電池に用いるカソードについては、詳細に後述する。 The cathode used in the microbial fuel cell will be described in detail later.
微生物燃料電池に用いる電解液は、プロトン伝導性を有し、微生物によって酸化分解される基質を含有する。基質は、電子を供与する微生物が代謝可能な物質であれば、特に限定されるものではない。例えば、糖類やタンパク質、脂質などの有機物の他、アンモニアなどの無機物などが挙げられ、それらを１種類以上含有してもよい。したがって、電解液は前記条件を満たす生活廃水、産業廃水、環境廃水（池、湖沼、河川、海）、土壌、汚泥等を用いることができる。また、微生物とアノードとの間で電子伝達を担うメディエーターを導入してもよく、メチレンブルーやニュートラルレッドなどが例示できる。 The electrolyte used in a microbial fuel cell has proton conductivity and contains a substrate that is oxidatively decomposed by microorganisms. The substrate is not particularly limited as long as it is a substance that can be metabolized by the microorganism that donates electrons. For example, in addition to organic substances such as sugars, proteins and lipids, inorganic substances such as ammonia may be mentioned, and one or more of them may be contained. Therefore, as the electrolytic solution, domestic wastewater, industrial wastewater, environmental wastewater (ponds, lakes, rivers, seas), soil, sludge, etc. that satisfy the above conditions can be used. Further, a mediator responsible for electron transfer between the microorganism and the anode may be introduced, and examples thereof include methylene blue and neutral red.
アノードにおいて電子を供与する微生物は、前記基質を酸化分解し電子を生成するアノード反応を生起するものであれば、単一種でも複数種であってもよい。また、微生物は電解槽内を浮遊あるいはアノード上へ固定化することで電解槽内に保持する。微生物種は特に限定されないが、Ｓｈｅｗａｎｅｌｌａ属やＧｅｏｂａｃｔｅｒ属に属するものが例示できる。 The microorganism that donates electrons at the anode may be a single type or a plurality of types as long as it causes an anode reaction that oxidatively decomposes the substrate to generate electrons. In addition, microorganisms are retained in the electrolytic cell by floating in the electrolytic cell or immobilizing on the anode. The microbial species are not particularly limited, and those belonging to the genus Shewanella and the genus Geobacter can be exemplified.
微生物燃料電池の構成としては、電子供与微生物が保持されたアノードと、酸素還元触媒材料を含むカソードを、電解液として有機廃水等を含む電解槽に隔壁を設けず差し込んだ一槽型構成や、固体高分子形燃料電池のように、固体高分子膜を利用して、アノード槽とカソード槽を隔てた二槽型構成でもよい。更に、面で囲われた電解槽だけでなく、水田や湖沼、河川、海のように囲われていない環境でもよい。例えば、電解液を保持する電解槽内部と酸素を含む大気等の電解槽外部を隔てる液面、側面、底面にカソードが設置される形態や、外気を取り入れることができるカセット型の電極を液中に浸漬する等の形態が考えられる。このとき、カソードの触媒層が電解液と接し、その裏面が酸素を含む大気等と接するように設置される。これにより、電解槽外部から酸素を含む大気等が直接カソードへ流入し、電解液に接したカソード中の触媒上で反応が生起する。 The configuration of the microbial fuel cell includes a one-tank type configuration in which an anode holding electron donating microorganisms and a cathode containing an oxygen reduction catalyst material are inserted into an electrolytic cell containing organic waste water as an electrolytic solution without a partition wall. Like a polymer electrolyte fuel cell, a two-tank configuration in which an anode tank and a cathode tank are separated by using a solid polymer membrane may be used. Further, not only the electrolytic cell surrounded by a surface but also an unenclosed environment such as a paddy field, a lake, a river, or the sea may be used. For example, a cathode is installed on the liquid surface, side surface, and bottom surface that separates the inside of the electrolytic cell that holds the electrolytic solution from the outside of the electrolytic cell such as the atmosphere containing oxygen, or a cassette type electrode that can take in outside air is placed in the liquid. A form such as immersing in is conceivable. At this time, the catalyst layer of the cathode is in contact with the electrolytic solution, and the back surface thereof is installed so as to be in contact with the atmosphere containing oxygen. As a result, the atmosphere containing oxygen directly flows into the cathode from the outside of the electrolytic cell, and a reaction occurs on the catalyst in the cathode in contact with the electrolytic solution.
＜微生物燃料電池カソード＞
以下、微生物燃料電池に用いられるカソードについて説明する。
<Microbial fuel cell cathode>
Hereinafter, the cathode used in the microbial fuel cell will be described.
（カソード用触媒）
カソードで使用出来る触媒について説明する。微生物燃料電池として機能する触媒であれば特に限定されるものではないが、酸素還元触媒を例に説明する。酸素還元触媒は貴金属触媒、卑金属酸化物触媒、炭素触媒、活性炭、還元酵素等が挙げられる。これらは単独で用いても、二種類以上組み合わせて用いても良い。
(Cathode catalyst)
The catalyst that can be used at the cathode will be described. The catalyst that functions as a microbial fuel cell is not particularly limited, but an oxygen reduction catalyst will be described as an example. Examples of the oxygen reduction catalyst include a noble metal catalyst, a base metal oxide catalyst, a carbon catalyst, activated carbon, a reductase and the like. These may be used alone or in combination of two or more.
（貴金属触媒）
貴金属触媒とは、遷移金属元素のうちルテニウム、ロジウム、パラジウム、銀、オスミウム、イリジウム、白金、金から選択される元素を一種以上含む触媒である。これら貴金属触媒は単体でも別の元素や化合物に担持されたものでも良い。中でも、触媒担持炭素材料が好例として挙げられる。触媒担持炭素材料とは、触媒粒子が触媒担時体としての炭素材料上に担持してなるものを指し、公知もしくは市販のものがある。
(Precious metal catalyst)
The noble metal catalyst is a catalyst containing at least one element selected from ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold among transition metal elements. These noble metal catalysts may be simple substances or supported on another element or compound. Among them, a catalyst-supported carbon material is a good example. The catalyst-supported carbon material refers to a material in which catalyst particles are supported on a carbon material as a catalyst carrier, and there are known or commercially available materials.
触媒粒子の炭素材料上への担持率は限定的ではない。触媒粒子として白金を用いた場合は、触媒粒子１００質量％に対して、通常１〜７０質量％程度までの担持が可能である。 The loading ratio of the catalyst particles on the carbon material is not limited. When platinum is used as the catalyst particles, it can usually be supported up to about 1 to 70% by mass with respect to 100% by mass of the catalyst particles.
本発明に用いる触媒担持体としての炭素材料は、無機材料由来の炭素粒子および／または有機材料を熱処理して得られる炭素粒子であれば特に限定されない。 The carbon material as the catalyst carrier used in the present invention is not particularly limited as long as it is carbon particles derived from an inorganic material and / or carbon particles obtained by heat-treating an organic material.
無機材料由来の炭素粒子としては、カーボンブラック（ファーネスブラック、アセチレンブラック、ケッチェンブラック、ミディアムサーマルカーボンブラック）、活性炭、黒鉛、カーボンナノチューブ、カーボンナノファイバー、カーボンナノホーン、グラフェンナノプレートレット、ナノポーラスカーボン、炭素繊維等が挙げられる。炭素材料は、種類やメーカーによって、粒子径、形状、ＢＥＴ比表面積、細孔容積、細孔径、嵩密度、ＤＢＰ吸油量、表面酸塩基度、表面親水度、導電性など様々な物性やコストが異なるため、使用する用途や要求性能に合わせて最適な材料を選択される。 Carbon particles derived from inorganic materials include carbon black (furness black, acetylene black, ketjen black, medium thermal carbon black), activated carbon, graphite, carbon nanotubes, carbon nanofibers, carbon nanohorns, graphene nanoplatelets, nanoporous carbon, etc. Examples include carbon fiber. Carbon materials have various physical properties and costs such as particle size, shape, BET specific surface area, pore volume, pore size, bulk density, DBP oil absorption, surface acid basicity, surface hydrophilicity, and conductivity, depending on the type and manufacturer. Since they are different, the optimum material is selected according to the intended use and required performance.
熱処理して炭素粒子となる有機材料としては、熱処理後炭素粒子となる材料であれば特に限定されない。具体的な有機材料としては、フェノール系樹脂、ポリイミド系樹脂、ポリアミド系樹脂、ポリアミドイミド系樹脂、ポリアクリロニトリル系樹脂、ポリアニリン系樹脂、フェノールホルムアルデヒド樹脂系樹脂、ポリイミダゾール系樹脂、ポリピロール系樹脂、ポリベンゾイミダゾール系樹脂、メラミン系樹脂、ピッチ、褐炭、ポリカルボジイミド、バイオマス、タンパク質、フミン酸等やそれらの誘導体などが挙げられる。 The organic material that becomes carbon particles by heat treatment is not particularly limited as long as it is a material that becomes carbon particles after heat treatment. Specific organic materials include phenol-based resin, polyimide-based resin, polyamide-based resin, polyamideimide-based resin, polyacrylonitrile-based resin, polyaniline-based resin, phenolformaldehyde resin-based resin, polyimidazole-based resin, polypyrrole-based resin, and poly. Examples thereof include benzoimidazole-based resins, melamine-based resins, pitches, brown charcoal, polycarbodiimide, biomass, proteins, fumic acid and the like, and derivatives thereof.
これら炭素材料は、一種類または二種類以上で用いられる。 These carbon materials are used in one kind or two or more kinds.
市販の触媒担持炭素材料としては、例えば、田中貴金属工業社製の
ＴＥＣ１０Ｅ５０Ｅ、ＴＥＣ１０Ｅ７０ＴＰＭ、ＴＥＣ１０Ｖ３０Ｅ、ＴＥＣ１０Ｖ５０Ｅ、ＴＥＣ６６Ｅ５０等の白金担持炭素粒子；
ＴＥＣ６６Ｅ５０、ＴＥＣ６２Ｅ５８等の白金−ルテニウム合金担持炭素粒子；
を購入することができるが、これらに限定されるものではない。
Examples of commercially available catalyst-supported carbon materials include platinum-supported carbon particles such as TEC10E50E, TEC10E70TPM, TEC10V30E, TEC10V50E, and TEC66E50 manufactured by Tanaka Kikinzoku Kogyo Co., Ltd .;
Platinum-ruthenium alloy-supported carbon particles such as TEC66E50 and TEC62E58;
Can be purchased, but is not limited to these.
（卑金属酸化物触媒）
本発明に用いる卑金属酸化物触媒としては、ジルコニウム、タンタル、チタン、ニオブ、バナジウム、鉄、マンガン、コバルト、ニッケル、銅、亜鉛、クロム、タングステン、およびモリブデンからなる群より選択された少なくとも１種の遷移金属を含む酸化物を使用することができ、より好ましくはこれら遷移金属元素の炭窒化物や、これら遷移金属元素の炭窒酸化物を使用することができる。
(Base metal oxide catalyst)
The base metal oxide catalyst used in the present invention is at least one selected from the group consisting of zirconium, tantalum, titanium, niobium, vanadium, iron, manganese, cobalt, nickel, copper, zinc, chromium, tungsten, and molybdenum. Oxides containing transition metals can be used, and more preferably carbon nitrides of these transition metal elements and carbon dioxide oxides of these transition metal elements can be used.
前記卑金属酸化物触媒の組成式は、例えば、Ｍ１ＣｐＮｑＯｒ（ただし、Ｍ１は遷移金属元素であり、ｐ、ｑ、ｒは原子数の比を表し、０≦ｐ≦３、０≦ｑ≦２、０＜ｒ≦３である。）、Ｍ２aＭ３bＣxＮyＯz（ただし、Ｍ２は、ジルコニウム、タンタル、チタン、ニオブ、バナジウム、鉄、マンガン、コバルト、ニッケル、銅、亜鉛、クロム、タングステン、およびモリブデンからなる群より選択される１種の金属であり、Ｍ３は、前記群より選択されるＭ２とは異なる少なくとも１種の金属である。ａ、ｂ、ｘ、ｙ、ｚは原子数の比を表し、０．５≦ａ＜１、０＜ｂ≦０．５、０＜ｘ≦３、０＜ｙ≦２、０＜ｚ≦３、かつａ＋ｂ＝１である。）で表される。また、これら化合物と導電性化合物を複合化した触媒も好適に使用することができる。 The composition formula of the base metal oxide catalyst is, for example, M1CpNqOr (where M1 is a transition metal element, p, q, r represent the ratio of the number of atoms, 0 ≦ p ≦ 3, 0 ≦ q ≦ 2,0. <R ≦ 3), M2aM3bCxNyOz (where M2 is selected from the group consisting of zirconium, tantalum, titanium, niobium, vanadium, iron, manganese, cobalt, nickel, copper, zinc, chromium, tungsten, and molybdenum. M3 is at least one metal different from M2 selected from the above group. A, b, x, y, z represent the ratio of the number of atoms, and 0.5 ≦ It is represented by a <1, 0 <b ≦ 0.5, 0 <x ≦ 3, 0 <y ≦ 2, 0 <z ≦ 3, and a + b = 1). Further, a catalyst in which these compounds and a conductive compound are combined can also be preferably used.
（炭素触媒）
炭素触媒は、１種または２種以上の、炭素材料と、窒素元素および卑金属元素を含有する化合物とを混合し、熱処理を行い作製された炭素触媒であって、従来公知のものを使用できる。炭素触媒に用いられる炭素材料は、無機材料由来の炭素粒子および／または有機材料を熱処理して得られる炭素粒子であれば特に限定されない。一般的に、炭素触媒の活性点としては、炭素粒子表面に卑金属−Ｎ４構造（卑金属元素を中心に４個の窒素元素が平面上に並んだ構造）に含まれる卑金属元素や、炭素粒子表面のエッジ部に導入された窒素元素近傍の炭素元素などが挙げられる。そのため、炭素触媒が、上記活性点を構成する窒素元素や卑金属元素を含有することは、酸素還元活性を有する上で重要である。更に、炭素触媒は、ＢＥＴ比表面積が２０〜２０００ｍ２／ｇが好ましく、４０〜１５００ｍ２／ｇがより好ましい。
(Carbon catalyst)
The carbon catalyst is a carbon catalyst produced by mixing one or more kinds of carbon materials and a compound containing a nitrogen element and a base metal element and performing heat treatment, and conventionally known carbon catalysts can be used. The carbon material used for the carbon catalyst is not particularly limited as long as it is a carbon particle derived from an inorganic material and / or a carbon particle obtained by heat-treating an organic material. Generally, the active points of the carbon catalyst include a base metal element contained in a base metal-N4 structure (a structure in which four nitrogen elements are arranged on a plane centering on the base metal element) on the surface of the carbon particles, and the surface of the carbon particles. Examples include carbon elements in the vicinity of nitrogen elements introduced into the edge portion. Therefore, it is important for the carbon catalyst to contain the nitrogen element and the base metal element constituting the active site in order to have the oxygen reduction activity. Further, the carbon catalyst, BET specific surface area of preferably 20~2000m 2 / g, 40~1500m 2 / g is more preferable.
（活性炭）
活性炭としては、具体的にはフェノール系、ヤシガラ系、レーヨン系、アクリル系、石炭−石油系ピッチコークス、メソカーボンマイクロビーズ（ＭＣＭＢ）等を賦活した活性炭を挙げることができる。同じ質量でもより広い面積の界面を形成することが可能な、比表面積の大きいものが好ましい。具体的には、比表面積が３０ｍ２／ｇ以上が好ましく、より好ましくは５００〜５０００ｍ２／ｇ、さらに好ましくは１０００〜３０００ｍ２／ｇである。
(Activated carbon)
Specific examples of the activated carbon include activated carbons activated by phenol-based, coconut husk-based, rayon-based, acrylic-based, coal-petroleum-based pitch coke, mesocarbon microbeads (MCMB) and the like. Those having a large specific surface area, which can form an interface having a wider area even with the same mass, are preferable. Specifically, the specific surface area is preferably 30 m 2 / g or more, more preferably 500 to 5000 m 2 / g, and further preferably 1000 to 3000 m 2 / g.
（還元酵素）
還元酵素としては、酸素を還元出来るものであれば、特に限定されない。具体的には、ビリルビンオキシダーゼ、ラッカーゼ等が挙げられ、１種類でも２種類以上であってもよい。また、必要に応じてメディエーターを含んでも良い。
(Reductase)
The reductase is not particularly limited as long as it can reduce oxygen. Specific examples thereof include bilirubin oxidase and laccase, which may be one type or two or more types. In addition, a mediator may be included if necessary.
以下に、実施例により本発明をさらに具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention.
＜アノード形成用組成物の調製＞
［実施例１］
導電材としてケッチェンブラックＥＣ−６００ＪＤ（ライオン・スペシャリティ・ケミカルズ社製）８．８質量％、水溶性樹脂としてＰＶＰ Ｋ−３０（ポリビニルピロリドン、ＩＳＰジャパン社製）０．２質量％、水性樹脂微粒子であるポリアクリルエマルション Ｗ−１６８（固形分５０質量％、トーヨーケム社製）２質量％、溶媒として水８９質量％、をミキサーに入れて混合し、更にサンドミルに入れて分散して固形分が１０質量％となるアノード形成用組成物（１）を得た。
<Preparation of composition for forming anode>
[Example 1]
Ketjen Black EC-600JD (manufactured by Lion Specialty Chemicals) 8.8% by mass as a conductive material, PVP K-30 (polyvinylpyrrolidone, manufactured by ISP Japan) 0.2% by mass as a water-soluble resin, aqueous resin fine particles Polyacrylic emulsion W-168 (solid content 50% by mass, manufactured by Toyochem Co., Ltd.) 2% by mass and 89% by mass of water as a solvent are mixed in a mixer and then put in a sand mill to be dispersed to have a solid content of 10. A composition for forming an anode (1) having a mass% of mass was obtained.
［実施例２〜１４、比較例１〜３］
表１に示す導電材、水溶性樹脂、水性樹脂微粒子、その他の樹脂、溶媒を用いて、アノード形成用組成物（１）と同様の方法でアノード形成用組成物（２）〜（１７）を作製した。なお、実施例１０では、導電材として、鱗状黒鉛ＦＢ−１５０（日本黒鉛社製）８．６４質量％とアセチレンブラックＨＳ−１００（デンカ社製）０．９６質量％とを使用した。また、実施例１１〜１３においては、導電材として、鱗状黒鉛ＦＢ−１５０（日本黒鉛社製）６．７５質量％とケッチェンブラックＥＣ−３００ＪＤ（ライオン・スペシャリティ・ケミカルズ社製）０．７５質量％とを使用した。
[Examples 2 to 14, Comparative Examples 1 to 3]
Using the conductive material, the water-soluble resin, the water-based resin fine particles, other resins, and the solvent shown in Table 1, the anode-forming compositions (2) to (17) are prepared in the same manner as the anode-forming composition (1). Made. In Example 10, scaly graphite FB-150 (manufactured by Nippon Graphite Co., Ltd.) 8.64% by mass and acetylene black HS-100 (manufactured by Denka Co., Ltd.) 0.96% by mass were used as the conductive material. Further, in Examples 11 to 13, as conductive materials, scaly graphite FB-150 (manufactured by Nippon Graphite Co., Ltd.) 6.75% by mass and Ketjen Black EC-300JD (manufactured by Lion Specialty Chemicals Co., Ltd.) 0.75% by mass. % And used.
＜微生物燃料電池用アノードの作製＞ <Manufacturing anodes for microbial fuel cells>
［実施例１５〜２８、比較例４〜６］
基材であるカーボンペーパー（大きさ１０ｃｍ×１０ｃｍ、東レ社製）上に、実施例１〜１４及び比較例１〜３のアノード形成用組成物（１）〜（１７）を目付け量が２ｍｇ/ｃｍ２となるように添加した後、１１０℃で１０分間加熱乾燥し微生物燃料電池用アノード（１）〜（１７）を作製した。
[Examples 15 to 28, Comparative Examples 4 to 6]
The anode forming compositions (1) to (17) of Examples 1 to 14 and Comparative Examples 1 to 3 were placed on a carbon paper (size 10 cm × 10 cm, manufactured by Toray Industries, Inc.) as a base material in an amount of 2 mg / After the addition to a size of cm 2 , the anodes (1) to (17) for a microbial fuel cell were prepared by heating and drying at 110 ° C. for 10 minutes.
微生物燃料電池用アノード（１５）は、塗膜が剥落したため、以降の評価を実施しなかった。 The anode (15) for the microbial fuel cell was not evaluated after that because the coating film was peeled off.
［比較例７］
基材であるカーボンペーパーをそのまま用いて微生物燃料電池用アノード（１８）とした。
[Comparative Example 7]
The carbon paper as the base material was used as it was as an anode (18) for a microbial fuel cell.
＜微生物燃料電池＞
［実施例２９］
図１に示す微生物燃料電池により評価を実施した。５００ｍＬの容量を持つ容器内に、土（花と野菜の土：あかぎ農園社）４００ｇと、カソード、アノードを配置し、土中に電解液である水道水２５０ｇを加えて微生物燃料電池を作製した。アノードは微生物燃料電池用アノード（１）を使用し、カソードはカーボンフェルトＬＦＰ−２１０（大きさ１０ｃｍ×１０ｃｍ、大阪ガスケミカル社製）を用いた。次に、カソードとアノードに配線を取り付けて外部抵抗（８ｋΩ）に接続し、微生物燃料電池を連続運転させた。
<Microbial fuel cell>
[Example 29]
The evaluation was carried out using the microbial fuel cell shown in FIG. A microbial fuel cell was prepared by arranging 400 g of soil (soil of flowers and vegetables: Akagi Farm Co., Ltd.), cathode and anode in a container with a capacity of 500 mL, and adding 250 g of tap water, which is an electrolytic solution, to the soil. .. An anode (1) for a microbial fuel cell was used as the anode, and carbon felt LFP-210 (size 10 cm × 10 cm, manufactured by Osaka Gas Chemical Co., Ltd.) was used as the cathode. Next, wiring was attached to the cathode and anode and connected to an external resistor (8 kΩ) to continuously operate the microbial fuel cell.
［実施例３０〜４２、比較例８〜１０］
表１に示す通り、微生物燃料電池用アノード（１）の代わりに微生物燃料電池用アノード（２）〜（１４）、（１６）〜（１８）を使用した以外は実施例２９と同様にして、微生物燃料電池を連続運転させた。
[Examples 30 to 42, Comparative Examples 8 to 10]
As shown in Table 1, the same as in Example 29 except that the anodes (2) to (14) and (16) to (18) for the microbial fuel cell were used instead of the anode (1) for the microbial fuel cell. The microbial fuel cell was continuously operated.
（発電特性評価）
３週間後の微生物燃料電池の電圧と電流をテスターで測定して出力を算出した。下記に判断基準を示し、結果を表１に示す。
◎：発電特性 ２５μＷ以上（極めて良好）
〇：発電特性 ２０μＷ以上２５μＷ未満（良好）
〇△：発電特性 １５μＷ以上２０μＷ未満（実用上問題なし）
△：発電特性 ５μＷ以上１５μＷ未満（不良）
×：発電特性 ５μＷ未満（極めて不良）
(Evaluation of power generation characteristics)
The voltage and current of the microbial fuel cell after 3 weeks were measured with a tester to calculate the output. The criteria are shown below, and the results are shown in Table 1.
⊚: Power generation characteristics 25 μW or more (extremely good)
〇: Power generation characteristics 20 μW or more and less than 25 μW (good)
〇 △: Power generation characteristics 15 μW or more and less than 20 μW (no problem in practical use)
Δ: Power generation characteristics 5 μW or more and less than 15 μW (defective)
×: Power generation characteristics less than 5 μW (extremely defective)
（耐久性評価）
発電特性評価を実施した時点での発電特性を１００％とし、さらに３週間後の発電特性を測定して発電特性の維持率を算出して評価した。下記に判断基準を示し、結果を表１に示す。
◎：発電特性維持率 ８０％以上（極めて良好）
〇：発電特性維持率 ７０％以上８０％未満（良好）
〇△：発電特性維持率 ６０％以上７０％未満（実用上問題なし）
△：発電特性維持率 ４０％以上６０％未満（不良）
×：発電特性維持率 ４０％未満（極めて不良）
(Durability evaluation)
The power generation characteristics at the time when the power generation characteristics were evaluated were set to 100%, and the power generation characteristics after 3 weeks were measured to calculate and evaluate the maintenance rate of the power generation characteristics. The criteria are shown below, and the results are shown in Table 1.
⊚: Power generation characteristic maintenance rate 80% or more (extremely good)
〇: Power generation characteristic maintenance rate 70% or more and less than 80% (good)
〇 △: Power generation characteristic maintenance rate 60% or more and less than 70% (no problem in practical use)
Δ: Power generation characteristic maintenance rate 40% or more and less than 60% (defective)
×: Power generation characteristic maintenance rate less than 40% (extremely defective)
表１に示す結果から、本発明のアノード形成用組成物を用いた場合、導電材と水溶性樹脂との組み合わせにより発電特性および耐久性が増大していることが分かる。これは、電極表面近傍に水溶性樹脂が存在することで微生物に対する親和性が高まり、微生物の担持量が増えたため、発電特性とともに耐久性も改善されたためと考えられる。また、水溶性樹脂の水との高い親和性による電極の電解液に対する濡れ性の向上とともに、水溶性樹脂の膨潤、あるいは水溶性樹脂の溶出による流路の形成により、プロトンの拡散が改善され、発電特性が向上したものと考えられる。また、全固形分の合計１００質量％に対して、組成物中の導電材の含有率が、８０質量％以上の場合、より高い発電特性を示した。導電材間の電子パスが十分存在することから、表面により多くの導電材が露出することによって導電材と微生物の間の電子パスが増加したためと考える。加えて、水溶性樹脂の含有率が２０質量％以下の場合、耐久性がより良好であった。これは、電解液に触れた際に溶出・膨潤する成分が少ないことで、アノードの物理的強度が改善されたためと推察される。 From the results shown in Table 1, it can be seen that when the anode-forming composition of the present invention is used, the power generation characteristics and durability are increased by the combination of the conductive material and the water-soluble resin. It is considered that this is because the presence of the water-soluble resin near the surface of the electrode enhances the affinity for microorganisms and increases the amount of microorganisms supported, so that the durability as well as the power generation characteristics are improved. In addition, the high affinity of the water-soluble resin with water improves the wettability of the electrode with respect to the electrolytic solution, and the swelling of the water-soluble resin or the formation of a flow path due to the elution of the water-soluble resin improves the diffusion of protons. It is considered that the power generation characteristics have improved. Further, when the content of the conductive material in the composition was 80% by mass or more with respect to the total solid content of 100% by mass, higher power generation characteristics were exhibited. Since there are sufficient electron paths between the conductive materials, it is considered that the electron paths between the conductive materials and the microorganisms increased due to the exposure of more conductive materials on the surface. In addition, when the content of the water-soluble resin was 20% by mass or less, the durability was better. It is presumed that this is because the physical strength of the anode is improved because there are few components that elute and swell when it comes into contact with the electrolytic solution.
さらに、水性樹脂微粒子を使用したものは発電特性や耐久性がより改善した。この理由として、粒子間や粒子−電極基材間を水性樹脂微粒子が点結着したため、微生物が付着しやすい表面形態が形成されて担持量が増加し、かつ、反応界面が増大したことで発電特性が向上したものと考えられる。また、水性樹脂微粒子による強固な結着により耐久性も向上したものと考えられる。また、全固形分の合計１００質量％に対して、水性樹脂微粒子の含有率が１５質量％以下の場合、発電特性や耐久性がより高かった。これは、水性樹脂微粒子と導電材との点結着により、微生物の吸着に適した表面形態が形成されたためと考察する。さらに、水性樹脂微粒子の含有量が８質量％以下である場合、発電特性が改善された。塗膜表面において導電材がより多く露出することで、微生物と導電材とが接触しやすくなり、アノード反応が促進されたものと考える。 Furthermore, those using water-based resin fine particles have further improved power generation characteristics and durability. The reason for this is that the aqueous resin fine particles are dotted between the particles or between the particles and the electrode base material, so that a surface morphology to which microorganisms easily adhere is formed, the amount of the particles supported increases, and the reaction interface increases, so that power is generated. It is considered that the characteristics have improved. In addition, it is considered that the durability is also improved by the strong binding by the water-based resin fine particles. Further, when the content of the aqueous resin fine particles was 15% by mass or less with respect to the total solid content of 100% by mass, the power generation characteristics and durability were higher. It is considered that this is because the surface morphology suitable for the adsorption of microorganisms was formed by the point binding between the aqueous resin fine particles and the conductive material. Furthermore, when the content of the aqueous resin fine particles was 8% by mass or less, the power generation characteristics were improved. It is considered that the more the conductive material is exposed on the surface of the coating film, the easier the contact between the microorganism and the conductive material is, and the anodic reaction is promoted.
また、導電材として、グラファイトとそれ以外の炭素材料を組み合わせることによって、電池性能が改善したことから、微生物の吸着に好適な表面形態が形成されたと考察した。また、導電材の平均比表面積が５ｍ２／ｇ以上である場合、発電特性が向上した。これは、アノードの表面積が大きくなり、微生物の吸着性が向上したためと考える。また、平均比表面積が３００ｍ２／ｇ以下である場合、耐久性が改善した。アノードの表面粗さが大きくなり、微生物の吸着性が向上したものと考察する。 In addition, it was considered that the combination of graphite and other carbon materials as the conductive material improved the battery performance, and thus a surface morphology suitable for adsorption of microorganisms was formed. Further, when the average specific surface area of the conductive material was 5 m 2 / g or more, the power generation characteristics were improved. It is considered that this is because the surface area of the anode is increased and the adsorptivity of microorganisms is improved. Further, when the average specific surface area was 300 m 2 / g or less, the durability was improved. It is considered that the surface roughness of the anode is increased and the adsorptivity of microorganisms is improved.
１容器
２カソード
３アノード
４土
５外部抵抗
1 container 2 cathode 3 anode 4 soil 5 external resistance
Claims (7)
A microbial fuel cell according to claim 6, wherein the anode for the microbial fuel cell is used.
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| JP2020181810A true JP2020181810A (en) | 2020-11-05 |
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