JP4949971B2 - Carbon electrode material, carbon electrode material mixture, carbon electrode material manufacturing method, electric double layer capacitor, lithium ion battery, and lithium ion capacitor - Google Patents
Carbon electrode material, carbon electrode material mixture, carbon electrode material manufacturing method, electric double layer capacitor, lithium ion battery, and lithium ion capacitor Download PDFInfo
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- JP4949971B2 JP4949971B2 JP2007214781A JP2007214781A JP4949971B2 JP 4949971 B2 JP4949971 B2 JP 4949971B2 JP 2007214781 A JP2007214781 A JP 2007214781A JP 2007214781 A JP2007214781 A JP 2007214781A JP 4949971 B2 JP4949971 B2 JP 4949971B2
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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
Abstract
Description
本発明は、炭素電極材、炭素電極材混合物および炭素電極材の製造方法に関する。また、本発明は、当該炭素電極材、炭素電極材混合物を用いた電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタに関する。 The present invention relates to a carbon electrode material, a carbon electrode material mixture, and a method for producing a carbon electrode material. The present invention also relates to an electric double layer capacitor, a lithium ion battery, and a lithium ion capacitor using the carbon electrode material and the carbon electrode material mixture.
近年、エレクトロニクス機器、特に、パソコンや携帯用情報通信機器等の市場は、急速に発展している。これに伴い、これらの機器に用いられる蓄電源の高性能化、すなわち、高エネルギー密度化、高電圧化、高出力化、長寿命化、小型軽量化、低価格化等の要求が一層高まっている。また、環境問題への対策から、鉛蓄電池やニッケル・カドミウム電池のような有害重金属を含有する電池に対する規制も次第に強まりつつある。 In recent years, the market for electronic devices, particularly personal computers and portable information communication devices, has been rapidly developing. Along with this, the demand for higher performance of storage power sources used in these devices, that is, higher energy density, higher voltage, higher output, longer life, smaller size, lighter weight, lower price, etc., has further increased. Yes. Moreover, regulations for batteries containing toxic heavy metals such as lead storage batteries and nickel / cadmium batteries are gradually becoming stronger as a countermeasure to environmental problems.
このような状況下、従来の鉛蓄電池やニッケル・カドミウム電池に替わる、新たな蓄電源として、リチウムイオン電池、電気二重層キャパシタおよびリチウムイオンキャパシタ等が開発された。これらは従来の蓄電源と比較して、エネルギー密度、寿命、出力等においてより優れており、たとえば携帯用電気機器等の用途に応じて蓄電源として使用が進められている。 Under such circumstances, lithium ion batteries, electric double layer capacitors, lithium ion capacitors, and the like have been developed as new storage power sources to replace conventional lead storage batteries and nickel cadmium batteries. These are more excellent in energy density, life, output, and the like than conventional storage power sources, and are being used as storage power sources according to applications such as portable electric devices.
ここで、リチウムイオン電池は、通常、炭素質材料を負極に、リチウム含有化合物を正極に使用し、正極と負極との間でリチウムイオンを移動させることにより充放電を行なう。また、電気二重層キャパシタは、正極および負極に比較的比表面積の大きい炭素質材料を使用し、電解質イオンの吸脱着により充放電を行なう。 Here, a lithium ion battery normally performs charging / discharging by using a carbonaceous material for a negative electrode and a lithium-containing compound for a positive electrode, and moving lithium ions between the positive electrode and the negative electrode. The electric double layer capacitor uses a carbonaceous material having a relatively large specific surface area for the positive electrode and the negative electrode, and performs charge / discharge by adsorption / desorption of electrolyte ions.
最近提案されたリチウムイオンキャパシタは、正極に通常のキャパシタと同様の比較的比表面積が大きい炭素質材料を使用し、負極には、リチウムイオン電池と同様の炭素質材料を使用する。リチウムイオンキャパシタは、リチウムイオンおよび電解質イオンの吸脱着により充放電を行なうものであり、電気二重層キャパシタのエネルギー密度を改善した新しいタイプのキャパシタとして注目されている。 A recently proposed lithium ion capacitor uses a carbonaceous material having a relatively large specific surface area similar to that of an ordinary capacitor for the positive electrode, and uses a carbonaceous material similar to that of the lithium ion battery for the negative electrode. Lithium ion capacitors charge and discharge by absorbing and desorbing lithium ions and electrolyte ions, and are attracting attention as a new type of capacitor in which the energy density of electric double layer capacitors is improved.
これらリチウムイオン電池、電気二重層キャパシタおよびリチウムイオンキャパシタのさらなる高性能化のためには、高性能化された炭素電極材、すなわち、単位体積当たりの静電容量および出力密度が高い炭素電極材の開発が不可欠である。従来より、このような高性能化された炭素電極材を得るべく、種々の検討がなされており、単位体積当たりの充填性を向上させることや電解液との接触界面面積を向上させるために、粒子径の小さい粒状炭素材が提案されてきた。 In order to further improve the performance of these lithium ion batteries, electric double layer capacitors and lithium ion capacitors, high performance carbon electrode materials, that is, carbon electrode materials having a high capacitance per unit volume and high output density are required. Development is essential. Conventionally, various studies have been made to obtain such a high-performance carbon electrode material, in order to improve the filling performance per unit volume and the contact interface area with the electrolyte, A granular carbon material having a small particle diameter has been proposed.
たとえば、特許文献１には、球状フェノール樹脂を炭化、賦活することにより調製した平均粒径が１〜１０μｍの球状活性炭を電気二重層キャパシタ用電極に用いることが開示されている。また、粒子径が比較的小さい粒状炭素材として、特許文献２には、平均粒径が０．５〜２０００μｍの範囲である球状活性炭素材が開示されている。また、特許文献３には、粒径が０．１〜１５０ミクロンの球状一次粒子を含有する粒状ないし粉末状炭素微粒子が開示されている。 For example, Patent Document 1 discloses that a spherical activated carbon having an average particle size of 1 to 10 μm prepared by carbonizing and activating a spherical phenol resin is used for an electrode for an electric double layer capacitor. Further, as a granular carbon material having a relatively small particle size, Patent Document 2 discloses a spherical activated carbon material having an average particle size in the range of 0.5 to 2000 μm. Patent Document 3 discloses granular or powdered carbon fine particles containing spherical primary particles having a particle size of 0.1 to 150 microns.
しかし、いずれにおいても、十分な空間充填性を有しているとは言い難く、したがって、より高性能化されたリチウムイオン電池等を得るためには、炭素電極材についてさらなる改善が必要であった。
本発明は、このような状況に鑑みなされたものであり、その目的は、単位体積当たりの静電容量および出力密度が高い粒状炭素電極材であって、リチウムイオン電池、電気二重層キャパシタおよびリチウムイオンキャパシタ用として好適に使用できる粒状炭素電極材およびその製造方法を提供することである。また、本発明の他の目的は、かかる粒状炭素電極材を用いた電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタを提供することである。 The present invention has been made in view of such circumstances, and an object of the present invention is a granular carbon electrode material having a high capacitance per unit volume and high output density, which is a lithium ion battery, an electric double layer capacitor, and lithium. The object is to provide a granular carbon electrode material that can be suitably used for an ion capacitor and a method for producing the same. Another object of the present invention is to provide an electric double layer capacitor, a lithium ion battery and a lithium ion capacitor using such granular carbon electrode material.
本発明者らは、鋭意研究の結果、炭素電極材の単位体積当たりの静電容量および出力密度を向上させるためには、粒状炭素電極材の平均粒径を小さくするだけでなく、その粒径分布が十分に狭く、かつ１次粒子の凝集による２次凝集物の含有率が十分に低い（単粒子率が十分に高い）必要があることを見出した。また、本発明者らは、かかる特性を有する粒状炭素電極材を制御よく調製する方法を開発した。すなわち、本発明は以下のとおりである。 As a result of intensive studies, the present inventors have not only made the average particle size of the granular carbon electrode material small, but also its particle size in order to improve the capacitance per unit volume of the carbon electrode material and the output density. It has been found that the distribution needs to be sufficiently narrow and the content of secondary aggregates due to the aggregation of primary particles needs to be sufficiently low (single particle ratio is sufficiently high). In addition, the present inventors have developed a method for preparing a granular carbon electrode material having such characteristics with good control. That is, the present invention is as follows.
本発明の粒状炭素電極材は、平均粒径が１０μｍ以下、単粒子率が０．７以上であり、かつ、下記式［１］で示される粒径分布の変動係数が、０．６５以下であることを特徴とする。 The granular carbon electrode material of the present invention has an average particle size of 10 μm or less, a single particle ratio of 0.7 or more, and a coefficient of variation of the particle size distribution represented by the following formula [1] is 0.65 or less. It is characterized by being.
粒径分布の変動係数＝（ｄ84%−ｄ16%）／（２×平均粒径） ［１］
ここで、ｄ84%、ｄ16%はそれぞれ、レーザー回折・散乱法によって得られた頻度分布において累積頻度８４％、１６％を示す粒径である。
Coefficient of variation of particle size distribution = (d 84% −d 16% ) / (2 × average particle size) [1]
Here, d 84% and d 16% are particle diameters showing cumulative frequencies of 84% and 16%, respectively, in the frequency distribution obtained by the laser diffraction / scattering method.
本発明の粒状炭素電極材においては、粒子の真球度は０．５以上であることが好ましい。また本発明は、平均粒子径が異なる２種以上の上記本発明の粒状炭素電極材を混合してなる粒状炭素電極材混合物を提供する。 In the granular carbon electrode material of the present invention, the sphericity of the particles is preferably 0.5 or more. Moreover, this invention provides the granular carbon electrode material mixture formed by mixing the 2 or more types of said granular carbon electrode material of this invention from which an average particle diameter differs.
また本発明により、上記粒状炭素電極材を製造するための方法であって、（１）反応液中におけるモル濃度が２．０ｍｏｌ／Ｌ以上である酸性触媒と、保護コロイド剤との存在下、水性媒体中でアルデヒド類とフェノール類とを反応させることにより粒状フェノール樹脂を形成する、粒状フェノール樹脂形成工程と、（２）該粒状フェノール樹脂を含有する反応液を加熱して非熱溶融性の粒状フェノール樹脂を形成する、加熱工程と、（３）該非熱溶融性の粒状フェノール樹脂を反応液から分離する、分離工程と、（４）該非熱溶融性の粒状フェノール樹脂を焼成する焼成工程と、を含む粒状炭素電極材の製造方法が提供される。 Further, according to the present invention, there is provided a method for producing the granular carbon electrode material, wherein (1) the presence of an acidic catalyst having a molar concentration of 2.0 mol / L or more in the reaction solution and a protective colloid agent, A granular phenol resin forming step of forming a granular phenol resin by reacting an aldehyde and a phenol in an aqueous medium; and (2) heating the reaction liquid containing the granular phenol resin to form a non-thermomeltable material. A heating step for forming a granular phenol resin, (3) a separation step for separating the non-heat-meltable granular phenol resin from the reaction solution, and (4) a firing step for firing the non-heat-meltable granular phenol resin. The manufacturing method of the granular carbon electrode material containing these is provided.
ここで、上記酸性触媒は塩酸であり、上記アルデヒド類は、ホルムアルデヒド、パラホルムアルデヒドまたはこれらの混合物であることが好ましい。また、上記アルデヒド類に対する上記フェノール類の仕込みモル比は、０．９以下であることが好ましい。上記保護コロイド剤は、水溶性多糖類誘導体であることが好ましい。さらに、上記非熱溶融性粒状フェノール樹脂の遊離フェノール含有量は、５００ｐｐｍ以下であることが好ましい。 Here, the acidic catalyst is hydrochloric acid, and the aldehyde is preferably formaldehyde, paraformaldehyde or a mixture thereof. The molar ratio of the phenols to the aldehydes is preferably 0.9 or less. The protective colloid agent is preferably a water-soluble polysaccharide derivative. Furthermore, the free phenol content of the non-heat-meltable granular phenol resin is preferably 500 ppm or less.
さらに本発明は、上記粒状炭素電極材または粒状炭素電極材混合物を用いた電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタを提供する。 Furthermore, the present invention provides an electric double layer capacitor, a lithium ion battery, and a lithium ion capacitor using the granular carbon electrode material or the granular carbon electrode material mixture.
本発明によれば、平均粒径が１０μｍ以下と、非常に微小な粒径を有し、粒径分布が狭小であり、かつ当該微小な１次粒子の凝集による２次凝集物をほとんど含まない、すなわち単粒子率が高い粒状炭素電極材が提供される。このような本発明の粒状炭素電極材は、単位体積当たりの静電容量および出力密度の向上が図られており、電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタ用電極材料として好適に用いることができる。 According to the present invention, the average particle size is 10 μm or less, the particle size is very small, the particle size distribution is narrow, and there are almost no secondary aggregates due to the aggregation of the fine primary particles. That is, a granular carbon electrode material having a high single particle ratio is provided. Such a granular carbon electrode material of the present invention is improved in electrostatic capacity and output density per unit volume, and is preferably used as an electrode material for electric double layer capacitors, lithium ion batteries and lithium ion capacitors. Can do.
また、本発明は、上記のような優れた特性を具備する粒状炭素電極材を製造するのに好適な方法を提供する。本発明の粒状炭素電極材の製造方法によれば、比較的簡便な方法で優れた特性を有する粒状炭素電極材を制御よく製造することが可能である。 The present invention also provides a method suitable for producing a granular carbon electrode material having the above-described excellent characteristics. According to the method for producing a granular carbon electrode material of the present invention, a granular carbon electrode material having excellent characteristics can be produced with good control by a relatively simple method.
＜粒状炭素電極材＞
図１は、本発明の粒状炭素電極材の好ましい一例の走査型電子顕微鏡写真（以下、ＳＥＭ写真という。）を示す。図１に示されるように、本発明の粒状炭素電極材は、粒径の微小な粒状フェノール樹脂であって、当該粒子（１次粒子）の凝集による２次凝集物が少なく、かつ狭い粒径分布を示す。なお、図１の粒状炭素電極材は、以下に定義される平均粒径が４μｍ、単粒子率が０．９８、粒径分布の変動係数が０．５１のものである。
<Granular carbon electrode material>
FIG. 1 shows a scanning electron micrograph (hereinafter referred to as SEM photograph) of a preferred example of the granular carbon electrode material of the present invention. As shown in FIG. 1, the granular carbon electrode material of the present invention is a granular phenol resin having a small particle size, and has a small secondary particle size due to aggregation of the particles (primary particles) and a narrow particle size. Show the distribution. The granular carbon electrode material of FIG. 1 has an average particle size defined below of 4 μm, a single particle ratio of 0.98, and a variation coefficient of particle size distribution of 0.51.
本発明の粒状炭素電極材は、粒子（２次凝集物に対する用語として、１次粒子とも称する。）の平均粒径が１０μｍ以下である。平均粒径を１０μｍ以下と小さくすることにより、炭素粒子の外表面積が大きくなる。これにより、リチウムイオンや電解質イオンの炭素粒子内への侵入頻度が増加し、かつこれらのイオンの粒状炭素電極材内部における拡散距離も短くなるため、充放電の際の該イオンの出入りが速くなり、結果、出力密度を向上させることができる。また、後述するように、平均粒径がより小さい炭素電極材と、より大きい炭素電極材とを適宜の比率で組み合わせることにより、炭素電極材の充填密度を向上させることが可能であり、これにより単位体積当たりの静電容量を増加させることができる。平均粒径の下限値は特に制限されないが、あまり微小すぎると、本発明の粒状炭素電極材の原料として好ましく用いられる非熱溶融性フェノール樹脂粒子を製造する際において、固液分離が困難となる場合がある。また、平均粒径があまりに微小すぎると、該粒状炭素電極材を使用してスラリーを調製し、集電体上にこれを塗布して塗布電極を製造するに際して、該スラリーがダイラタンシー性に基づく流動性の低下を引き起こし、塗工効率の低下が見られる場合がある。したがって、このような観点からは、粒状炭素電極材の平均粒径は、０．５μｍ以上が好ましく、１μｍ以上がより好ましい。 In the granular carbon electrode material of the present invention, the average particle diameter of particles (also referred to as primary particles as a term for secondary aggregates) is 10 μm or less. By reducing the average particle size to 10 μm or less, the outer surface area of the carbon particles is increased. As a result, the penetration frequency of lithium ions and electrolyte ions into the carbon particles increases, and the diffusion distance of these ions inside the granular carbon electrode material also shortens, so that the ions enter and exit during charge / discharge faster. As a result, the output density can be improved. Further, as will be described later, it is possible to improve the packing density of the carbon electrode material by combining the carbon electrode material having a smaller average particle diameter and the larger carbon electrode material in an appropriate ratio. The capacitance per unit volume can be increased. The lower limit of the average particle diameter is not particularly limited, but if it is too small, solid-liquid separation becomes difficult when producing non-heat-meltable phenol resin particles that are preferably used as a raw material for the granular carbon electrode material of the present invention. There is a case. On the other hand, if the average particle size is too small, a slurry is prepared using the granular carbon electrode material, and when the coated electrode is produced by applying the slurry on a current collector, the slurry flows based on dilatancy. In some cases, the coating efficiency is lowered and the coating efficiency is lowered. Therefore, from such a viewpoint, the average particle diameter of the granular carbon electrode material is preferably 0.5 μm or more, and more preferably 1 μm or more.
ここで、本明細書中において「平均粒径」とは、レーザー回折式粒度測定機を用いた測定方法、すなわちレーザー回折・散乱法（マイクロトラック法）によって得られた頻度分布の累積頻度５０％値を意味する。レーザー回折式粒度測定機としては、日機装（株）製 Ｍｉｃｒｏｔｒａｃ Ｘ１００を好適に用いることができる。 Here, in this specification, the “average particle diameter” means a measurement method using a laser diffraction particle size measuring machine, that is, a cumulative frequency of 50% obtained by a laser diffraction / scattering method (microtrack method). Mean value. As a laser diffraction particle size measuring instrument, Microtrac X100 manufactured by Nikkiso Co., Ltd. can be suitably used.
また、本発明の粒状炭素電極材は、狭い粒径分布を有しており、具体的には、本発明の粒状炭素電極材を構成する粒子（１次粒子）の粒径分布の変動係数は、０．６５以下である。粒径分布の変動係数は、さらに好ましくは、０．６以下である。本明細書中において「粒径分布の変動係数」とは、下記式［１］により算出される値である。 The granular carbon electrode material of the present invention has a narrow particle size distribution. Specifically, the coefficient of variation of the particle size distribution of the particles (primary particles) constituting the granular carbon electrode material of the present invention is 0.65 or less. The variation coefficient of the particle size distribution is more preferably 0.6 or less. In the present specification, the “coefficient of variation in particle size distribution” is a value calculated by the following equation [1].
粒径分布の変動係数＝（ｄ84%−ｄ16%）／（２×平均粒径） ［１］
ここで、上記式［１］において、ｄ84%、ｄ16%はそれぞれ、レーザー回折・散乱法によって得られた頻度分布において累積頻度８４％、１６％を示す粒径であり、平均粒径とは上記で定義される平均粒径である。レーザー回折式粒度測定機としては、日機装（株）製 Ｍｉｃｒｏｔｒａｃ Ｘ１００を好適に用いることができる。上記したように、平均粒径がより小さい炭素電極材と、より大きい炭素電極材とを適宜の比率で組み合わせることにより、炭素電極材の充填密度を向上させることが可能であるが、これらの粒状炭素電極材の粒径分布が広い（変動係数が０．６５を超える）と、十分に高い充填密度を得ることが困難であり、したがって、静電容量の向上が十分でない。
Coefficient of variation of particle size distribution = (d 84% −d 16% ) / (2 × average particle size) [1]
Here, in the above formula [1], d 84% and d 16% are particle diameters showing cumulative frequencies of 84% and 16% in the frequency distribution obtained by the laser diffraction / scattering method, respectively. Is the average particle size defined above. As a laser diffraction particle size measuring instrument, Microtrac X100 manufactured by Nikkiso Co., Ltd. can be suitably used. As described above, it is possible to improve the packing density of the carbon electrode material by combining the carbon electrode material having a smaller average particle diameter and the larger carbon electrode material in an appropriate ratio. When the particle size distribution of the carbon electrode material is wide (coefficient of variation exceeds 0.65), it is difficult to obtain a sufficiently high packing density, and thus the capacitance is not sufficiently improved.
また、本発明の粒状炭素電極材の単粒子率は、０．７以上であり、好ましくは０．８以上である。単粒子率が０．７未満であり、２次凝集物が多く存在すると、１次粒子の間隙に、より平均粒径の小さい炭素電極材を充填させることが困難となることにより、充填密度を向上させることができないだけでなく、炭素電極材を電解液を用いてスラリー化した際の該スラリーの流動性が低下する傾向にある。ここで、本明細書中において「単粒子」とは、凝集による２次凝集物を形成していない１次粒子を意味し、「単粒子率」とは、水滴中に粒状炭素電極材を分散して光学顕微鏡観察を行ない、１次粒子を約３００個含む、無作為に選択した視野において、１次粒子の総個数および単粒子の個数を数えたときの当該比、すなわち、単粒子個数／１次粒子総個数を意味する。 Moreover, the single particle ratio of the granular carbon electrode material of the present invention is 0.7 or more, and preferably 0.8 or more. If the single particle ratio is less than 0.7 and there are many secondary aggregates, it becomes difficult to fill the gaps between the primary particles with a carbon electrode material having a smaller average particle diameter. Not only can it not be improved, but also the fluidity of the slurry when the carbon electrode material is slurried using an electrolytic solution tends to decrease. Here, in this specification, “single particle” means primary particles that do not form secondary aggregates due to aggregation, and “single particle ratio” means that the granular carbon electrode material is dispersed in water droplets. In the randomly selected field of view including about 300 primary particles, the ratio when the total number of primary particles and the number of single particles are counted, that is, the number of single particles / It means the total number of primary particles.
さらに、本発明の粒状炭素電極材の粒子形状は、真球状に近いほど好ましい。具体的には、真球度が０．５以上であることが好ましく、０．７以上であることがより好ましく、０．９以上であることが特に好ましい。粒子形状が真球状に近いほど、すなわち、真球度が１．０により近いほど、粒状炭素電極材の充填密度をより向上させることができるとともに、炭素電極材を電解液を用いてスラリー化した際の該スラリーの流動性をより向上させることができる。ここで、本明細書中において「真球度」とは、光学顕微鏡観察において約３００個の１次粒子を含む視野を無作為に決定し、アスペクト比（すなわち、短径／長径の比）が最も低い１次粒子を１０個選択して、これら１０個の１次粒子各々について、その投影断面におけるアスペクト比を測定したときの、これら１０のアスペクト比の平均値を意味する。 Furthermore, the particle shape of the granular carbon electrode material of the present invention is preferably closer to a true sphere. Specifically, the sphericity is preferably 0.5 or more, more preferably 0.7 or more, and particularly preferably 0.9 or more. The closer the particle shape is to a true sphere, that is, the closer the sphericity is to 1.0, the more the packing density of the granular carbon electrode material can be improved, and the carbon electrode material is slurried using an electrolytic solution. The fluidity of the slurry at the time can be further improved. In this specification, “sphericity” means a field of view containing about 300 primary particles in an optical microscope observation, and an aspect ratio (that is, a ratio of minor axis / major axis) is determined. It means the average value of these 10 aspect ratios when 10 lowest primary particles are selected and the aspect ratio in the projected cross section is measured for each of these 10 primary particles.
本発明の粒状炭素電極材の窒素吸着によるＢＥＴ法により測定される比表面積は、特に限定されないが、リチウムイオン電池またはリチウムイオンキャパシタの負極材として使用する場合には、１〜１００ｍ2／ｇであることが好ましく、１〜５０ｍ2／ｇであることがより好ましい。比表面積が１００ｍ2／ｇを超えると、充電容量に対する放電容量の比率が低下する傾向がある。また、電気二重層キャパシタ用電極材として使用する場合には、比表面積は、６００〜２３００ｍ2／ｇであることが好ましく、８００〜２０００ｍ2／ｇであることがより好ましい。比表面積が６００ｍ2／ｇ未満である場合には、電解質イオンの細孔内への侵入がスムーズに行なわれない傾向があり、２３００ｍ2／ｇを超えると、電解質イオンの吸脱着に利用される細孔以外の大きな細孔が生成することとなり、電極材の密度が低下し十分な静電容量を確保できない傾向がある。 The specific surface area measured by the BET method by nitrogen adsorption of the granular carbon electrode material of the present invention is not particularly limited, but is 1 to 100 m 2 / g when used as a negative electrode material of a lithium ion battery or a lithium ion capacitor. It is preferably 1 to 50 m 2 / g. When the specific surface area exceeds 100 m 2 / g, the ratio of the discharge capacity to the charge capacity tends to decrease. When used as an electric double layer capacitor electrode material, the specific surface area is preferably 600~2300m 2 / g, more preferably 800~2000m 2 / g. When the specific surface area is less than 600 m 2 / g, there is a tendency that electrolyte ions do not smoothly penetrate into the pores. When the specific surface area exceeds 2300 m 2 / g, it is used for adsorption / desorption of electrolyte ions. Large pores other than the pores are generated, and the density of the electrode material is lowered, and there is a tendency that sufficient electrostatic capacity cannot be secured.
本発明の粒状炭素電極材の原料としては、上記した特定の特性を有する炭素電極材を得ることができる限り特に制限されるものではなく、従来公知の原料を使用することができる。かかる原料としては、たとえば、フェノール樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂等の熱硬化性樹脂を挙げることができる。本発明の粒状炭素電極材は、好ましくは、これら樹脂の粒状物を焼成（炭化）および／または賦活することに得られる。上記樹脂のなかでもフェノール樹脂が残炭率の点から好ましく、後述する本発明の方法に従い調製された非熱溶融性粒状フェノール樹脂を用いることが特に好ましい。 The raw material for the granular carbon electrode material of the present invention is not particularly limited as long as the carbon electrode material having the specific characteristics described above can be obtained, and conventionally known raw materials can be used. Examples of such raw materials include thermosetting resins such as phenol resins, melamine resins, urea resins, and epoxy resins. The granular carbon electrode material of the present invention is preferably obtained by firing (carbonizing) and / or activating the granular material of these resins. Among the above resins, a phenol resin is preferable from the viewpoint of the residual carbon ratio, and it is particularly preferable to use a non-heat-meltable granular phenol resin prepared according to the method of the present invention described later.
ここで、粒状炭素電極材の原料として好適に用いられる非熱溶融性粒状フェノール樹脂について説明する。当該非熱溶融性粒状フェノール樹脂は、フェノール類とアルデヒド類との反応生成物からなる、非熱溶融性のフェノール樹脂である。ここで、フェノール類とアルデヒド類との反応生成物とは、基本的にはこれらが付加反応および縮合反応することにより得られる生成物であるが、一部付加反応のみ起こした生成物も含まれる。フェノール類としては、特に限定されないが、たとえばフェノール、ナフトール、ハイドロキノン、レゾルシン、キシレノール、ピロガロールなどを挙げることができる。フェノール類は１種であってもよく、２種以上組み合わせて用いてもよい。なかでも、最終的に得られる粒状炭素電極材の性能とコストとのバランスを考慮すると、フェノール類はフェノールであることが好ましい。また、アルデヒド類としては、特に制限されるものではないが、たとえばホルムアルデヒド、パラホルムアルデヒド、グリオキサール、ベンズアルデヒドなどを挙げることができる。アルデヒド類は１種であってもよく、２種以上組み合わせて用いてもよい。なかでも、アルデヒド類は、ホルムアルデヒド、パラホルムアルデヒドまたはこれらの混合物であることが好ましい。 Here, the non-heat-meltable granular phenol resin used suitably as a raw material of a granular carbon electrode material is demonstrated. The said non-heat-meltable granular phenol resin is a non-heat-meltable phenol resin which consists of a reaction product of phenols and aldehydes. Here, the reaction product of phenols and aldehydes is basically a product obtained by an addition reaction and a condensation reaction, but also includes a product that has undergone only an addition reaction. . Although it does not specifically limit as phenols, For example, phenol, naphthol, hydroquinone, resorcin, xylenol, pyrogallol etc. can be mentioned. One type of phenol may be used, or two or more types may be used in combination. Especially, when the balance of the performance and cost of the granular carbon electrode material finally obtained is considered, it is preferable that phenols are phenol. The aldehydes are not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, glyoxal, and benzaldehyde. The aldehydes may be used alone or in combination of two or more. Especially, it is preferable that aldehydes are formaldehyde, paraformaldehyde, or these mixtures.
ここで、本明細書中において「非熱溶融性」とは、特定の高温加圧条件下において粒状フェノール樹脂が融着しないことを意味するものであり、具体的には、粒状フェノール樹脂試料（乾燥品）約５ｇを、２枚の０．２ｍｍ厚ステンレス板間に挿入し、あらかじめ１００℃に加温したプレス機で、５０ｋｇの総荷重で２分間プレスしたときに、溶融および／または融着により、粒状フェノール樹脂が平板を形成したり、フェノール樹脂粒子が変形したり、またはフェノール樹脂粒子同士が互いに接着しない性質と定義される。このような性質は、粒状フェノール樹脂の製造において、フェノール類とアルデヒド類との反応によりフェノール樹脂を合成した後、該フェノール樹脂を架橋・硬化させることによって付与することができる。架橋・硬化は、たとえばフェノール類とアルデヒド類との反応を行なった反応液を加熱することによって行なうことができる。 Here, in the present specification, “non-thermal meltability” means that the granular phenol resin is not fused under a specific high-temperature pressurization condition. Specifically, a granular phenol resin sample ( About 5 g of dried product) was inserted between two 0.2 mm thick stainless steel plates and melted and / or fused when pressed at a total load of 50 kg for 2 minutes with a press machine preheated to 100 ° C. Therefore, it is defined that the granular phenol resin forms a flat plate, the phenol resin particles are deformed, or the phenol resin particles do not adhere to each other. Such properties can be imparted in the production of a granular phenol resin by synthesizing a phenol resin by a reaction between phenols and aldehydes, and then crosslinking and curing the phenol resin. Crosslinking / curing can be performed, for example, by heating a reaction solution obtained by reacting phenols with aldehydes.
非熱溶融性粒状フェノール樹脂の煮沸メタノール溶解度は、３０％未満であることが好ましく、より好ましくは２０％未満である。本明細書中において「煮沸メタノール溶解度」とは、粒状フェノール樹脂中の煮沸メタノール可溶成分の含有量を意味し、具体的には、次のような試験により算出された値と定義される。すなわち、フェノール樹脂試料（乾燥品）約１０ｇを精秤し、実質的に無水のメタノール約５００ｍＬ中で３０分間還流下に加熱した後、Ｎｏ．３のガラスフィルターで濾過し、さらにガラスフィルター上の残渣を約１００ｍＬの無水メタノールで洗浄する。ついで、洗浄後のガラスフィルター上の残渣を４０℃で５時間乾燥した後、当該残渣を精秤する。以下の式［２］により算出された値を「煮沸メタノール溶解度」とする。 The boiling methanol solubility of the non-heat-meltable granular phenolic resin is preferably less than 30%, more preferably less than 20%. In the present specification, “boiling methanol solubility” means the content of the boiling methanol-soluble component in the granular phenol resin, and is specifically defined as a value calculated by the following test. That is, about 10 g of a phenol resin sample (dry product) was precisely weighed and heated under reflux in about 500 mL of substantially anhydrous methanol for 30 minutes. Filter through 3 glass filter and wash the residue on the glass filter with about 100 mL of anhydrous methanol. Next, the residue on the glass filter after washing is dried at 40 ° C. for 5 hours, and then the residue is precisely weighed. The value calculated by the following formula [2] is defined as “boiling methanol solubility”.
煮沸メタノール溶解度（重量％）＝（フェノール樹脂試料重量と乾燥後の残渣重量との差）／（フェノール樹脂試料重量）×１００ ［２］
「煮沸メタノール溶解度」は、該フェノール樹脂が「非熱溶融性」を有するか否かの直接的な判断基準ではないが、フェノール樹脂の熱溶融性の程度を知る上での１つの指標となり得るものである。すなわち、「煮沸メタノール溶解度」が低いほど、熱溶融性も低い傾向にある。煮沸メタノール溶解度が３０％以上になると、使用の際の加熱や加圧により熱溶融性を示し、粒子が変形したり融着したりする場合がある。したがって、本発明においては、基本的には粒状炭素電極材の真球度および単粒子率は、原料となる粒状フェノール樹脂製造時における原料組成や反応条件の調整により制御できるが、煮沸メタノール溶解度が３０％未満である粒状フェノール樹脂を用いることによっても、得られる粒状炭度電極材の真球度および単粒子率を向上させ得る。本発明に従う製造方法によれば、粒状フェノール樹脂の煮沸メタノール溶解度を３０％未満とすることが可能である。
Boiling methanol solubility (% by weight) = (difference between phenol resin sample weight and residue weight after drying) / (phenol resin sample weight) × 100 [2]
“Boiled methanol solubility” is not a direct criterion for determining whether or not the phenol resin has “non-heat meltability”, but can be an index for knowing the degree of heat meltability of the phenol resin. Is. That is, the lower the “solubility of boiling methanol”, the lower the heat melting property. When the boiling methanol solubility is 30% or more, there are cases where the particles exhibit deformation or fusion due to heat melting due to heating or pressurization during use. Therefore, in the present invention, basically, the sphericity and single particle ratio of the granular carbon electrode material can be controlled by adjusting the raw material composition and reaction conditions during the production of the granular phenol resin as the raw material, but the boiling methanol solubility is low. By using a granular phenol resin that is less than 30%, the sphericity and single particle ratio of the obtained granular carbonity electrode material can be improved. According to the production method according to the present invention, the boiling methanol solubility of the granular phenol resin can be less than 30%.
さらに、非熱溶融性粒状フェノール樹脂の遊離フェノール含有量は、５００ｐｐｍ以下であることが好ましい。当該遊離フェノール含有量は、より好ましくは３００ｐｐｍ以下であり、さらに好ましくは２００ｐｐｍ以下である。遊離フェノール含有量を５００ｐｐｍ以下とすることにより、焼成に伴う微小クラックの発生や残炭率の低下を抑制または回避することでき、また賦活後の細孔径分布がシャープな粒状炭素電極材を得ることができる。また、遊離フェノールは人体や環境に有害であるため、このような粒状フェノール樹脂を用いることにより、人体や環境に対し安全性の高い製造方法が提供される。ここで、本明細書中において「遊離フェノール含有量」とは、次のような試験により算出された値と定義される。すなわち、フェノール樹脂試料（乾燥品）約１０ｇを精秤し、１９０ｍＬのメタノール中で還流下３０分間抽出し、ガラスフィルターで濾過する。濾液中のフェノール類濃度を液体クロマトグラフィーにより定量して、該濾液中のフェノール類重量を算出する。該フェノール類重量と試料重量との比、すなわち、フェノール類重量／フェノール樹脂試料重量を「遊離フェノール含有量」とする。 Furthermore, the free phenol content of the non-heat-meltable granular phenol resin is preferably 500 ppm or less. The free phenol content is more preferably 300 ppm or less, still more preferably 200 ppm or less. By setting the free phenol content to 500 ppm or less, it is possible to suppress or avoid the generation of microcracks and a decrease in the residual carbon ratio due to firing, and obtain a granular carbon electrode material having a sharp pore size distribution after activation. Can do. Moreover, since free phenol is harmful to the human body and the environment, the use of such a granular phenol resin provides a production method that is highly safe for the human body and the environment. Here, in this specification, “free phenol content” is defined as a value calculated by the following test. That is, about 10 g of a phenol resin sample (dried product) is precisely weighed, extracted in 190 mL of methanol under reflux for 30 minutes, and filtered through a glass filter. The concentration of phenols in the filtrate is quantified by liquid chromatography, and the weight of phenols in the filtrate is calculated. The ratio between the phenol weight and the sample weight, that is, the phenol weight / phenol resin sample weight is defined as “free phenol content”.
ここで、本発明の粒状炭素電極材を電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタ用電極材料として用いる場合、平均粒径が異なる２種以上の粒状炭素電極材を混合して用いてもよい。後述する本発明の製造方法によれば、粒状炭素電極材の平均粒径を所望の値に制御することが可能であるため、所望の平均粒径を有し、しかもその粒径分布がシャープであり、単粒子率の高い粒状炭素電極材を提供することができる。なお、「２種以上」における「種」とは平均粒径の相違を示している。平均粒径が異なる２種以上の粒状炭素電極材を混合して用いることにより、平均粒径がより大きな炭素電極材の間隙に、平均粒径がより小さな炭素電極材が入り込むことができるため、炭素電極材の充填密度を向上させることができる。平均粒径が異なる２種以上の粒状炭素電極材を混合する場合における、その最適な混合比率は、それら炭素電極材の平均粒径等に依存するため一概に定めることはできず、混合させる炭素電極材の平均粒径等に応じて、単位体積当たりの静電容量が最も高くなるよう適宜設定されることが好ましい。 Here, when the granular carbon electrode material of the present invention is used as an electrode material for an electric double layer capacitor, a lithium ion battery and a lithium ion capacitor, a mixture of two or more types of granular carbon electrode materials having different average particle diameters may be used. Good. According to the production method of the present invention described later, the average particle diameter of the granular carbon electrode material can be controlled to a desired value, so that it has a desired average particle diameter and the particle diameter distribution is sharp. In addition, a granular carbon electrode material having a high single particle ratio can be provided. The “seed” in “two or more” indicates a difference in average particle diameter. By mixing and using two or more types of granular carbon electrode materials having different average particle diameters, carbon electrode materials having smaller average particle diameters can enter the gaps between carbon electrode materials having larger average particle diameters. The packing density of the carbon electrode material can be improved. When mixing two or more types of granular carbon electrode materials having different average particle diameters, the optimum mixing ratio depends on the average particle diameter of the carbon electrode materials and the like, and cannot be determined unconditionally. It is preferable that the capacitance per unit volume is set appropriately according to the average particle diameter of the electrode material.
平均粒径が異なる２種以上の粒状炭素電極材を混合して炭素電極材混合物を得る場合、少なくとも１つの炭素電極材成分は、本発明の炭素電極材である必要がある。充填密度および出力密度向上の効果を効果的に得るためには、すべての炭素電極材成分が本発明の炭素電極材であることが好ましい。すなわち、混合されるすべての炭素電極材成分の平均粒径を１０μｍ以下とすることにより、炭素電極材混合物全体としての出力密度を効果的に向上させることができる。また、各炭素電極材成分の粒径分布がシャープであると、より平均粒径の大きい粒子が構成する空隙はおよそ一定の大きさを示すこととなり、該空隙を埋めることができる適切な大きさを有する、より微小な粒子を混合するという混合設計が可能となるため、炭素電極材混合物全体としての充填性を簡便に向上させることができる。一方、粒径分布がより広い電極材成分を混合する場合には、より平均粒径の大きい粒子が構成する空隙は、様々な大きさで分布することとなるが、このような様々な大きさの空隙を適切に埋めるような粒度分布を有するより微小な粒子を製造することは困難である。仮に、このような複雑な粒径分布を有する電極材成分を得ることが可能であっても、それぞれの粒径に見合った空隙に全ての粒子を収めるには、特殊な混合操作が必要である、混合に長時間を要する等の不具合が生じる。なお、充填性向上の観点から、すべての炭素電極材成分は真球状に近い（真球度０．５以上）ことが好ましい。 When two or more types of granular carbon electrode materials having different average particle diameters are mixed to obtain a carbon electrode material mixture, at least one carbon electrode material component needs to be the carbon electrode material of the present invention. In order to effectively obtain the effect of improving the packing density and the power density, it is preferable that all the carbon electrode material components are the carbon electrode material of the present invention. That is, by setting the average particle diameter of all the carbon electrode material components to be mixed to 10 μm or less, the output density of the entire carbon electrode material mixture can be effectively improved. In addition, when the particle size distribution of each carbon electrode material component is sharp, the voids formed by the particles having a larger average particle size will exhibit an approximately constant size, and an appropriate size capable of filling the voids. Therefore, it is possible to easily improve the filling property of the carbon electrode material mixture as a whole. On the other hand, when mixing electrode material components having a wider particle size distribution, the voids formed by particles having a larger average particle size will be distributed in various sizes. It is difficult to produce finer particles having a particle size distribution that appropriately fills the voids. Even if it is possible to obtain an electrode material component having such a complicated particle size distribution, a special mixing operation is required in order to put all the particles in the gap corresponding to each particle size. , Problems such as long time for mixing occur. In addition, from the viewpoint of improving the filling property, it is preferable that all the carbon electrode material components are nearly spherical (sphericity of 0.5 or more).
＜粒状炭素電極材の製造方法＞
以下に示す本発明の粒状炭素電極材の製造方法は、上記本発明の粒状炭素電極材を製造するための方法として好適に用いられるものである。本発明の方法によれば、保護コロイド剤の濃度の調整により、得られる粒状炭素電極材の平均粒径を制御することが可能である。また、本発明の方法によれば、中間原料となるフェノール樹脂および炭素電極材に機械的破砕を施すことなく、平均粒径が微小で、粒径分布が狭く、かつ単粒子率の高い炭素電極材を得ることができる。
<Method for producing granular carbon electrode material>
The manufacturing method of the granular carbon electrode material of the present invention shown below is suitably used as a method for manufacturing the granular carbon electrode material of the present invention. According to the method of the present invention, it is possible to control the average particle size of the obtained granular carbon electrode material by adjusting the concentration of the protective colloid agent. In addition, according to the method of the present invention, a carbon electrode having a small average particle size, a narrow particle size distribution, and a high single particle ratio without mechanically crushing the phenol resin and the carbon electrode material as intermediate raw materials A material can be obtained.
本発明の粒状炭素電極材の製造方法は、次に示す工程（１）〜（４）を含む。以下、各工程について詳細に説明する。
（１）反応液中におけるモル濃度が２．０ｍｏｌ／Ｌ以上である酸性触媒と、保護コロイド剤との存在下、水性媒体中でアルデヒド類とフェノール類とを反応させることにより粒状フェノール樹脂を形成する、粒状フェノール樹脂形成工程、
（２）該粒状フェノール樹脂を含有する反応液を加熱して非熱溶融性の粒状フェノール樹脂を形成する、加熱工程、
（３）該非熱溶融性の粒状フェノール樹脂を反応液から分離する、分離工程、および、
（４）該非熱溶融性の粒状フェノール樹脂を焼成する焼成工程。
The method for producing a granular carbon electrode material of the present invention includes the following steps (1) to (4). Hereinafter, each step will be described in detail.
(1) A granular phenol resin is formed by reacting an aldehyde and a phenol in an aqueous medium in the presence of an acidic catalyst having a molar concentration of 2.0 mol / L or more in the reaction solution and a protective colloid agent. A granular phenol resin forming step,
(2) a heating step of heating the reaction solution containing the granular phenol resin to form a non-heat-meltable granular phenol resin;
(3) a separation step of separating the non-heat-meltable granular phenol resin from the reaction solution; and
(4) A baking step of baking the non-heat-meltable granular phenol resin.
（１）粒状フェノール樹脂形成工程
本工程において、酸性触媒および保護コロイド剤の存在下、水性媒体中でアルデヒド類とフェノール類とを反応させることにより、粒状のフェノール樹脂を形成する。アルデヒド類としては、特に制限されるものではないが、たとえばホルムアルデヒド、パラホルムアルデヒド、グリオキサール、ベンズアルデヒドなどを挙げることができる。アルデヒド類は１種であってもよく、２種以上組み合わせて用いてもよい。なかでも、アルデヒド類は、ホルムアルデヒド、パラホルムアルデヒドまたはこれらの混合物であることが好ましい。なお、後述するように、本発明の方法の特徴の１つは、高濃度の酸性触媒を用いることにあるが、アルデヒド類としてホルムアルデヒドの重合物であるパラホルムアルデヒドを用いた場合、このような条件下においては、パラアルデヒドは解重合されるため、実質的に反応に寄与するのはホルムアルデヒドであると考えられる。使用するアルデヒド類の種類およびその使用量は、反応時において水性媒体中に溶解するように選択されることが好ましい。
(1) Granular phenol resin formation process In this process, granular phenol resin is formed by making aldehydes and phenols react in an aqueous medium in presence of an acidic catalyst and a protective colloid agent. The aldehydes are not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, glyoxal, and benzaldehyde. The aldehydes may be used alone or in combination of two or more. Especially, it is preferable that aldehydes are formaldehyde, paraformaldehyde, or these mixtures. As will be described later, one of the features of the method of the present invention is that a high concentration acidic catalyst is used. However, when paraformaldehyde, which is a polymer of formaldehyde, is used as the aldehyde, such a condition is used. Underneath, paraaldehyde is depolymerized, so it is believed that formaldehyde contributes substantially to the reaction. The type of aldehydes used and the amount used are preferably selected so as to dissolve in an aqueous medium during the reaction.
フェノール類としては、特に限定されないが、たとえばフェノール、ナフトール、ハイドロキノン、レゾルシン、キシレノール、ピロガロールなどを挙げることができる。フェノール類は１種であってもよく、２種以上組み合わせて用いてもよい。なかでも、水への溶解性および得られる炭素電極材の性能とコストとのバランスを考慮すると、フェノール類はフェノールであることが好ましい。使用するフェノール類の種類およびその使用量は、反応時において水性媒体中に溶解するように選択されることが好ましい。 Although it does not specifically limit as phenols, For example, phenol, naphthol, hydroquinone, resorcin, xylenol, pyrogallol etc. can be mentioned. One type of phenol may be used, or two or more types may be used in combination. Among these, the phenol is preferably phenol in consideration of the solubility in water and the balance between the performance and cost of the obtained carbon electrode material. The type of phenols to be used and the amount used are preferably selected so as to dissolve in an aqueous medium during the reaction.
具体的には、たとえばフェノール類としてフェノール等を用いる場合には、フェノール類の使用量（仕込み量）は、反応液全重量に対するフェノール類の濃度（重量比）が１０重量％以下となるように選択されることが好ましい。水への溶解度がより低いフェノール類（たとえばナフトール等）を用いる場合には、反応時における水性媒体中への溶解を保証し、粒状フェノール樹脂に優れた特性（微小な平均粒径および高単粒子率等）を発現させるために、さらに低い濃度を採用することが望ましい。ここで、「反応液全重量」とは、フェノール類、アルデヒド類、酸性触媒、保護コロイド剤および水性媒体の合計重量である。反応液全重量に対するフェノール類の濃度を１０重量％以下とすることにより、反応開始段階から粒状フェノール樹脂形成段階に至る温度管理を容易に行なうことができる。たとえば、常温付近で反応を開始する場合においては、フェノール類の濃度を１０重量％以下とすれば、特に反応初期において暴走反応等による過度の発熱を伴わないため、温度管理をほとんど行なうことなく、平均粒径が小さく、２次凝集が抑えられた粒状フェノール樹脂を形成させることができる。なお、反応液全重量に対するフェノール類の濃度（重量比）を１０重量％より高くすることも可能であるが、その場合には、反応時の温度管理を適切に行なう必要があることが多い。 Specifically, for example, when phenol or the like is used as the phenol, the amount of phenol used (amount charged) is such that the concentration (weight ratio) of the phenol with respect to the total weight of the reaction solution is 10% by weight or less. Preferably it is selected. When phenols with lower water solubility (for example, naphthol) are used, they are guaranteed to dissolve in an aqueous medium during the reaction and have excellent characteristics (fine average particle size and high single particle) It is desirable to employ a lower concentration in order to express the rate). Here, the “total weight of the reaction solution” is the total weight of phenols, aldehydes, acidic catalyst, protective colloid agent and aqueous medium. By setting the concentration of phenols to 10% by weight or less based on the total weight of the reaction solution, temperature control from the reaction start stage to the granular phenol resin formation stage can be easily performed. For example, in the case of starting the reaction at around room temperature, if the concentration of phenols is 10% by weight or less, there is no excessive heat generation due to a runaway reaction or the like particularly in the initial stage of the reaction. A granular phenol resin having a small average particle size and suppressed secondary aggregation can be formed. In addition, although it is possible to make the density | concentration (weight ratio) of phenols with respect to the reaction liquid total weight higher than 10 weight%, in that case, it is often necessary to perform temperature management at the time of reaction appropriately.
また、上記アルデヒド類の使用量（仕込み量）は、アルデヒド類に対するフェノール類の仕込みモル比が、０．９以下となるように選択されることが好ましい。アルデヒド類に対するフェノール類の仕込みモル比は、より好ましくは０．７５以下であり、さらに好ましくは０．５以下である。アルデヒド類に対するフェノール類の仕込みモル比を０．９以下とすることにより、平均粒径が小さく、２次凝集が抑えられ、さらには真球状により近く、粒径分布が狭く、遊離フェノール含有量の少ない粒状フェノール樹脂を形成させることが可能となる。また、アルデヒド類に対するフェノール類の仕込みモル比を０．７５以下とすることにより、さらに２次凝集を抑えることができる。これら粒状フェノール樹脂に係る特性をさらに良好なものとするためには、アルデヒド類に対するフェノール類の仕込みモル比を０．５以下とすることが特に好ましい。アルデヒド類に対するフェノール類の仕込みモル比の下限値については、特に制限はなく、たとえば水性媒体に溶解する範囲内でアルデヒド類を増やすことによってアルデヒド類に対するフェノール類の仕込みモル比を小さくすることができるが、反応の効率を考慮すると、アルデヒド類に対するフェノール類の仕込みモル比は０．１以上であることが好ましい。 Moreover, it is preferable that the usage-amount (preparation amount) of the said aldehydes is selected so that the molar ratio of the phenols with respect to aldehydes may be 0.9 or less. The charging molar ratio of phenols to aldehydes is more preferably 0.75 or less, and further preferably 0.5 or less. By setting the molar ratio of phenols to aldehydes to 0.9 or less, the average particle size is small, secondary agglomeration is suppressed, and closer to a true sphere, the particle size distribution is narrow, and the free phenol content is reduced. A small amount of granular phenol resin can be formed. Moreover, secondary aggregation can be further suppressed by setting the charged molar ratio of phenols to aldehydes to 0.75 or less. In order to further improve the characteristics relating to these granular phenol resins, it is particularly preferable to set the molar ratio of phenols to aldehydes to 0.5 or less. There is no particular limitation on the lower limit of the molar charge ratio of phenols to aldehydes. For example, the molar charge ratio of phenols to aldehydes can be reduced by increasing the aldehydes within a range that dissolves in an aqueous medium. However, in consideration of the efficiency of the reaction, the molar ratio of the phenols to the aldehydes is preferably 0.1 or more.
本工程において、上記のようなアルデヒド類とフェノール類とを水性媒体中で反応させるが、本発明の製造方法の特徴の１つは、当該反応を高濃度の酸性触媒を用いて行なう点にある。当該酸性触媒は、強酸性の触媒であることが好ましい。そのようなものとしては、たとえば塩酸、リン酸、硫酸等を挙げることができる。なかでも、揮発性の酸であり乾燥操作により容易に除去できるため、残留酸成分による酸化反応が粒状フェノール樹脂の表面化学特性や強度に悪影響を与えることの少ない、塩酸であることがより好ましい。高濃度とは、具体的には、反応を常温付近で開始する場合、反応液中における酸性触媒のモル濃度が２．０ｍｏｌ／Ｌ以上であることを意味し、より好ましくは、３ｍｏｌ／Ｌ以上である。平均粒径が小さく、２次凝集が抑えられた粒状フェノール樹脂、さらにこれらに加えて真球状により近く、粒径分布が狭く、遊離フェノール含有量の少ない粒状フェノール樹脂を得るためには、反応を常温付近で開始する場合、反応液中における酸性触媒のモル濃度を２．０ｍｏｌ／Ｌ以上にすることが必要である。また、工業生産に適した反応速度および付帯設備の耐酸性の観点からは、酸性触媒のモル濃度は、６ｍｏｌ／Ｌ以下であることが好ましい。なお、反応の開始温度を常温より高くすることにより、同等の反応速度を達成するために必要な酸性触媒のモル濃度は、反応開始温度が常温付近の場合よりも若干低くなる。 In this step, the aldehydes and phenols as described above are reacted in an aqueous medium. One of the characteristics of the production method of the present invention is that the reaction is performed using a high concentration acidic catalyst. . The acidic catalyst is preferably a strongly acidic catalyst. Examples of such include hydrochloric acid, phosphoric acid, sulfuric acid and the like. Among these, hydrochloric acid is more preferable because it is a volatile acid and can be easily removed by a drying operation, so that the oxidation reaction by the residual acid component does not adversely affect the surface chemical characteristics and strength of the granular phenol resin. Specifically, the high concentration means that the molar concentration of the acidic catalyst in the reaction solution is 2.0 mol / L or more, and more preferably 3 mol / L or more when the reaction is started near room temperature. It is. In order to obtain a granular phenol resin having a small average particle size and reduced secondary agglomeration, and a granular phenol resin having a particle size distribution close to that of a spherical shape and a small free phenol content. When starting near normal temperature, it is necessary to make the molar concentration of the acidic catalyst in the reaction liquid 2.0 mol / L or more. Moreover, from the viewpoint of the reaction rate suitable for industrial production and the acid resistance of the incidental equipment, the molar concentration of the acidic catalyst is preferably 6 mol / L or less. Note that by increasing the reaction start temperature above room temperature, the molar concentration of the acidic catalyst necessary to achieve the same reaction rate is slightly lower than when the reaction start temperature is near room temperature.
本発明の製造方法のもう１つの特徴は、アルデヒド類とフェノール類との反応を保護コロイド剤の存在下に行なう点にある。ここで、保護コロイド剤は、粒状のフェノール樹脂を形成するのに寄与するものである。平均粒径が小さく、２次凝集が抑えられた粒状フェノール樹脂、さらにこれらに加えて真球状により近く、粒径分布が狭く、遊離フェノール含有量の少ない粒状フェノール樹脂を形成するためには、このような保護コロイド剤を使用することが必要である。本発明においては、保護コロイド剤として、水溶性の保護コロイド剤を使用することが好ましい。水溶性保護コロイド剤としては、たとえば水溶性の多糖類誘導体を好適に用いることができる。好適に用いることができる水溶性の多糖類誘導体の具体例を挙げれば、カルボキシメチルセルロースのアルカリ金属塩またはアンモニウム塩；アラビアゴム、アカシア、グアーガム、ローカストビーンガム等の水溶性多糖類誘導体を主成分とする天然糊料などである。カルボキシメチルセルロースのアルカリ金属塩またはアンモニウム塩を使用する場合、セルロースのカルボキシメチル化度は、特に限定されるものではないが、カルボキシメチル化度７５％程度のものが市販されており、これを好適に用いることができる。なお、保護コロイド剤は、乾燥粉末として入手される場合、これを直接反応液に添加、溶解してもよく、あるいは、あらかじめ保護コロイド剤の水溶液を調製し、これを反応液に添加してもよい。 Another feature of the production method of the present invention is that the reaction between aldehydes and phenols is carried out in the presence of a protective colloid agent. Here, the protective colloid agent contributes to the formation of a granular phenol resin. In order to form a granular phenol resin having a small average particle size and reduced secondary agglomeration, and also a granular phenol resin that is closer to a true sphere, has a narrow particle size distribution, and has a low free phenol content. It is necessary to use such protective colloid agents. In the present invention, it is preferable to use a water-soluble protective colloid agent as the protective colloid agent. As the water-soluble protective colloid agent, for example, a water-soluble polysaccharide derivative can be preferably used. Specific examples of water-soluble polysaccharide derivatives that can be suitably used include alkali metal salts or ammonium salts of carboxymethyl cellulose; water-soluble polysaccharide derivatives such as gum arabic, acacia, guar gum, locust bean gum and the like as main components. Natural glue. When the alkali metal salt or ammonium salt of carboxymethyl cellulose is used, the degree of carboxymethylation of cellulose is not particularly limited, but those having a degree of carboxymethylation of about 75% are commercially available. Can be used. When the protective colloid agent is obtained as a dry powder, it may be directly added to and dissolved in the reaction solution, or an aqueous solution of the protective colloid agent may be prepared in advance and added to the reaction solution. Good.
上記保護コロイド剤の使用量は、固形分重量で、上記フェノール類の使用量の０．０４重量％程度以上とすることが好ましい。保護コロイド剤の使用量が０．０４重量％未満である場合には、粒状炭素電極材の平均粒径を１０μｍ以下とするには不十分であり、たとえばフェノール類使用量や攪拌速度など他のパラメータによる粒度制御が必要とされる。また、保護コロイド剤の使用量の上限に特に制限はないが、好ましくは、フェノール類の使用量の３重量％以下である。３重量％より多い場合、平均粒径が１０μｍ以下の粒状炭素電極材を得ることはできるが、３重量％を超える量の保護コロイド剤を添加しても、それに見合うだけの効果が得られない傾向にある一方、反応液の粘度上昇により、後述の分離工程等において分離速度が低下する傾向にある。ここで、特筆すべきは、粒状炭素電極材の平均粒径を保護コロイド剤の使用量を調整することによって制御可能であるという点である。 The use amount of the protective colloid agent is preferably about 0.04% by weight or more of the use amount of the phenols in terms of solid content. When the amount of the protective colloid agent used is less than 0.04% by weight, it is insufficient to make the average particle size of the granular carbon electrode material 10 μm or less. Granularity control by parameters is required. Moreover, there is no restriction | limiting in particular in the upper limit of the usage-amount of a protective colloid agent, However, Preferably it is 3 weight% or less of the usage-amount of phenols. When the amount is more than 3% by weight, it is possible to obtain a granular carbon electrode material having an average particle diameter of 10 μm or less, but even if an amount of the protective colloid agent exceeding 3% by weight is added, an effect commensurate with it cannot be obtained. On the other hand, due to the increase in the viscosity of the reaction solution, the separation rate tends to decrease in the separation step described later. Here, it should be noted that the average particle diameter of the granular carbon electrode material can be controlled by adjusting the amount of the protective colloid agent used.
上記水性媒体としては、水または水と水溶性有機溶媒との混合溶媒を挙げることができるが、本発明においては、水溶媒が好ましく用いられる。水性媒体の使用量は、酸性触媒の濃度が上記範囲内となるように選択され、好ましくは、さらにフェノール類の濃度が上記好ましい範囲内となるように選択される。 Examples of the aqueous medium include water or a mixed solvent of water and a water-soluble organic solvent. In the present invention, an aqueous solvent is preferably used. The amount of the aqueous medium used is selected so that the concentration of the acidic catalyst is within the above range, and preferably the concentration of the phenol is further within the above preferable range.
次に、上記したアルデヒド類、フェノール類、酸性触媒および保護コロイド剤を用いて反応を行なう具体的方法について述べる。反応の具体的方法としては、次の２つの方法を挙げることができる。（ｉ）水性媒体に酸性触媒と保護コロイド剤とアルデヒド類とを混合して混合液を調製した後、該混合液を攪拌しながらフェノール類を添加する方法、（ｉｉ）水性媒体に保護コロイド剤とアルデヒド類とフェノール類とを混合して混合液を調製した後、該混合液を攪拌しながら酸性触媒を添加する方法。 Next, a specific method for carrying out the reaction using the aldehydes, phenols, acidic catalyst and protective colloid agent will be described. Specific examples of the reaction include the following two methods. (I) a method in which an acidic catalyst, a protective colloid agent and aldehydes are mixed in an aqueous medium to prepare a mixed solution, and then a phenol is added while stirring the mixed solution; (ii) a protective colloid agent in the aqueous medium A method in which a mixed solution is prepared by mixing aldehydes and phenols, and then an acidic catalyst is added while stirring the mixed solution.
ここで、上記（ｉ）および（ｉｉ）のいずれの方法においても、上記混合液は略均一な溶液であることが好ましい。すなわち、水性媒体に混合する溶質が完全に溶解しているか、または少なくともほぼ完全に溶解していることが好ましい。混合液の調製において、混合の順序は特に制限されるものではない。また、当該混合液の反応開始時の温度は、特に制限されないが、好ましくは１０〜５０℃程度、さらに好ましくは２０〜４０℃程度である。 Here, in any of the methods (i) and (ii), the mixed solution is preferably a substantially uniform solution. That is, it is preferable that the solute mixed in the aqueous medium is completely dissolved or at least almost completely dissolved. In the preparation of the mixed solution, the order of mixing is not particularly limited. The temperature at the start of the reaction of the mixed solution is not particularly limited, but is preferably about 10 to 50 ° C, more preferably about 20 to 40 ° C.
上記（ｉ）の方法においては、上記混合液を攪拌しながらフェノール類を添加することにより、アルデヒド類とフェノール類との反応を行なう。フェノール類の添加は、フェノール類を直接混合液に添加することにより行なってもよく、あるいは、あらかじめフェノール類を水に溶解して、当該水溶液を混合液に添加するようにしてもよい。当該反応は、反応温度が１０〜６０℃程度、好ましくは２０〜５０℃程度となるように制御されることが好ましい。反応温度が約１０℃未満である場合、反応速度が小さくなる傾向にあり、反応温度が６０℃を超えると、粒径の粗大化や２次凝集物の増加を起こす虞がある。なお、上記混合液の反応開始時の温度を２０〜３０℃程度の常温付近とし、反応液全重量に対するフェノール類の濃度を１０重量％以下とすることにより、過度の発熱を伴わないため、温度管理をほとんど行なうことなく、上記好ましい温度範囲で反応を行なわせることが可能である。 In the method (i), the reaction between the aldehyde and the phenol is carried out by adding the phenol while stirring the mixed solution. The phenols may be added by adding the phenols directly to the mixed solution, or the phenols may be dissolved in water in advance and the aqueous solution added to the mixed solution. The reaction is preferably controlled so that the reaction temperature is about 10 to 60 ° C, preferably about 20 to 50 ° C. When the reaction temperature is less than about 10 ° C., the reaction rate tends to be low, and when the reaction temperature exceeds 60 ° C., there is a possibility that the particle size becomes coarse and secondary aggregates increase. The temperature at the start of the reaction of the mixed solution is about 20 to 30 ° C. and the concentration of phenols is 10% by weight or less with respect to the total weight of the reaction solution. The reaction can be carried out in the preferred temperature range with little management.
上記（ｉｉ）の方法においては、上記混合液を攪拌しながら酸性触媒を添加することにより、アルデヒド類とフェノール類との反応を行なう。酸性触媒の添加は、一度に行なってもよく、あるいは一定の時間をかけて滴下により行なってもよい。また、酸性触媒の添加は、酸性触媒を直接混合液に添加することにより行なってもよく、あるいは酸性触媒を水で希釈して、当該希釈液を混合液に添加するようにしてもよい。反応温度は、上記（ｉ）の場合と同様に、１０〜６０℃程度、好ましくは２０〜５０℃程度となるように制御されることが好ましい。 In the method (ii), the reaction between the aldehyde and the phenol is performed by adding an acidic catalyst while stirring the mixed solution. The acidic catalyst may be added all at once, or may be added dropwise over a certain period of time. The addition of the acidic catalyst may be performed by directly adding the acidic catalyst to the mixed solution, or the acidic catalyst may be diluted with water and the diluted solution may be added to the mixed solution. The reaction temperature is preferably controlled to be about 10 to 60 ° C., preferably about 20 to 50 ° C., as in the case of (i) above.
上記（ｉ）および（ｉｉ）の方法のいずれにおいても、反応が進行するにつれ、反応液は次第に白濁化（懸濁化）し、粒状フェノール樹脂が形成されるが、このような白濁化は、典型的にはフェノール類または酸性触媒の添加後、数十秒〜数分後に起こる。白濁化、すなわちフェノール樹脂粒子の析出に要する時間は、（ｉｉ）の方法の方が（ｉ）の方法よりも短い傾向にある。また、白濁化の後、典型的には反応液は、淡いピンク色〜濃ピンク色を呈するが、本発明においては、このような着色が見られるまで反応を継続することが好ましい。白濁後着色を呈するまでの時間は、概して数十分〜数時間程度である。なお、たとえば特開昭５７−１７７０１１号公報に記載の方法においては、粒子が集合して餅状となるのを避けるために、フェノール樹脂粒子析出後は攪拌を停止する必要があったが、保護コロイド剤を用いる本発明の製造方法によれば、フェノール樹脂粒子の析出後もそのまま継続して攪拌を行なうことができる。したがって、本発明の製造方法によれば、反応液の温度をより厳密に制御することができ、ひいてはフェノール樹脂の重合度および架橋度が均一な状態で、次の加熱工程に供することが可能となる。このことは、得られる粒状フェノール樹脂の均質性に寄与し得る。 In any of the above methods (i) and (ii), as the reaction proceeds, the reaction solution gradually becomes clouded (suspended) and a granular phenol resin is formed. Typically, this occurs several tens of seconds to several minutes after the addition of phenols or acidic catalyst. The time required for whitening, that is, precipitation of phenol resin particles, tends to be shorter in the method (ii) than in the method (i). Further, after the white turbidity, the reaction solution typically exhibits a light pink color to a deep pink color. In the present invention, it is preferable to continue the reaction until such coloring is observed. The time until coloring after clouding is generally several tens of minutes to several hours. For example, in the method described in Japanese Patent Application Laid-Open No. 57-177011, it was necessary to stop the stirring after the precipitation of the phenol resin particles in order to prevent the particles from collecting and forming a bowl-like shape. According to the production method of the present invention using a colloid agent, stirring can be continued as it is even after precipitation of phenol resin particles. Therefore, according to the production method of the present invention, the temperature of the reaction solution can be more strictly controlled, and as a result, the phenol resin can be subjected to the next heating step in a uniform polymerization degree and crosslinking degree. Become. This can contribute to the homogeneity of the resulting granular phenolic resin.
（２）加熱工程
本工程において、上記粒状フェノール樹脂を含有する反応液を加熱することにより、該粒状フェノール樹脂を非熱溶融性とする。このような非熱溶融性は、加熱による樹脂の架橋、硬化によってもたらされるものである。本工程における反応液の加熱温度は、６０℃以上であることが好ましく、より好ましくは７０℃以上である。また、反応液の加熱温度は、好ましくは１００℃以下であり、より好ましくは９０℃以下である。加熱温度が６０℃未満である場合には、十分な非熱溶融性が得られない虞がある。なお、ここでいう十分な非熱溶融性とは、上記で定義した「非熱溶融性」を有することをいう。また、加熱温度が１００℃を超える場合には、コンデンサを有する反応器が必要であったり、付帯設備等の耐酸性が問題となる虞がある。なお、加熱温度が６０℃程度と比較的低い場合であっても、十分な保持時間を設けることにより十分な非熱溶融性を付与することが可能である。加熱温度および加熱時間を、上記好ましい範囲において調整することにより、用途に応じて所望の重合度および架橋度に調整することができる。
(2) Heating step In this step, the granular phenol resin is made non-heat-meltable by heating the reaction solution containing the granular phenol resin. Such non-heat melting property is brought about by crosslinking and curing of the resin by heating. The heating temperature of the reaction liquid in this step is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. Moreover, the heating temperature of the reaction solution is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. When the heating temperature is less than 60 ° C., there is a possibility that sufficient non-thermal meltability cannot be obtained. In addition, sufficient non-thermal meltability here means having "non-heat meltability" defined above. Moreover, when heating temperature exceeds 100 degreeC, there exists a possibility that the reactor which has a capacitor | condenser may be required, or acid resistance, such as incidental equipment, may become a problem. Even when the heating temperature is as relatively low as about 60 ° C., it is possible to impart sufficient non-thermal meltability by providing a sufficient holding time. By adjusting the heating temperature and the heating time within the above preferred ranges, the degree of polymerization and the degree of crosslinking can be adjusted according to the intended use.
加熱時間は、粒状フェノール樹脂に十分な非熱溶融性を付与できる限り特に限定されるものではなく、加熱温度にもよるが、典型的には数分〜数時間程度である。また、当該加熱処理の終了後、次工程に進むにあたっては、適宜の温度まで反応液を冷却してもよく、あるいは反応液を冷却することなくそのまま次工程に進んでもよい。 The heating time is not particularly limited as long as sufficient non-thermal meltability can be imparted to the granular phenol resin, and is typically about several minutes to several hours although it depends on the heating temperature. In addition, after proceeding to the next step after the completion of the heat treatment, the reaction solution may be cooled to an appropriate temperature, or may proceed directly to the next step without cooling the reaction solution.
（３）分離工程
本工程において、得られた非熱溶融性粒状フェノール樹脂を反応液から分離する。分離方法としては、たとえば濾過や圧搾などを好適に用いることができる。このような分離操作のための装置として、たとえば、濾過装置、遠心脱水機、ベルトプレス、フィルタープレスなどを用いることができる。減圧留去、スプレードライなどの蒸発を利用した分離方法は、反応液が高濃度の酸性触媒を含むことから機器を傷める可能性があり、好ましくない。濾過による分離操作を行なう場合、珪藻土等の各種濾過助剤や凝集剤を用いてもよい。なお、得られる非熱溶融性粒状フェノール樹脂は、概して、比重が約１．２〜１．３であり、静置により沈降することから、当該分離操作に先立ってデカンテーション等の予備操作を行なってもよい。
(3) Separation step In this step, the obtained non-heat-meltable granular phenol resin is separated from the reaction solution. As the separation method, for example, filtration or pressing can be suitably used. As a device for such a separation operation, for example, a filtration device, a centrifugal dehydrator, a belt press, a filter press, or the like can be used. Separation methods using evaporation such as distillation under reduced pressure or spray drying are not preferable because the reaction solution contains a high concentration acidic catalyst and may damage the equipment. When performing the separation operation by filtration, various filter aids such as diatomaceous earth and flocculants may be used. The obtained non-heat-meltable granular phenol resin generally has a specific gravity of about 1.2 to 1.3, and settles by standing, so that a preliminary operation such as decantation is performed prior to the separation operation. May be.
分離工程の後、分離した粒状フェノール樹脂を洗浄する工程を設けてもよい。洗浄の具体的方法としては、たとえば（ｉ）上記分離操作により分離されたフェノール樹脂ケーキに洗浄液を添加する方法（たとえば、分離された濾過機上のフェノール樹脂ケーキへ洗浄液を注ぎ、洗浄液を加圧または減圧により除去する等）、（ｉｉ）洗浄液中に分離されたフェノール樹脂ケーキを分散させた後、再度分離操作を行なう方法、を挙げることができる。洗浄液としては、水を好適に用いることができる。水を用いて洗浄することによりフェノール樹脂ケーキ中の酸性成分を除去することができる。 After the separation step, a step of washing the separated granular phenol resin may be provided. As a specific method of washing, for example, (i) a method of adding a washing solution to the phenol resin cake separated by the above separation operation (for example, pouring the washing solution into the phenol resin cake on the separated filter and pressurizing the washing solution) Or (ii) a method in which the phenol resin cake separated in the washing liquid is dispersed and then separated again. Water can be suitably used as the cleaning liquid. The acidic component in the phenol resin cake can be removed by washing with water.
また、洗浄操作の一部として、あるいは上記水による洗浄操作の代わりに、塩基性を呈する水溶液に接触させることにより中和反応を行なってもよい。中和反応を行なうことにより、粒状フェノール樹脂表面に付着した酸性触媒成分等を効果的に除去することができる。中和反応に用いる塩基性を呈する水溶液としては、有機または無機の弱塩基性水溶液を用いることが好ましい。強塩基性の濃厚な水溶液を用いると、フェノール樹脂粒子が変色したり、溶解する虞がある。弱塩基性水溶液としては、たとえばアンモニア水溶液を好適に用いることができる。アンモニア水溶液を用いた場合、生成する塩は水溶性であるため、水洗により当該塩を除去できる。また、微量の残留塩も加熱により昇華除去できる。 Moreover, you may perform neutralization reaction by making it contact with the aqueous solution which exhibits basicity as part of washing | cleaning operation or instead of the washing | cleaning operation by the said water. By performing the neutralization reaction, it is possible to effectively remove the acidic catalyst component and the like attached to the surface of the granular phenol resin. As the basic aqueous solution used for the neutralization reaction, an organic or inorganic weakly basic aqueous solution is preferably used. If a strongly basic concentrated aqueous solution is used, the phenol resin particles may be discolored or dissolved. As the weakly basic aqueous solution, for example, an aqueous ammonia solution can be suitably used. When an aqueous ammonia solution is used, the salt produced is water-soluble, so that the salt can be removed by washing with water. A trace amount of residual salt can also be removed by heating.
洗浄された粒状フェノール樹脂は、乾燥させることなく、含水状態のまま次工程に供されてもよいし、乾燥させてもよい。乾燥の方法としては、特に限定されないが、たとえば棚型の静置乾燥機、気流乾燥機、流動層乾燥機などを用いた方法を挙げることができる。乾燥を行なうことにより、含水率約５％以下の良好な流動性を示す非熱溶融性粒状フェノール樹脂を得ることができる。本発明の方法によれば、必要に応じて軽度の解砕を行なうことにより、高い単粒子率の粒状フェノール樹脂を得ることができるが、上記乾燥工程の際または後に、解砕機などを用いてさらに単粒子率を向上させてもよい。 The washed granular phenol resin may be supplied to the next step without being dried, or may be dried in a water-containing state. Although it does not specifically limit as a drying method, For example, the method using a shelf-type stationary dryer, an airflow dryer, a fluidized bed dryer etc. can be mentioned. By performing drying, a non-heat-meltable granular phenol resin exhibiting good fluidity with a water content of about 5% or less can be obtained. According to the method of the present invention, it is possible to obtain a granular phenol resin having a high single particle ratio by performing mild crushing as necessary, but using a crusher or the like during or after the drying step. Furthermore, the single particle ratio may be improved.
以上のようにして得られる非熱溶融性粒状フェノール樹脂は、典型的には、粒径分布の変動係数が０．６５以下であり、単粒子率が０．７以上である。また、平均粒径に関しても、保護コロイド剤の使用量の調整により、たとえば２０μｍ以下の範囲で所望の値とすることができる。なお、次工程の焼成工程および／または賦活工程により、粒子の平均粒径は、幾分（典型的には３割程度）縮小するため、この点を考慮して非熱溶融性粒状フェノール樹脂の平均粒径を制御する必要がある。粒状炭素電極材の特性（平均粒径、粒径分布、単粒子率等）は、中間原料である非熱溶融性粒状フェノール樹脂の特性によって定まる。本発明の方法によれば、非熱溶融性粒状フェノール樹脂の特性を適切な範囲に制御可能であるため、電気二重層キャパシタ、リチウムイオン電池およびリチウムイオンキャパシタ用電極材として望ましい特性を有する粒状炭素電極材を好適に得ることができる。また、上記方法によれば、遊離フェノール含量が非常に少ない（５００ｐｐｍ以下）非熱溶融性粒状フェノール樹脂を製造することができる。このような非熱溶融性粒状フェノール樹脂を用いて得られる粒状炭素電極材は、シャープな細孔径分布を有する。 The non-heat-meltable granular phenol resin obtained as described above typically has a variation coefficient of particle size distribution of 0.65 or less and a single particle ratio of 0.7 or more. Further, the average particle diameter can be set to a desired value within a range of 20 μm or less, for example, by adjusting the amount of the protective colloid agent used. In addition, since the average particle size of the particles is somewhat reduced (typically about 30%) by the firing step and / or activation step of the next step, in consideration of this point, the non-heat-meltable granular phenol resin It is necessary to control the average particle size. The characteristics (average particle diameter, particle diameter distribution, single particle ratio, etc.) of the granular carbon electrode material are determined by the characteristics of the non-heat-meltable granular phenol resin that is an intermediate raw material. According to the method of the present invention, the characteristics of the non-heat-meltable granular phenol resin can be controlled within an appropriate range, so that the granular carbon having desirable characteristics as an electric double layer capacitor, a lithium ion battery and an electrode material for a lithium ion capacitor. An electrode material can be suitably obtained. Moreover, according to the said method, the non-heat-meltable granular phenol resin with very little free phenol content (500 ppm or less) can be manufactured. The granular carbon electrode material obtained using such a non-heat-meltable granular phenol resin has a sharp pore size distribution.
（４）焼成工程
非熱溶融性粒状フェノール樹脂の焼成（炭化）は、窒素、アルゴン、ヘリウムなどの不活性ガスの非酸化性雰囲気下、５００〜２５００℃、好ましくは５００〜１２００℃、より好ましくは５５０〜１０００℃の温度範囲で行なわれる。焼成工程の後、賦活処理を行なう場合には、焼成温度を９００℃程度以下とした方が、賦活を効率的に進めることができるため好ましい。焼成を行なう装置としては、たとえば電気炉、外熱式ガス炉などの従来公知の装置を用いることができる。
(4) Firing step Firing (carbonization) of the non-heat-meltable granular phenol resin is performed at 500 to 2500 ° C, preferably 500 to 1200 ° C, more preferably in a non-oxidizing atmosphere of an inert gas such as nitrogen, argon, or helium. Is performed in a temperature range of 550 to 1000 ° C. When the activation process is performed after the firing step, it is preferable to set the firing temperature to about 900 ° C. or lower because the activation can proceed efficiently. As an apparatus for performing the firing, for example, a conventionally known apparatus such as an electric furnace or an external heating gas furnace can be used.
焼成工程に引き続き、必要に応じて賦活処理が行なわれる。賦活処理の温度は、５００〜１１００℃、好ましくは８００〜１０００℃、さらに好ましくは８５０〜９５０℃である。賦活処理の温度が、１１００℃より高い場合には、炭素電極材表面の酸化、炭素骨格の酸化による、残炭率の低下等が生じる場合がある。また、５００℃より低い場合には、賦活処理による細孔形成が十分に進行しない。 Following the firing step, an activation treatment is performed as necessary. The temperature of an activation process is 500-1100 degreeC, Preferably it is 800-1000 degreeC, More preferably, it is 850-950 degreeC. When the temperature of activation processing is higher than 1100 degreeC, the fall of the residual carbon ratio by the oxidation of the carbon electrode material surface, oxidation of a carbon skeleton, etc. may arise. On the other hand, when the temperature is lower than 500 ° C., pore formation by the activation treatment does not proceed sufficiently.
賦活処理には、酸素、二酸化炭素、水蒸気もしくはこれらの２種以上の混合ガス、またはこれらのガスを含む、窒素、アルゴン、ヘリウム等の雰囲気ガス、メタン、プロパン、ブタン等の燃焼ガスなどを用いることができる。賦活処理は、賦活による炭素材の重量減少率が５〜９０％となるように行なわれることが好ましい。また、メソポアと呼ばれる比較的大きな細孔を形成する場合には、ニッケル、コバルト、鉄等の金属または金属化合物を適宜添加して賦活処理を行なってもよい。さらに、水酸化カリウム、塩化亜鉛等の薬品を添加する薬品賦活を行なってもよい。 For the activation treatment, oxygen, carbon dioxide, water vapor or a mixed gas of two or more of these, or an atmospheric gas such as nitrogen, argon or helium containing these gases, or a combustion gas such as methane, propane or butane is used. be able to. The activation treatment is preferably performed so that the weight reduction rate of the carbon material due to activation is 5 to 90%. When relatively large pores called mesopores are formed, activation treatment may be performed by appropriately adding a metal such as nickel, cobalt, iron, or a metal compound. Furthermore, chemical activation by adding chemicals such as potassium hydroxide and zinc chloride may be performed.
上記工程（１）〜（３）を経て得られた非熱溶融性粒状フェノール樹脂をそのまま用いて焼成および／または賦活処理を行なう場合、焼成炉内等でフェノール樹脂粒子が舞い、これが排ガスと同伴して排出されることにより、収率の低下、操業性の低下が生じる場合がある。このような場合には、焼成工程に先立ち、１次粒子を適度な強度および大きさを有する粒子に造粒してもよい。造粒においては、バインダーとして、コールタール、ピッチ、クレオソート油、液状フェノール樹脂、液状メラミン樹脂、ポリビニルアルコール、澱粉、結晶性セルロース粉末、メチルセルロース等を用いることができる。これらは単独で用いてもよく、または２種以上組み合わせて用いてもよい。 When the non-heat-meltable granular phenol resin obtained through the above steps (1) to (3) is used as it is, and the firing and / or activation treatment is performed, the phenol resin particles dance in the firing furnace or the like, and this is accompanied by the exhaust gas. As a result, the yield may decrease and the operability may decrease. In such a case, the primary particles may be granulated into particles having appropriate strength and size prior to the firing step. In granulation, coal tar, pitch, creosote oil, liquid phenol resin, liquid melamine resin, polyvinyl alcohol, starch, crystalline cellulose powder, methyl cellulose, and the like can be used as a binder. These may be used alone or in combination of two or more.
造粒は、非熱溶融性粒状フェノール樹脂およびバインダーを、ニーダー等の混合機を用いて均一に混合した後、湿式押出造粒機、竪型造粒機、半乾式ディスクペレッター、顆粒製造機等を用いて、粒状物に成形することにより行なうことができる。成形は、通常室温で行なわれるが、ピッチ成分等が多い場合には、加熱下で実施してもよい。造粒物の形状、大きさは特に制限されないが、たとえば直径０．５〜５ｍｍ、長さ１〜１０ｍｍ程度の円柱状、直径０．１〜１０ｍｍ程度の球状などとすることができる。なお、混合、成形時の作業性の向上等を目的として、たとえばエチレングリコール、ポリオキシエチレン、アルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリカルボン酸アンモニウム塩等の界面活性剤、液状熱硬化性樹脂等の硬化剤、ポリビニルアルコール等の糊料、押出造粒用の可塑剤などが添加されてもよい。造粒物の強度は、焼成および／または賦活処理の間ある程度形状を保持でき、これらの処理の終了後に解砕可能な強度である。解砕は、たとえば、ボールミル、振動ミル、ローターミル、ハンマーミル、ジェットミル等の粉砕機、解砕機を用いて行なうことができる。 For granulation, a non-heat-meltable granular phenol resin and a binder are mixed uniformly using a kneader or other mixer, followed by a wet extrusion granulator, a vertical granulator, a semi-dry disc pelleter, a granule manufacturing machine. It can carry out by shape | molding into a granular material using etc. Molding is usually performed at room temperature, but may be performed under heating when the pitch component is large. The shape and size of the granulated product are not particularly limited, and can be, for example, a cylindrical shape having a diameter of 0.5 to 5 mm, a length of about 1 to 10 mm, or a spherical shape having a diameter of about 0.1 to 10 mm. For the purpose of improving workability during mixing and molding, for example, surfactants such as ethylene glycol, polyoxyethylene, alkyl ether, polyoxyethylene fatty acid ester, polycarboxylic acid ammonium salt, liquid thermosetting resin, etc. A curing agent, a paste such as polyvinyl alcohol, and a plasticizer for extrusion granulation may be added. The strength of the granulated product is a strength that can maintain a certain shape during the firing and / or activation treatment and can be crushed after the completion of these treatments. The crushing can be performed using a crusher such as a ball mill, a vibration mill, a rotor mill, a hammer mill, a jet mill, or the like.
以下、実施例および比較例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these.
［粒状炭素電極剤の調製］
＜実施例１＞
３５重量％塩酸と３６重量％ホルムアルデヒド水溶液とを用いて、ホルムアルデヒド濃度１０重量％および塩酸濃度１６重量％である混合溶液２００００ｇを調製した後、該混合溶液にカルボキシメチルセルロースナトリウム塩の２重量％水溶液８０ｇを添加し、攪拌して均一溶液とした。次に、該均一溶液の温度を２０℃に調整した後、攪拌しながら、３０℃の９５重量％フェノール７００ｇを加えた。なお、反応液全重量に対するフェノール類の濃度は３．２重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．１１、反応液中の塩酸のモル濃度は４．７ｍｏｌ／Ｌである。フェノールの添加から約１２０秒で反応液は白濁化した。白濁化後も攪拌速度を落として反応を継続したところ、フェノールの添加から約３０分後に反応液は淡いピンク色に着色した。このとき、反応液の温度は３０℃に達していた。反応液の着色後、外部加熱により反応液を８０℃に加熱し、この温度で３０分間保持した。ついで、この反応液を濾過し、得られたケーキを５０００ｇの水で洗浄した後、５０００ｇの０．５重量％アンモニア水溶液に懸濁させて、４０℃で１時間中和反応を行なった。中和反応後、当該懸濁液をアスピレータを用いて吸引濾過し、５０００ｇの水で洗浄し、５０℃の乾燥機で１０時間乾燥させることにより、淡黄色の粒状フェノール樹脂８０４ｇを得た。
[Preparation of granular carbon electrode]
<Example 1>
After preparing 20000 g of a mixed solution having a formaldehyde concentration of 10 wt% and a hydrochloric acid concentration of 16 wt% using 35 wt% hydrochloric acid and a 36 wt% aqueous formaldehyde solution, 80 g of a 2 wt% aqueous solution of carboxymethylcellulose sodium salt was added to the mixed solution. And stirred to make a homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 700 g of 95 wt% phenol at 30 ° C. was added with stirring. The concentration of phenols relative to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.11, and the molar concentration of hydrochloric acid in the reaction solution is 4.7 mol / L. About 120 seconds after the addition of phenol, the reaction solution became cloudy. After the white turbidity, the reaction was continued at a reduced stirring speed. As a result, about 30 minutes after the addition of phenol, the reaction solution was colored pale pink. At this time, the temperature of the reaction solution had reached 30 ° C. After coloring the reaction solution, the reaction solution was heated to 80 ° C. by external heating and kept at this temperature for 30 minutes. Next, this reaction solution was filtered, and the resulting cake was washed with 5000 g of water, then suspended in 5000 g of 0.5 wt% aqueous ammonia solution, and neutralized at 40 ° C. for 1 hour. After the neutralization reaction, the suspension was subjected to suction filtration using an aspirator, washed with 5000 g of water, and dried with a dryer at 50 ° C. for 10 hours to obtain 804 g of pale yellow granular phenol resin.
次に、当該粒状フェノール樹脂のうちの６８０ｇを、粒状フェノール樹脂Ｉ（２００ｇ）、粒状フェノール樹脂ＩＩ（２００ｇ）、粒状フェノール樹脂ＩＩＩ（２００ｇ）および粒状フェノール樹脂ＩＶ（８０ｇ）の４つに分け、次に示す条件により、それぞれ焼成・賦活処理を行ない、炭素電極材１〜４をそれぞれ得た。
（１）炭素電極材１（収量９４ｇ）：粒状フェノール樹脂Ｉを坩堝に入れ、該坩堝を電気炉に入れた。電気炉内を充分に窒素ガスで置換した後、引き続き窒素を流しながら、室温から１００℃／時間の速度で昇温し、６００℃に到達した時点で３時間熱処理した。その後、再び１００℃／時間の速度で昇温し、８５０℃にて５時間、水蒸気を飽和した窒素気流中で賦活した。賦活程度を示す重量減少率は３３％であった。
（２）炭素電極材２（収量６０ｇ）：賦活処理時の温度を９００℃としたこと以外は、粒状フェノール樹脂Ｉと同様にして粒状フェノール樹脂ＩＩを焼成、賦活処理した。重量減少率は５６％であった。
（３）炭素電極材３（収量３５ｇ）：賦活処理時の温度を９５０℃としたこと以外は、粒状フェノール樹脂Ｉと同様にして粒状フェノール樹脂ＩＩＩを焼成、賦活処理した。重量減少率は７５％であった。
（４）炭素電極材４（収量４４ｇ）：粒状フェノール樹脂ＩＶを坩堝に入れ、該坩堝を電気炉に入れた。電気炉内を充分に窒素ガスで置換した後、引き続き窒素を流しながら、室温から１００℃／時間の速度で昇温し、９５０℃に到達した時点で３時間熱処理した。
Next, 680 g of the granular phenol resin is divided into four parts: granular phenol resin I (200 g), granular phenol resin II (200 g), granular phenol resin III (200 g), and granular phenol resin IV (80 g). Under the conditions shown below, firing and activation treatments were performed to obtain carbon electrode materials 1 to 4, respectively.
(1) Carbon electrode material 1 (yield 94 g): The granular phenol resin I was put in a crucible, and the crucible was put in an electric furnace. After sufficiently replacing the inside of the electric furnace with nitrogen gas, the temperature was raised from room temperature at a rate of 100 ° C./hour while flowing nitrogen, and when the temperature reached 600 ° C., heat treatment was performed for 3 hours. Thereafter, the temperature was increased again at a rate of 100 ° C./hour, and activation was performed in a nitrogen stream saturated with water vapor at 850 ° C. for 5 hours. The weight reduction rate indicating the degree of activation was 33%.
(2) Carbon electrode material 2 (yield 60 g): The granular phenol resin II was baked and activated in the same manner as the granular phenol resin I except that the temperature during the activation treatment was 900 ° C. The weight reduction rate was 56%.
(3) Carbon electrode material 3 (yield 35 g): The granular phenol resin III was baked and activated in the same manner as the granular phenol resin I except that the temperature during the activation treatment was 950 ° C. The weight loss rate was 75%.
(4) Carbon electrode material 4 (yield 44 g): The granular phenol resin IV was put in a crucible, and the crucible was put in an electric furnace. After sufficiently replacing the inside of the electric furnace with nitrogen gas, the temperature was raised from room temperature at a rate of 100 ° C./hour while flowing nitrogen, and when the temperature reached 950 ° C., heat treatment was performed for 3 hours.
＜実施例２＞
混合液中のホルムアルデヒド濃度を１８重量％、塩酸濃度を１８重量％としたこと以外は、実施例１と同様に反応を行ない、粒状フェノール樹脂を得た。反応液全重量に対するフェノール類の濃度は３．２重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．０６、反応液中の塩酸のモル濃度は５．３ｍｏｌ／Ｌである。反応液の白濁化は、フェノールの添加から約１５０秒後であり、器壁への樹脂の付着などの操作上の問題もなかった。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３６％の炭素電極材５を９０ｇ得た。
<Example 2>
A granular phenol resin was obtained by carrying out the reaction in the same manner as in Example 1 except that the formaldehyde concentration in the mixed solution was 18 wt% and the hydrochloric acid concentration was 18 wt%. The concentration of phenols with respect to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.06, and the molar concentration of hydrochloric acid in the reaction solution is 5.3 mol / L. The reaction solution was clouded about 150 seconds after the addition of phenol, and there were no operational problems such as adhesion of the resin to the vessel wall. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as the granular phenol resin I of Example 1, and the carbon electrode material 5 having a weight reduction rate of 36% during the activation treatment. 90 g was obtained.
＜実施例３＞
混合液中のホルムアルデヒド濃度を７重量％、塩酸濃度を２０重量％としたこと以外は、実施例１と同様に反応を行ない、粒状フェノール樹脂を得た。反応液全重量に対するフェノール類の濃度は３．２重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．１５、反応液中の塩酸のモル濃度は５．９ｍｏｌ／Ｌである。反応液の白濁化は、フェノールの添加から約３０秒後であり、器壁への樹脂の付着などの操作上の問題もなかった。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３５％の炭素電極材６を９１ｇ得た。
<Example 3>
A granular phenol resin was obtained by carrying out the reaction in the same manner as in Example 1 except that the formaldehyde concentration in the mixed solution was 7 wt% and the hydrochloric acid concentration was 20 wt%. The concentration of phenols with respect to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.15, and the molar concentration of hydrochloric acid in the reaction solution is 5.9 mol / L. The reaction solution was clouded about 30 seconds after the addition of phenol, and there were no operational problems such as adhesion of the resin to the vessel wall. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as the granular phenol resin I of Example 1, and the carbon electrode material 6 having a weight reduction rate of 35% during the activation treatment. 91 g was obtained.
＜実施例４＞
９５重量％フェノールを５２０ｇ添加したこと以外は、実施例１と同様に反応を行ない、粒状フェノール樹脂を得た。反応液全重量に対するフェノール類の濃度は２．４重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．０８、反応液中の塩酸のモル濃度は４．８ｍｏｌ／Ｌである。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３５％の炭素電極材７を９１ｇ得た。
<Example 4>
A reaction was carried out in the same manner as in Example 1 except that 520 g of 95% by weight phenol was added to obtain a granular phenol resin. The concentration of phenols relative to the total weight of the reaction solution is 2.4% by weight, the molar ratio of phenol to formaldehyde is 0.08, and the molar concentration of hydrochloric acid in the reaction solution is 4.8 mol / L. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as in the granular phenol resin I of Example 1, and the carbon electrode material 7 having a weight reduction rate of 35% during the activation treatment was used. 91 g was obtained.
＜実施例５＞
９５重量％フェノールを１０５０ｇ添加したこと以外は、実施例１と同様に反応を行ない、粒状フェノール樹脂を得た。反応液全重量に対するフェノール類の濃度は４．７重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．１６、反応液中の塩酸のモル濃度は４．６ｍｏｌ／Ｌである。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３４％の炭素電極材８を９２ｇ得た。
<Example 5>
A reaction was carried out in the same manner as in Example 1 except that 1050 g of 95 wt% phenol was added to obtain a granular phenol resin. The concentration of phenols with respect to the total weight of the reaction solution is 4.7% by weight, the molar ratio of phenol to formaldehyde is 0.16, and the molar concentration of hydrochloric acid in the reaction solution is 4.6 mol / L. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as the granular phenol resin I of Example 1, and a carbon electrode material 8 having a weight reduction rate of 34% during the activation treatment. 92 g was obtained.
＜実施例６＞
３６重量％ホルムアルデヒド水溶液１６６８ｇと、９５重量％フェノール２１０ｇと、水１５９０ｇとを混合して混合溶液３４６８ｇを調製した後、該混合溶液にカルボキシメチルセルロースナトリウム塩の２重量％水溶液２４ｇを添加し、攪拌して均一溶液とした。次に、該均一溶液の温度を２０℃に調整した後、攪拌しながら、３０℃の３５重量％塩酸２７４２ｇを加えた。なお、反応液全重量に対するフェノール類の濃度は３．２重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．１１、反応液中の塩酸のモル濃度は４．７ｍｏｌ／Ｌであり、実施例１と同じである。塩酸の添加から約２０秒で反応液は白濁化した。白濁化後も反応を継続したところ、塩酸添加から約３０分後に反応液はピンク色に着色した。その後、実施例１と同様にして、加熱、分離、洗浄および乾燥を行ない、粒状フェノール樹脂を得た。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３６％の炭素電極材９を９０ｇ得た。図２に、本実施例の粒状炭素電極材の光学顕微鏡写真を示す。
<Example 6>
A mixed solution 3468 g was prepared by mixing 1668 g of a 36 wt% formaldehyde aqueous solution, 210 g of 95 wt% phenol, and 1590 g of water. Then, 24 g of a 2 wt% aqueous solution of carboxymethyl cellulose sodium salt was added to the mixed solution and stirred. To obtain a homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 2742 g of 35 wt% hydrochloric acid at 30 ° C. was added with stirring. The concentration of phenols with respect to the total weight of the reaction solution was 3.2% by weight, the molar ratio of phenol to formaldehyde was 0.11, and the molar concentration of hydrochloric acid in the reaction solution was 4.7 mol / L. Is the same. About 20 seconds after the addition of hydrochloric acid, the reaction solution became cloudy. When the reaction was continued even after white turbidity, the reaction solution colored pink about 30 minutes after the addition of hydrochloric acid. Thereafter, heating, separation, washing and drying were carried out in the same manner as in Example 1 to obtain a granular phenol resin. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as in the granular phenol resin I of Example 1, and a carbon electrode material 9 having a weight reduction rate of 36% during the activation treatment. 90 g was obtained. In FIG. 2, the optical microscope photograph of the granular carbon electrode material of a present Example is shown.
＜実施例７＞
９５重量％フェノールを６１２ｇ用いたこと以外は、実施例６と同様に反応、焼成および賦活処理を行ない、賦活処理時の重量減少率が３４％の炭素電極材１０を９２ｇ得た。なお、反応液全重量に対するフェノール類の濃度は８．８重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．３１、反応液中の塩酸のモル濃度は４．４ｍｏｌ／Ｌである。
<Example 7>
Except for using 612 g of 95 wt% phenol, the reaction, firing and activation treatment were performed in the same manner as in Example 6 to obtain 92 g of carbon electrode material 10 having a weight reduction rate of 34% during the activation treatment. The concentration of phenols with respect to the total weight of the reaction solution is 8.8% by weight, the molar ratio of phenol to formaldehyde is 0.31, and the molar concentration of hydrochloric acid in the reaction solution is 4.4 mol / L.
＜実施例８＞
混合液の調製に３６重量％ホルムアルデヒド水溶液８３４ｇと、９５重量％フェノール６１２ｇと、水２４０９ｇとを用いたこと以外は、実施例６と同様に反応、焼成および賦活処理を行ない、賦活処理時の重量減少率が３２％の炭素電極材１１を９５ｇ得た。なお、反応液全重量に対するフェノール類の濃度は８．８重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．６２、反応液中の塩酸のモル濃度は４．４ｍｏｌ／Ｌである。図３に、本実施例の粒状炭素電極材の光学顕微鏡写真を示す。
<Example 8>
Except for using 834 g of 36 wt% formaldehyde aqueous solution, 612 g of 95 wt% phenol, and 2409 g of water for the preparation of the mixed solution, the reaction, firing and activation treatment were performed in the same manner as in Example 6, and the activation treatment was performed. 95 g of carbon electrode material 11 having a weight reduction rate of 32% was obtained. The concentration of phenols relative to the total weight of the reaction solution is 8.8% by weight, the molar ratio of phenol to formaldehyde is 0.62, and the molar concentration of hydrochloric acid in the reaction solution is 4.4 mol / L. In FIG. 3, the optical microscope photograph of the granular carbon electrode material of a present Example is shown.
＜実施例９＞
３６重量％ホルムアルデヒド水溶液を用いる代わりに、同じ重量濃度のパラホルムアルデヒド水溶液を用いること以外は、実施例１と同様にして反応を行ない、粒状フェノール樹脂を得た。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３６％の炭素電極材１２を９０ｇ得た。反応の経過は、実施例１とほとんど同じであった。
<Example 9>
A granular phenol resin was obtained in the same manner as in Example 1 except that a paraformaldehyde aqueous solution having the same weight concentration was used instead of the 36% by weight aqueous formaldehyde solution. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as the granular phenol resin I of Example 1, and the carbon electrode material 12 having a weight reduction rate of 36% during the activation treatment. 90 g was obtained. The course of the reaction was almost the same as in Example 1.
＜実施例１０＞
混合溶液中の塩酸濃度を８重量％としたこと、および９５重量％フェノール添加後、外部加熱により反応液を５０℃に昇温し、反応液の着色後８０℃に加熱したこと以外は、実施例１と同様にして反応を行ない、粒状フェノール樹脂を得た。反応液全重量に対するフェノール類の濃度は３．２重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は０．１１、反応液中の塩酸のモル濃度は２．３ｍｏｌ／Ｌである。次に、得られた粒状フェノール樹脂の２００ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３５％の炭素電極材１３を９１ｇ得た。
<Example 10>
The procedure was carried out except that the hydrochloric acid concentration in the mixed solution was 8% by weight, and after adding 95% by weight phenol, the reaction solution was heated to 50 ° C. by external heating and heated to 80 ° C. after coloring the reaction solution. Reaction was carried out in the same manner as in Example 1 to obtain a granular phenol resin. The concentration of phenols relative to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.11, and the molar concentration of hydrochloric acid in the reaction solution is 2.3 mol / L. Next, using 200 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as the granular phenol resin I of Example 1, and the carbon electrode material 13 having a weight reduction rate of 35% during the activation treatment. 91 g was obtained.
＜比較例１＞
カルボキシメチルセルロースナトリウム塩の２重量％水溶液８０ｇの代わりに、水を８０ｇ用いたこと以外は、実施例１と同様にして反応を行ない、粒状フェノール樹脂を得た。反応の経過は、フェノール添加後約９５秒後に反応液が白濁したこと以外は、実施例１と同様であった。次に、得られた粒状フェノール樹脂の７０ｇを用い、実施例１の粒状フェノール樹脂Ｉと同様の条件にて焼成、賦活処理を行ない、賦活処理時の重量減少率が３０％の炭素電極材１４を３５ｇ得た。図４に、本比較例で得られた粒状フェノール樹脂の光学顕微鏡写真を示す。
<Comparative Example 1>
A granular phenol resin was obtained in the same manner as in Example 1 except that 80 g of water was used instead of 80 g of the 2 wt% aqueous solution of sodium carboxymethylcellulose. The course of the reaction was the same as in Example 1 except that the reaction solution became cloudy about 95 seconds after the addition of phenol. Next, using 70 g of the obtained granular phenol resin, firing and activation treatment were performed under the same conditions as in the granular phenol resin I of Example 1, and the carbon electrode material 14 having a weight reduction rate of 30% during the activation treatment. 35 g of was obtained. In FIG. 4, the optical microscope photograph of the granular phenol resin obtained by this comparative example is shown.
＜比較例２＞
混合溶液２００００ｇ中の塩酸濃度を５重量％としたこと以外は、実施例１と同様にして反応を行ない、粒状フェノール樹脂を得た。反応液の白濁は見られず、粒状フェノール樹脂が得られなかったため、炭素電極材を調製することはできなかった。なお、反応液中の塩酸のモル濃度は１．５ｍｏｌ／Ｌである。
<Comparative example 2>
A reaction was carried out in the same manner as in Example 1 except that the hydrochloric acid concentration in 20000 g of the mixed solution was changed to 5% by weight to obtain a granular phenol resin. No white turbidity was observed in the reaction solution, and no granular phenol resin was obtained, so that the carbon electrode material could not be prepared. The molar concentration of hydrochloric acid in the reaction solution is 1.5 mol / L.
＜比較例３＞
混合液の調製に３６重量％ホルムアルデヒド水溶液４２０ｇと、９５重量％フェノール６１２ｇと、水２８２０ｇとを用いたこと以外は、実施例６と同様に反応、焼成および賦活処理を行ない、賦活処理時の重量減少率が３０％の炭素電極材１５を８８ｇ得た。反応液全重量に対するフェノール類の濃度は８．８重量％、ホルムアルデヒドに対するフェノールの仕込みモル比は１．２３、反応液中の塩酸のモル濃度は４．４ｍｏｌ／Ｌである。
<Comparative Example 3>
Except having used 420 g of 36 weight% formaldehyde aqueous solution, 612 g of 95 weight% phenol, and 2820 g of water for preparation of a liquid mixture, reaction, baking, and activation treatment were performed similarly to Example 6, and activation treatment was carried out. 88 g of carbon electrode material 15 having a weight reduction rate of 30% was obtained. The concentration of phenols with respect to the total weight of the reaction solution is 8.8% by weight, the molar ratio of phenol to formaldehyde is 1.23, and the molar concentration of hydrochloric acid in the reaction solution is 4.4 mol / L.
＜比較例４＞
乾燥したヤシガラを坩堝に入れ、該坩堝を電気炉に入れた。電気炉内を充分に窒素ガスで置換した後、引き続き窒素を流しながら、室温から１００℃／時間の速度で昇温し、６００℃に到達した時点で３時間熱処理して焼成を行なった。その後、引き続き１００℃／時間の速度で昇温し８５０℃で５時間、水蒸気を飽和した窒素気流中で賦活した。これをダイナミックミル〔ＭＹＤ〕（三井鉱山株式会社製）にて、平均粒径が９μｍとなるまで粉砕し粒状炭素電極材１６とした。
<Comparative example 4>
The dried coconut shell was put in a crucible, and the crucible was put in an electric furnace. After sufficiently replacing the inside of the electric furnace with nitrogen gas, the temperature was raised from room temperature at a rate of 100 ° C./hour while flowing nitrogen, and when the temperature reached 600 ° C., heat treatment was performed for 3 hours to perform firing. Thereafter, the temperature was continuously increased at a rate of 100 ° C./hour, and activated in a nitrogen stream saturated with water vapor at 850 ° C. for 5 hours. This was pulverized with a dynamic mill [MYD] (manufactured by Mitsui Mining Co., Ltd.) until the average particle size became 9 μm to obtain a granular carbon electrode material 16.
＜比較例５＞
カルボキシメチルセルロースナトリウム塩の２重量％水溶液８０ｇの代わりに、水を８０ｇ用いたこと以外は、実施例１と同様にして反応を行ない、粒状フェノール樹脂を得た。反応の経過は、フェノール添加後約９５秒後に反応液が白濁したこと以外は、実施例１と同様であった。次に、得られた粒状フェノール樹脂の７０ｇを用い、実施例１の粒状フェノール樹脂ＩＶと同様の条件にて焼成を行ない、炭素電極材１７を３６ｇ得た。
<Comparative Example 5>
A granular phenol resin was obtained in the same manner as in Example 1 except that 80 g of water was used instead of 80 g of the 2 wt% aqueous solution of sodium carboxymethylcellulose. The course of the reaction was the same as in Example 1 except that the reaction solution became cloudy about 95 seconds after the addition of phenol. Next, using 70 g of the obtained granular phenol resin, firing was performed under the same conditions as the granular phenol resin IV of Example 1 to obtain 36 g of the carbon electrode material 17.
上記粒状炭素電極材１〜１７、および粒状炭素電極材１〜１５および１７の中間原料である粒状フェノール樹脂について、以下に掲げる特性を測定した。測定方法および測定条件は、次のとおりである。粒状炭素電極材１〜１７についての測定結果を表１に、粒状フェノール樹脂についての測定結果を、粒状フェノール樹脂調製時の反応条件とともに、表２に示す。なお、表１および表２における比較例３の粒状炭素電極材１５および粒状フェノール樹脂において、単粒子率および真球度が「−」となっているのは、不定形の粒子が多く存在しており、測定不可能であったことを意味する。 About the granular phenol resin which is the intermediate | middle raw material of the said granular carbon electrode materials 1-17 and the granular carbon electrode materials 1-15 and 17, the characteristic hung up below was measured. The measurement method and measurement conditions are as follows. The measurement results for the granular carbon electrode materials 1 to 17 are shown in Table 1, and the measurement results for the granular phenol resin are shown in Table 2 together with the reaction conditions when preparing the granular phenol resin. In addition, in the granular carbon electrode material 15 and granular phenol resin of Comparative Example 3 in Table 1 and Table 2, the single particle ratio and the sphericity are “−” because there are many amorphous particles. It means that it was impossible to measure.
（１）平均粒径：炭素電極材または粒状フェノール樹脂を用いて水分散液を調製し、レーザー回折式粒度測定機（日機装（株）製 Ｍｉｃｒｏｔｒａｃ Ｘ１００）により計測された頻度分布において累積頻度５０％値である。
（２）単粒子率：水滴中に炭素電極材または粒状フェノール樹脂を分散して光学顕微鏡により観察を行ない、１次粒子を約３００個含む、無作為に選択した視野において、１次粒子の総個数および単粒子の個数を数えたときの当該比、すなわち、単粒子個数／１次粒子総個数である。
（３）粒径分布の変動係数：炭素電極材または粒状フェノール樹脂を用いて水分散液を調製し、レーザー回折式粒度測定機（日機装（株）製 Ｍｉｃｒｏｔｒａｃ Ｘ１００）により計測された頻度分布から下記式［１］により算出した。
粒径分布の変動係数＝（ｄ84%−ｄ16%）／（２×平均粒径） ［１］
ここで、上記式［１］において、ｄ84%、ｄ16%はそれぞれ、得られた頻度分布において累積頻度８４％、１６％を示す粒径である。変動係数が０．６５以下である場合に狭い粒度分布を有すると判定した。
（４）真球度：光学顕微鏡による観察において約３００個の１次粒子を含む視野を無作為に決定し、アスペクト比（すなわち、短径／長径の比）が最も低い１次粒子を１０個選択して、これら１０個の１次粒子各々について、その投影断面におけるアスペクト比を測定したときの、これら１０のアスペクト比の平均値である。
（５）比表面積：炭素電極材約０．１gを正確に秤量した後、高精度全自動ガス吸着装置ＢＥＬＳＯＲＰ−ｍｉｎｉＩＩ（日本ベル株式会社製）の専用セルに入れ窒素吸着によるＢ．Ｅ．Ｔ法により求めた。
（６）非熱溶融性：粒状フェノール樹脂試料約５ｇを、２枚の０．２ｍｍ厚ステンレス板間に挿入し、あらかじめ１００℃に加温したプレス機で、５０ｋｇの総荷重で２分間プレスしたときに、溶融および／または融着により、粒状フェノール樹脂が平板を形成したり、フェノール樹脂粒子が変形したり、またはフェノール樹脂粒子同士が互いに接着しない場合を「非熱溶融性」を有すると判定した。
（７）煮沸メタノール溶解度：粒状フェノール樹脂試料約１０ｇを精秤し、実質的に無水のメタノール約５００ｍＬ中で３０分間還流下に加熱した後、Ｎｏ．３のガラスフィルターで濾過し、さらにガラスフィルター上の残渣を約１００ｍＬの無水メタノールで洗浄する。ついで、洗浄後のガラスフィルター上の残渣を４０℃で５時間乾燥した後、当該残渣を精秤する。得られた乾燥後の残渣重量と粒状フェノール樹脂試料重量から、以下の式に基づき、煮沸メタノール溶解度を算出する。
(1) Average particle diameter: An aqueous dispersion was prepared using a carbon electrode material or a granular phenol resin, and the cumulative frequency was 50% in the frequency distribution measured by a laser diffraction particle size analyzer (Microtrac X100 manufactured by Nikkiso Co., Ltd.). Value.
(2) Single particle ratio: A carbon electrode material or a granular phenol resin is dispersed in water droplets and observed with an optical microscope. In a randomly selected field of view containing about 300 primary particles, the total number of primary particles The ratio when the number and the number of single particles are counted, that is, the number of single particles / the total number of primary particles.
(3) Coefficient of variation of particle size distribution: A water dispersion was prepared using a carbon electrode material or a granular phenol resin, and the frequency distribution measured by a laser diffraction particle size analyzer (Microtrac X100 manufactured by Nikkiso Co., Ltd.) It calculated by Formula [1].
Coefficient of variation of particle size distribution = (d 84% −d 16% ) / (2 × average particle size) [1]
Here, in the above formula [1], d 84% and d 16% are particle diameters indicating the cumulative frequencies of 84% and 16%, respectively, in the obtained frequency distribution. When the coefficient of variation was 0.65 or less, it was determined to have a narrow particle size distribution.
(4) Sphericity: A field of view containing about 300 primary particles is randomly determined in observation with an optical microscope, and 10 primary particles having the lowest aspect ratio (ie, ratio of minor axis / major axis). It is the average value of these 10 aspect ratios when the aspect ratio in the projected cross section is measured for each of these 10 primary particles.
(5) Specific surface area: About 0.1 g of carbon electrode material was accurately weighed and then placed in a dedicated cell of a high-precision fully automatic gas adsorption device BELSORP-mini II (made by Nippon Bell Co., Ltd.). E. Determined by T method.
(6) Non-thermomeltability: About 5 g of granular phenol resin sample was inserted between two 0.2 mm thick stainless steel plates and pressed for 2 minutes at a total load of 50 kg with a press machine preheated to 100 ° C. Sometimes, when melting and / or fusing, the granular phenolic resin forms a flat plate, the phenolic resin particles are deformed, or the phenolic resin particles do not adhere to each other, it is determined as having “non-thermomeltability” did.
(7) Boiling methanol solubility: About 10 g of granular phenol resin sample was precisely weighed and heated under reflux in about 500 mL of substantially anhydrous methanol for 30 minutes. Filter through 3 glass filter and wash the residue on the glass filter with about 100 mL of anhydrous methanol. Next, the residue on the glass filter after washing is dried at 40 ° C. for 5 hours, and then the residue is precisely weighed. Based on the weight of the residue after drying and the weight of the granular phenol resin sample, the boiling methanol solubility is calculated based on the following formula.
煮沸メタノール溶解度（重量％）＝（粒状フェノール樹脂試料重量と乾燥後の残渣重量との差）／（粒状フェノール樹脂試料重量）×１００
（８）遊離フェノール含有量：次のような試験により算出された値と定義される。すなわち、粒状フェノール樹脂試料約１０ｇを精秤し、１９０ｍＬのメタノール中で還流下３０分間抽出し、ガラスフィルターで濾過する。濾液中のフェノール類濃度を液体クロマトグラフィーにより定量して、該濾液中のフェノール類重量を算出する。該フェノール類重量と試料重量との比、すなわち、フェノール類重量／粒状フェノール樹脂試料重量を「遊離フェノール含有量」とする。
Boiling methanol solubility (% by weight) = (Difference between the weight of the granular phenolic resin sample and the weight of the residue after drying) / (weight of the granular phenolic resin sample) × 100
(8) Free phenol content: defined as a value calculated by the following test. That is, about 10 g of a granular phenol resin sample is precisely weighed, extracted in 190 mL of methanol under reflux for 30 minutes, and filtered through a glass filter. The concentration of phenols in the filtrate is quantified by liquid chromatography, and the weight of phenols in the filtrate is calculated. The ratio between the phenol weight and the sample weight, that is, the phenol weight / particulate phenol resin sample weight is defined as “free phenol content”.
＜実施例１１＞
保護コロイド剤であるカルボキシメチルセルロースナトリウム塩のフェノールに対する量を種々変化させたこと以外は、実施例１と同様にして粒状フェノール樹脂の調製および焼成を行なった後、８５０℃で５時間賦活処理を行ない、粒状炭素電極材を得、粒状炭素電極材の平均粒径を上記方法に従って測定した。図５は、保護コロイド剤の濃度（反応液全重量に対する保護コロイド剤の重量（ｐｐｍ））と粒状炭素電極材の平均粒径との関係を示すグラフである。なお、保護コロイド剤濃度の測定範囲１３〜約１０３ｐｐｍは、保護コロイド剤使用量／フェノール使用量比（重量％）に換算すると、０．０４〜０．３２重量％の範囲に相当する。図５に示されるように、保護コロイド剤の使用量を調整することによって得られる粒状炭素電極材の平均粒径を制御できることがわかった。すなわち、保護コロイド剤の使用量を増やすことによって、平均粒径を小さくできることがわかった。
<Example 11>
A granular phenol resin was prepared and calcined in the same manner as in Example 1 except that the amount of carboxymethylcellulose sodium salt, which is a protective colloid agent, with respect to phenol was varied. Then, activation treatment was performed at 850 ° C. for 5 hours. The granular carbon electrode material was obtained, and the average particle diameter of the granular carbon electrode material was measured according to the above method. FIG. 5 is a graph showing the relationship between the concentration of the protective colloid agent (weight (ppm) of the protective colloid agent relative to the total weight of the reaction solution) and the average particle diameter of the granular carbon electrode material. The measurement range of the protective colloid agent concentration of 13 to about 103 ppm corresponds to a range of 0.04 to 0.32% by weight when converted to a protective colloid agent use amount / phenol use amount ratio (% by weight). As shown in FIG. 5, it was found that the average particle diameter of the granular carbon electrode material obtained by adjusting the amount of the protective colloid agent used can be controlled. That is, it was found that the average particle size can be reduced by increasing the amount of the protective colloid agent used.
＜実施例１２＞
以下に示す手順に従い、図６に示される構造の簡易型電気二重層キャパシタを作製した。図６は、試作した電気二重層キャパシタを示す概略断面図である。まず、集電体６０２として厚さ１ｍｍ、外径１８ｍｍの円盤状の白金板を用い、この集電体６０２に、スペーサー６０４としての厚さ０．５ｍｍ、内径３ｍｍ、外径１８ｍｍの円盤状のシリコンゴムを圧着し、集電体６０２とスペーサー６０４とで形成された深さ０．５ｍｍ、内径３ｍｍの孔内に、別途調製したスラリー状の炭素電極材６０１を充填し、これを分極性電極とした。このような分極性電極を２個作製した。次に、その２個の分極性電極間に厚さ２５μｍ、外径１８ｍｍの円盤状のポリプロピレン製セパレータ６０３を挟んで、この２個の分極性電極を対向させた。次に、端子取り出しのためのステンレス製の端子板６０５を両側から集電体６０２に圧着した。さらに固定のためステンレス製の端子板６０５の上側から１０ｋｇの加重をかけることにより、電気二重層キャパシタを作製した。
<Example 12>
A simple electric double layer capacitor having the structure shown in FIG. 6 was produced according to the following procedure. FIG. 6 is a schematic cross-sectional view showing a prototype electric double layer capacitor. First, a disc-shaped platinum plate having a thickness of 1 mm and an outer diameter of 18 mm is used as the current collector 602, and a disc-shaped platinum plate having a thickness of 0.5 mm, an inner diameter of 3 mm, and an outer diameter of 18 mm is used as the current collector 602. Silicon rubber is pressure-bonded, and a separately prepared slurry-like carbon electrode material 601 is filled in a hole formed by a current collector 602 and a spacer 604 having a depth of 0.5 mm and an inner diameter of 3 mm. It was. Two such polarizable electrodes were produced. Next, a disc-shaped polypropylene separator 603 having a thickness of 25 μm and an outer diameter of 18 mm was sandwiched between the two polarizable electrodes, and the two polarizable electrodes were opposed to each other. Next, a stainless steel terminal plate 605 for taking out the terminals was crimped to the current collector 602 from both sides. Further, an electric double layer capacitor was manufactured by applying a load of 10 kg from the upper side of the stainless steel terminal plate 605 for fixing.
上記スラリー状の炭素電極材６０１は次のようにして調製した。容器に、表３に示される重量比率で、実施例１０の粒状炭素電極材（炭素電極材１３、平均粒径９μｍ）と実施例６の粒状炭素電極材（炭素電極材９、平均粒径１μｍ）とを加えた後、電解液である３０重量％硫酸水溶液を一定量加え、脱気を行なった。ついで、該混合液に、攪拌しながら、３０重量％硫酸水溶液を徐々に添加し、容器内の混合物が粘土状からスラリー状に変化したところで添加を止め、スラリー状炭素電極材を得た。このような手順で表３に示される合計７種類のスラリー状炭素電極材（スラリー１〜７）を調製した。炭素電極材１ｇあたりに使用した電解液量（ｇ）を「電解液／電極材比率」と称し、表３に示している。 The slurry-like carbon electrode material 601 was prepared as follows. In the container, the granular carbon electrode material of Example 10 (carbon electrode material 13, average particle size 9 μm) and the granular carbon electrode material of Example 6 (carbon electrode material 9, average particle size 1 μm) in the weight ratio shown in Table 3 Then, a certain amount of 30% by weight sulfuric acid aqueous solution as an electrolytic solution was added to perform deaeration. Next, a 30% by weight sulfuric acid aqueous solution was gradually added to the mixed solution while stirring, and the addition was stopped when the mixture in the container changed from clay to slurry, and a slurry-like carbon electrode material was obtained. A total of seven types of slurry-like carbon electrode materials (slurries 1 to 7) shown in Table 3 were prepared by such a procedure. The amount (g) of the electrolytic solution used per 1 g of the carbon electrode material is referred to as “electrolyte / electrode material ratio” and is shown in Table 3.
次に、スラリー状の炭素電極材６０１の種類が異なる７種の電気二重層キャパシタのそれぞれについて、炭素電極材単位重量あたりの静電容量（Ｆ／ｇ）を測定した。炭素電極材単位重量あたりの静電容量（Ｆ／ｇ）は、電気二重層キャパシタの両極間に０．９Ｖの電圧を印加し、６時間定電圧充電を行なった後、１００μＡで定電流放電させ、電圧が０．５４Ｖから０．４５Ｖに降下するのに要した時間から電気二重層キャパシタの静電容量（Ｆ）を求め、この値と、一組（２個）の分極性電極の重量から算出した。結果を表３に示す。 Next, the electrostatic capacity (F / g) per unit weight of the carbon electrode material was measured for each of the seven types of electric double layer capacitors having different types of the slurry-like carbon electrode material 601. The capacitance per unit weight of the carbon electrode material (F / g) was determined by applying a voltage of 0.9 V between both electrodes of the electric double layer capacitor and performing a constant voltage charge for 6 hours, followed by a constant current discharge at 100 μA. From the time required for the voltage to drop from 0.54 V to 0.45 V, the capacitance (F) of the electric double layer capacitor is obtained, and from this value and the weight of the pair (two) polarizable electrodes Calculated. The results are shown in Table 3.
また、炭素電極材単位重量あたりの静電容量（Ｆ／ｇ）、用いた炭素電極材の重量および添加した電解液の重量から、下記式により、単位体積あたりの静電容量係数を求めた。結果を表３に示す。
単位体積あたりの静電容量係数＝
（炭素電極材単位重量あたりの静電容量（Ｆ／ｇ））×（炭素電極材重量）／（炭素電極材重量＋電解液重量）
Moreover, the electrostatic capacitance coefficient per unit volume was calculated | required by the following formula from the electrostatic capacitance (F / g) per unit weight of carbon electrode material, the weight of the used carbon electrode material, and the weight of the added electrolyte solution. The results are shown in Table 3.
Capacitance coefficient per unit volume =
(Capacitance per unit weight of carbon electrode material (F / g)) × (weight of carbon electrode material) / (weight of carbon electrode material + weight of electrolyte)
平均粒径、粒度分布および単粒子率を厳密に制御して作製した本発明の炭素電極材９および１３を混合して使用することにより、単独で使用する場合と比較して、より少ない電解液でスラリー調整が可能なため、電気二重層キャパシタ内により多くの炭素電極材を充填でき、したがって、単位体積あたりの静電容量係数をより大きくできることがわかる。特に、炭素電極材９および１３を１５対８５（重量比）で混合した場合（スラリー４）に、単位体積あたりの静電容量係数が最も高くなることがわかった。 By mixing and using the carbon electrode materials 9 and 13 of the present invention prepared by strictly controlling the average particle size, the particle size distribution and the single particle ratio, it is possible to reduce the amount of electrolyte compared to the case of using alone. Thus, it can be seen that since the slurry can be adjusted, more carbon electrode material can be filled in the electric double layer capacitor, and therefore the capacitance coefficient per unit volume can be further increased. In particular, when the carbon electrode materials 9 and 13 were mixed at 15 to 85 (weight ratio) (slurry 4), it was found that the capacitance coefficient per unit volume was the highest.
なお、比較例４の粒状炭素電極材（炭素電極材１６、平均粒径９μｍ）の「電解液／電極材比率」を測定したところ、１．４９であり、実施例１０の粒状炭素電極材（炭素電極材１３、平均粒径９μｍ）の１．３７（表３のスラリー７参照）と比較して高い値を示した。これは、比較例４の粒状炭素電極材は、粒径分布が広いとともに、真球度が低いため、スラリー中の炭素電極材の間隙が大きくなり、スラリー化のために、より多量の電解液を要するためであると推測できる。 The “electrolyte / electrode material ratio” of the granular carbon electrode material of Comparative Example 4 (carbon electrode material 16, average particle size 9 μm) was 1.49, and the granular carbon electrode material of Example 10 ( The value was higher than 1.37 (see slurry 7 in Table 3) of carbon electrode material 13, average particle size 9 μm). This is because the granular carbon electrode material of Comparative Example 4 has a wide particle size distribution and low sphericity, so that the gap between the carbon electrode materials in the slurry becomes large, and a larger amount of electrolyte solution is required for slurrying. It can be guessed that this is necessary.
＜実施例１３＞
実施例１の粒状炭素電極材（炭素電極材１、平均粒径４μｍ）、比較例１の粒状炭素電極材（炭素電極材１４、平均粒径１５μｍ）を用い、それぞれについて、実施例１２と同様の手順で電気二重層キャパシタを作製し、静電容量を測定した。この際、放電電流量を０．１ｍＡから１．０ｍＡまで変化させ、それぞれの放電電流における静電容量を測定した。結果を表４に示す。
<Example 13>
The granular carbon electrode material of Example 1 (carbon electrode material 1, average particle diameter of 4 μm) and the granular carbon electrode material of Comparative Example 1 (carbon electrode material 14, average particle diameter of 15 μm) were used, and each was the same as in Example 12. The electric double layer capacitor was produced by the procedure described above, and the capacitance was measured. At this time, the discharge current amount was changed from 0.1 mA to 1.0 mA, and the capacitance at each discharge current was measured. The results are shown in Table 4.
比較例１の粒状炭素電極材を用いた電気二重層キャパシタは、放電電流の増加とともに、静電容量が大きく低下したが、実施例１の粒状炭素電極材を用いた電気二重層キャパシタでは、静電容量の低下が少ないことがわかる。これは、炭素電極材１の場合は、炭素電極材１４に比して電極材の平均粒径が小さいことから、１）炭素電極材と電解質との界面における接触割合が増加していることにより、充放電による電解質イオンの炭素電極材に対する吸脱着がスムーズに進行すること、および、２）炭素電極材内部におけるイオンの拡散距離が短くなるため、充放電による電解質イオンの炭素電極材に対する吸脱着がスムーズに進行すること、によるものと考えられる、すなわち、炭素電極材の平均粒径が小さい場合には、放電電流を増加させても電解質イオンの脱着が迅速に応答するが、平均粒径が大きい場合には、電解質イオンの脱着が迅速に応答できず、放電電流の増加に伴い静電容量が低下する。 In the electric double layer capacitor using the granular carbon electrode material of Comparative Example 1, the electrostatic capacity greatly decreased as the discharge current increased, but in the electric double layer capacitor using the granular carbon electrode material of Example 1, the electrostatic double layer capacitor It can be seen that there is little decrease in electric capacity. This is because, in the case of the carbon electrode material 1, the average particle size of the electrode material is smaller than that of the carbon electrode material 14, and 1) the contact ratio at the interface between the carbon electrode material and the electrolyte is increased. The adsorption / desorption of electrolyte ions to / from the carbon electrode material by charging / discharging smoothly, and 2) the diffusion distance of ions inside the carbon electrode material is shortened, so that the adsorption / desorption of electrolyte ions to / from the carbon electrode material by charging / discharging is performed. In other words, when the average particle size of the carbon electrode material is small, desorption of electrolyte ions responds quickly even when the discharge current is increased, but the average particle size is If it is large, the desorption of the electrolyte ions cannot be quickly responded, and the capacitance decreases as the discharge current increases.
＜実施例１４＞
本発明の粒状炭素電極材のリチウムイオン電池またはリチウムイオンキャパシタ用の負極材としての評価を次のようにして行なった。実施例１の粒状炭素電極材（炭素電極材４、平均粒径３μｍ）１００重量部と、ポリフッ化ビニリデン粉末１０重量部をＮ−メチルピロリドン８０重量部に溶解した溶液とを充分に混合することによりスラリーとし、このスラリーを銅箔（２０μｍ厚）に塗布し、乾燥、プレスして負極を得た。この負極を１．５ｃｍ×２．０ｃｍサイズに切り出し、評価用負極とした。評価用負極と、対極として１．５ｃｍ×２．０ｃｍサイズ、厚み２００μｍの金属リチウムと、セパレータとしての厚さ５０μｍのポリエチレン製不織布とを用い、評価用セルを組んだ。参照極として金属リチウムを用いた。電解液としては、プロピレンカーボネートに、１ｍｏｌ／Ｌの濃度にＬｉＰＦ6を溶解した溶液を用いた。比較のため、比較例５の粒状炭素電極材（炭素電極材１７、平均粒径１５μｍ）を用い、同様の評価用セルを作製した。
<Example 14>
The granular carbon electrode material of the present invention was evaluated as a negative electrode material for a lithium ion battery or a lithium ion capacitor as follows. 100 parts by weight of the granular carbon electrode material (carbon electrode material 4, average particle size 3 μm) of Example 1 and a solution prepared by dissolving 10 parts by weight of polyvinylidene fluoride powder in 80 parts by weight of N-methylpyrrolidone are sufficiently mixed. The slurry was applied to a copper foil (20 μm thick), dried and pressed to obtain a negative electrode. This negative electrode was cut into a size of 1.5 cm × 2.0 cm to obtain a negative electrode for evaluation. An evaluation cell was assembled using a negative electrode for evaluation, a lithium metal having a size of 1.5 cm × 2.0 cm and a thickness of 200 μm as a counter electrode, and a 50 μm thick non-woven fabric made of polyethylene as a separator. Metallic lithium was used as a reference electrode. As the electrolytic solution, a solution obtained by dissolving LiPF 6 in propylene carbonate at a concentration of 1 mol / L was used. For comparison, a similar evaluation cell was prepared using the granular carbon electrode material of Comparative Example 5 (carbon electrode material 17, average particle diameter of 15 μm).
上記各評価用セルについて充放電試験を行なった。初回充放電は、電位規制のもと、充電、放電ともに０．２ｍＡ／ｃｍ2で行なった。電位範囲はリチウム基準で０Ｖから２Ｖとした。次に、２回目〜７回目の充放電を、０．２ｍＡ／ｃｍ2で０Ｖから０．５Ｖの電位範囲で行ない、さらに８回目〜１５回目の充放電を、１．０ｍＡ／ｃｍ2で０Ｖから０．５Ｖの電位範囲で行なった。 A charge / discharge test was performed on each of the evaluation cells. The first charge / discharge was performed at 0.2 mA / cm 2 for both charging and discharging under potential regulation. The potential range was 0 V to 2 V on the basis of lithium. Next, the second to seventh charging / discharging is performed at 0.2 mA / cm 2 in a potential range of 0 V to 0.5 V, and the eighth to 15th charging / discharging is performed at 0 mA at 1.0 mA / cm 2 . To 0.5V.
電流密度０．２ｍＡ／ｃｍ2で評価した第７回目における放電容量と１．０ｍＡ／ｃｍ2で評価した第１５回目における放電容量の比率（容量保持率、％）は、実施例１の粒状炭素電極材４について９２％、比較例５の粒状炭素電極材１７について６９％であった。この結果から、本発明の粒状炭素電極材を用いることよって、電流密度を高くしても放電容量の低下を抑制できることがわかった。 The ratio of the discharge capacity at the seventh time evaluated at a current density of 0.2 mA / cm 2 and the discharge capacity at the 15th time evaluated at 1.0 mA / cm 2 (capacity retention,%) is the granular carbon of Example 1. It was 92% for the electrode material 4 and 69% for the granular carbon electrode material 17 of Comparative Example 5. From this result, it was found that by using the granular carbon electrode material of the present invention, the reduction in discharge capacity can be suppressed even when the current density is increased.
今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
Claims (9)
粒径分布の変動係数＝（ｄ84%−ｄ16%）／（２×平均粒径） ［１］
ここで、ｄ84%、ｄ16%はそれぞれ、レーザー回折・散乱法によって得られた頻度分布において累積頻度８４％、１６％を示す粒径である。 A granular carbon electrode having an average particle size of 10 μm or less, a single particle ratio of 0.7 or more, and a coefficient of variation of the particle size distribution represented by the following formula [1] of 0.65 or less Wood.
Coefficient of variation of particle size distribution = (d 84% −d 16% ) / (2 × average particle size) [1]
Here, d 84% and d 16% are particle diameters showing cumulative frequencies of 84% and 16%, respectively, in the frequency distribution obtained by the laser diffraction / scattering method.
（１）反応液中におけるモル濃度が２．０ｍｏｌ／Ｌ以上である酸性触媒と、保護コロイド剤との存在下、水性媒体中でアルデヒド類とフェノール類とを反応させることにより粒状フェノール樹脂を形成する、粒状フェノール樹脂形成工程と、
（２）前記粒状フェノール樹脂を含有する反応液を加熱して非熱溶融性の粒状フェノール樹脂を形成する、加熱工程と、
（３）前記非熱溶融性の粒状フェノール樹脂を反応液から分離する、分離工程と、
（４）前記非熱溶融性の粒状フェノール樹脂を焼成する焼成工程と、を含む粒状炭素電極材の製造方法。 A method for producing the granular carbon electrode material according to claim 1 or 2,
(1) A granular phenol resin is formed by reacting an aldehyde and a phenol in an aqueous medium in the presence of an acidic catalyst having a molar concentration of 2.0 mol / L or more in the reaction solution and a protective colloid agent. A granular phenol resin forming step;
(2) A heating step of heating the reaction solution containing the granular phenol resin to form a non-heat-meltable granular phenol resin,
(3) a separation step of separating the non-heat-meltable granular phenol resin from the reaction solution;
(4) The manufacturing method of the granular carbon electrode material including the baking process which bakes the said non-heat-meltable granular phenol resin.
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| JP2007214781A JP4949971B2 (en) | 2007-08-21 | 2007-08-21 | Carbon electrode material, carbon electrode material mixture, carbon electrode material manufacturing method, electric double layer capacitor, lithium ion battery, and lithium ion capacitor |
| CN2009101734092A CN101661809B (en) | 2006-10-20 | 2007-10-12 | Granular carbon electrode material and its manufacturing method |
| KR1020097018340A KR101342773B1 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| EP07829663.9A EP2078734B1 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| ES07829663.9T ES2577554T3 (en) | 2006-10-20 | 2007-10-12 | Granular non-hot melt phenolic resin, method for producing it, thermosetting resin composition, sealing material for semiconductor, and semiconductor adhesive |
| KR1020097018339A KR101311038B1 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| CN2009101734105A CN101659410B (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible phenol resin powder and method for producing the same |
| US12/311,045 US8293860B2 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible phenol resin powder, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| KR1020097005459A KR101381483B1 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
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| PCT/JP2007/069927 WO2008047700A1 (en) | 2006-10-20 | 2007-10-12 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| EP09011645.0A EP2145906B1 (en) | 2006-10-20 | 2007-10-12 | Pellet-type molecular sieve carbon |
| EP09011644.3A EP2141184B1 (en) | 2006-10-20 | 2007-10-12 | Carbon electrode material powder |
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| TW098129926A TWI411576B (en) | 2006-10-20 | 2007-10-18 | A non-thermofusible granular phenol resin and a method for producing the same, and a thermosetting resin composition, a filler for semiconductor and a bonding agent for a semiconductor (2) |
| TW096138990A TWI401282B (en) | 2006-10-20 | 2007-10-18 | A non-thermofusible granular phenol resin and a method for producing the same, and a thermosetting resin composition, a semiconductor filler, and a semiconductor adhesive |
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| US12/585,147 US8158095B2 (en) | 2006-10-20 | 2009-09-04 | Non-thermofusible phenol resin powder, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
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| US13/364,899 US8658120B2 (en) | 2006-10-20 | 2012-02-02 | Non-thermofusible phenol resin powder, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| US13/420,566 US8411415B2 (en) | 2006-10-20 | 2012-03-14 | Non-thermofusible phenol resin powder, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
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