JP2021116196A - Carbonaceous material and method for producing the same, and battery including carbonaceous material - Google Patents
Carbonaceous material and method for producing the same, and battery including carbonaceous material Download PDFInfo
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- JP2021116196A JP2021116196A JP2020009389A JP2020009389A JP2021116196A JP 2021116196 A JP2021116196 A JP 2021116196A JP 2020009389 A JP2020009389 A JP 2020009389A JP 2020009389 A JP2020009389 A JP 2020009389A JP 2021116196 A JP2021116196 A JP 2021116196A
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- Prior art keywords
- carbonaceous material
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- mass
- carbonization step
- battery
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- 239000011593 sulfur Substances 0.000 claims abstract description 33
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- 238000004438 BET method Methods 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims description 63
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- 239000000203 mixture Substances 0.000 claims description 15
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- 239000004913 cyclooctene Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000010333 wet classification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、炭素質材料、該炭素質材料の製造方法、および該炭素質材料を用いた電池に関する。 The present invention relates to a carbonaceous material, a method for producing the carbonaceous material, and a battery using the carbonaceous material.
炭素質材料は、鉛炭素電池のような水系電解質電池、リチウムイオン電池およびナトリウムイオン電池のような非水系電解質電池、全固体電池、燃料電池等の様々な電極に用いられており、用途に応じた特性を有する炭素質材料が求められている。例えば、電気自動車またはハイブリッド自動車に搭載される非水系電解質電池は、制限された質量および空間でより航続距離の長い電池を搭載するために、高い放電容量が求められる。また、該電池の充放電はブレーキおよびアクセルの踏込み時に行われるため、低抵抗な電池による短時間での急速な充放電特性が求められる。 Carbonaceous materials are used for various electrodes such as water-based electrolyte batteries such as lead-carbon batteries, non-aqueous electrolyte batteries such as lithium-ion batteries and sodium-ion batteries, all-solid-state batteries, and fuel cells, depending on the application. There is a demand for a carbonaceous material having such properties. For example, a non-aqueous electrolyte battery mounted on an electric vehicle or a hybrid vehicle is required to have a high discharge capacity in order to mount a battery having a longer cruising range in a limited mass and space. Further, since charging / discharging of the battery is performed when the brake and the accelerator are depressed, rapid charging / discharging characteristics in a short time by a low resistance battery are required.
このような非水系電解質電池の電極には難黒鉛化炭素由来の炭素質材料が使用されている。これまで難黒鉛化炭素の炭素源としては、石油ピッチまたは石炭ピッチ等が用いられていたが、近年、地球環境への影響および埋蔵量の減少を懸念して、これらに代わる炭素源を利用した炭素質材料が求められている。製紙業のパルプの製造工程で、副生成物として大量に排出されるリグニンを炭素源として用いた炭素質材料はその一例である。 A carbonaceous material derived from non-graphitized carbon is used for the electrodes of such a non-aqueous electrolyte battery. Until now, petroleum pitch or coal pitch has been used as the carbon source for graphitized carbon, but in recent years, due to concerns about the impact on the global environment and the decrease in reserves, carbon sources have been used instead. Carbonaceous materials are required. One example is a carbonaceous material that uses lignin as a carbon source, which is discharged in large quantities as a by-product in the pulp manufacturing process of the paper industry.
非特許文献１には、水酸化カリウム溶液に溶解したリグニンを炭化して得られた炭素質材料が記載されている。 Non-Patent Document 1 describes a carbonaceous material obtained by carbonizing lignin dissolved in a potassium hydroxide solution.
非特許文献２には、リグニンとエポキシ樹脂をアルコール溶液に溶解し、硬化後炭化して得られた炭素質材料が記載されている。 Non-Patent Document 2 describes a carbonaceous material obtained by dissolving lignin and an epoxy resin in an alcohol solution and carbonizing after curing.
非特許文献３には、メラミンとリグニンとをホルムアルデヒドに溶解して作製したリグニン−メラミン樹脂を、炭化および焼結して得られた炭素質材料が記載されている。 Non-Patent Document 3 describes a carbonaceous material obtained by carbonizing and sintering a lignin-melamine resin prepared by dissolving melamine and lignin in formaldehyde.
しかし、本発明者らの検討によれば、非特許文献１〜３に記載の方法には、下記課題がある。非特許文献１に記載された方法では、反応に使用したアルカリ金属の除去等の工程数が多い。また、非特許文献２および非特許文献３にそれぞれ記載された方法は、他の物質と複合化する等、工程が複雑である。更に、いずれの方法で得られた炭素質材料も、放電容量が小さく充電効率が低いことから電池材料としての性能が十分なものではない。 However, according to the studies by the present inventors, the methods described in Non-Patent Documents 1 to 3 have the following problems. In the method described in Non-Patent Document 1, the number of steps such as removal of the alkali metal used in the reaction is large. Further, the methods described in Non-Patent Document 2 and Non-Patent Document 3, respectively, have complicated steps such as compounding with other substances. Further, the carbonaceous material obtained by either method has a small discharge capacity and a low charging efficiency, so that the performance as a battery material is not sufficient.
従って、本発明の課題は、放電容量、充放電効率および低抵抗性に優れた電池をもたらす炭素質材料、および工程数の少ない該炭素質材料の製造方法を提供することである。 Therefore, an object of the present invention is to provide a carbonaceous material that provides a battery excellent in discharge capacity, charge / discharge efficiency, and low resistance, and a method for producing the carbonaceous material with a small number of steps.
本発明者らは、上記課題を解決するために、炭素質材料、および該炭素質材料の製造方法について詳細に検討を重ねた結果、本発明を完成するに至った。
すなわち、本発明は、以下の好適な態様を包含する。
〔１〕硫黄元素含有量は０．８質量％以上であり、ＢＥＴ法により求めた比表面積は４０ｍ２／ｇ以下であり、ブタノール法により求めた真密度は１．４８ｇ／ｃｍ３以上１．６２ｇ／ｃｍ３以下である、炭素質材料。
〔２〕前記炭素質材料の酸素元素含有量は１．７質量％以下である、前記〔１〕に記載の炭素質材料。
〔３〕前記炭素質材料の六角網面積層方向Ｌｃの大きさは１１Å以下である、前記〔１〕または〔２〕に記載の炭素質材料。
〔４〕前記炭素質材料の体積平均粒径は２μｍ以上２０μｍ以下である、前記〔１〕〜〔３〕のいずれかに記載の炭素質材料。
〔５〕ＣｕＫα線を用いて測定される前記炭素質材料の（００２）面の面間隔ｄ００２は３．８Å以上である、前記〔１〕〜〔４〕のいずれかに記載の炭素質材料。
〔６〕硫黄元素含有量が０．１質量％以上であり、融点が２１０℃以上のリグニンを炭化して、炭素前駆体を得る第一の炭化工程と、
前記炭素前駆体とコーティング剤との混合物を非酸化性ガス雰囲気下９００℃以上１４００℃以下の温度で炭化して炭素質材料を得る第二の炭化工程と
を含む、前記〔１〕〜〔５〕のいずれかに記載の炭素質材料の製造方法。
〔７〕前記炭素前駆体を２０μｍ以下の体積平均粒径に粉砕する粉砕工程を更に含む、前記〔６〕に記載の方法。
〔８〕前記第一の炭化工程は、前記リグニンを非酸化性ガス雰囲気下３００℃以上８００℃以下の温度で加熱することを含む、前記〔６〕または〔７〕に記載の方法。
〔９〕前記〔１〕〜〔５〕のいずれかに記載の炭素質材料を含む、電極。
〔１０〕前記〔９〕に記載の電極を含む、電池。
The present inventors have completed the present invention as a result of repeated studies in detail on the carbonaceous material and the method for producing the carbonaceous material in order to solve the above-mentioned problems.
That is, the present invention includes the following preferred embodiments.
[1] The sulfur element content is 0.8% by mass or more, the specific surface area determined by the BET method is 40 m 2 / g or less, and the true density determined by the butanol method is 1.48 g / cm 3 or more. A carbonaceous material that is 62 g / cm 3 or less.
[2] The carbonaceous material according to the above [1], wherein the oxygen element content of the carbonaceous material is 1.7% by mass or less.
[3] The carbonaceous material according to the above [1] or [2], wherein the size of the hexagonal net area layer direction Lc of the carbonaceous material is 11 Å or less.
[4] The carbonaceous material according to any one of [1] to [3] above, wherein the volume average particle diameter of the carbonaceous material is 2 μm or more and 20 μm or less.
[5] The carbonaceous material according to any one of [1] to [4] above, wherein the surface spacing d 002 of the (002) plane of the carbonaceous material measured using CuKα rays is 3.8 Å or more. ..
[6] The first carbonization step of carbonizing lignin having a sulfur element content of 0.1% by mass or more and a melting point of 210 ° C. or more to obtain a carbon precursor.
The second carbonization step of carbonizing a mixture of the carbon precursor and the coating agent at a temperature of 900 ° C. or higher and 1400 ° C. or lower in a non-oxidizing gas atmosphere to obtain a carbonaceous material is included in the above [1] to [5]. ] The method for producing a carbonaceous material according to any one of.
[7] The method according to [6] above, further comprising a pulverization step of pulverizing the carbon precursor to a volume average particle size of 20 μm or less.
[8] The method according to [6] or [7] above, wherein the first carbonization step comprises heating the lignin at a temperature of 300 ° C. or higher and 800 ° C. or lower in a non-oxidizing gas atmosphere.
[9] An electrode containing the carbonaceous material according to any one of [1] to [5] above.
[10] A battery including the electrode according to the above [9].
本発明によれば、放電容量、充放電効率および低抵抗性に優れた電池をもたらす炭素質材料、および工程数の少ない該炭素質材料の製造方法を提供することができる。 According to the present invention, it is possible to provide a carbonaceous material that provides a battery having excellent discharge capacity, charge / discharge efficiency, and low resistance, and a method for producing the carbonaceous material with a small number of steps.
以下、本発明の実施形態について、詳細に説明する。なお、以下は本発明の実施形態を例示する説明であって、本発明を以下の実施形態に限定することは意図されていない。 Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the following is an example of an embodiment of the present invention, and it is not intended to limit the present invention to the following embodiments.
［炭素質材料］
本発明の炭素質材料において、硫黄元素含有量は０．８質量％以上であり、ＢＥＴ法により求めた比表面積は４０ｍ２／ｇ以下であり、ブタノール法により求めた真密度は１．４８ｇ／ｃｍ３以上１．６２ｇ／ｃｍ３以下である。
[Carbonate material]
In the carbonaceous material of the present invention, the sulfur element content is 0.8% by mass or more, the specific surface area determined by the BET method is 40 m 2 / g or less, and the true density determined by the butanol method is 1.48 g / g. It is cm 3 or more and 1.62 g / cm 3 or less.
〔硫黄元素含有量〕
炭素質材料の硫黄元素含有量は、０．８質量％以上である。硫黄元素含有量が０．８質量％未満であると、電池容量の優れた電池を得ることは困難である。硫黄元素含有量は、好ましくは０．８５質量％以上、より好ましくは０．９質量％以上である。硫黄元素含有量の上限値は特に限定されない。硫黄元素含有量は、通常は３．０質量％以下であり、好ましくは２．０質量％以下、より好ましくは１．８質量％以下である。硫黄元素含有量が前記下限値以上であり前記上限値以下であると、電池容量のより優れた電池を得やすい。硫黄元素含有量は、例えば、炭素質材料を製造する際に使用する（硫黄元素を含有する）出発材料を（例えば苛性ソーダ水溶液と一緒に加熱する等の方法により）加水分解することによって、或いは出発材料を硫酸等の硫黄元素含有成分で変性し、その変性量を調整することによって、前記下限値以上および前記上限値以下に調整できる。硫黄元素含有量は、例えば元素分析または蛍光Ｘ線分析によって、求めることができる。
[Sulfur element content]
The sulfur element content of the carbonaceous material is 0.8% by mass or more. If the sulfur element content is less than 0.8% by mass, it is difficult to obtain a battery having an excellent battery capacity. The sulfur element content is preferably 0.85% by mass or more, more preferably 0.9% by mass or more. The upper limit of the sulfur element content is not particularly limited. The sulfur element content is usually 3.0% by mass or less, preferably 2.0% by mass or less, and more preferably 1.8% by mass or less. When the sulfur element content is at least the lower limit value and at least the upper limit value, it is easy to obtain a battery having a better battery capacity. The sulfur element content is determined, for example, by hydrolyzing the starting material (containing sulfur) used in the production of carbonaceous materials (eg, by heating with an aqueous solution of caustic soda), or by starting. By modifying the material with a sulfur element-containing component such as sulfuric acid and adjusting the modification amount, the material can be adjusted to be equal to or higher than the lower limit value and lower than the upper limit value. The sulfur element content can be determined, for example, by elemental analysis or fluorescent X-ray analysis.
〔ＢＥＴ法により求めた比表面積〕
炭素質材料のＢＥＴ法により求めた比表面積（以下において、単に「比表面積」とも称する）は４０ｍ２／ｇ以下である。比表面積が４０ｍ２／ｇより大きいと、電解液の分解反応が進行しやすく、充放電効率および低抵抗性に優れた電池を得ることは困難である。比表面積は、好ましくは２０ｍ２／ｇ以下、より好ましくは１５ｍ２／ｇ以下、特に好ましくは１０ｍ２／ｇ以下である。比表面積はまた、通常１ｍ２／ｇ以上、好ましくは１．５ｍ２／ｇ以上、より好ましくは２ｍ２／ｇ以上、特に好ましくは３ｍ２／ｇ以上である。比表面積が前記上限値以下であり前記下限値以上であると、電解液の分解反応を抑制しやすく、充放電効率および低抵抗性に優れた電池を得やすい。比表面積は、例えば、加熱温度（例えば第一の炭化工程の温度または第二の炭化工程の温度）、またはコーティング剤の添加量により、前記上限値以下および前記下限値以上に調整できる。比表面積は、後述の実施例に記載の通り、窒素吸着等温線を測定する方法によって求めることができる。
[Specific surface area determined by the BET method]
The specific surface area of the carbonaceous material determined by the BET method (hereinafter, also simply referred to as “specific surface area”) is 40 m 2 / g or less. If the specific surface area is larger than 40 m 2 / g, the decomposition reaction of the electrolytic solution tends to proceed, and it is difficult to obtain a battery having excellent charge / discharge efficiency and low resistance. The specific surface area is preferably 20 m 2 / g or less, more preferably 15 m 2 / g or less, and particularly preferably 10 m 2 / g or less. The specific surface area is also usually 1 m 2 / g or more, preferably 1.5 m 2 / g or more, more preferably 2 m 2 / g or more, and particularly preferably 3 m 2 / g or more. When the specific surface area is not more than the upper limit value and not more than the lower limit value, it is easy to suppress the decomposition reaction of the electrolytic solution, and it is easy to obtain a battery having excellent charge / discharge efficiency and low resistance. The specific surface area can be adjusted to be equal to or lower than the upper limit value and higher than the lower limit value by, for example, the heating temperature (for example, the temperature of the first carbonization step or the temperature of the second carbonization step) or the amount of the coating agent added. The specific surface area can be determined by a method of measuring the nitrogen adsorption isotherm as described in Examples described later.
〔ブタノール法により求めた真密度〕
炭素質材料のブタノール法により求めた真密度（以下において、単に「真密度」とも称する）は１．４８ｇ／ｃｍ３以上１．６２ｇ／ｃｍ３以下である。真密度が１．４８ｇ／ｃｍ３未満であるかまたは１．６２ｇ／ｃｍ３より大きいと、所望の電池容量を得ることは困難である。真密度は、好ましくは１．４９ｇ／ｃｍ３以上、より好ましくは１．５０ｇ／ｃｍ３以上であり、好ましくは１．６１ｇ／ｃｍ３以下である。真密度が前記下限値以上であり前記上限値以下であると、より優れた電池容量を有する電池を得やすい。真密度は、例えば、加熱温度（例えば第一の炭化工程の温度または第二の炭化工程の温度）により、前記下限値以上および前記上限値以下に調整できる。真密度は、ＪＩＳ Ｒ ７２１２に定められた方法に従い測定できる。
[True density obtained by the butanol method]
(Hereinafter, simply referred to as "true density") true density determined by butanol method of the carbonaceous material is 1.48 g / cm 3 or more 1.62 g / cm 3 or less. It is difficult to true density obtained with greater or 1.62 g / cm 3 is less than 1.48 g / cm 3, a desired battery capacity. The true density is preferably 1.49 g / cm 3 or more, more preferably 1.50 g / cm 3 or more, and preferably 1.61 g / cm 3 or less. When the true density is not less than the lower limit value and not more than the upper limit value, it is easy to obtain a battery having a better battery capacity. The true density can be adjusted to be equal to or higher than the lower limit value and lower than the upper limit value by, for example, the heating temperature (for example, the temperature of the first carbonization step or the temperature of the second carbonization step). The true density can be measured according to the method specified in JIS R 7212.
〔酸素元素含有量〕
炭素質材料の酸素元素含有量は、好ましくは１．７質量％以下、より好ましくは１．２質量％以下、更に好ましくは０．５質量％以下である。また、酸素元素含有量は、通常０．１質量％以上、好ましくは０．１５質量％以上である。酸素元素含有量が前記上限値以下であり前記下限値以上であると、イオン吸着による不可逆性を抑制しやすく、電解液親和性に優れた電池を得やすい。酸素元素含有量は、例えば、加熱温度（例えば第一の炭化工程の温度または第二の炭化工程の温度）により、前記上限値以下および前記下限値以上に調整できる。酸素元素含有量は、元素分析または蛍光Ｘ線分析により求めることができる。
[Oxygen element content]
The oxygen element content of the carbonaceous material is preferably 1.7% by mass or less, more preferably 1.2% by mass or less, and further preferably 0.5% by mass or less. The oxygen element content is usually 0.1% by mass or more, preferably 0.15% by mass or more. When the oxygen element content is not less than the upper limit value and not more than the lower limit value, irreversibility due to ion adsorption can be easily suppressed, and a battery having excellent electrolyte affinity can be easily obtained. The oxygen element content can be adjusted to be equal to or lower than the upper limit value and higher than the lower limit value by, for example, the heating temperature (for example, the temperature of the first carbonization step or the temperature of the second carbonization step). The oxygen element content can be determined by elemental analysis or fluorescent X-ray analysis.
〔六角網面積層方向Ｌｃの大きさ〕
炭素質材料の六角網面積層方向Ｌｃの大きさは、好ましくは１１Å以下、より好ましくは１０Å以下である。また、六角網面積層方向Ｌｃの大きさは、通常４Å以上、好ましくは５Å以上である。六角網面積層方向Ｌｃの大きさが前記上限値以下であり前記下限値以上であると、金属イオンおよび水素イオンの移動がしやすくなり、より低抵抗であり出力特性に優れる電池を得やすい。六角網面積層方向Ｌｃの大きさは、例えば、加熱温度（例えば第一の炭化工程の温度または第二の炭化工程の温度）により、前記下限値以上および前記上限値以下に調整できる。六角網面積層方向Ｌｃの大きさは、Ｘ線回折により、２θ＝２６°付近のピーク強度から得られる半値幅に基づき求めることができる。また、前記上限値以下であり前記下限値以上である六角網面積層方向Ｌｃの大きさを有する炭素質材料は、出力特性が大きい傾向にあり、リチウムイオン二次電池のみならず、ナトリウムイオン二次電池または鉛電池にも好適な電極を得やすい。
[Hexagonal net area Lc size in the layer direction]
The size of the hexagonal net area layer direction Lc of the carbonaceous material is preferably 11 Å or less, more preferably 10 Å or less. The size of Lc in the hexagonal net area layer direction is usually 4 Å or more, preferably 5 Å or more. When the size of the hexagonal net area layer direction Lc is not more than the upper limit value and not more than the lower limit value, the movement of metal ions and hydrogen ions becomes easy, and it is easy to obtain a battery having lower resistance and excellent output characteristics. The size of the hexagonal net area layer direction Lc can be adjusted to be equal to or higher than the lower limit value and lower than the upper limit value by, for example, the heating temperature (for example, the temperature of the first carbonization step or the temperature of the second carbonization step). The magnitude of the hexagonal net area layer direction Lc can be obtained by X-ray diffraction based on the full width at half maximum obtained from the peak intensity near 2θ = 26 °. Further, a carbonaceous material having a size of Lc in the hexagonal network area layer direction, which is equal to or less than the upper limit value and is equal to or more than the lower limit value, tends to have a large output characteristic, and not only a lithium ion secondary battery but also a sodium ion secondary battery. It is easy to obtain electrodes suitable for secondary batteries or lead batteries.
〔ＣｕＫα線を用いて測定される（００２）面の面間隔ｄ００２〕
炭素質材料のＣｕＫα線を用いて測定される（００２）面の面間隔ｄ００２（以下において、単に「面間隔ｄ００２」とも称する）は、好ましくは３．８Å以上、より好ましくは３．８２Å以上である。また、面間隔ｄ００２は、好ましくは３．９５Å以下、より好ましくは３．９２Å以下である。面間隔ｄ００２が前記下限値以上であり前記上限値以下であると、低温での電池容量維持率に優れた電池を得やすい。また、イオンの侵入がより容易になるため、リチウムイオン二次電池のみならず、ナトリウムイオン二次電池および鉛電池にも好適な電極を得やすい。面間隔ｄ００２は、例えば、加熱温度（例えば第一の炭化工程の温度または第二の炭化工程の温度）により、前記上限値以下および前記下限値以上に調整できる。面間隔ｄ００２は、Ｘ線回折で求めることができる。
[Surface spacing d 002 of the (002) plane measured using CuKα rays]
The surface spacing d 002 of the (002) plane (hereinafter, also simply referred to as “plane spacing d 002 ”) measured using CuKα rays of a carbonaceous material is preferably 3.8 Å or more, more preferably 3.82 Å or more. That is all. The surface spacing d 002 is preferably 3.95 Å or less, more preferably 3.92 Å or less. When the surface spacing d 002 is not less than the lower limit value and not more than the upper limit value, it is easy to obtain a battery having an excellent battery capacity retention rate at a low temperature. Further, since the invasion of ions becomes easier, it is easy to obtain electrodes suitable not only for lithium ion secondary batteries but also for sodium ion secondary batteries and lead batteries. The surface spacing d 002 can be adjusted to be equal to or lower than the upper limit value and higher than the lower limit value by, for example, the heating temperature (for example, the temperature of the first carbonization step or the temperature of the second carbonization step). The surface spacing d 002 can be obtained by X-ray diffraction.
〔体積平均粒径〕
炭素質材料の体積平均粒径は、好ましくは２μｍ以上、より好ましくは２．２μｍ以上、特に好ましくは２．５μｍ以上であり、好ましくは２０μｍ以下、より好ましくは１５μｍ以下、特に好ましくは１０μｍ以下である。体積平均粒径が前記下限値以上であると、炭素質材料の比表面積の増大の要因である微粉が少なくなる傾向にあり、炭素質材料と電解液との過剰な反応が抑制されやすくなり、その結果、充電しても放電しない容量である不可逆容量が低下し、正極の容量が無駄になることが抑制されやすい。体積平均粒径が前記上限値以下であると、炭素質材料内での金属イオンまたは水素イオンの拡散自由行程が小さくなる傾向にあり、また、電子を伝導する導電材としての炭素質材料間の接触率が高くなる傾向にあるため好ましい。体積平均粒径は、例えば、炭素質材料を製造する際に使用する出発材料の選択、または粉砕工程によって、前記下限値以上および前記上限値以下に調整できる。体積平均粒径は、レーザー回折散乱法またはコールター法によって求めることができる。
[Volume average particle size]
The volume average particle size of the carbonaceous material is preferably 2 μm or more, more preferably 2.2 μm or more, particularly preferably 2.5 μm or more, preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. be. When the volume average particle diameter is at least the above lower limit value, the amount of fine powder, which is a factor of increasing the specific surface area of the carbonaceous material, tends to decrease, and the excessive reaction between the carbonaceous material and the electrolytic solution tends to be suppressed. As a result, the irreversible capacity, which is the capacity that does not discharge even when charged, is reduced, and it is easy to prevent the positive electrode capacity from being wasted. When the volume mean particle size is not more than the above upper limit value, the diffusion free path of metal ions or hydrogen ions in the carbonaceous material tends to be small, and between carbonaceous materials as a conductive material for conducting electrons. This is preferable because the contact rate tends to be high. The volume average particle size can be adjusted to be equal to or higher than the lower limit value and lower than the upper limit value by, for example, selecting a starting material to be used in producing a carbonaceous material or a pulverization step. The volume average particle size can be determined by the laser diffraction scattering method or the Coulter method.
［炭素質材料の製造方法］
本発明の炭素質材料は、例えば、
硫黄元素含有量が０．１質量％以上であり、融点が２１０℃以上のリグニンを炭化して、炭素前駆体を得る第一の炭化工程と、
前記炭素前駆体とコーティング剤との混合物を非酸化性ガス雰囲気下９００℃以上１４００℃以下の温度で炭化して炭素質材料を得る第二の炭化工程と
を含む製造方法により製造できる。この製造方法により、本発明の炭素質材料は少ない工程数で製造できる。
[Manufacturing method of carbonaceous material]
The carbonaceous material of the present invention is, for example,
The first carbonization step of carbonizing lignin having a sulfur element content of 0.1% by mass or more and a melting point of 210 ° C. or more to obtain a carbon precursor.
It can be produced by a production method including a second carbonization step of carbonizing a mixture of the carbon precursor and a coating agent at a temperature of 900 ° C. or higher and 1400 ° C. or lower in a non-oxidizing gas atmosphere to obtain a carbonaceous material. By this production method, the carbonaceous material of the present invention can be produced with a small number of steps.
〔出発材料〕
本発明の炭素質材料の出発材料は特に限定されない。使用できる出発材料として、例えばスルホン酸型イオン交換樹脂およびリグニンが挙げられる。
好ましい出発材料は、硫黄元素含有量が好ましくは０．１質量％以上であり、融点が好ましくは２００℃以上であるリグニンである。このようなリグニンは、一般的にはクラフトリグニンと呼ばれており、製紙業においてセルロース抽出後の廃棄物として得られる。具体的には、例えばパルプの製造過程で生成した黒液を酸性化し、析出した沈殿を洗浄して調製することができる。このようにして得られたリグニンは、調製工程中で、その主要な結合であるエーテル結合が切断され、著しく低分子化されるので、その数平均分子量は通常３５００〜４５００となる。炭化前の比較的低い温度で融解し、融解時に結晶状態を密度の高い状態に変化させやすく、その結果、優れた充放電効率および低い抵抗を有する電池を得やすい観点から、好ましくは２１０℃以上、より好ましくは２３０℃以上で融解するリグニンを使用することが特に好ましい。また、通常クラフトリグニンは他の方法で得られたリグニンに比べ、多量のフェノール性水酸基を有しており、化学的活性に富んでいることも、高い密度の炭素形成に好ましい。
[Starting material]
The starting material for the carbonaceous material of the present invention is not particularly limited. Examples of starting materials that can be used include sulfonic acid type ion exchange resins and lignin.
A preferable starting material is lignin having a sulfur element content of preferably 0.1% by mass or more and a melting point of preferably 200 ° C. or more. Such lignin is generally called kraft lignin, and is obtained as waste after cellulose extraction in the paper industry. Specifically, for example, it can be prepared by acidifying the black liquor produced in the process of producing pulp and washing the precipitated precipitate. The number average molecular weight of the lignin thus obtained is usually 3500 to 4500 because the ether bond, which is the main bond thereof, is cleaved during the preparation step and the molecular weight is remarkably reduced. From the viewpoint that it melts at a relatively low temperature before carbonization and easily changes the crystal state to a dense state at the time of melting, and as a result, a battery having excellent charge / discharge efficiency and low resistance can be easily obtained, it is preferably 210 ° C. or higher. , More preferably, it is particularly preferable to use lignin that melts at 230 ° C. or higher. In addition, kraft lignin usually has a large amount of phenolic hydroxyl groups as compared with lignin obtained by other methods, and is rich in chemical activity, which is also preferable for high-density carbon formation.
リグニンの硫黄元素含有量は、リグニンの分子量の低下を抑制しやすく、その結果炭素縮合が十分に進みやすい観点から、好ましくは０．１質量％以上、より好ましくは０．２質量％以上、更に好ましくは０．５質量％以上である。また、硫黄元素含有量は、使用する機器を腐食する可能性のある二酸化硫黄等の排出が抑制されやすい観点から、好ましくは５質量％以下、より好ましくは４．５質量％以下である。硫黄元素含有量は、例えば、硫黄元素を含有するリグニンを（例えば苛性ソーダ水溶液と加熱する等の方法により）加水分解することにより、或いはリグニンを硫酸等の硫黄元素含有成分で変性し、その変性量を調整することにより、前記下限値以上および前記上限値以下に調整できる。硫黄元素含有量は、元素分析または蛍光Ｘ線分析によって測定できる。 The sulfur element content of lignin is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further, from the viewpoint that it is easy to suppress a decrease in the molecular weight of lignin, and as a result, carbon condensation is sufficiently promoted. It is preferably 0.5% by mass or more. The sulfur element content is preferably 5% by mass or less, more preferably 4.5% by mass or less, from the viewpoint that the emission of sulfur dioxide or the like that may corrode the equipment used is easily suppressed. The sulfur element content is determined, for example, by hydrolyzing a sulfur element-containing lignin (for example, by heating with a caustic soda aqueous solution), or by modifying the lignin with a sulfur element-containing component such as sulfuric acid, and the modification amount thereof. By adjusting, it is possible to adjust to the lower limit value or more and the upper limit value or less. The sulfur element content can be measured by elemental analysis or fluorescent X-ray analysis.
リグニンは１種のみを使用してもよいし、硫黄元素含有量、融点、分子量および揮発性成分含有量の１つ以上が異なる２種以上のリグニンを組み合わせて使用してもよい。２種以上のリグニンを組み合わせて使用する場合、そのうちの少なくとも１種のリグニンは、好ましくは、上述した好ましい硫黄元素含有量、融点および／または分子量を有する。
リグニンは、体積平均粒径を粉砕により調整した後に出発材料として用いてもよい。体積平均粒径は、好ましくは０．００１ｍｍ以上５０ｍｍ以下、より好ましくは０．０１ｍｍ以上２０ｍｍ以下、更に好ましくは０．１ｍｍ以上１０ｍｍ以下である。体積平均粒径が前記下限値以上であると、作業者の粉塵の吸引または粉塵爆発等が起こりにくい。体積平均粒径が前記上限値以下であると、炭化時に発生する水によりリグニンが酸化され、炭素物性が損なわれる問題が回避されやすい。通常、第一の炭化工程でリグニンは収縮せず、従って、第一の炭化工程前後で体積平均粒径は変化しない。粉砕に用いる粉砕機は、特に限定されず、後述の〔粉砕工程〕の段落で例示する粉砕機を使用できる。また、後述の〔分級工程〕の段落に記載の手順と同様に、リグニンを分級工程に付してもよい。
リグニンは、酸性水で洗浄することによりリグニン中に存在する金属を低減させた後に出発材料として用いてもよい。
Only one type of lignin may be used, or two or more types of lignin having one or more different sulfur element content, melting point, molecular weight and volatile component content may be used in combination. When two or more lignins are used in combination, at least one of them preferably has the preferred sulfur element content, melting point and / or molecular weight described above.
Lignin may be used as a starting material after adjusting the volume average particle size by pulverization. The volume average particle size is preferably 0.001 mm or more and 50 mm or less, more preferably 0.01 mm or more and 20 mm or less, and further preferably 0.1 mm or more and 10 mm or less. When the volume average particle diameter is at least the above lower limit value, it is difficult for the operator to suck dust or cause a dust explosion. When the volume average particle diameter is not more than the upper limit value, it is easy to avoid the problem that lignin is oxidized by water generated during carbonization and the carbon physical characteristics are impaired. Normally, lignin does not shrink in the first carbonization step, and therefore the volume average particle size does not change before and after the first carbonization step. The crusher used for crushing is not particularly limited, and the crusher exemplified in the paragraph [Crushing Step] described later can be used. In addition, lignin may be added to the classification step in the same manner as in the procedure described in the paragraph of [Classification step] described later.
Lignin may be used as a starting material after reducing the metals present in lignin by washing with acidic water.
〔第一の炭化工程〕
第一の炭化工程では、好ましくは、硫黄元素含有量が０．１質量％以上であり、融点が２１０℃以上のリグニンを炭化して、炭素前駆体を得る。
第一の炭化工程は、好ましくは非酸化性ガス雰囲気下で行う。非酸化性ガスとしては、例えばヘリウム、窒素またはアルゴン等を単独でまたは２種以上組み合わせて使用することができる。非酸化性ガス中に酸化性ガスが含まれている場合、その含有量は低いほど好ましい。そのような場合、非酸化性ガス中の酸化性ガス（特に酸素）の含有量は、通常１体積％以下、好ましくは０．１体積％以下である。酸化性ガスの含有量が前記上限値以下であると、炭素前駆体生成過程で、酸化が進行しにくく、所望の構造構築が進みやすく、また、生成した構造の酸化分解が起きにくい。
[First carbonization step]
In the first carbonization step, lignin having a sulfur element content of 0.1% by mass or more and a melting point of 210 ° C. or more is preferably carbonized to obtain a carbon precursor.
The first carbonization step is preferably carried out in a non-oxidizing gas atmosphere. As the non-oxidizing gas, for example, helium, nitrogen, argon or the like can be used alone or in combination of two or more. When the non-oxidizing gas contains an oxidizing gas, the lower the content, the more preferable. In such a case, the content of the oxidizing gas (particularly oxygen) in the non-oxidizing gas is usually 1% by volume or less, preferably 0.1% by volume or less. When the content of the oxidizing gas is not more than the above upper limit value, oxidation is unlikely to proceed in the carbon precursor formation process, desired structure construction is easy to proceed, and oxidative decomposition of the formed structure is unlikely to occur.
非酸化性ガスの供給量（流通量）は、特に限定されない。出発材料１ｇ当たり、通常１ｍＬ／分以上、好ましくは１０ｍＬ／分以上、更に好ましくは３０ｍＬ／分以上であり、通常５００ｍＬ／分以下である。また、第一の炭化工程は、減圧下で、例えば１０ＫＰａ以下で行うこともできる。 The supply amount (distribution amount) of the non-oxidizing gas is not particularly limited. It is usually 1 mL / min or more, preferably 10 mL / min or more, more preferably 30 mL / min or more, and usually 500 mL / min or less, per 1 g of the starting material. Further, the first carbonization step can be performed under reduced pressure, for example, at 10 KPa or less.
第一の炭化工程の昇温速度は特に限定されない。加熱の方法により異なるが、好ましくは１℃／分以上、より好ましくは２℃／分以上であり、好ましくは２０℃／分以下、より好ましくは１８℃／分以下である。昇温速度が前記下限値以上であり前記上限値以下であると、良好な生産性を得やすく、経済性の観点からも好ましい。また、発生する乾留ガスによる賦活の進行が抑制されやすく、良好な炭素密度を得やすい。 The rate of temperature rise in the first carbonization step is not particularly limited. Although it depends on the heating method, it is preferably 1 ° C./min or more, more preferably 2 ° C./min or more, preferably 20 ° C./min or less, and more preferably 18 ° C./min or less. When the rate of temperature rise is not less than the lower limit value and not more than the upper limit value, good productivity can be easily obtained, which is preferable from the viewpoint of economy. In addition, the progress of activation by the carbonization gas generated is easily suppressed, and a good carbon density is easily obtained.
第一の炭化工程の温度は、好ましくは３００℃以上、より好ましくは４００℃以上、更に好ましくは５００℃以上であり、好ましくは８００℃以下、より好ましくは７００℃以下である。第一の炭化工程の温度が前記下限値以上であり前記上限値以下であると、所望の物性（例えば、元素含有量、比表面積、真密度、六角網面積層方向Ｌｃの大きさおよび／または面間隔ｄ００２）を得やすい。 The temperature of the first carbonization step is preferably 300 ° C. or higher, more preferably 400 ° C. or higher, further preferably 500 ° C. or higher, preferably 800 ° C. or lower, and more preferably 700 ° C. or lower. When the temperature of the first carbonization step is equal to or higher than the lower limit value and lower than the upper limit value, desired physical properties (for example, element content, specific surface area, true density, hexagonal net area layer direction Lc size and / or It is easy to obtain the surface area d 002).
第一の炭化工程の温度の保持時間は、特に限定されない。保持時間は、好ましくは０．１時間以上、より好ましくは０．５時間以上であり、好ましくは２０時間以下、より好ましくは１５時間以下である。保持時間が前記下限値以上であり前記上限値以下であると、炭化が十分に進行しやすいため、炭素質材料を製造する過程で炭化物の発火が生じにくくなる。また、経済性の観点から、適度な時間であるため好ましい。 The temperature holding time of the first carbonization step is not particularly limited. The holding time is preferably 0.1 hours or more, more preferably 0.5 hours or more, preferably 20 hours or less, and more preferably 15 hours or less. When the holding time is not less than the lower limit value and not more than the upper limit value, carbonization is likely to proceed sufficiently, so that ignition of carbonized material is less likely to occur in the process of producing the carbonaceous material. Further, from the viewpoint of economy, it is preferable because the time is appropriate.
〔第二の炭化工程〕
第一の炭化工程の後に実施する第二の炭化工程では、好ましくは、炭素前駆体とコーティング剤との混合物を非酸化性ガス雰囲気下９００℃以上１４００℃以下の温度で炭化して炭素質材料を得る。第二の炭化工程に付されることにより、本発明の炭素質材料は、良好な放電容量、良好な充放電効率および低い抵抗性とともに、酸化劣化に対する良好な耐性を有する電池をもたらすことができる。
[Second carbonization step]
In the second carbonization step carried out after the first carbonization step, preferably, a mixture of the carbon precursor and the coating agent is carbonized at a temperature of 900 ° C. or higher and 1400 ° C. or lower in a non-oxidizing gas atmosphere to carbonize the carbon material. To get. By being subjected to the second carbonization step, the carbonaceous material of the present invention can provide a battery having good resistance to oxidative deterioration as well as good discharge capacity, good charge / discharge efficiency and low resistance. ..
非酸化性ガスの例としては、ヘリウム、窒素およびアルゴン等を挙げることができ、これらを単独でまたは組み合わせて用いることができる。また、塩素等のハロゲンガスを前記非酸化性ガスと混合したガス雰囲気下で、第二の炭化工程を行ってもよい。非酸化性ガス中に酸化性ガスが含まれている場合、その含有量は低いほど好ましい。そのような場合、非酸化性ガス中の酸化性ガス（特に酸素）の含有量は、通常１体積％以下、好ましくは０．１体積％以下である。酸化性ガスの含有量が前記上限値以下であると、炭素前駆体生成過程で、酸化が進行しにくく、所望の構造構築が進みやすく、また、生成した構造の酸化分解が起きにくい。 Examples of non-oxidizing gases include helium, nitrogen, argon and the like, which can be used alone or in combination. Further, the second carbonization step may be performed in a gas atmosphere in which a halogen gas such as chlorine is mixed with the non-oxidizing gas. When the non-oxidizing gas contains an oxidizing gas, the lower the content, the more preferable. In such a case, the content of the oxidizing gas (particularly oxygen) in the non-oxidizing gas is usually 1% by volume or less, preferably 0.1% by volume or less. When the content of the oxidizing gas is not more than the above upper limit value, oxidation is unlikely to proceed in the carbon precursor formation process, desired structure construction is easy to proceed, and oxidative decomposition of the formed structure is unlikely to occur.
非酸化性ガスの供給量（流通量）は、特に限定されない。炭素前駆体１ｇ当たり、通常１ｍＬ／分以上、好ましくは１０ｍＬ／分以上、更に好ましくは１００ｍＬ／分以上であり、通常１０００ｍＬ／分以下である。また、第二の炭化工程は、減圧下で、例えば１０ＫＰａ以下で行うこともできる。 The supply amount (distribution amount) of the non-oxidizing gas is not particularly limited. It is usually 1 mL / min or more, preferably 10 mL / min or more, more preferably 100 mL / min or more, and usually 1000 mL / min or less per 1 g of carbon precursor. The second carbonization step can also be carried out under reduced pressure, for example, at 10 KPa or less.
第二の炭化工程の昇温速度は特に限定されない。加熱の方法により異なるが、好ましくは１℃／分以上、より好ましくは２℃／分以上であり、好ましくは２０℃／分以下、より好ましくは１８℃／分以下である。昇温速度が前記下限値以上であり前記上限値以下であると、良好な生産性を得やすく、経済性の観点からも好ましい。また、発生する乾留ガスによる賦活の進行が抑制されやすく、良好な炭素密度を得やすい。 The rate of temperature rise in the second carbonization step is not particularly limited. Although it depends on the heating method, it is preferably 1 ° C./min or more, more preferably 2 ° C./min or more, preferably 20 ° C./min or less, and more preferably 18 ° C./min or less. When the rate of temperature rise is not less than the lower limit value and not more than the upper limit value, good productivity can be easily obtained, which is preferable from the viewpoint of economy. In addition, the progress of activation by the carbonization gas generated is easily suppressed, and a good carbon density is easily obtained.
第二の炭化工程の温度は、好ましくは９００℃以上、より好ましくは１０００℃以上、更に好ましくは１１００℃以上、特に好ましくは１１５０℃以上であり、好ましくは１４００℃以下、より好ましくは１３８０℃以下、更に好ましくは１３５０℃以下である。第二の炭化工程の温度が前記下限値以上であり前記上限値以下であると、炭素質材料の官能基の残存量を減らしやすく、不可逆容量の増大を招き得る炭素質材料とリチウムとの反応を抑制しやすい。また、炭素六角平面の選択的配向性の増大による放電容量の低下を抑制しやすい。更に、所望の物性（例えば、元素含有量、比表面積、真密度、六角網面積層方向Ｌｃの大きさおよび／または面間隔ｄ００２）を得やすい。 The temperature of the second carbonization step is preferably 900 ° C. or higher, more preferably 1000 ° C. or higher, further preferably 1100 ° C. or higher, particularly preferably 1150 ° C. or higher, preferably 1400 ° C. or lower, more preferably 1380 ° C. or lower. More preferably, it is 1350 ° C. or lower. When the temperature of the second carbonization step is equal to or higher than the lower limit value and lower than the upper limit value, the residual amount of functional groups of the carbonaceous material can be easily reduced, and the reaction between the carbonic material and lithium, which can lead to an increase in irreversible capacity. Is easy to suppress. In addition, it is easy to suppress a decrease in discharge capacity due to an increase in the selective orientation of the carbon hexagonal plane. Further, it is easy to obtain desired physical properties (for example, element content, specific surface area, true density, hexagonal net area Lc size in the layer direction and / or surface spacing d 002).
第二の炭化工程の温度の保持時間は、特に限定されない。例えば１０００℃以上に保持する時間は、通常０．０５時間以上１０時間以下であり、好ましくは０．０５時間以上３時間以下、より好ましくは０．０５時間以上１時間以下である。保持時間が前記下限値以上であり前記上限値以下であると、所望の物性（例えば、元素含有量、比表面積、真密度、六角網面積層方向Ｌｃの大きさ、および／または面間隔ｄ００２）を得やすい。また、経済性の観点から、適度な時間であるため好ましい。 The temperature holding time of the second carbonization step is not particularly limited. For example, the time for holding at 1000 ° C. or higher is usually 0.05 hours or more and 10 hours or less, preferably 0.05 hours or more and 3 hours or less, and more preferably 0.05 hours or more and 1 hour or less. When the holding time is not less than the lower limit value and not more than the upper limit value, desired physical properties (for example, element content, specific surface area, true density, size of hexagonal net area layer direction Lc, and / or surface spacing d 002 ) Is easy to obtain. Further, from the viewpoint of economy, it is preferable because the time is appropriate.
第二の炭化工程において、炭素前駆体とコーティング剤との混合物を炭化することによって、本発明の炭素質材料が得られる。炭素前駆体とコーティング剤とを混合して炭化することにより、得られる炭素質材料の比表面積を低減させることができ、所望の比表面積を得ることができる。更に、炭素質材料への二酸化炭素の吸着量を調整することができる。 In the second carbonization step, the carbonaceous material of the present invention is obtained by carbonizing the mixture of the carbon precursor and the coating agent. By mixing and carbonizing the carbon precursor and the coating agent, the specific surface area of the obtained carbonaceous material can be reduced, and a desired specific surface area can be obtained. Further, the amount of carbon dioxide adsorbed on the carbonaceous material can be adjusted.
炭素前駆体とコーティング剤とを混合して炭化することによって炭素質材料の比表面積が低減される機構は、詳細には解明されていないが、以下のように考えることができる。しかしながら、本発明は、以下の説明によって限定されるものではない。
炭素前駆体とコーティング剤とを混合して炭化することにより、炭素前駆体の表面に、コーティング剤の熱処理により得られる炭素質被膜が形成され、この炭素質被膜により、得られる炭素質材料の比表面積が低減すると考えられる。その結果、炭素質材料とアルカリ金属、例えば、リチウムまたはナトリウムとの反応によるＳＥＩ（Solid Electrolyte Interphase）と呼ばれる被膜の形成反応が抑制されるので、不可逆容量を低減させることが期待できる。また、生成した炭素質被膜もリチウムまたはナトリウムをドープおよび脱ドープすることができるため、容量が増加する効果も期待できる。
The mechanism by which the specific surface area of the carbonaceous material is reduced by mixing and carbonizing the carbon precursor and the coating agent has not been elucidated in detail, but can be considered as follows. However, the present invention is not limited by the following description.
By mixing and carbonizing the carbon precursor and the coating agent, a carbonaceous film obtained by heat treatment of the coating agent is formed on the surface of the carbon precursor, and the ratio of the carbonaceous material obtained by this carbonaceous film is formed. It is thought that the surface area will be reduced. As a result, the formation reaction of a film called SEI (Solid Electrolyte Interphase) due to the reaction between the carbonaceous material and the alkali metal, for example, lithium or sodium is suppressed, so that the irreversible capacity can be expected to be reduced. Further, since the formed carbonaceous film can also be doped and dedoped with lithium or sodium, the effect of increasing the capacity can be expected.
＜コーティング剤＞
コーティング剤は、好ましくは、炭素前駆体の比表面積を低減させることのできる揮発物質（例えば、炭化水素系ガスおよびタール成分）を十分発生できる剤である。
<Coating agent>
The coating agent is preferably an agent capable of sufficiently generating a volatile substance (for example, a hydrocarbon gas and a tar component) capable of reducing the specific surface area of the carbon precursor.
コーティング剤の残炭率は、第二の炭化工程を実施する機器の安定稼働の観点および炭素質材料の性状の観点（すなわち、局所的に性状の異なる炭素質材料が生成しにくい観点）から、好ましくは５質量％以下、より好ましくは３質量％以下である。
本発明における残炭率は、コーティング剤を８００℃で灰化した場合の残炭率である。残炭率は、試料を不活性ガス雰囲気下で強熱した後の強熱残分の炭素量を定量することにより測定できる。具体的には、試料およそ１ｇ〔この正確な質量をＷ１（ｇ）とする〕を坩堝に入れ、２０Ｌ／分で窒素を流通させながら坩堝を電気炉にて１０℃／分の昇温速度で室温から８００℃まで昇温させ、次いで８００℃で１時間強熱する。このときの残存物を強熱残分とし、その質量をＷ２（ｇ）とする。
その後、上記強熱残分について、ＪＩＳ Ｍ８８１９に定められた方法に準拠して元素分析を行い、炭素の質量割合Ｐ１（質量％）を測定する。残炭率Ｐ２（質量％）は下記式により算出できる。
Ｐ２＝Ｐ１×Ｗ２／Ｗ１
The residual carbon content of the coating agent is determined from the viewpoint of stable operation of the equipment that carries out the second carbonization step and the viewpoint of the properties of the carbonaceous material (that is, the viewpoint that it is difficult to locally generate carbonic materials having different properties). It is preferably 5% by mass or less, more preferably 3% by mass or less.
The residual coal ratio in the present invention is the residual coal ratio when the coating agent is incinerated at 800 ° C. The residual coal ratio can be measured by quantifying the amount of carbon in the strong heat residue after the sample is strongly heated in an inert gas atmosphere. Specifically, about 1 g of a sample [this accurate mass is W1 (g)] is placed in a crucible, and the crucible is heated in an electric furnace at a heating rate of 10 ° C./min while nitrogen is circulated at 20 L / min. The temperature is raised from room temperature to 800 ° C., and then ignited at 800 ° C. for 1 hour. The residue at this time is defined as ignition residue, and its mass is defined as W2 (g).
Then, the ignition residue is subjected to elemental analysis according to the method specified in JIS M8819, and the mass ratio P1 (mass%) of carbon is measured. The residual coal ratio P2 (mass%) can be calculated by the following formula.
P2 = P1 x W2 / W1
そのようなコーティング剤の例としては、例えば熱可塑性樹脂および低分子有機化合物が挙げられる。
熱可塑性樹脂の例としては、オレフィン系樹脂、スチレン系樹脂および（メタ）アクリル酸系樹脂を挙げることができる。オレフィン系樹脂の例としては、ポリエチレン、ポリプロピレン、エチレンとプロピレンとのランダム共重合体、およびエチレンとプロピレンとのブロック共重合体等を挙げることができる。スチレン系樹脂の例としては、ポリスチレン、ポリ（α−メチルスチレン）、およびスチレンと（メタ）アクリル酸アルキルエステル（アルキル基の炭素数は１〜１２、好ましくは１〜６）との共重合体等を挙げることができる。（メタ）アクリル酸系樹脂の例としては、ポリアクリル酸、ポリメタクリル酸、および（メタ）アクリル酸アルキルエステル重合体（アルキル基の炭素数は１〜１２、好ましくは１〜６）等を挙げることができる。なお、この明細書において、（メタ）アクリル酸とは、アクリル酸とメタクリル酸の総称である。
Examples of such coating agents include, for example, thermoplastic resins and small molecule organic compounds.
Examples of the thermoplastic resin include an olefin resin, a styrene resin, and a (meth) acrylic acid resin. Examples of the olefin resin include polyethylene, polypropylene, a random copolymer of ethylene and propylene, and a block copolymer of ethylene and propylene. Examples of styrene resins include polystyrene, poly (α-methylstyrene), and copolymers of styrene and (meth) acrylic acid alkyl esters (alkyl groups having 1-12 carbon atoms, preferably 1-6 carbon atoms). And so on. Examples of the (meth) acrylic acid-based resin include polyacrylic acid, polymethacrylic acid, and (meth) acrylic acid alkyl ester polymers (alkyl groups having 1 to 12, preferably 1 to 6 carbon atoms) and the like. be able to. In this specification, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid.
低分子有機化合物の例としては、例えば炭素数が１〜２０の炭化水素化合物を挙げることができる。炭化水素化合物の炭素数は、好ましくは２〜１８、より好ましくは３〜１６である。炭化水素化合物は、飽和炭化水素化合物でも不飽和炭化水素化合物でもよく、鎖状炭化水素化合物でも環式炭化水素化合物でもよい。炭化水素化合物が不飽和炭化水素化合物の場合、不飽和結合は二重結合でも三重結合でもよく、１分子に含まれる不飽和結合の数も特に限定されない。例えば、鎖状炭化水素化合物は、脂肪族炭化水素化合物であり、その例としては、直鎖状または分枝状のアルカン、アルケンまたはアルキンを挙げることができる。環式炭化水素化合物の例としては、脂環式炭化水素化合物（例えば、シクロアルカン、シクロアルケン、シクロアルキン）および芳香族炭化水素化合物を挙げることができる。脂肪族炭化水素化合物の具体的な例としては、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、オクタン、ノナン、デカン、エチレン、プロピレン、ブテン、ペンテン、ヘキセンおよびアセチレン等を挙げることができる。脂環式炭化水素化合物の具体的な例としては、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロノナン、シクロプロパン、シクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、デカリン、ノルボルネン、メチルシクロヘキサン、およびノルボルナジエン等を挙げることができる。芳香族炭化水素化合物の具体的な例としては、ベンゼン、トルエン、キシレン、メシチレン、クメン、ブチルベンゼン、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、ビニルキシレン、ｐｅｒｔ−ブチルスチレン、エチルスチレン等の単環芳香族化合物、ナフタレン、フェナントレン、アントラセン、ピレン等の３環〜６環の縮合多環芳香族化合物を挙げることができるが、好ましくは縮合多環芳香族化合物であり、より好ましくはナフタレン、フェナントレン、アントラセンまたはピレンである。ここで、前記炭化水素化合物は、任意の置換基を有していてよい。置換基は特に限定されない。置換基の例としては、炭素数１〜４のアルキル基（好ましくは炭素数１〜２のアルキル基）、炭素数２〜４のアルケニル基（好ましくは炭素数２のアルケニル基）、および炭素数３〜８のシクロアルキル基（好ましくは炭素数３〜６のシクロアルキル基）を挙げることができる。 Examples of small molecule organic compounds include hydrocarbon compounds having 1 to 20 carbon atoms. The hydrocarbon compound preferably has 2 to 18 carbon atoms, more preferably 3 to 16 carbon atoms. The hydrocarbon compound may be a saturated hydrocarbon compound or an unsaturated hydrocarbon compound, and may be a chain hydrocarbon compound or a cyclic hydrocarbon compound. When the hydrocarbon compound is an unsaturated hydrocarbon compound, the unsaturated bond may be a double bond or a triple bond, and the number of unsaturated bonds contained in one molecule is not particularly limited. For example, the chain hydrocarbon compound is an aliphatic hydrocarbon compound, and examples thereof include linear or branched alkanes, alkenes, and alkynes. Examples of cyclic hydrocarbon compounds include alicyclic hydrocarbon compounds (eg, cycloalkane, cycloalkyne, cycloalkyne) and aromatic hydrocarbon compounds. Specific examples of the aliphatic hydrocarbon compound include methane, ethane, propane, butane, pentane, hexane, octane, nonane, decane, ethylene, propylene, butene, pentene, hexene and acetylene. Specific examples of the alicyclic hydrocarbon compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclopropane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, decalin, norbornene, methylcyclohexane, and norbornadiene. Can be mentioned. Specific examples of aromatic hydrocarbon compounds include benzene, toluene, xylene, mecitylene, cumene, butylbenzene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and vinylxylene. , Pert-butylstyrene, ethylstyrene and other monocyclic aromatic compounds, and 3 to 6 ring fused polycyclic aromatic compounds such as naphthalene, phenanthrene, anthracene and pyrene, but preferably condensed polycyclic aromatic compounds. It is a group compound, more preferably naphthalene, phenylene, anthracene or pyrene. Here, the hydrocarbon compound may have an arbitrary substituent. The substituent is not particularly limited. Examples of substituents are an alkyl group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 2 carbon atoms), an alkenyl group having 2 to 4 carbon atoms (preferably an alkenyl group having 2 carbon atoms), and an alkenyl group having 2 carbon atoms. Cycloalkyl groups of 3 to 8 (preferably cycloalkyl groups having 3 to 6 carbon atoms) can be mentioned.
コーティング剤は、混合の容易さおよび均一分散の観点から、常温で固体であることが好ましく、例えばポリスチレン、ポリエチレンまたはポリプロピレン等の常温で固体の熱可塑性樹脂、または、ナフタレン、フェナントレン、アントラセンまたはピレン等の常温で固体の低分子有機化合物がより好ましい。第二の炭化工程の温度下で揮発および熱分解した際に、炭素前駆体の表面を酸化賦活しないものが好ましいことから、熱可塑性樹脂としては、オレフィン系樹脂およびスチレン系樹脂が好ましく、ポリエチレン、ポリプロピレンおよびポリスチレンがより好ましい。低分子有機化合物としては、常温下で揮発性がより小さいことが安全上好ましいことから、炭素数１〜２０の炭化水素化合物が好ましく、縮合多環芳香族化合物がより好ましく、ナフタレン、フェナントレン、アントラセンまたはピレンが更に好ましい。更に、炭素前駆体との混合しやすさの観点から、熱可塑性樹脂が好ましく、オレフィン系樹脂およびスチレン系樹脂がより好ましく、ポリエチレン、ポリプロピレンおよびポリスチレンが更に好ましく、ポリエチレンおよびポリスチレンが特に好ましい。 The coating agent is preferably solid at room temperature from the viewpoint of ease of mixing and uniform dispersion, for example, a thermoplastic resin such as polystyrene, polyethylene or polypropylene which is solid at room temperature, naphthalene, phenanthrene, anthracene or pyrene or the like. Low molecular weight organic compounds that are solid at room temperature are more preferred. As the thermoplastic resin, an olefin resin and a styrene resin are preferable, and polyethylene, which does not oxidize and activate the surface of the carbon precursor when volatilized and thermally decomposed at the temperature of the second carbonization step. Polypropylene and polystyrene are more preferred. As the low molecular weight organic compound, a hydrocarbon compound having 1 to 20 carbon atoms is preferable, a condensed polycyclic aromatic compound is more preferable, and naphthalene, phenanthrene, and anthracene are preferable because it is preferable for safety that the volatileness is smaller at room temperature. Alternatively, pyrene is more preferred. Further, from the viewpoint of ease of mixing with the carbon precursor, a thermoplastic resin is preferable, an olefin resin and a styrene resin are more preferable, polyethylene, polypropylene and polystyrene are further preferable, and polyethylene and polystyrene are particularly preferable.
炭素前駆体とコーティング剤とを混合する際の炭素前駆体とコーティング剤との質量比は、特に限定されない。炭素前駆体とコーティング剤との質量比は、好ましくは９７：３〜４０：６０、より好ましくは９５：５〜６０：４０、更に好ましくは９３：７〜８０：２０である。例えば、コーティング剤が炭素前駆体の質量に対して３質量部以上であると、比表面積を十分に低減させやすい。また、コーティング剤が炭素前駆体の質量に対して６０質量部以下であると、比表面積の低減効果が飽和に達しているにもかかわらず過剰に存在するコーティング剤が消費される無駄を回避できるため、工業的に有利である。 The mass ratio of the carbon precursor and the coating agent when the carbon precursor and the coating agent are mixed is not particularly limited. The mass ratio of the carbon precursor to the coating agent is preferably 97: 3 to 40:60, more preferably 95: 5 to 60:40, and even more preferably 93: 7 to 80:20. For example, when the coating agent is 3 parts by mass or more with respect to the mass of the carbon precursor, the specific surface area can be sufficiently reduced. Further, when the coating agent is 60 parts by mass or less with respect to the mass of the carbon precursor, it is possible to avoid waste that the coating agent present in excess is consumed even though the effect of reducing the specific surface area has reached saturation. Therefore, it is industrially advantageous.
炭素前駆体とコーティング剤との混合は、第一の炭化工程と第二の炭化工程との間に行う。第一の炭化工程と第二の炭化工程との間に、後述する粉砕工程を行う場合は、前記混合は、粉砕工程の前または粉砕工程の後のいずれに行ってもよい。
粉砕工程の前に炭素前駆体とコーティング剤とを混合する場合には、炭素前駆体と常温で液体または固体のコーティング剤とを計量しながら、粉砕装置に同時に供給することにより粉砕と混合とを同時に行うことができる。
粉砕工程の後に炭素前駆体とコーティング剤とを混合する場合には、混合は両者が均一に混合される手法であれば、公知の方法で実施できる。コーティング剤が常温で固体の場合、コーティング剤は好ましくは粒子状である。その場合、粒子の形または粒径は特に限定されないが、コーティング剤と粉砕された炭素前駆体とを均一に分散させやすい観点からは、コーティング剤の体積平均粒径は好ましくは０．１〜２０００μｍ、より好ましくは１〜１０００μｍ、更に好ましくは２〜６００μｍである。
コーティング剤が常温で気体の場合、コーティング剤を含む非酸化性ガスを、第二の炭化工程を実施する機器内に流通させ熱分解させることにより、該機器内に導入された炭素前駆体と混合させる方法を用いることができる。
The carbon precursor and the coating agent are mixed between the first carbonization step and the second carbonization step. When the pulverization step described later is performed between the first carbonization step and the second carbonization step, the mixing may be performed either before the pulverization step or after the pulverization step.
When the carbon precursor and the coating agent are mixed before the pulverization step, the carbon precursor and the liquid or solid coating agent at room temperature are weighed and simultaneously supplied to the pulverizer to perform pulverization and mixing. Can be done at the same time.
When the carbon precursor and the coating agent are mixed after the pulverization step, the mixing can be carried out by a known method as long as both are uniformly mixed. When the coating agent is solid at room temperature, the coating agent is preferably particulate. In that case, the shape or particle size of the particles is not particularly limited, but the volume average particle size of the coating agent is preferably 0.1 to 2000 μm from the viewpoint of easily uniformly dispersing the coating agent and the crushed carbon precursor. , More preferably 1 to 1000 μm, still more preferably 2 to 600 μm.
When the coating agent is a gas at room temperature, the non-oxidizing gas containing the coating agent is circulated in the equipment for carrying out the second carbonization step and thermally decomposed to be mixed with the carbon precursor introduced into the equipment. A method of causing can be used.
炭素前駆体とコーティング剤との混合物は、炭素前駆体およびコーティング剤以外の他の成分を含んでもよい。例えば、天然黒鉛、人造黒鉛、金属系材料、合金系材料および酸化物系材料からなる群から選択される１以上の成分を含んでよい。炭素前駆体とコーティング剤との混合物がそのような成分を含む場合、そのような成分の含有量は、特に限定されるものではなく、混合物１００質量部に対して、好ましくは５０質量部以下、より好ましくは３０質量部以下、更に好ましくは２０質量部以下、特に好ましくは１０質量部以下である。 The mixture of the carbon precursor and the coating agent may contain other components other than the carbon precursor and the coating agent. For example, it may contain one or more components selected from the group consisting of natural graphite, artificial graphite, metal-based materials, alloy-based materials and oxide-based materials. When the mixture of the carbon precursor and the coating agent contains such a component, the content of such a component is not particularly limited, and is preferably 50 parts by mass or less with respect to 100 parts by mass of the mixture. It is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
〔粉砕工程〕
本発明の製造方法は、必要に応じて、第一の炭化工程後または第二の炭化工程後に粉砕工程を含んでいてもよい。この工程では、炭化により凝集した炭化物（炭素前駆体または炭素質材料）を粉砕し、目的の大きさに調整することができる。
粉砕工程を行う場合、第一の炭化工程後に行うことが好ましい。この理由は、粉砕により表面積を大きくすることで、第二の炭化工程で発生する分解ガスによる構造変化の影響を最小限にできるからである。また、別の理由は、第二の炭化工程後に粉砕を実施した場合には、粉砕によって新たに生じた結晶面が電池内で電解液等と反応し、電池機能が損なわれる可能性があるからである。従って、本発明の好ましい一実施態様では、本発明の製造方法は、炭素前駆体を好ましくは２０μｍ以下、より好ましくは１５μｍ以下、特に好ましくは１０μｍ以下の体積平均粒径に粉砕する粉砕工程を更に含む。前記体積平均粒径は、好ましくは２μｍ以上、より好ましくは２．２μｍ以上、特に好ましくは２．５μｍ以上である。しかしながら、第二の炭化工程の後に粉砕することは排除されない。
[Crushing process]
The production method of the present invention may include a pulverization step after the first carbonization step or after the second carbonization step, if necessary. In this step, the carbonized material (carbon precursor or carbonaceous material) aggregated by carbonization can be crushed and adjusted to a desired size.
When the pulverization step is performed, it is preferably performed after the first carbonization step. The reason for this is that by increasing the surface area by pulverization, the influence of structural changes due to the decomposition gas generated in the second carbonization step can be minimized. Another reason is that when pulverization is performed after the second carbonization step, the crystal plane newly generated by the pulverization may react with the electrolytic solution or the like in the battery, and the battery function may be impaired. Is. Therefore, in a preferred embodiment of the present invention, the production method of the present invention further comprises a pulverization step of pulverizing the carbon precursor to a volume average particle size of preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. include. The volume average particle size is preferably 2 μm or more, more preferably 2.2 μm or more, and particularly preferably 2.5 μm or more. However, milling after the second carbonization step is not excluded.
粉砕に用いる粉砕機は、特に限定されない。例えばジェットミル、ミキサーミル、ボールミル、ハンマーミル、またはロッドミル等を単独でまたは組み合わせて使用することができる。微粉の発生が少ないという観点からは、分級機能を備えたジェットミルが好ましい。一方、ミキサーミル、ボールミル、ハンマーミル、またはロッドミル等を用いる場合は、粉砕後に分級を行うことで微粉を除くことができる。 The crusher used for crushing is not particularly limited. For example, a jet mill, a mixer mill, a ball mill, a hammer mill, a rod mill, or the like can be used alone or in combination. From the viewpoint of generating less fine powder, a jet mill having a classification function is preferable. On the other hand, when a mixer mill, a ball mill, a hammer mill, a rod mill or the like is used, fine powder can be removed by classifying after pulverization.
〔分級工程〕
本発明の製造方法は、炭化工程後または必要に応じて行ってよい粉砕工程の後に分級を実施してもよい。分級によって、炭素前駆体または炭素質材料の体積平均粒径をより正確に調整することができ、また、特定の寸法より小さい（例えば体積平均粒径が１μｍ以下の）炭素前駆体若しくは炭素質材料、または特定の寸法より大きい（例えば体積平均粒径が３０μｍ以上の）炭素前駆体若しくは炭素質材料を除去することもできる。
分級を行う場合、その例として篩による分級、湿式分級、または乾式分級を挙げることができる。湿式分級機としては、例えば重力分級、慣性分級、水力分級、または遠心分級等の原理を利用した分級機を挙げることができる。乾式分級機としては、沈降分級、機械的分級、または遠心分級の原理を利用した分級機を挙げることができる。
[Classification process]
In the production method of the present invention, classification may be carried out after a carbonization step or a pulverization step which may be carried out as needed. Classification allows the volume average particle size of the carbon precursor or carbonaceous material to be adjusted more accurately, and the carbon precursor or carbonaceous material smaller than a specific dimension (for example, the volume average particle size is 1 μm or less). , Or carbon precursors or carbonaceous materials larger than certain dimensions (eg, volume average particle size of 30 μm or greater) can also be removed.
When performing classification, examples thereof include sieve classification, wet classification, and dry classification. Examples of the wet classifier include a classifier using principles such as gravity classification, inertial classification, hydraulic classification, and centrifugal classification. Examples of the dry classifier include a classifier using the principle of sedimentation classification, mechanical classification, or centrifugal classification.
粉砕工程後に分級を行う場合、上述したように、粉砕と分級は、１つの装置（例えば、乾式の分級機能を備えたジェットミル）を用いて行うことができる。或いは、粉砕機と分級機とが独立した装置を用いることもでき、この場合、粉砕と分級とは連続して行ってもよいし、不連続に行ってもよい。 When classification is performed after the pulverization step, as described above, pulverization and classification can be performed using one device (for example, a jet mill having a dry classification function). Alternatively, an apparatus in which the crusher and the classifier are independent can be used, and in this case, the crushing and the classification may be performed continuously or discontinuously.
［電極］
本発明の炭素質材料は電極に使用できる。従って、本発明はまた、本発明の炭素質材料を含む電極も対象とする。
[electrode]
The carbonaceous material of the present invention can be used for electrodes. Therefore, the present invention also covers electrodes containing the carbonaceous material of the present invention.
［電極の製造方法］
本発明の電極は、例えば、炭素質材料、結合剤（バインダー）および溶媒を混練することにより、電極合剤を調製し、金属板等からなる集電板に塗布し、乾燥した後、加圧成形することにより電極を製造することができる。
[Method of manufacturing electrodes]
For the electrode of the present invention, for example, a carbonaceous material, a binder, and a solvent are kneaded to prepare an electrode mixture, which is applied to a current collector plate made of a metal plate or the like, dried, and then pressurized. The electrode can be manufactured by molding.
結合剤は、電解液と反応しないものであれば特に限定されない。結合剤の例としては、ＰＶＤＦ（ポリフッ化ビニリデン）、ポリテトラフルオロエチレン、およびＳＢＲ（スチレン・ブタジエン・ラバー）とＣＭＣ（カルボキシメチルセルロース）との混合物等が挙げられる。中でもＰＶＤＦは、活物質表面に付着したＰＶＤＦがリチウムイオン移動を阻害することが少なく、良好な入出力特性を得るために好ましい。ＰＶＤＦを溶解しスラリーを形成するために、Ｎ−メチルピロリドン（ＮＭＰ）等の極性溶媒が好ましく用いられるが、ＳＢＲ等の水性エマルジョンまたはＣＭＣの水溶液を用いることもできる。結合剤の添加量が多すぎると、得られる電極の抵抗が大きくなるため、電池の内部抵抗が大きくなり電池特性を低下させるので好ましくない。また、結合剤の添加量が少なすぎると、負極材料粒子相互および集電材との結合が不十分となり好ましくない。結合剤の好ましい添加量は、使用する結合剤の種類によっても異なるが、ＰＶＤＦ系の結合剤では、炭素質材料および結合剤の総質量に対して、好ましくは２〜１３質量％であり、より好ましくは２〜１０質量％である。一方、溶媒に水を使用する結合剤では、ＳＢＲとＣＭＣとの混合物等、複数の結合剤を混合して使用することが多く、使用する結合剤の総添加量は、炭素質材料および結合剤の総質量に対して、好ましくは０．５〜５質量％であり、より好ましくは１〜４質量％である。 The binder is not particularly limited as long as it does not react with the electrolytic solution. Examples of the binder include PVDF (polyvinylidene fluoride), polytetrafluoroethylene, and a mixture of SBR (styrene butadiene rubber) and CMC (carboxymethyl cellulose). Among them, PVDF is preferable because PVDF adhering to the surface of the active material does not hinder the movement of lithium ions and obtains good input / output characteristics. A polar solvent such as N-methylpyrrolidone (NMP) is preferably used to dissolve PVDF and form a slurry, but an aqueous emulsion such as SBR or an aqueous solution of CMC can also be used. If the amount of the binder added is too large, the resistance of the obtained electrode increases, which increases the internal resistance of the battery and deteriorates the battery characteristics, which is not preferable. Further, if the amount of the binder added is too small, the bonding between the negative electrode material particles and the current collector is insufficient, which is not preferable. The preferable amount of the binder added varies depending on the type of the binder used, but the PVDF-based binder is preferably 2 to 13% by mass, more preferably 2 to 13% by mass, based on the total mass of the carbonaceous material and the binder. It is preferably 2 to 10% by mass. On the other hand, in a binder using water as a solvent, a plurality of binders such as a mixture of SBR and CMC are often mixed and used, and the total amount of the binder to be used is a carbonaceous material and a binder. It is preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass, based on the total mass of the above.
本発明の炭素質材料を用いることにより、特に導電助剤を添加しなくとも高い導電性を有する電極を製造することができるが、更に高い導電性を付与することを目的に、必要に応じて電極合剤を調製する際に導電助剤を添加してよい。導電助剤としては、導電性のカーボンブラック、気相成長炭素繊維（ＶＧＣＦ）、およびナノチューブ等を単独でまたは２種以上組み合わせて用いることができる。添加量は、使用する導電助剤の種類によっても異なるが、添加する量が少なすぎると期待する導電性を得にくいので好ましくなく、多すぎると電極合剤中での分散が悪くなるので好ましくない。このような観点から、導電助剤を添加する場合の導電助剤の割合は、好ましくは０．５〜１０質量％［ここで、活物質（炭素質材料）量＋結合剤量＋導電助剤量＝１００質量％とする］であり、より好ましくは０．５〜７質量％、更に好ましくは０．５〜５質量％である。 By using the carbonaceous material of the present invention, it is possible to produce an electrode having high conductivity without adding a conductive auxiliary agent, but for the purpose of imparting even higher conductivity, if necessary. A conductive auxiliary agent may be added when preparing the electrode mixture. As the conductive auxiliary agent, conductive carbon black, vapor-grown carbon fiber (VGCF), nanotubes and the like can be used alone or in combination of two or more. The amount to be added varies depending on the type of the conductive additive used, but it is not preferable if the amount added is too small because it is difficult to obtain the expected conductivity, and if it is too large, the dispersion in the electrode mixture is deteriorated, which is not preferable. .. From this point of view, the ratio of the conductive auxiliary agent when the conductive auxiliary agent is added is preferably 0.5 to 10% by mass [here, the amount of the active material (carbonaceous material) + the amount of the binder + the conductive auxiliary agent. Amount = 100% by mass], more preferably 0.5 to 7% by mass, still more preferably 0.5 to 5% by mass.
電極活物質層は、通常は集電板の両面に形成するが、必要に応じて片面に形成してもよい。電極活物質層が厚いほど、集電板およびセパレータ等が少なくて済むため高容量化には好ましいが、電極活物質層が厚すぎると、電極内のイオン拡散抵抗が増大し、入出力特性が低下するため好ましくない。好ましい電極活物質層（片面当たり）の厚さは、１０〜８０μｍであり、より好ましくは２０〜７５μｍ、更に好ましくは２０〜６０μｍである。 The electrode active material layer is usually formed on both sides of the current collector plate, but may be formed on one side if necessary. The thicker the electrode active material layer, the smaller the number of current collector plates and separators, which is preferable for increasing the capacity. However, if the electrode active material layer is too thick, the ion diffusion resistance in the electrode increases and the input / output characteristics are deteriorated. It is not preferable because it decreases. The thickness of the electrode active material layer (per one side) is preferably 10 to 80 μm, more preferably 20 to 75 μm, and further preferably 20 to 60 μm.
［電池］
本発明はまた、本発明の電極を含む電池も対象とする。本発明の電池、例えば非水電解質二次電池は本発明の炭素質材料を用いて製造されるため、放電容量、充放電効率および低抵抗性に優れている。
[battery]
The present invention also covers batteries comprising the electrodes of the present invention. Since the battery of the present invention, for example, a non-aqueous electrolyte secondary battery, is manufactured using the carbonaceous material of the present invention, it is excellent in discharge capacity, charge / discharge efficiency, and low resistance.
本発明における非水電解質二次電池において、本発明の電極（負極）以外の材料、すなわち、正極材料、セパレータおよび電解液等の材料は特に限定されず、非水電解質二次電池において従来使用され、または提案されている種々の材料を使用することが可能である。
例えば、正極材料としては、層状酸化物系［ＬｉＭＯ２（ここで、Ｍは金属を表す）で表されるもの：例えばＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎＯ２、またはＬｉＮｉｘＣｏｙＭｏｚＯ２（ここで、ｘ、ｙ、ｚは組成比を表わす）］、オリビン系［ＬｉＭＰＯ４（ここで、Ｍは金属を表す）と表されるもの：例えばＬｉＦｅＰＯ４等］、およびスピネル系［ＬｉＭ２Ｏ４（ここで、Ｍは金属を表す）で表されるもの：例えばＬｉＭｎ２Ｏ４等］の複合金属カルコゲン化合物が好ましく、これらのカルコゲン化合物を必要に応じて混合してもよい。例えば、これらの正極材料を適当な結合剤と電極に導電性を付与するための炭素質材料とともに成形して、導電性の集電材上に層形成することにより、正極を製造できる。
In the non-aqueous electrolyte secondary battery of the present invention, materials other than the electrode (negative electrode) of the present invention, that is, materials such as a positive electrode material, a separator, and an electrolytic solution are not particularly limited, and are conventionally used in the non-aqueous electrolyte secondary battery. , Or the various materials proposed can be used.
For example, as the positive electrode material, a layered oxide [LiMO 2 (where, M represents a metal) as represented by: for example LiCoO 2, LiNiO 2, LiMnO 2 or LiNi x Co y Mo z O 2 , ( Here, x, y, z represent a composition ratio)], an olivine type [LiMPO 4 (where M represents a metal): for example, LiFePO 4 etc.], and a spinel type [LiM 2 O]. 4 (where M represents a metal): a composite metal chalcogen compound of [for example, LiMn 2 O 4 or the like] is preferable, and these chalcogen compounds may be mixed if necessary. For example, a positive electrode can be manufactured by molding these positive electrode materials together with an appropriate binder and a carbonaceous material for imparting conductivity to the electrodes and forming a layer on the conductive current collector.
これら正極と負極との組み合わせで用いられる非水溶媒型電解液は、一般に非水溶媒に電解質を溶解することにより形成される。非水溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、ジメトキシエタン、ジエトキシエタン、γ−ブチルラクトン、テトラヒドロフラン、２−メチルテトラヒドロフラン、スルホラン、または１，３−ジオキソラン等の有機溶媒の１種または２種以上を組み合わせて用いることができる。また、電解質としては、例えばＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＡｓＦ６、ＬｉＣｌ、ＬｉＢｒ、ＬｉＢ（Ｃ６Ｈ５）４、またはＬｉＮ（ＳＯ３ＣＦ３）２等を用いることができる。
非水電解質二次電池は一般に、上述したようにして製造した正極と負極とを、必要に応じて透過性セパレータ（例えば、不織布、またはその他の多孔質材料等）を介して対向させ、電解液中に浸漬させることにより製造される。セパレータに代えて、またはセパレータと一緒に、電解液を含浸させたポリマーゲルからなる固体電解質を用いることもできる。
The non-aqueous solvent type electrolytic solution used in combination with the positive electrode and the negative electrode is generally formed by dissolving the electrolyte in a non-aqueous solvent. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethoxyethane, diethoxyethane, γ-butyl lactone, tetrahydrofuran, 2-methyl tetrahydrofuran, sulfolane, or 1,3-dioxolane. One type or a combination of two or more kinds of organic solvents such as the above can be used. As the electrolyte, for example, LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiCl, LiBr, LiB (C 6 H 5 ) 4 , LiN (SO 3 CF 3 ) 2, or the like can be used. Can be done.
In a non-aqueous electrolyte secondary battery, a positive electrode and a negative electrode manufactured as described above are generally opposed to each other via a permeable separator (for example, a non-woven fabric or other porous material) as required, and an electrolytic solution is used. Manufactured by immersing in. A solid electrolyte consisting of a polymer gel impregnated with an electrolytic solution can also be used in place of or in combination with the separator.
以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。
なお、以下に本発明の炭素質材料の物性値（「元素含有量」、「比表面積」、「真密度」、「六角網面積層方向Ｌｃの大きさ」、「体積平均粒径」および「（００２）面の面間隔ｄ００２」）の測定法を記載するが、実施例を含めて、本明細書中に記載する物性値は、以下の方法により求めた値に基づくものである。
Hereinafter, the present invention will be specifically described with reference to Examples, but these do not limit the scope of the present invention.
The physical property values of the carbonaceous material of the present invention (“element content”, “specific surface area”, “true density”, “magnitude of Lc in the hexagonal net area layer direction”, “volume average particle diameter” and “volume average particle diameter” are described below. (002) Plane spacing d 002 ") will be described, but the physical property values described in the present specification, including the examples, are based on the values obtained by the following method.
［分析方法］
〔硫黄元素含有量〕
株式会社堀場製作所製「炭素・硫黄分析装置ＥＭＩＡ−９２０Ｖ２ ＨＯＲＩＢＡ製」を用いて硫黄元素含有量の測定を行った。
この装置の検出方法は、酸素気流中燃焼（高周波誘導加熱炉方式）−非分散赤外吸収法（ＮＤＩＲ）であり、校正は、アルミナ坩堝に助燃剤であるＷ（タングステン）とＳｎ（スズ）のみを入れてブランクとし、標準物質であるＪＳＳ１５２−１８［Ｃ：０．２７７％、Ｓ：０．００５６％］およびＪＳＳ１５０−１６［Ｓ：０．０２９６％］を用いて行った。前処理として２５０℃で約１０分間脱水処理を施した試料５０ｍｇ、粒子状タングステン１．５ｇ、粒子状スズ０．３ｇをアルミナ坩堝に量り取り、炭素・硫黄分析装置内で３０秒間脱ガスした後、純酸素気流下で高周波により加熱燃焼させ、測定を行った。３検体を分析し、その平均値を分析値とした。
[Analysis method]
[Sulfur element content]
The sulfur element content was measured using "Carbon / Sulfur Analyzer EMIA-920V2 HORIBA" manufactured by HORIBA, Ltd.
The detection method of this device is combustion in oxygen stream (radio frequency induction heating furnace method) -non-dispersion infrared absorption method (NDIR), and the calibration is performed on the alumina crucible with the combustion improvers W (tungsten) and Sn (tin). Only was added to make a blank, and the standard substances JSS152-18 [C: 0.277%, S: 0.0056%] and JSS150-16 [S: 0.0296%] were used. As a pretreatment, 50 mg of a sample dehydrated at 250 ° C. for about 10 minutes, 1.5 g of particulate tungsten, and 0.3 g of particulate tin were weighed in an alumina crucible and degassed in a carbon / sulfur analyzer for 30 seconds. , The measurement was carried out by heating and burning with a high frequency under a pure oxygen stream. Three samples were analyzed and the average value was used as the analysis value.
〔酸素元素含有量〕
株式会社堀場製作所製「酸素・窒素・水素分析装置ＥＭＧＡ−９３０」を用いて酸素元素含有量の測定を行った。
この装置の検出方法は、不活性ガス融解−非分散型赤外線吸収法（ＮＤＩＲ）であり、校正は、Ｓｎカプセル、およびＳＳ−３（標準試料）により行った。前処理として２５０℃で約１０分間脱水処理を施した試料２０ｍｇを、Ｓｎカプセルに量り取り、酸素・窒素・水素分析装置内で３０秒間脱ガスした後、測定を行った。３検体を分析し、その平均値を分析値とした。
[Oxygen element content]
The oxygen element content was measured using "Oxygen / Nitrogen / Hydrogen Analyzer EMGA-930" manufactured by HORIBA, Ltd.
The detection method of this device was inert gas melting-non-dispersive infrared absorption (NDIR), and calibration was performed with Sn capsules and SS-3 (standard sample). As a pretreatment, 20 mg of a sample dehydrated at 250 ° C. for about 10 minutes was weighed into Sn capsules, degassed in an oxygen / nitrogen / hydrogen analyzer for 30 seconds, and then measured. Three samples were analyzed and the average value was used as the analysis value.
〔比表面積〕
以下にＢＥＴの式から誘導された近似式を記す。
具体的には、日本BELL社製「BELL Sorb Mini」を用いて、以下のようにして液体窒素温度における炭素質材料への窒素の吸着量を測定した。炭素質材料を試料管に充填し、試料管を−１９６℃に冷却した状態で、一旦減圧し、その後所望の相対圧にて炭素質材料に窒素（純度９９．９９９％）を吸着させた。各所望の相対圧にて平衡圧に達した時の試料に吸着した窒素量を吸着ガス量ｖとした。
〔Specific surface area〕
The approximate expression derived from the BET equation is described below.
Specifically, using "BELL Sorb Mini" manufactured by BELL Japan, the amount of nitrogen adsorbed on the carbonaceous material at the liquid nitrogen temperature was measured as follows. The sample tube was filled with the carbonaceous material, the sample tube was cooled to -196 ° C., the pressure was reduced once, and then nitrogen (purity 99.999%) was adsorbed on the carbonaceous material at a desired relative pressure. The amount of nitrogen adsorbed on the sample when the equilibrium pressure was reached at each desired relative pressure was defined as the amount of adsorbed gas v.
〔真密度〕
真密度ρＢｔは、ＪＩＳ Ｒ ７２１２に定められた方法に従い、ブタノール法により測定した。具体的な手順を以下に示す。
内容積約４０ｍＬの側管付比重瓶の質量（ｍ１）を正確に秤量し、次に、その底部に試料を約１０ｍｍの厚さになるように平らに導入した後、試料入りの側管付比重瓶の質量（ｍ２）を正確に秤量した。これに、底から液面までの深さが２０ｍｍ程度になるよう１−ブタノールを静かに加えた。続いて、比重瓶に軽い振動を加えて、大きな気泡の発生がなくなったのを確かめた後、真空デシケーター内に入れ、徐々に排気して真空デシケーター内の圧力を２．０〜２．７ｋＰａにした。この圧力を２０分間以上保ち、気泡の発生が止まった後に比重瓶を取り出した。この比重瓶に１−ブタノールを添加し、栓をして（３０±０．０３℃に調節した）恒温水槽に１５分間以上浸し、１−ブタノールの液面を標線に合わせた。次に、これを取り出して外部をよくぬぐって室温まで冷却した後、質量（ｍ４）を正確に秤量した。
次に、同じ側管付比重瓶に１−ブタノールだけを満たし、前記と同様に恒温水槽に浸し、標線に合わせた後、質量（ｍ３）を量った。
更に、使用直前に沸騰させて溶解した気体を除いた蒸留水を比重瓶に導入し、前記と同様に恒温水槽に浸し、標線に合わせた後、質量（ｍ５）を量った。
真密度ρＢｔは次の式により計算した。このとき、ｄは水の３０℃における比重（０．９９４６）である。
The true density ρ Bt was measured by the butanol method according to the method specified in JIS R 7212. The specific procedure is shown below.
Accurately weigh the mass (m 1 ) of a specific gravity bottle with a side tube with an internal volume of about 40 mL, then flatly introduce the sample to the bottom to a thickness of about 10 mm, and then the side tube containing the sample. The mass (m 2 ) of the relative density bottle was accurately weighed. To this, 1-butanol was gently added so that the depth from the bottom to the liquid surface was about 20 mm. Then, lightly vibrate the specific density bottle to confirm that the generation of large bubbles has disappeared, then put it in the vacuum desiccator and gradually exhaust it to increase the pressure in the vacuum desiccator to 2.0 to 2.7 kPa. did. This pressure was maintained for 20 minutes or more, and the specific density bottle was taken out after the generation of bubbles stopped. 1-Butanol was added to this density bottle, stoppered, and immersed in a constant temperature water tank (adjusted to 30 ± 0.03 ° C.) for 15 minutes or more, and the liquid level of 1-Butanol was aligned with the marked line. Next, it was taken out, wiped well and cooled to room temperature, and then the mass (m 4 ) was accurately weighed.
Next, the same specific gravity bottle with a side tube was filled with only 1-butanol, immersed in a constant temperature water tank in the same manner as described above, aligned with the marked line, and then weighed (m 3 ).
Further, distilled water from which the gas dissolved by boiling immediately before use was removed was introduced into a specific gravity bottle, immersed in a constant temperature water tank in the same manner as described above, aligned with the marked line, and then weighed (m 5 ).
The true density ρ Bt was calculated by the following formula. At this time, d is the specific gravity (0.9946) of water at 30 ° C.
〔六角網面積層方向Ｌｃの大きさ〕
六角網面積層方向Ｌｃは、株式会社リガク製「ＭｉｎｉＦｌｅｘＩＩ」を用いたＸ線回折試験により求めた。炭素質材料を試料ホルダーに充填し、Ｎｉフィルターにより単色化したＣｕＫα線を線源とし、Ｘ線回折図形を得た。Ｘ線回折図形のピーク位置は重心法（回折線の重心位置を求め、これに対応する２θ値でピーク位置を求める方法）により求め、標準物質用高純度シリコン粉末の（１１１）面の回折ピークを用いて補正した。ＣｕＫα線の波長を０．１５４１８ｎｍとし、以下に示すＳｃｈｅｒｒｅｒの式に代入することにより六角網面積層方向Ｌｃを算出した。
The hexagonal net area layer direction Lc was determined by an X-ray diffraction test using "MiniFlexII" manufactured by Rigaku Co., Ltd. An X-ray diffraction pattern was obtained by filling a sample holder with a carbonaceous material and using CuKα rays monochromaticized by a Ni filter as a radiation source. The peak position of the X-ray diffraction pattern is obtained by the center of gravity method (a method of obtaining the position of the center of gravity of the diffraction line and obtaining the peak position by the corresponding 2θ value), and the diffraction peak on the (111) plane of the high-purity silicon powder for a standard substance. Was corrected using. The wavelength of the CuKα ray was set to 0.15418 nm, and the hexagonal net area layer direction Lc was calculated by substituting it into the Scherrer equation shown below.
〔体積平均粒径〕
体積平均粒径（粒度分布）は、以下の方法により測定した。界面活性剤［和光純薬工業株式会社製「ＴｒｉｔｏｎＸ１００」］を０．３質量％含む水溶液に試料を投入し、超音波洗浄器で１０分以上処理し、試料を水溶液中に分散させた。この分散液を用いて粒度分布を測定した。粒度分布測定は、粒径・粒度分布測定器（日機装株式会社製「マイクロトラックＭ Ｔ３０００」）を用いて行った。Ｄ５０は、累積体積が５０％となる粒径であり、この値を体積平均粒径として用いた。
[Volume average particle size]
The volume average particle size (particle size distribution) was measured by the following method. The sample was put into an aqueous solution containing 0.3% by mass of a surfactant [“Triton X100” manufactured by Wako Pure Chemical Industries, Ltd.], treated with an ultrasonic cleaner for 10 minutes or more, and the sample was dispersed in the aqueous solution. The particle size distribution was measured using this dispersion. The particle size distribution measurement was performed using a particle size / particle size distribution measuring device (“Microtrack MT3000” manufactured by Nikkiso Co., Ltd.). D 50 is a particle size having a cumulative volume of 50%, and this value was used as the volume average particle size.
〔（００２）面の面間隔ｄ００２〕
炭素質材料を試料ホルダーに充填し、「株式会社リガク製ＭｉｎｉＦｌｅｘＩＩ」を用い、Ｎｉフィルターにより単色化したＣｕＫα線を線源とし、Ｘ線回折図形を得た。Ｘ線回折図形のピーク位置は重心法（回折線の重心位置を求め、これに対応する２θ値でピーク位置を求める方法）により求め、標準物質用高純度シリコン粉末の（１１１）面の回折ピークを用いて補正した。ＣｕＫα線の波長を０．１５４１８ｎｍとし、以下に記すＢｒａｇｇの公式により面間隔ｄ００２を算出した。
A carbonaceous material was filled in a sample holder, and an X-ray diffraction pattern was obtained using "MiniFlexII manufactured by Rigaku Co., Ltd." and using CuKα ray monochromaticized by a Ni filter as a radiation source. The peak position of the X-ray diffraction pattern is obtained by the center of gravity method (a method of obtaining the position of the center of gravity of the diffraction line and obtaining the peak position by the corresponding 2θ value), and the diffraction peak on the (111) plane of the high-purity silicon powder for a standard substance. Was corrected using. The wavelength of the CuKα ray was set to 0.15418 nm, and the surface spacing d 002 was calculated by the Bragg's formula described below.
［炭素質材料の製造］
〔実施例１〕
硫黄元素含有量が２質量％であり、融点が２５０℃であるリグニン１８．０ｇを舟形坩堝に入れ、株式会社モトヤマ製環状炉（管径２００ｍｍφ×１８００ｍｍ）に導入した。５Ｌ／分の流量で窒素を１時間導入して炉内を窒素置換し、室温から６００℃まで昇温（昇温速度２．５℃／分）させ、６００℃で１時間保持し、１２時間かけて６００℃から室温に自然放冷した後、炭素前駆体を取り出した（第一の炭化工程）。８．１８ｇの炭素前駆体を得た（収率４５．４質量％）。得られた炭素前駆体を、ミキサーミルで体積平均粒径８．１３μｍに粗粉砕した後、粉砕物７．０６ｇおよびポリスチレン０．７０ｇを混合して得た混合物を舟形坩堝に入れ、再び環状炉に導入した。５Ｌ／分の流量で窒素を１時間導入して炉内を窒素置換し、室温から１０００℃まで昇温（昇温速度１０℃／分）させ、１０００℃で３０分間保持し、１２時間かけて室温まで冷却した後、炭素質材料を取り出した（第二の炭化工程）。６．３７ｇの炭素質材料を得た（収率９０．３質量％）。得られた炭素質材料の物性を表１に示す。
[Manufacturing of carbonaceous materials]
[Example 1]
18.0 g of lignin having a sulfur element content of 2% by mass and a melting point of 250 ° C. was placed in a boat-shaped crucible and introduced into an annular furnace manufactured by Motoyama Co., Ltd. (tube diameter 200 mmφ × 1800 mm). Nitrogen is introduced at a flow rate of 5 L / min for 1 hour to replace the inside of the furnace with nitrogen, the temperature is raised from room temperature to 600 ° C. (heating rate 2.5 ° C./min), held at 600 ° C. for 1 hour, and held for 12 hours. After allowing to cool naturally from 600 ° C. to room temperature, the carbon precursor was taken out (first carbonization step). 8.18 g of carbon precursor was obtained (yield 45.4% by mass). The obtained carbon precursor was roughly pulverized with a mixer mill to a volume average particle size of 8.13 μm, and then the mixture obtained by mixing 7.06 g of the pulverized product and 0.70 g of polystyrene was placed in a boat-shaped crucible and again in a ring crucible. Introduced in. Nitrogen is introduced at a flow rate of 5 L / min for 1 hour to replace the inside of the furnace with nitrogen, the temperature is raised from room temperature to 1000 ° C. (heating rate 10 ° C./min), held at 1000 ° C. for 30 minutes, and over 12 hours. After cooling to room temperature, the carbonaceous material was taken out (second carbonization step). 6.37 g of carbonaceous material was obtained (yield 90.3% by mass). Table 1 shows the physical characteristics of the obtained carbonaceous material.
〔実施例２〕
第二の炭化工程の温度を１０００℃から１２００℃に変更したこと以外は実施例１と同様にして炭素質材料を得た。収率は８８．３質量％であった。得られた炭素質材料の物性を表１に示す。
[Example 2]
A carbonaceous material was obtained in the same manner as in Example 1 except that the temperature of the second carbonization step was changed from 1000 ° C. to 1200 ° C. The yield was 88.3% by mass. Table 1 shows the physical characteristics of the obtained carbonaceous material.
〔実施例３〕
第二の炭化工程の温度を１０００℃から１３００℃に変更したこと以外は実施例１と同様にして炭素質材料を得た。収率は８６．９質量％であった。得られた炭素質材料の物性を表１に示す。
[Example 3]
A carbonaceous material was obtained in the same manner as in Example 1 except that the temperature of the second carbonization step was changed from 1000 ° C. to 1300 ° C. The yield was 86.9% by mass. Table 1 shows the physical characteristics of the obtained carbonaceous material.
〔比較例１〕
ポリスチレンを添加しなかったこと以外は実施例１と同様にして炭素質材料を得た。収率は９８．４質量％であった。得られた炭素質材料の物性を表１に示す。
[Comparative Example 1]
A carbonaceous material was obtained in the same manner as in Example 1 except that polystyrene was not added. The yield was 98.4% by mass. Table 1 shows the physical characteristics of the obtained carbonaceous material.
［ドープ−脱ドープ試験］
実施例および比較例で得られた炭素質材料用いて、負極電極および非水電解質二次電池を作製し、性能の評価を行った。
[Doping-dedoping test]
Using the carbonaceous materials obtained in Examples and Comparative Examples, a negative electrode and a non-aqueous electrolyte secondary battery were prepared and their performance was evaluated.
〔負極電極の作製〕
炭素質材料９５質量部、導電性カーボンブラック（TIMCAL製「Super-P（登録商標）」）２質量部、ＰＶＤＦ（株式会社クレハ製）３質量部およびＮＭＰ９０質量部を混合し、スラリーを得た。得られたスラリーを厚さ１８μｍの銅箔に塗布し、乾燥後プレスして、厚さ４５μｍの電極を得た。
[Manufacturing of negative electrode]
A slurry was obtained by mixing 95 parts by mass of a carbonaceous material, 2 parts by mass of conductive carbon black ("Super-P (registered trademark)" manufactured by TIMCAL), 3 parts by mass of PVDF (manufactured by Kureha Corporation) and 90 parts by mass of NMP. .. The obtained slurry was applied to a copper foil having a thickness of 18 μm, dried and pressed to obtain an electrode having a thickness of 45 μm.
〔非水電解質二次電池の作製〕
本発明の炭素質材料が非水電解質二次電池の負極電極を構成するのに適していることを示すため、下記手順により試験用の非水電解質二次電池を作製した。
電池活物質の放電容量（脱ドープ量）および不可逆容量（非脱ドープ量）を、対極の性能のバラツキに影響されることなく精度良く評価するために、特性の安定したリチウム金属を対極として用い、上記手順に従い作製した負極電極を用いて非水電解質二次電池を作製した。電解液としては、エチレンカーボネートとジメチルカーボネートとエチルメチルカーボネートとを体積比１：１：１となるように混合して得た溶媒に、電解質ＬｉＰＦ６を溶解した溶液（濃度１ｍｏｌ／Ｌ）を用いた。セパレータとしては、ポリプロピレン膜を使用した。アルゴン雰囲気下のグローブボックス内でコインセルを作製した。
[Manufacturing of non-aqueous electrolyte secondary battery]
In order to show that the carbonaceous material of the present invention is suitable for forming a negative electrode of a non-aqueous electrolyte secondary battery, a test non-aqueous electrolyte secondary battery was prepared by the following procedure.
In order to accurately evaluate the discharge capacity (dedoping amount) and irreversible capacity (non-dedoping amount) of the battery active material without being affected by the variation in the performance of the counter electrode, a lithium metal with stable characteristics is used as the counter electrode. , A non-aqueous electrolyte secondary battery was prepared using the negative electrode prepared according to the above procedure. As the electrolytic solution, a solution (concentration 1 mol / L) in which the electrolyte LiPF 6 was dissolved in a solvent obtained by mixing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate so as to have a volume ratio of 1: 1: 1 was used. board. A polypropylene film was used as the separator. A coin cell was prepared in a glove box under an argon atmosphere.
〔電池初期充放電時の不可逆容量と充放電効率〕
上記構成の非水電解質二次電池について、充放電試験装置（株式会社東洋システム製「ＴＯＳＣＡＴ」）を用いて２５℃にて充放電試験を行った。炭素極へのリチウムのドープ反応を定電流定電圧法により行い、脱ドープ反応を定電流法で行った。ここで、正極にリチウムカルコゲン化合物を使用した電池では、炭素極へのリチウムのドープ反応が「充電」であり、本発明の試験用電池のように対極にリチウム金属を使用した電池では、炭素極へのドープ反応が「放電」と呼ぶことになり、用いる対極により同じ炭素極へのリチウムのドープ反応の呼び方が異なる。そこで、ここでは、便宜上炭素極へのリチウムのドープ反応を「充電」と記述することにする。逆に「放電」とは試験用電池では充電反応であるが、炭素質材料からのリチウムの脱ドープ反応であるため便宜上「放電」と記述することにする。ここで採用した充電方法は定電流定電圧法であり、具体的には初期直流抵抗（Ω）を測定した後に端子電圧が０ｍＶになるまで０．５ｍＡ／ｃｍ２で定電流充電を行い、端子電圧を０ｍＶに達した後、端子電圧０ｍＶで定電圧充電を行い電流値が２０μＡに達するまで充電を継続した。このときの充電全容量を電極の炭素質材料の質量で除した値を、炭素質材料の単位質量当たりの充電容量（ｍＡｈ／ｇ）と定義する。充電終了後、３０分間電池回路を開放し、その後放電を行った。放電は０．５ｍＡ／ｃｍ２で定電流放電を行い、終止電圧を１．５Ｖとした。このとき放電した電気量を電極の炭素質材料の質量で除した値を、炭素質材料の単位質量当たりの放電容量（ｍＡｈ／ｇ）と定義する。充電容量に対する放電容量の比を、充放電効率（％）と定義し、電池内におけるリチウムイオンの利用効率の指標とした。結果を表２にまとめる。
[Irreversible capacity and charge / discharge efficiency during initial battery charge / discharge]
The non-aqueous electrolyte secondary battery having the above configuration was subjected to a charge / discharge test at 25 ° C. using a charge / discharge test device (“TOSCAT” manufactured by Toyo System Co., Ltd.). The doping reaction of lithium to the carbon electrode was carried out by the constant current constant voltage method, and the dedoping reaction was carried out by the constant current method. Here, in a battery using a lithium chalcogen compound for the positive electrode, the doping reaction of lithium to the carbon electrode is "charging", and in a battery using a lithium metal as the counter electrode like the test battery of the present invention, the carbon electrode The doping reaction to the same carbon electrode is called "discharge", and the name of the lithium doping reaction to the same carbon electrode differs depending on the counter electrode used. Therefore, here, for convenience, the doping reaction of lithium to the carbon electrode will be described as "charging". On the contrary, "discharge" is a charging reaction in a test battery, but since it is a dedoped reaction of lithium from a carbonaceous material, it will be described as "discharge" for convenience. The charging method adopted here is the constant current constant voltage method. Specifically, after measuring the initial DC resistance (Ω), constant current charging is performed at 0.5 mA / cm 2 until the terminal voltage reaches 0 mV, and the terminal is charged. After the voltage reached 0 mV, constant voltage charging was performed at a terminal voltage of 0 mV, and charging was continued until the current value reached 20 μA. The value obtained by dividing the total charge capacity at this time by the mass of the carbonaceous material of the electrode is defined as the charge capacity (mAh / g) per unit mass of the carbonaceous material. After the charging was completed, the battery circuit was opened for 30 minutes, and then the battery was discharged. The discharge was a constant current discharge at 0.5 mA / cm 2 , and the final voltage was 1.5 V. The value obtained by dividing the amount of electricity discharged at this time by the mass of the carbonaceous material of the electrode is defined as the discharge capacity (mAh / g) per unit mass of the carbonic material. The ratio of the discharge capacity to the charge capacity was defined as the charge / discharge efficiency (%) and used as an index of the lithium ion utilization efficiency in the battery. The results are summarized in Table 2.
表２に示されている通り、本発明の炭素質材料を使用することにより、放電容量、充放電効率、初期抵抗に優れた電池を製造できることが分かる。また、本発明の炭素質材料は少ない工程で製造できた。
一方、比較例１の炭素質材料は、充放電効率および初期抵抗に劣る電池しかもたらさないことが分かる。
As shown in Table 2, it can be seen that by using the carbonaceous material of the present invention, a battery having excellent discharge capacity, charge / discharge efficiency, and initial resistance can be manufactured. Moreover, the carbonaceous material of the present invention could be produced in a small number of steps.
On the other hand, it can be seen that the carbonaceous material of Comparative Example 1 produces only a battery inferior in charge / discharge efficiency and initial resistance.
本発明の炭素質材料は少ない工程で製造でき、また該炭素質材料を使用した電極を用いた電池は、放電容量、充放電効率、低抵抗性に優れている。従って、様々な電池に適用できる可能性がある。 The carbonaceous material of the present invention can be produced in a small number of steps, and a battery using an electrode using the carbonaceous material is excellent in discharge capacity, charge / discharge efficiency, and low resistance. Therefore, it may be applicable to various batteries.
Claims (10)
前記炭素前駆体とコーティング剤との混合物を非酸化性ガス雰囲気下９００℃以上１４００℃以下の温度で炭化して炭素質材料を得る第二の炭化工程と
を含む、請求項１〜５のいずれかに記載の炭素質材料の製造方法。 The first carbonization step of carbonizing lignin having a sulfur element content of 0.1% by mass or more and a melting point of 210 ° C. or more to obtain a carbon precursor.
Any of claims 1 to 5, further comprising a second carbonization step of carbonizing the mixture of the carbon precursor and the coating agent at a temperature of 900 ° C. or higher and 1400 ° C. or lower in a non-oxidizing gas atmosphere to obtain a carbonaceous material. The method for producing a carbonaceous material described in Crab.
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| WO2023157610A1 (en) * | 2022-02-21 | 2023-08-24 | 株式会社クラレ | Carbonaceous material |
| SE2230138A1 (en) * | 2022-05-09 | 2023-11-10 | Stora Enso Oyj | Method for removing sulfur from a carbon material |
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| JP5472514B1 (en) | 2012-12-07 | 2014-04-16 | 住友ベークライト株式会社 | Negative electrode material, negative electrode active material, negative electrode and alkali metal ion battery |
| JP5894688B2 (en) | 2014-02-28 | 2016-03-30 | 株式会社クレハ | Non-aqueous electrolyte secondary battery carbonaceous material and manufacturing method thereof, non-aqueous electrolyte secondary battery negative electrode and non-aqueous electrolyte secondary battery |
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| SE2230138A1 (en) * | 2022-05-09 | 2023-11-10 | Stora Enso Oyj | Method for removing sulfur from a carbon material |
| WO2023218334A1 (en) * | 2022-05-09 | 2023-11-16 | Stora Enso Oyj | Method for removing sulfur from a carbon material |
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