WO2010074243A1 - 電極用炭素粒子の製造方法、電極用炭素粒子及びリチウムイオン二次電池用負極材料 - Google Patents
電極用炭素粒子の製造方法、電極用炭素粒子及びリチウムイオン二次電池用負極材料 Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a method for producing carbon particles for an electrode that is suitable for an electrode material and can exhibit high charge / discharge efficiency and durability when used as a negative electrode material for a lithium ion secondary battery.
- Carbon materials made of carbonaceous fired bodies are used for electrode materials such as lithium ion secondary batteries, electric double layer capacitors, and capacitors.
- a carbon material is used as a negative electrode active material, lithium is occluded (intercalated) into the carbon material in an ionic state when the battery is charged, and released as ions (deintercalation) during discharge. It uses a “rocking chair type” battery configuration.
- the present invention provides a method for producing carbon particles for an electrode that is suitable for an electrode material and can exhibit high charge / discharge efficiency and durability when used as a negative electrode material for a lithium ion secondary battery. Objective.
- the present invention contains metal particles that form an alloy with lithium, is formed by gathering a large number of fine particles made of carbon, and a plurality of pores connected to each other in the gaps between the fine particles.
- a method for producing carbon particles for an electrode having a hollow cell structure, the monomer having low compatibility with the resulting polymer, the organic solvent having low compatibility with the resulting polymer, and the metal particles forming an alloy with lithium To prepare a monomer-containing mixture, to disperse the monomer-containing mixture in an aqueous phase to prepare a suspension in which oil droplets of the monomer-containing mixture are dispersed, and to the oil in the suspension
- It is the manufacturing method of the carbon particle for electrodes which has the process of polymerizing a droplet and preparing a resin particle, and the process of baking the said resin particle. The present invention is described in detail below.
- the method for producing carbon particles for an electrode of the present invention comprises mixing a monomer having low compatibility with the obtained polymer, an organic solvent having low compatibility with the obtained polymer, and metal particles forming an alloy with lithium.
- low compatibility with the resulting polymer is also simply referred to as “low compatibility”
- metal particles that form an alloy with lithium are simply referred to as “metal particles”.
- low compatibility with the obtained polymer means that the difference between the solubility parameter (SP value) of the monomer or organic solvent and the solubility parameter (SP value) of the polymer is 1.5 or more.
- the solubility parameter (SP value) means a value calculated by the Fedors equation.
- the monomer having low compatibility constitutes a carbon component of the obtained carbon particles for an electrode by firing after polymerization.
- the resulting carbon particles for electrodes are formed by gathering a large number of fine particles made of carbon. It has an open cell hollow structure in which a plurality of holes connected to each other are formed in the gap.
- low compatibility monomer examples include divinylbenzene, vinyl chloride, acrylonitrile and the like.
- the said organic solvent with low compatibility plays a role of a hollow agent in the manufacturing method of the carbon particle for electrodes of this invention.
- an appropriate organic solvent is selected in accordance with the monomer having low compatibility.
- examples thereof include linear hydrocarbons such as n-heptane, and alicyclic hydrocarbons such as cyclohexane.
- the preferable lower limit of the blending amount of the low compatibility organic solvent with respect to 100 parts by weight of the low compatibility monomer is 5 parts by weight, and the preferable upper limit is 75 parts by weight.
- the amount of the organic solvent is less than 5 parts by weight, sufficient voids are not formed inside the obtained carbon particles for electrodes, and the volume change of the metal forming the alloy with lithium during continuous charge / discharge can be absorbed. In some cases, the carbon particles for the electrode may be easily damaged.
- the blending amount of the organic solvent exceeds 75 parts by weight, the strength of the obtained carbon particles for electrodes may be lowered, or it may be difficult to maintain the particle shape.
- the more preferable lower limit of the amount of the organic solvent is 10 parts by weight, and the more preferable upper limit is 70 parts by weight.
- Examples of the metal that forms an alloy with lithium constituting the metal particles include silicon, tin, magnesium, titanium, vanadium, cadmium, selenium, iron, cobalt, nickel, manganese, platinum, and boron.
- silicon or tin is preferable because silicon can exhibit a particularly high lithium storage / release capacity, and silicon is more preferable.
- a preferable upper limit of the average particle diameter of the metal particles is 1 ⁇ m.
- the average particle diameter exceeds 1 ⁇ m, the lithium storage / release capacity of the obtained carbon particles for an electrode may be lowered.
- the surface of the metal particles is preferably treated with a pigment dispersant. Dispersibility in the monomer-containing mixture is improved by treating the surface with a pigment dispersant.
- the pigment dispersant include high molecular weight polyester acid amide amine salts, acrylic polymers, aliphatic polyvalent carboxylic acids, polyester amine salts, polyvinyl alcohol, polyvinyl pyrrolidone, and methyl cellulose.
- the pigment dispersant may be added to the monomer mixture together with the metal particles.
- a preferred lower limit of the amount of the metal particles to be added relative to 100 parts by weight of the monomer having low compatibility is 1 part by weight.
- the blending amount of the metal particles is less than 1 part by weight, the obtained electrode carbon particles may not exhibit a high lithium storage / release capacity.
- a more preferable lower limit of the amount of the metal particles is 5 parts by weight.
- the upper limit of the compounding amount of the metal particles is not particularly limited. The more the metal particles are contained, the more carbon particles for electrodes that can exhibit a high lithium storage / release capacity. However, when the compounding amount of the metal particles is too large, the conductivity of the obtained carbon particles for electrodes may be insufficient.
- a preferred upper limit of the amount of the metal particles is 95 parts by weight.
- the monomer-containing mixture contains a polymerization initiator.
- a polymerization initiator conventionally well-known polymerization initiators, such as an organic peroxide, an azo compound, a metal ion redox initiator, a photoinitiator, a persulfate, can be used, for example.
- a necessary amount of the polymerization initiator in the monomer-containing mixture may be blended.
- the polymerization initiator is too small, the monomer may not be sufficiently polymerized and particles may not be formed. If it is added excessively, the molecular weight will not increase, and the post-treatment of the resulting carbon particles for electrodes will be hindered. Sometimes.
- the monomer-containing mixture may contain other additives as necessary.
- it may further contain at least one conductive aid selected from the group consisting of graphite, carbon black, carbon nanotube, graphene and fullerene.
- the conductive aid By containing the conductive aid, the conductivity of the obtained electrode carbon particles can be further improved.
- the said monomer containing mixture contains graphite, in addition to the role as a conductive support agent, the increase effect of discharge capacity can also be anticipated.
- the monomer having low compatibility, the organic solvent having low compatibility, the metal particles, and an additive to be added as necessary are mixed and ultrasonically dispersed. And the like.
- the method for producing electrode carbon particles of the present invention includes a step of dispersing the monomer-containing mixture in an aqueous phase to prepare a suspension in which oil droplets of the monomer-containing mixture are dispersed.
- the aqueous medium constituting the aqueous phase include water, alcohol, and ketones.
- the aqueous medium preferably contains a dispersant such as polyvinyl alcohol, methyl cellulose, polyvinyl pyrrolidone, insoluble inorganic fine particles, and a polymer surfactant.
- the monomer-containing mixture is added to an aqueous medium, and a stirrer such as a homogenizer, a static static mixer, an ultrasonic mixer, an ultrasonic homogenizer, a shirasu porous filter, a stirring blade, or the like.
- a stirrer such as a homogenizer, a static static mixer, an ultrasonic mixer, an ultrasonic homogenizer, a shirasu porous filter, a stirring blade, or the like.
- the method of stirring with is mentioned.
- the method for producing carbon particles for an electrode according to the present invention includes a step of preparing resin particles by polymerizing oil droplets in the suspension.
- Polymerization conditions for preparing resin particles by polymerizing the oil droplets include, for example, a method of stirring the suspension in a nitrogen stream at 30 to 95 ° C. for about 1 to 50 hours.
- the obtained resin particles are separated from the suspension, and subjected to subsequent steps through operations such as washing with water, drying, and classification.
- the manufacturing method of the carbon particle for electrodes of this invention has the process of baking the said resin particle.
- the firing conditions may be appropriately selected depending on the resin particles.
- the firing temperature may be 1000 ° C. or lower, 1000 to 2500 ° C., 2500 ° C. or higher.
- the firing temperature is 1000 ° C. or lower, when the obtained electrode carbon particles are used as a negative electrode material for a lithium ion secondary battery, an extremely high lithium storage / release capacity can be exhibited, and a high output can be obtained.
- the output of the lithium ion secondary battery may become unstable.
- the firing temperature is 1000 to 2500 ° C.
- stable output characteristics and cycle life can be exhibited when the obtained carbon particles for an electrode are used as a negative electrode material for a lithium ion secondary battery.
- the lithium storage / release capacity becomes low, and a high-power lithium ion secondary battery may not be obtained.
- the firing temperature is 2500 ° C. or higher, when the obtained electrode carbon particles are used as a negative electrode material for a lithium ion secondary battery, a very high lithium storage / release capacity can be exhibited, and a high output can be obtained.
- the carbon particles for electrodes produced by the method for producing carbon particles for electrodes according to the present invention have a higher lithium occlusion / release capacity than conventional carbon particles made of only carbon, and are damaged even if continuous charge / discharge is performed. It has excellent performance that it is difficult to do.
- the carbon particles for electrodes produced by the method for producing carbon particles for electrodes of the present invention contains metal particles that form an alloy with lithium and is formed by gathering many fine particles made of carbon.
- it has an open cell hollow structure in which a plurality of pores connected to each other are formed in the gaps between the fine particles.
- a schematic diagram illustrating the hollow cell structure is shown in FIG.
- the electrode carbon particles 1 produced by the method for producing electrode carbon particles of the present invention are formed by gathering a large number of fine particles 11 made of carbon, and a plurality of carbon particles 1 connected to each other in the gap between the fine particles 11.
- a hole 12 is formed. And inside the several hole 12 connected mutually, the metal particle 13 which forms an alloy with lithium so that it may contact the fine particle 11 which consists of carbon is contained.
- the carbon particles for electrodes produced by the method for producing carbon particles for electrodes according to the present invention have such a continuous cell hollow structure, and thus have high lithium occlusion / release capacity by containing metal particles that form an alloy with lithium. On the other hand, it is considered that excellent performance that it is difficult to break even if continuous charge and discharge is performed can be exhibited. Also in the carbon particles for electrodes produced by the method for producing carbon particles for electrodes of the present invention, the volume change of the metal particles forming an alloy with lithium occurs when continuous charge and discharge are performed. However, it is thought that it does not reach the point of failure because it has a solid cell hollow structure that can disperse and absorb the stress due to the volume change. An open cell hollow structure containing metal particles that form an alloy with lithium, formed of a large number of fine particles made of carbon, and a plurality of pores connected to each other between the fine particles.
- the electrode carbon particles are also one aspect of the present invention.
- the lower limit of the average particle diameter of the carbon particles for electrodes of the present invention is 10 nm, and the upper limit is 1 mm.
- the average particle diameter is less than 10 nm, coalescence occurs during firing when producing the carbon particles for an electrode of the present invention, and it may be difficult to make a single particle.
- the average particle diameter exceeds 1 mm, the electrode material is molded. In some cases, it may not be possible to mold into a desired shape or size.
- the preferable lower limit of the average particle diameter is 1000 nm, and the preferable upper limit is 500 ⁇ m.
- the preferred lower limit of the content of metal particles forming an alloy with lithium is 1% by weight.
- the content of the metal particles is less than 1% by weight, a high lithium storage / release capacity may not be exhibited.
- a more preferable lower limit of the content of the metal particles is 5% by weight.
- the higher the metal particles are contained the higher the lithium storage / release capacity can be exhibited.
- the upper limit with preferable content of the said metal particle is 95 weight%.
- the preferable lower limit of the porosity of the carbon particles for an electrode of the present invention is 5%, and the preferable upper limit is 95%.
- the porosity is less than 5%, the volume change of the metal particles forming the alloy with lithium during continuous charge / discharge may not be sufficiently absorbed, and the electrode carbon particles may be easily damaged, and 95% If it exceeds, the strength of the obtained carbon material or the like may be low, or the carbon content may be too low, resulting in a decrease in conductivity.
- the porosity can be calculated by the Archimedes method, for example, from the specific gravity measured with a pycnometer true density measuring instrument or the like.
- the carbon particles for an electrode of the present invention have a high lithium storage / release capacity and are not easily damaged even after continuous charging / discharging. Can do. Moreover, it can use suitably also for the electrode material for electric double layer capacitors, and the electrode material for capacitors.
- the negative electrode material for lithium ion secondary batteries containing the electrode particles of the present invention and a binder resin is also one aspect of the present invention.
- the said binder resin plays the role of the binder which couple
- the binder resin include polyvinylidene fluoride and styrene butadiene rubber.
- the negative electrode material for a lithium ion secondary battery of the present invention preferably further contains at least one conductive aid selected from the group consisting of graphite, carbon black, carbon nanotubes, graphene, and fullerene.
- the conductivity of the negative electrode material for a lithium ion secondary battery of the present invention is further improved.
- a preferable lower limit of the blending amount of the conductive assistant is 1% by weight, and a preferable upper limit is 90% by weight. If the blending amount of the conductive aid is less than 1% by weight, a sufficient conductivity improving effect may not be obtained, and if it exceeds 90% by weight, the lithium storage capacity may be lowered.
- the said conductive support agent is mix
- the compounding quantity of binder resin can be reduced and higher electroconductivity can be exhibited.
- the method for producing the negative electrode material for a lithium ion secondary battery of the present invention includes, for example, a method in which the mixture is obtained by mixing the carbon particles for an electrode of the present invention, a conductive additive and a binder resin, and then molding the mixture.
- the mixture may contain an organic solvent so that it can be easily molded.
- the organic solvent may be any solvent that can dissolve the binder resin, and examples thereof include N-methylpyrrolidone and N, N-dimethylformamide.
- ADVANTAGE OF THE INVENTION it is suitable for an electrode material and provides the manufacturing method of the carbon particle for electrodes which can exhibit high charging / discharging efficiency and durability when it uses as a negative electrode material of a lithium ion secondary battery. be able to.
- FIG. 14 is an electron micrograph of a cross section of carbon particles for an electrode prepared in Example 14.
- Example 1 Preparation of carbon particles for electrodes As oil phase components, 100 parts by weight of divinylbenzene as a monomer, 100 parts by weight of n-heptane as a hollow agent, silicon particles as metal particles (silicon nanopowder manufactured by Aldrich) 5 Part by weight and 5 parts by weight of a pigment dispersant (manufactured by Enomoto Kasei Co., Ltd., DA-7301) were mixed and dispersed ultrasonically, and then an organic peroxide was added as a polymerization initiator to prepare a monomer mixture. On the other hand, 500 parts by weight of pure water as a water phase component and 5 parts by weight of polyvinyl alcohol as a dispersant were mixed.
- a pigment dispersant manufactured by Enomoto Kasei Co., Ltd., DA-7301
- the obtained oil phase component and aqueous phase component were mixed and stirred and dispersed with a homogenizer to prepare a suspension.
- the obtained suspension was polymerized by stirring and maintaining at 80 ° C. for 12 hours under a nitrogen stream.
- the particles obtained by the polymerization were washed, classified according to the particle size, and then dried to obtain resin particles.
- the obtained resin particles were heat-treated at 300 ° C. for 3 hours in an air atmosphere, and then fired at 1000 ° C. for 3 hours in a nitrogen atmosphere to obtain carbon particles for electrodes.
- the obtained carbon particles for an electrode had an average particle size of 20 ⁇ m and a Cv value of the particle size of 5%.
- the average particle size and Cv value were determined by observing about 100 arbitrary particles using an electron microscope (S-4300SE / N, manufactured by Hitachi High-Technology Corporation).
- Examples 2 to 14 The same as in Example 1 except that the type and amount of the oil phase component in the particle polymerization composition, the processing conditions of the polymer particles and the type and amount of the conductive auxiliary agent in the negative electrode composition, and the binder resin amount were changed as shown in Table 1.
- electrode particles and a negative electrode material for a lithium ion secondary battery were obtained.
- the carbon nanotube used was a multi-walled carbon nanotube manufactured by Showa Denko KK, and the graphite used was SNO-3 manufactured by SEC Carbon.
- the electron micrograph (magnification 20,000 times) of the cross section of the carbon particle for electrodes produced in Example 14 was shown in FIG.
- FIG. 3 is an electron micrograph of the cross section of the electrode carbon particles produced in Example 14 (magnification 100,000 times, FIG. 3 (a)) and an EDS (Energy Dispersive X-Ray Spectrometer) element map image (magnification 10).
- FIG. 3 (b) shows a carbon element image
- FIG. 3 (c) shows a silicon element image.
- Example 1 A negative electrode material for a lithium ion secondary battery was obtained in the same manner as in Example 1 except that graphite particles (manufactured by Wako Pure Chemical Industries Ltd., average particle size 20 ⁇ m, particle size Cv value 50%) were used as the negative electrode agent particles. It was.
- Example 2 A negative electrode for a lithium ion secondary battery in the same manner as in Example 1 except that activated carbon particles (Norit SX Plus, average particle diameter 160 ⁇ m, particle size Cv value 120%, manufactured by Norit Japan Ltd.) were used as the negative electrode particles. Obtained material.
- activated carbon particles Neit SX Plus, average particle diameter 160 ⁇ m, particle size Cv value 120%, manufactured by Norit Japan Ltd.
- Example 3 A negative electrode material for a lithium ion secondary battery was obtained in the same manner as in Example 1 except that silicon powder (manufactured by Aldrich, silicon nanopowder) was used as the negative electrode agent particles.
- a coin type model cell was produced using the lithium ion secondary battery negative electrode materials obtained in Examples and Comparative Examples. That is, a lithium ion secondary battery negative electrode material and a counter electrode lithium metal having a diameter of 16 mm were laminated via a separator. After impregnating the separator with the electrolytic solution, these were caulked with an upper can and a lower can through a gasket. The upper can and the lower can were brought into contact with the negative electrode and the counter electrode lithium, respectively.
- As the separator a polyethylene microporous film having a thickness of 25 ⁇ m and a diameter of 24 mm was used.
- electrolyte a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 2 was used, and LiPF 6 was used as the electrolyte at a concentration of 1 mol. A solution dissolved so as to be / L was used.
- Cycle characteristics The above cycle was repeated 10 times, and the cycle characteristics were calculated using the following formula.
- Capacity maintenance rate at the 10th cycle from the beginning (%) (Discharge capacity in the 10th cycle / Discharge capacity in the 1st cycle) ⁇ 100
- Capacity maintenance rate (%) from 2nd cycle to 10th cycle (Discharge capacity in the 10th cycle / discharge capacity in the 2nd cycle) ⁇ 100
- ADVANTAGE OF THE INVENTION it is suitable for an electrode material and provides the manufacturing method of the carbon particle for electrodes which can exhibit high charging / discharging efficiency and durability when it uses as a negative electrode material of a lithium ion secondary battery. be able to.
Abstract
Description
例えば、リチウムイオン二次電池においては、負極活物質として炭素材料を用い、電池の充電時にはリチウムをイオン状態で炭素材料中に吸蔵(インターカレーション)し、放電時にはイオンとして放出(デインターカレーション)させるという“ロッキングチェアー型”の電池構成を採用している。
以下に本発明を詳述する。
本明細書において「得られるポリマーとの相溶性の低い」とは、モノマー又は有機溶剤の溶解性パラメータ(SP値)とポリマーの溶解性パラメータ(SP値)との差が1.5以上あることを意味する。
また、本明細書において溶解性パラメータ(SP値)とは、Fedorsの式により算出される値を意味する。
上記相溶性の低い有機溶剤は、上記相溶性の低いモノマーにあわせて適当な有機溶剤を選択する。例えば、上記相溶性の低いモノマーとしてジビニルベンゼンを用いる場合には、n-ヘプタン等の直鎖状炭化水素や、シクロヘキサン等の脂環式炭化水素等が挙げられる。
上記顔料分散剤としては、例えば、高分子量ポリエステル酸のアマイドアミン塩、アクリル系重合物、脂肪族系多価カルボン酸、ポリエステルのアミン塩、ポリビニルアルコール、ポリビニルピロリドン、メチルセルロース等が挙げられる。
なお、上記顔料分散剤は、上記金属粒子とともに上記モノマー混合物中に添加されてもよい。
上記重合開始剤としては、例えば、有機過酸化物、アゾ系化合物、金属イオンレドックス開始剤、光重合開始剤、過硫酸塩等の従来公知の重合開始剤を用いることができる。
上記モノマー含有混合物中の上記重合開始剤は必要量が配合されればよい。ただし、重合開始剤が少なすぎると上記モノマーが充分に重合せずに粒子が形成されないことがあり、過剰に配合されると分子量が上がらず、得られる電極用炭素粒子の後処理に支障が出ることがある。
上記水相を構成する水系媒体としては、例えば、水、アルコール、ケトン類等が挙げられる。
上記水系媒体は、例えば、ポリビニルアルコール、メチルセルロース、ポリビニルピロリドン、不溶性無機微粒子、高分子界面活性剤等の分散剤を含有することが好ましい。
上記撹拌の条件により懸濁液中のモノマー含有混合物の油滴の大きさを制御することにより、得られる電極用炭素粒子の粒子径を調整することができる。
上記油滴を重合させて樹脂粒子を調製する際の重合条件は、例えば、上記懸濁液を窒素気流下、30~95℃、1~50時間程度撹拌する方法等が挙げられる。
得られた樹脂粒子は、懸濁液から分離され、水洗、乾燥、分級等の操作を経てその後の工程に供される。
上記焼成の条件は、樹脂粒子により適宜選択すればよい。焼成温度は、1000℃以下、1000~2500℃、2500℃以上の場合が考えられる。
焼成温度を1000℃以下とすると、得られる電極用炭素粒子をリチウムイオン二次電池負極材料に用いた場合に、極めて高いリチウム吸蔵放出容量を発揮することができ、高い出力を得ることができる。ただし、リチウムイオン二次電池の出力が不安定となることがある。
焼成温度を1000~2500℃とすると、得られる電極用炭素粒子をリチウムイオン二次電池負極材料に用いた場合に、安定した出力特性とサイクル寿命とを発揮することができる。ただし、リチウム吸蔵放出容量は低くなり、高い出力のリチウムイオン二次電池は得られないことがある。
焼成温度を2500℃以上とすると、得られる電極用炭素粒子をリチウムイオン二次電池負極材料に用いた場合に、極めて高いリチウム吸蔵放出容量を発揮することができ、高い出力を得ることができる。
本発明の電極用炭素粒子の製造方法により製造された電極用炭素粒子1は、炭素からなる微細粒子11が多数寄せ集まって形成されており、該微細粒子11同士の間隙に互いに繋がった複数の孔12が形成されている。そして、互いに繋がった複数の孔12の内側に、炭素からなる微細粒子11に接触するようにしてリチウムと合金を形成する金属粒子13が含有されている。
リチウムと合金を形成する金属粒子を含有し、炭素からなる微細粒子が多数寄せ集まって形成されており、該微細粒子同士の間隙に互いに繋がった複数の孔が形成されている連胞中空構造を有する電極用炭素粒子もまた、本発明の1つである。
一方、金属粒子を大量に含有するほど、高いリチウム吸蔵放出容量を発揮できる。ただし、金属粒子の含有量が多くなりすぎると、連続充放電時の金属粒子の体積変化を吸収できずに、電極用炭素粒子が破損しやすくなることがある。上記金属粒子の含有量の好ましい上限は95重量%である。
なお、上記空隙率は、例えば、ピクノメーター法真密度測定器等により測定した比重から、アルキメデス法により算出することができる。
本発明の電極用粒子とバインダー樹脂とを含有するリチウムイオン二次電池用負極材料もまた、本発明の1つである。
上記バインダー樹脂は、例えば、ポリフッ化ビニリデン、スチレンブタジエンゴム等が挙げられる。
なお、上記導電助剤をある程度以上配合すると、電極用炭素粒子同士を結合させる結着剤の役割を発揮することもできる。上記導電助剤が結着剤の役割を発揮する場合には、バインダー樹脂の配合量を低減させることができ、より高い導電性を発揮することができる。
上記混合物は、容易に成型できるように、有機溶剤を含有してもよい。
上記有機溶剤は、上記バインダー樹脂を溶解可能な溶媒であればよく、例えば、N-メチルピロリドン、N,N-ジメチルホルムアミド等が挙げられる。
(1)電極用炭素粒子の調製
油相成分として、モノマーであるジビニルベンゼン100重量部と、中空剤であるn-ヘプタン100重量部、金属粒子であるケイ素粒子(アルドリッチ社製シリコンナノパウダー)5重量部、顔料分散剤(楠本化成社製、DA-7301)5重量部を混合し、超音波分散した後、更に重合開始剤として有機過酸化物を添加し、モノマー混合物を調製した。一方、水相成分として、純水500重量部、分散剤としてポリビニルアルコールを5重量部混合した。
得られた油相成分と水相成分とを混合し、ホモジナイザーで撹拌分散して懸濁液を調製した。得られた懸濁液を窒素気流下、80℃で12時間、撹拌、保持し、重合した。重合により得られた粒子を、洗浄し、粒径に従って分級した後、乾燥して、樹脂粒子を得た。
得られた樹脂粒子を、大気雰囲気下、300℃で3時間熱処理した後、窒素雰囲気下、1000℃で3時間焼成して電極用炭素粒子を得た。
得られた電極用炭素粒子は、平均粒子径が20μm、粒子径のCv値が5%であった。なお、平均粒子径及びCv値は、電子顕微鏡(日立ハイテクノロジー社製、S-4300SE/N)を用いて任意の粒子約100個について観測することにより求めた。
得られた電極用炭素粒子100重量部に対して、導電助剤としてカーボンブラック(三菱化学社製、♯3230B)10重量部、バインダー樹脂としてポリフッ化ビニリデン10重量部、有機溶剤としてN-メチルピロリドンを混合して混合液を調製した。
得られた混合液を、厚さ18μmのCu箔の片面に塗布し、乾燥した後、プレスロールで加圧成形して負極シートを得た。得られた負極シートを直径14mmの円盤状に打抜き、リチウムイオン二次電池用負極材料を作製した。
粒子重合組成のうち油相成分の種類と量、重合粒子の処理条件及び負極剤組成のうち導電助剤の種類と量、バインダー樹脂量を表1のように変更した以外は実施例1と同様にして電極用粒子及びリチウムイオン二次電池用負極材料を得た。なお、カーボンナノチューブは昭和電工社製の多層カーボンナノチューブ、黒鉛はSECカーボン社製、SNO-3を使用した。
なお、実施例14で作製した電極用炭素粒子の断面の電子顕微鏡写真(倍率2万倍)を図2に示した。また、図3に、実施例14で作製した電極用炭素粒子の断面の電子顕微鏡写真(倍率10万倍、図3(a))及びEDS(Energy Dispersive X-Ray Spectrometer)元素マップ像(倍率10万倍、図3(b)は炭素元素像、図3(c)はケイ素元素像)を示した。
負極剤用粒子として黒鉛粒子(和光純薬社製、平均粒子径20μm、粒子径のCv値50%)を用いたこと以外は実施例1と同様にしてリチウムイオン二次電池用負極材料を得た。
負極剤用粒子として活性炭粒子(日本ノリット社製、Norit SX Plus、平均粒子径160μm、粒子径のCv値120%)を用いたこと以外は実施例1と同様にしてリチウムイオン二次電池用負極材料を得た。
負極剤用粒子としてケイ素粉末(アルドリッチ社製、シリコンナノパウダー)を用いたこと以外は実施例1と同様にしてリチウムイオン二次電池用負極材料を得た。
粒子重合組成、重合粒子の処理条件及び負極剤組成を表1のように変更した以外は実施例1と同様にして電極用粒子及びリチウムイオン二次電池用負極材料を得た。
実施例及び比較例で得られたリチウムイオン二次電池負極材料について、下記のように評価を行った。
結果を表1、表2及び表3に示した。
なお、比較例3は、評価を行おうとしたが、測定不能であった。
実施例及び比較例で得られたリチウムイオン二次電池負極材料を用いてコイン型モデルセルを作製した。
即ち、リチウムイオン二次電池負極材料と直径16mmの対極リチウム金属とをセパレータを介して積層した。セパレータに電解液を含浸した後、これらを上部缶と下部缶によりガスケットを介してかしめ付けた。上部缶と下部缶には、負極及び対極リチウムがそれぞれ接触して導通がとられるようにした。
なお、セパレータとしては、厚さ25μm、直径24mmのポリエチレン製微孔膜を用い、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の体積比1:2の混合溶媒に、電解質としてLiPF6を濃度1mol/Lとなるように溶解した溶液を用いた。
充放電条件は、電圧、電流を0で4時間休止後、1Cに相当する電流で0.002Vまで電圧が降下した後、3時間保持し、充電した。10分間休止した後、電流0.2Cで電圧が3Vになるまで放電した。10分間休止した後、この放充電を繰り返した。その間の通電量から充放電容量を求めた。
また、下記式から初期充放電効率(%)及び2サイクル目の充放電効率(%)を計算した。なお、この試験では、リチウムを負極材料へ吸蔵する過程を充電、離脱する過程を放電とした。
初期充放電効率(%)
=(第1サイクルの放電容量/第1サイクルの充電容量)×100
2サイクル目の充放電効率(%)
=(第2サイクルの放電容量/第2サイクルの充電容量)×100
上記サイクルを10回繰り返し、下記式を用いてサイクル特性を計算した。
初期から10サイクル目の容量維持率(%)
=(第10サイクルにおける放電容量/第1サイクルにおける放電容量)×100
2サイクル目から10サイクル目の容量維持率(%)
=(第10サイクルにおける放電容量/第2サイクルにおける放電容量)×100
11 炭素からなる微細粒子
12 互いに繋がった複数の孔
13 リチウムと合金を形成する金属
Claims (6)
- リチウムと合金を形成する金属粒子を含有し、炭素からなる微細粒子が多数寄せ集まって形成されており、該微細粒子同士の間隙に互いに繋がった複数の孔が形成されている連胞中空構造を有する電極用炭素粒子を製造する方法であって、
得られるポリマーとの相溶性の低いモノマー、得られるポリマーとの相溶性の低い有機溶剤、及び、リチウムと合金を形成する金属粒子を混合してモノマー含有混合物を調製する工程と、前記モノマー含有混合物を水相に分散して、モノマー含有混合物の油滴が分散した懸濁液を調製する工程と、前記懸濁液中の油滴を重合させて樹脂粒子を調製する工程と、前記樹脂粒子を焼成する工程とを有する
ことを特徴とする電極用炭素粒子の製造方法。 - リチウムと合金を形成する金属粒子は、ケイ素からなることを特徴とする請求項1記載の電極用炭素粒子の製造方法。
- モノマー含有混合物は、黒鉛、カーボンブラック、カーボンナノチューブ、グラフェン及びフラーレンからなる群より選択される少なくとも1種の導電助剤を更に含有することを特徴とする請求項1記載の電極用炭素粒子の製造方法。
- リチウムと合金を形成する金属粒子を含有し、炭素からなる微細粒子が多数寄せ集まって形成されており、該微細粒子同士の間隙に互いに繋がった複数の孔が形成されている連胞中空構造を有することを特徴とする電極用炭素粒子。
- 請求項4記載の電極用炭素粒子とバインダー樹脂とを含有することを特徴とするリチウムイオン二次電池用負極材料。
- 黒鉛、カーボンブラック、カーボンナノチューブ、グラフェン及びフラーレンからなる群より選択される少なくとも1種の導電助剤が配合されていることを特徴とする請求項5記載のリチウムイオン二次電池用負極材料。
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JP2012209217A (ja) * | 2011-03-30 | 2012-10-25 | Sekisui Chem Co Ltd | リチウムイオン二次電池 |
JP2012209218A (ja) * | 2011-03-30 | 2012-10-25 | Sekisui Chem Co Ltd | リチウムイオン二次電池の製造方法及びリチウムイオン二次電池 |
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JP2022033182A (ja) * | 2014-04-25 | 2022-02-28 | サウス ダコタ ボード オブ リージェンツ | 大容量電極 |
JP2016013967A (ja) * | 2014-07-03 | 2016-01-28 | オーシーアイ カンパニー リミテッドOCI Company Ltd. | 炭素‐シリコン複合体及びその製造方法 |
Also Published As
Publication number | Publication date |
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US20110278506A1 (en) | 2011-11-17 |
EP2383224A4 (en) | 2013-08-28 |
JP4922457B2 (ja) | 2012-04-25 |
US20160056465A1 (en) | 2016-02-25 |
JP2012038735A (ja) | 2012-02-23 |
MY152442A (en) | 2014-09-30 |
KR20110100290A (ko) | 2011-09-09 |
US8940192B2 (en) | 2015-01-27 |
EP2383224A1 (en) | 2011-11-02 |
RU2011131045A (ru) | 2013-02-10 |
EP2383224B1 (en) | 2016-11-16 |
KR101511821B1 (ko) | 2015-05-18 |
JPWO2010074243A1 (ja) | 2012-06-21 |
JP5771104B2 (ja) | 2015-08-26 |
CN102256897A (zh) | 2011-11-23 |
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