WO2012014259A1 - 非水電解液二次電池 - Google Patents
非水電解液二次電池 Download PDFInfo
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- WO2012014259A1 WO2012014259A1 PCT/JP2010/004842 JP2010004842W WO2012014259A1 WO 2012014259 A1 WO2012014259 A1 WO 2012014259A1 JP 2010004842 W JP2010004842 W JP 2010004842W WO 2012014259 A1 WO2012014259 A1 WO 2012014259A1
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- graphitizable carbon
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- secondary battery
- graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery using a carbon material as a negative electrode active material.
- a feature of the present invention that solves the above problems is a mixture of graphitizable carbon, non-graphitizable carbon, and graphite, the composite particles having a structure in which the non-graphitizable carbon is attached to the surface of the graphitizable carbon particles, and graphite
- the negative electrode active material which consists of these is provided.
- the negative electrode active material is mainly graphitizable carbon, and the content of graphite with respect to the total weight of the mixture is preferably 1 to 30 parts by mass, particularly 5 to 20 parts by mass.
- the non-graphitizable carbon is preferably mixed in an amount of 0.5 to 10 parts by mass with respect to the total weight of the mixture.
- the ratio of non-graphitizable carbon to graphitizable carbon is preferably 10% or less.
- composite particles particles produced by mechanochemical treatment of graphitizable carbon and non-graphitizable carbon can be used.
- non-aqueous electrolyte secondary battery that uses amorphous carbon as a negative electrode main component, has a high energy density, has little capacity deterioration during storage of charge state, and has a long cycle life due to repeated charge and discharge.
- FIG. 2 is a conceptual diagram of a composite powder 23 obtained by mechanochemically treating non-graphitizable carbon 22 with graphitizable carbon 21.
- FIG. It is a plot of the discharge capacity with respect to the compounding ratio of non-graphitizable carbon. It is a plot of the discharge capacity retention ratio after standing versus the ratio of non-graphitizable carbon and graphitizable carbon. It is a plot of the discharge capacity maintenance factor after a cycle to the compounding ratio of non-graphitizable carbon. It is a plot of the discharge capacity maintenance factor after a cycle of an example which shows a high characteristic by evaluation 1, evaluation 2, and evaluation 3.
- a carbon material is used as the active material of the negative electrode, and graphite powder and amorphous carbon powder are being studied.
- the negative electrode active material is a mixture of graphitizable carbon, non-graphitizable carbon, and graphite, and the content ratio of the non-graphitizable carbon to the total weight of the mixture is 0.5 to 7%.
- the graphite content relative to the weight is 5 to 20%, and the non-graphitizable carbon is present on the surface of the graphitizable carbon particles after mechanochemical treatment.
- the non-aqueous electrolyte secondary battery using graphite powder with high crystallinity has the following characteristics. That is, since the true density of the graphite powder is high, the packing density of the active material can be increased, and as a result, it is possible to increase the energy density of the non-aqueous electrolyte secondary battery. Moreover, there is little decomposition
- batteries using graphite powder as the negative electrode active material also have the following drawbacks.
- the space to hold the electrolyte solution is small because the graphite powder is filled, and lithium ion diffusion during charge / discharge reactions deteriorates, and overvoltage increases especially during high-rate discharge. The voltage is lowered.
- the volume expansion and contraction associated with the insertion and extraction of lithium ions is larger than that of amorphous carbon powder, so that the carbon structure tends to collapse due to high rate charge and discharge, and the cycle life characteristics are short. It is a problem.
- Amorphous carbon includes non-graphitizable carbon (hard carbon) that does not easily become graphite when heated at 2000 to 3000 ° C. and easily graphitized carbon (soft carbon) that tends to become graphite. Since graphitizable carbon has high Coulomb efficiency and high packing density, it becomes a high energy density battery as a non-aqueous electrolyte secondary battery using amorphous carbon as a negative electrode. Furthermore, the capacity maintenance characteristic in a charged state is excellent. However, the amount of lithium ions that can be occluded is less than that of non-graphitizable carbon, and the cycle life due to repeated charge and discharge is short. On the other hand, non-graphitizable carbon has a good cycle life because the structural change due to insertion and extraction of lithium ions is small.
- the present inventors decided to improve the cycle life of graphitizable carbon by coating the surface of the graphitizable carbon particles with non-graphitizable carbon by mechanochemical treatment. Moreover, the amount of lithium ions that can be occluded can be increased by including graphite in the negative electrode mixture, and the capacity retention characteristics in the charged state can be further improved. As a result, amorphous carbon is used as the main component of the negative electrode, and the battery has a high energy density. In addition, the battery has excellent capacity maintenance characteristics even when stored in a charged state, and can have a long cycle life due to repeated charge and discharge.
- Graphitizable carbon is produced by various methods, and is obtained from a carbon material obtained by firing petroleum pitch, polyacene, polysiloxane, polyparaphenylene, polyfurfuryl alcohol, or the like at about 800 ° C. to 1000 ° C. Further, non-graphitizable carbon is obtained from a carbon material obtained by firing petroleum pitch, polyacene, polysiloxane, polyparaphenylene, polyfurfuryl alcohol or the like at about 500 ° C. to 800 ° C. Although graphite is naturally produced, it can also be obtained by firing a raw material (graphitizable carbon) that is graphitized by firing at a high temperature.
- FIG. 1 shows an example of a 18650 type non-aqueous electrolyte secondary battery 20.
- a positive electrode obtained by applying the positive electrode active material 2 to the positive electrode current collector 1 and a negative electrode obtained by applying the negative electrode active material 4 to the negative electrode current collector 3 are wound through a separator 5 to produce an electrode group 15.
- the electrode group 15 is inserted into the battery can 6 and the electrolyte is injected to be sealed.
- Cycle life characteristics of non-graphitizable carbon are superior to those of graphitizable carbon and graphite. Roughly, the discharge capacity retention rate after the cycle life characteristic test of graphitizable carbon and graphite is 60 to 70% of that of non-graphitizable carbon. On the other hand, the capacity of the non-graphitizable carbon to be stored in a charged state is more easily deteriorated than that of graphitizable carbon and graphite, and the capacity retention rate of the non-graphitizable carbon is about 70 to 80% of these materials. Therefore, it is necessary to achieve high cycle life characteristics and charge state storage characteristics by combining them.
- the negative electrode active material of the secondary battery 20 is a mixture of graphitizable carbon, non-graphitizable carbon, and graphite, and the graphitizable carbon 21 and the non-graphitizable carbon 22 are mechanochemically treated.
- the features that each has are used.
- graphitizable carbon and non-graphitizable carbon are combined.
- This solution was applied as a positive electrode active material layer 2 to both surfaces of a positive electrode current collector aluminum foil 1 having a thickness of 15 ⁇ m by a roll-to-roll method transfer, dried, and then pressed to be integrated.
- the thickness of the positive electrode was 85 to 95 ⁇ m, and the density of the positive electrode active material layer 2 was 2.7 g / cm 3 .
- the density of the positive electrode active material layer 2 is hardly changed, but the positive electrode current collector 1 is stretched to cause a dimensional change. Thereafter, the strip was cut into a width of 54 mm and a length of 725 mm to produce a strip-shaped positive electrode.
- a mixed powder of graphitizable carbon and non-graphitizable carbon was produced.
- the obtained mixed powder is compressed and ground to adhere the non-graphitizable carbon particles to the surface of the graphitizable carbon particles to cause a mechanochemical reaction to form a composite powder 23 as shown in FIG. It was. It is obtained by changing the weight ratio (graphitizable carbon: non-graphitizable carbon) in the range of 99.5: 0.5 to 90:10 and subjecting the graphitizable carbon 21 to mechanochemical treatment of the non-graphitizable carbon 22. A plurality of samples of the composite powder 23 were prepared.
- the mixed powder was subjected to compression grinding using a compression grinding mill (Miracle KCK-32, manufactured by Asada Tekko Co., Ltd.).
- the compression milling type pulverizer includes a screw feeder that forms a constant internal space and continuously supplies a certain amount of graphitizable carbon and non-graphitizable carbon at a rotational speed, and a fixed blade fixed to a fixed shaft of the screw feeder. And a rotating blade.
- the mechanochemical reaction is caused by adjusting the compressive shear stress according to the shape of the fixed blade and the rotating blade, the number of rotations, and the supply amount of each powder.
- composite particles having a structure in which particles of non-graphitizable carbon are attached to the surface of graphitizable carbon particles are formed.
- the load current of the compression mill type pulverizer was set to 18 A
- the cooling water temperature was set to 20 ° C.
- the spindle speed was set to 70 rpm.
- composite powder and graphite were mixed such that the weight ratio (composite powder: graphite) was in the range of 99: 1 to 70:30, to obtain a negative electrode active material.
- Polyvinylidene fluoride (trade name: KF # 9130, manufactured by Kureha Chemical Industry Co., Ltd.) as a binder is added to the prepared negative electrode active material at a weight ratio of 95: 5, and N-methyl-2-pyrrolidone as a solvent is added.
- This dispersion solution was applied to both surfaces of a copper foil 3 (negative electrode current collector) having a thickness of 10 ⁇ m by roll-to-roll method transfer, dried, and then pressed and integrated to prepare a negative electrode active material layer 4.
- the press pressure depends on the type and mixing ratio of the carbon material used, the press pressure was set within a range in which dimensional change due to the elongation of the negative electrode current collector 3 did not occur. Thereafter, the strip was cut into a width of 56 mm and a length of 775 mm to produce a strip-shaped negative electrode.
- FIG. 1 is a schematic cross-sectional view of a 18650 type non-aqueous electrolyte secondary battery 20.
- An electrode group 15 is produced in which a positive electrode and a negative electrode are spirally wound through a separator 5 made of a polyethylene porous film having a thickness of 30 ⁇ m and a width of 58.5 mm.
- the electrode group 15 was inserted into the battery can 6, one end of the negative electrode tab terminal 9 was welded to the negative electrode current collector 3, and the other end of the negative electrode tab terminal 9 was welded to the bottom of the battery can 6.
- a mixed solvent of ethylene carbonate, diethyl carbonate and dimethyl carbonate having a volume ratio of 1: 1: 1 was used as an electrolytic solution, and 1M LiPF 6 was dissolved therein, and 5 ml thereof was injected into the battery container.
- 1M LiPF 6 was dissolved therein, and 5 ml thereof was injected into the battery container.
- the upper lid 7 was disposed on the upper part of the battery can 6 via an insulating gasket 12, and this part was crimped to seal the battery.
- the manufactured nonaqueous electrolyte secondary battery was charged at an ambient temperature of 25 ° C. and a constant voltage of 4.1 V for 5 hours, then discharged to a final voltage of 2.7 V at a current value of 1 C, and the initial discharge capacity was measured. Further, after charging at an ambient temperature of 25 ° C. and a constant voltage of 4.1 V for 5 hours, the battery was allowed to stand at an ambient temperature of 50 ° C. for 30 days, and then the discharge capacity was measured. Further, after charging / discharging for 300 cycles in the range of 2.7 V to 4.1 V at a current value of 1 C at an ambient temperature of 50 ° C., the discharge capacity was measured to evaluate the cycle life.
- Table 1 shows the compositions of the non-aqueous electrolyte secondary batteries (Examples 1 to 20) prepared according to the above-described Examples. Table 1 also shows comparative examples (Comparative Examples 1 to 4) manufactured for comparison. As shown in Table 1, a negative electrode is formed by using only graphitizable carbon in Comparative Example 1, only non-graphitizable carbon in Comparative Example 2, and only graphite in Comparative Example 3, respectively. The indicated non-aqueous electrolyte secondary battery was produced. In Comparative Example 4, a negative electrode was formed using the same composition as in Example 8 and a mixture of graphitizable carbon, non-graphitizable carbon, and graphite without mechanochemical treatment, and is shown in this embodiment. A non-aqueous electrolyte secondary battery was prepared.
- FIG. 3 is a plot of the initial discharge capacity, and shows the discharge capacity with respect to the ratio of non-graphitizable carbon for each ratio of graphite.
- the blending ratio of graphite was 5 to 30.
- the initial discharge capacity exceeded 100% with respect to the nonaqueous electrolyte secondary battery of Comparative Example 1 using only graphitizable carbon, and it was found that the battery capacity was improved.
- the volume of the 18650 type battery is the same in all Examples, the improvement of the energy density of the battery was also confirmed.
- FIG. 4 shows the results obtained by determining the ratio of the discharge capacity after being left to the discharge capacity before being left to stand in each example as a percentage of the discharge capacity maintenance rate by the leave test.
- FIG. 4 is a plot of the discharge capacity retention ratio after standing, and shows the discharge capacity retention ratio after standing with respect to the blending ratio of non-graphitizable carbon for each blending ratio of graphite.
- Non-graphitizable carbon has a lower capacity retention rate when charged and left as compared to graphite and graphitizable carbon materials.
- the capacity retention rate of this example is inferior to the nonaqueous electrolyte secondary battery of Comparative Example 1 using only graphitizable carbon and Comparative Example 3 using only graphite. There was no value.
- the graphite content is 5 parts by mass or more because long-term storage is improved.
- the weight ratio between the amount of non-graphitizable carbon and the graphitizable carbon exceed 10%, the discharge capacity retention rate decreased. This is probably because if the amount of non-graphitizable carbon is too large compared to the amount of graphitizable carbon, the characteristics of graphitizable carbon are suppressed. Therefore, the weight ratio between the amount of non-graphitizable carbon and the graphitizable carbon is preferably 10% or less.
- FIG. 5 is a plot of the post-cycle discharge capacity retention ratio shown in Table 2, and shows the post-cycle discharge capacity retention ratio with respect to the non-graphitizable carbon composition ratio for each graphite composition ratio.
- the mixing ratio of non-graphitizable carbon is 0.
- the discharge capacity retention rate after cycle was high.
- FIG. 6 shows a plot of the post-cycle discharge capacity retention rate of the examples showing high characteristics in Evaluation 1, Evaluation 2, and Evaluation 3.
- FIG. 6 shows that the compounding ratio of non-graphitizable carbon is 0.5 to 7 parts by mass as a compounding ratio with a large energy density, little capacity deterioration during storage of the charged state, and excellent cycle life characteristics. It can be seen that the blending ratio is preferably in the range of 5 to 20 parts by mass.
- the mixing ratio of graphitizable carbon and non-graphitizable carbon and the mixing ratio of composite powder and graphite are optimized, and the graphitizable carbon and non-graphitizing are optimized.
- a non-aqueous electrolyte secondary battery excellent in battery capacity, cycle life and storage characteristics can be provided. This can be achieved by mixing graphite with a large capacity and little capacity deterioration due to storage, and can suppress capacity deterioration due to high capacity and storage, and it is easy by mechanochemical treatment of non-graphitizable carbon to graphitizable carbon.
- the negative electrode manufacturing process of this example is simple because it is not necessary to significantly change the conventional process, and thus the industrial utility value is extremely large.
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Abstract
Description
a)易黒鉛化炭素を含んでいるため、エネルギー密度が大きく、充電状態保存での容量劣化を少なくすることが可能となる。
b)難黒鉛化炭素を易黒鉛化炭素の表面にメカノケミカル処理することで、リチウムイオンの吸蔵・放出に伴う負極用活物質の体積の膨張・収縮を少なくできるため、活物質層が崩壊しにくい構造となり、充放電サイクルによる容量劣化が改善され、寿命化が可能となる。
c)黒鉛を含んでいるため高容量化と、充電状態保存での容量劣化を少なくすることが可能となる。
以下、作製した非水電解液二次電池の実施例を用いて、本発明の具体例を説明する。
平均粒子径が5.8~8.6μmのマンガン酸リチウム、平均粒子径が0.5μmの黒鉛粉末とアセチレンブラック,炭酸リチウム,結着剤としてのポリフッ化ビニリデン(商品名:KF#1120、呉羽化学工業(株)製)とを84.5:9.0:2.0:1.5:3.0の重量比率で、溶媒であるN-メチル-2-ピロリドンに分散させてスラリー状の溶液を作製した。この溶液を正極活物質層2として、正極集電体である厚みが15μmのアルミニウム箔1の両面にロールtoロール法転写により塗布し、乾燥した後、プレスして一体化した。正極の厚さは85~95μmとし、正極活物質層2の密度として2.7g/cm3とした。なお、これ以上のプレスをすると、正極活物質層2の密度はほとんど変わらないものの、正極集電体1が伸びて寸法変化が生ずる。その後、幅が54mm、長さが725mmに切断して短冊状の正極を作製した。
負極活物質として、まず易黒鉛化炭素と難黒鉛化炭素の混合粉末を作製した。得られた混合粉末を圧縮摩砕して、易黒鉛化炭素粒子の表面に難黒鉛化炭素粒子を付着させ、メカノケミカル反応を起こさせて、図2に示されるような複合粉末23を形成させた。重量割合(易黒鉛化炭素:難黒鉛化炭素)を99.5:0.5~90:10の範囲で変化させ、易黒鉛化炭素21に難黒鉛化炭素22をメカノケミカル処理して得られる複合粉末23のサンプルを複数作成した。本例では、圧縮摩砕式粉砕機(浅田鉄工株式会社製、ミラクルKCK-32)を用い混合粉末を圧縮摩砕した。圧縮摩砕式粉砕機は、一定の内部空間が形成され回転速度により易黒鉛化炭素および難黒鉛化炭素を一定量供給し続けるスクリューフィーダと、このスクリューフィーダの固定軸に固定された固定ブレードと、回転ブレードとを備えている。固定ブレードおよび回転ブレードの形状,回転数、並びに、各粉末の供給量により圧縮剪断応力を調整することでメカノケミカル反応を起こさせる。この反応により、易黒鉛化炭素粒子の表面に難黒鉛化炭素の粒子が付着した構造の複合粒子が形成される。本例では、圧縮摩砕式粉砕機の負荷電流を18A、冷却水温度を20℃、主軸回転数を70rpmにそれぞれ設定した。
図1は18650形非水電解液二次電池20の断面模式図である。正極と負極を、厚さが30μm、幅が58.5mmのポリエチレン多孔膜からなるセパレータ5を介して渦巻き状に巻いた電極群15を作製する。この電極群15を電池缶6に挿入し、負極集電体3に負極タブ端子9の一方を溶接した後、負極タブ端子9の他方を電池缶6の底に溶接した。電解液としてエチレンカーボネート,ジエチルカーボネート及びジメチルカーボネートの体積比1:1:1の混合溶媒を用い、それにLiPF6を1M溶解させて作製し、これを電池容器に5ml注入した。正極集電体1に正極タブ端子8の一方を溶接した後、正極タブ端子8の他方を上蓋7に溶接する。上蓋7を絶縁性のガスケット12を介して電池缶6の上部に配置し、この部分をかしめて電池を密閉した。
作製した非水電解液二次電池について、周囲温度25℃、4.1Vの定電圧で5時間充電した後、1Cの電流値で終止電圧2.7Vまで放電して初期放電容量を測定した。易黒鉛化炭素のみを用いた比較例1の初期放電容量に対する各実施例の電池の初期放電容量の比を百分率で求めた。結果を図3に示す。
作製した非水電解液二次電池について、周囲温度25℃、4.1Vの定電圧で5時間充電した後、周囲温度50℃の環境下で、30日間放置した後の放電容量を測定した。放置試験による放電容量維持率として各実施例の放置前の放電容量に対する放置後の放電容量の比を百分率で求めた結果を図4に示す。
作製した非水電解液二次電池について、周囲温度50℃、1Cの電流値、2.7V~4.1Vの範囲で300サイクル充放電を行い、その後の放電容量を測定し、サイクル寿命を評価した。各実施例の1サイクル目の放電容量に対する300サイクル目の放電容量の比を百分率で求めた結果を表2,図5に示す。
2 正極活物質層
3 負極集電体(銅箔)
4 負極活物質層
5 セパレータ
6 電池缶
7 上蓋
8 正極タブ端子
9 負極タブ端子
12 ガスケット
15 電極群
20 非水電解液二次電池
Claims (6)
- 正極活物質としてリチウムを含む遷移金属複合酸化物を用いた正極と、負極活物質として炭素材料を用いた負極を備え、この正極と負極を非水電解液に浸漬させた非水電解液二次電池であって、前記炭素材料が易黒鉛化炭素と難黒鉛化炭素と黒鉛を含み、
前記易黒鉛化炭素と前記難黒鉛化炭素は複合粒子を形成しており、前記複合粒子は前記易黒鉛化炭素粒子の表面に前記難黒鉛化炭素の粒子が付着した構造であることを特徴とする非水電解液二次電池。 - 請求項1に記載の非水電解液二次電池であって、
前記炭素材料は、前記黒鉛を5質量%以上含み、前記難黒鉛化炭素の前記易黒鉛化炭素に対する比(難黒鉛化炭素重量/易黒鉛化炭素重量)が10%以下であることを特徴とする非水電解液二次電池。 - 請求項1または2に記載の非水電解液二次電池であって、
前記炭素材料は、前記難黒鉛化炭素を0.5質量部以上、前記黒鉛を20質量部以下含むことを特徴とする非水電解液二次電池。 - 請求項1に記載の非水電解液二次電池であって、
前記炭素材料は、前記易黒鉛化炭素,難黒鉛化炭素,黒鉛の総重量に対し、前記難黒鉛化炭素の配合比が0.5~7質量%であって、黒鉛の配合比が5~20質量%であることを特徴とする非水電解液二次電池。 - 請求項1ないし4のいずれかに記載の非水電解液二次電池であって、
前記複合粒子はメカノケミカル処理により一体化されていることを特徴とする非水電解液二次電池。 - 易黒鉛化炭素と、難黒鉛化炭素とを混合し、メカノケミカル処理を施して一体化した複合粒子を作製し、前記複合粒子と、黒鉛とを混合し、溶媒を加えて分散溶液を作製し、
前記分散溶液を導電体の表面に塗布し、塗布された分散溶液を乾燥させることを特徴とする非水電解液二次電池用負極の製造方法。
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PCT/JP2010/004842 WO2012014259A1 (ja) | 2010-07-30 | 2010-07-30 | 非水電解液二次電池 |
CN201080068362.4A CN103038929B (zh) | 2010-07-30 | 2010-07-30 | 非水电解液二次电池 |
JP2012526197A JP5481560B2 (ja) | 2010-07-30 | 2010-07-30 | 非水電解液二次電池 |
US13/813,309 US20130130114A1 (en) | 2010-07-30 | 2010-07-30 | Non-aqueous electrolyte secondary battery |
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US (1) | US20130130114A1 (ja) |
JP (1) | JP5481560B2 (ja) |
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Cited By (3)
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WO2016125819A1 (ja) * | 2015-02-06 | 2016-08-11 | 東ソー株式会社 | リチウム二次電池用複合活物質およびその製造方法 |
JP2016149340A (ja) * | 2015-02-06 | 2016-08-18 | 東ソー株式会社 | リチウム二次電池用複合活物質およびその製造方法、リチウム二次電池 |
US11024470B2 (en) | 2017-03-23 | 2021-06-01 | Gs Yuasa International Ltd. | Nonaqueous electrolyte energy storage device |
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- 2010-07-30 US US13/813,309 patent/US20130130114A1/en not_active Abandoned
- 2010-07-30 WO PCT/JP2010/004842 patent/WO2012014259A1/ja active Application Filing
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CN103038929A (zh) | 2013-04-10 |
JPWO2012014259A1 (ja) | 2013-09-09 |
JP5481560B2 (ja) | 2014-04-23 |
US20130130114A1 (en) | 2013-05-23 |
CN103038929B (zh) | 2015-11-25 |
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