WO2016035274A1 - 非水電解質二次電池用負極活物質 - Google Patents
非水電解質二次電池用負極活物質 Download PDFInfo
- Publication number
- WO2016035274A1 WO2016035274A1 PCT/JP2015/004186 JP2015004186W WO2016035274A1 WO 2016035274 A1 WO2016035274 A1 WO 2016035274A1 JP 2015004186 W JP2015004186 W JP 2015004186W WO 2016035274 A1 WO2016035274 A1 WO 2016035274A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- electrode active
- negative electrode
- sio
- carbon
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- H01M4/13—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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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 negative electrode active material for a non-aqueous electrolyte secondary battery.
- Patent Document 1 describes the use of SiO X and graphite with a carbon coating film formed on the surface as a negative electrode active material.
- the non-aqueous electrolyte secondary battery using silicon or silicon oxide as the negative electrode active material has a higher reactivity between the negative electrode active material and the electrolytic solution compared to the case where graphite is used as the negative electrode active material. There was a problem that cycle characteristics were low.
- a negative electrode active material for a non-aqueous electrolyte secondary battery is a particulate negative electrode active material used for a non-aqueous electrolyte secondary battery, and is a mother particle containing Si and SiO 2 And a mixed phase coating containing SiO 2 and carbon covering the surface of the mother particle, and a carbon coating covering the surface of the mixed phase coating.
- FIG. 1 is a first electron microscope image showing a cross section of negative electrode active material particles used in Experiment 1.
- a nonaqueous electrolyte secondary battery which is an example of an embodiment of the present invention includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a nonaqueous electrolyte including a nonaqueous solvent, and a separator.
- a positive electrode including a positive electrode active material a positive electrode active material
- a negative electrode including a negative electrode active material a nonaqueous electrolyte including a nonaqueous solvent
- separator As an example of the non-aqueous electrolyte secondary battery, there is a structure in which an electrode body in which a positive electrode and a negative electrode are wound via a separator and a non-aqueous electrolyte are accommodated in an exterior body.
- the positive electrode is preferably composed of a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
- a positive electrode current collector for example, a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the positive electrode such as aluminum, or a film having a metal surface layer such as aluminum is used.
- the positive electrode active material layer preferably contains a conductive material and a binder in addition to the positive electrode active material.
- the positive electrode active material is not particularly limited, but is preferably a lithium-containing transition metal oxide.
- the lithium-containing transition metal oxide may contain non-transition metal elements such as Mg and Al. Specific examples include lithium-containing transition metal oxides such as lithium cobaltate, olivine-type lithium phosphate represented by lithium iron phosphate, Ni—Co—Mn, Ni—Mn—Al, and Ni—Co—Al. It is done. These positive electrode active materials may be used alone or in combination of two or more.
- carbon materials such as carbon black, acetylene black, ketjen black, graphite, and a mixture of two or more thereof can be used.
- binder polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl acetate, polyacrylonitrile, polyvinyl alcohol, and a mixture of two or more thereof can be used.
- the negative electrode 10 preferably includes a negative electrode current collector 11 and a negative electrode active material layer 12 formed on the negative electrode current collector 11.
- a conductive thin film particularly a metal foil or alloy foil that is stable in the potential range of the negative electrode such as copper, or a film having a metal surface layer such as copper is used.
- the negative electrode active material layer 12 preferably contains a binder (not shown) in addition to the negative electrode active material 13.
- a binder polytetrafluoroethylene or the like can be used as in the case of the positive electrode, but styrene-butadiene rubber (SBR), polyimide, or the like is preferably used.
- SBR styrene-butadiene rubber
- the binder may be used in combination with a thickener such as carboxymethylcellulose.
- a negative electrode active material 13 a having a base particle 14, a mixed phase coating 15, and a carbon coating 16 is used for the negative electrode active material 13.
- the mother particle 14 includes Si and SiO 2 .
- the mixed phase coating 15 includes SiO 2 17 and carbon 18.
- the mixed phase coating 15 covers the surface of the mother particle 14.
- the carbon coating 16 covers the surface of the mixed phase coating 15.
- the negative electrode active material 13a is composed of a mother particle 14, a mixed phase coating 15, and a carbon coating 16 in this order from the center toward the surface.
- Examples of the mother particle 14 include SiO X (0.5 ⁇ X ⁇ 1.5).
- SiO X has, for example, a structure in which Si is dispersed in an amorphous SiO 2 matrix. When observed with a transmission electron microscope (TEM), the presence of dispersed Si can be confirmed.
- Examples of the mother particle 14 include Si having an oxide film. SiO 2 that is an oxide film is generated by natural oxidation or oxidation treatment of Si.
- the direct reaction between the electrolytic solution and the mother particles 14 can be relaxed.
- the direct reaction is relaxed and the conductivity of the negative electrode active material 13a is ensured.
- the mixed phase coating 15 is preferably composed only of SiO 2 and carbon.
- components other than SiO 2 and carbon are included, the diffusion of Li + into the mother particles 14 may be inhibited, and the conductivity of the negative electrode active material 13a may be reduced, or side reactions may easily occur. there's a possibility that.
- the ratio of SiO 2 to carbon in the mixed phase coating 15 is preferably 9: 1 to 1: 9. If the proportion of SiO 2 is too small, the direct reaction between the electrolytic solution and the mother particles 14 is difficult to be relaxed. On the other hand, when the ratio of carbon is too small, the conductivity of the negative electrode active material 13a tends to be lowered.
- the mixed phase coating 15 preferably has a substantially uniform thickness over the entire area.
- the average thickness of the mixed phase coating 15 can be measured by cross-sectional observation of the negative electrode active material particles 13a using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like.
- the average thickness of the mixed phase coating 15 is preferably 0.005 ⁇ m to 1 ⁇ m, and more preferably 0.01 to 0.3 ⁇ m. If the thickness of the mixed phase coating 15 becomes too thin, the effect of mitigating the direct reaction between the electrolytic solution and the mother particles 14 becomes small. On the other hand, when the thickness of the mixed phase coating 15 becomes too thick, the diffusion of Li + into the mother particle 14 is inhibited and the capacity tends to decrease.
- the surface of the mother particle 14 is preferably 100% covered with the mixed phase coating 15.
- the mother particle 14 being covered with the mixed phase coating 15 means that the particle phase is covered with the mixed phase coating 15 having a thickness of at least 1 nm when the particle cross section is observed with a TEM.
- the average thickness of the carbon coating 16 is preferably 1 to 200 nm and more preferably 5 to 100 nm in consideration of ensuring conductivity and diffusibility of Li + into the mother particles 14.
- the average thickness of the carbon coating 16 can be measured by observing a cross section of the negative electrode active material particles 13a using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like.
- SEM scanning electron microscope
- TEM transmission electron microscope
- the thickness of the carbon coating film 16 becomes too thin, the electrical conductivity decreases, and it becomes difficult to uniformly coat the particles composed of the mother particles 14 and the mixed phase coating film 15.
- the thickness of the carbon film 16 becomes too thick, the diffusion of Li + into the mother particle 14 is inhibited and the capacity tends to decrease.
- the ratio of the carbon film to the mother particles 14 is desirably 10% by mass or less.
- the carbon coating 16 covers 50% or more and 100% or less, preferably 100%, of the surface of the particles composed of the mother particles 14 and the mixed phase coating 15.
- the particles made of the mother particles 14 and the mixed phase coating 15 being covered with the carbon coating 16 are covered with the carbon coating 16 having a thickness of at least 1 nm when the particle cross section is observed by SEM. That's what it means.
- an aqueous solution containing an organic acid catalyst and the mother particle 14 are mixed, then hydrolyzed and polymerized at 80 to 120 ° C., and then water is evaporated. And can be obtained by heat treatment at 500 to 800 ° C.
- a lithium compound may be mixed.
- the organic acid catalyst include citric acid, malic acid, tartaric acid, lactic acid, and glycolic acid.
- the lithium compound include LiOH, Li 2 CO 3 , LiF, and LiCl.
- SiO 2 in the mother particle 14 and the organic acid catalyst react on the surface of the mother particle 14, thereby forming a mixed phase coating 15 containing SiO 2 and carbon on the surface of the mother particle 14.
- the mixed phase film 15 is formed between the carbon film 16 and the mother particle 14.
- the carbon film 16 can be formed using a general method such as a CVD method, a sputtering method, or a plating method (electrolytic / electroless plating).
- a general method such as a CVD method, a sputtering method, or a plating method (electrolytic / electroless plating).
- the carbon film 16 is formed on the surface of the SiO X particles by the CVD method, for example, the SiO X particles and the hydrocarbon-based gas are heated in the gas phase, and the carbon generated by the thermal decomposition of the hydrocarbon-based gas is removed. Deposit on SiO X particles.
- the hydrocarbon gas methane gas or acetylene gas can be used.
- the negative electrode active material 13a may be used alone, but from the viewpoint of achieving both high capacity and improved cycle characteristics, the volume change due to charge / discharge is smaller than that of the negative electrode active material 13a. It is preferable to use a mixture with the substance 13b.
- the negative electrode active material 13b is not particularly limited, but is preferably a carbon-based active material such as graphite or hard carbon.
- the ratio of the negative electrode active material 13a to graphite is 1:99 to 20:80 by mass ratio. preferable. If the mass ratio is within the range, it is easy to achieve both higher capacity and improved cycle characteristics. On the other hand, when the ratio of the negative electrode active material 13a to the total mass of the negative electrode active material 13 is lower than 1% by mass, the merit of increasing the capacity by adding the negative electrode active material 13a is reduced.
- the average particle diameter of the mother particles 14 is preferably 1 to 15 ⁇ m, and more preferably 4 to 10 ⁇ m.
- the “average particle diameter” means a particle diameter (volume average particle diameter; Dv 50 ) at which the volume integrated value becomes 50% in the particle size distribution measured by the laser diffraction scattering method. Dv 50 can be measured, for example, using “LA-750” manufactured by HORIBA.
- Dv 50 can be measured, for example, using “LA-750” manufactured by HORIBA.
- the average particle diameter of the mother particle 14 becomes too small, the particle surface area becomes too large, the reaction amount with the electrolytic solution becomes large, and the capacity may be reduced.
- the average particle size becomes too large, the influence of the volume expansion of the base particles 14 during charging increases, and the charge / discharge characteristics may deteriorate.
- carbon black, acetylene black, ketjen black, graphite, and a mixture of two or more thereof can be used as in the case of the conductive material of the positive electrode active material layer.
- the mother particle 14 may contain lithium silicate (Li 4 SiO 4 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 3 SiO 6 or the like) in the particle.
- lithium silicate Li 4 SiO 4 , Li 2 SiO 3 , Li 2 Si 2 O 5 , Li 3 SiO 6 or the like
- Non-aqueous electrolyte examples include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , and lower aliphatic carboxylic acid.
- Lithium, LiCl, LiBr, LiI, chloroborane lithium, borates, imide salts, and the like can be used.
- LiPF 6 is preferably used from the viewpoint of ion conductivity and electrochemical stability.
- One electrolyte salt may be used alone, or two or more electrolyte salts may be used in combination. These electrolyte salts are preferably contained at a ratio of 0.8 to 1.5 mol with respect to 1 L of the nonaqueous electrolyte.
- non-aqueous electrolyte solvent for example, cyclic carbonates, chain carbonates, cyclic carboxylic acid esters and the like are used.
- cyclic carbonate examples include propylene carbonate (PC) and ethylene carbonate (EC).
- chain carbonate examples include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
- a non-aqueous solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- separator a porous sheet having ion permeability and insulating properties is used.
- the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
- material of the separator polyolefin such as polyethylene and polypropylene is suitable.
- FIG. 3 shows an electron microscope image (TEM) of the obtained negative electrode active material particles.
- the region A is SiOx
- the region B of the slightly darker layer outside the region A is the mixed phase coating layer
- the white layer region outside the region B is the carbon coating layer.
- the average thickness of the mixed phase coating was 100 nm.
- the average thickness of the mixed phase coating was calculated as follows.
- the cross section of the negative electrode was exposed using a cross section polisher method, and the obtained cross section was confirmed by TEM.
- Five treated SiOx particles were randomly extracted, the thickness of the multiphase coating layer on each SiOx particle was measured at five points, and the average value thereof was defined as the coating layer thickness.
- SiO X after heat treatment and water washing and PAN (polyacrylonitrile) as a binder are mixed at a mass ratio of 95: 5, and NMP (N-methyl-2-pyrrolidone) as a dilution solvent is added. did.
- the negative electrode mixture slurry was applied on one surface of a copper foil so that the mass per lm 2 of the negative electrode mixture layer was 25 g / m 2 . Next, this was dried at 105 ° C. in the atmosphere and rolled to prepare a negative electrode.
- the filling density of the negative electrode mixture layer was 1.50 g / ml.
- an electrode body was produced using the above negative electrode with a Ni tab attached to the outer periphery, a lithium metal foil, and a polyethylene separator disposed between the negative electrode and the lithium metal foil.
- This electrode body was put in a battery casing made of aluminum laminate, and a non-aqueous electrolyte was injected into the battery casing, and then the battery casing was sealed to prepare a battery A1.
- Example 2 A battery A2 was produced in the same manner as in Experiment 1 except that the cooling time after the heat treatment was 1 hour.
- the average thickness of the mixed phase coating of SiO X particles after heat treatment and water washing was 40 nm.
- Example 3 A battery A3 was produced in the same manner as in Experiment 1 except that the cooling time after the heat treatment was 5 hours.
- the average thickness of the mixed phase coating of SiO X particles after the heat treatment and water washing was 130 nm.
- Example 4 A battery Z was produced in the same manner as in Experiment 1 except that untreated SiO X was used as SiO X as the negative electrode active material (that is, SiO X without a mixed phase coating was used).
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
本明細書において「略**」とは、「略同等」を例に挙げて説明すると、全く同一はもとより、実質的に同一と認められるものを含む意図である。実施形態の説明で参照する図面は、模式的に記載されたものであり、図面に描画された構成要素の寸法比率などは、現物と異なる場合がある。具体的な寸法比率等は、以下の説明を参酌して判断されるべきである。
正極は、正極集電体と、正極集電体上に形成された正極活物質層とで構成されることが好適である。正極集電体には、例えば、導電性を有する薄膜体、特にアルミニウムなどの正極の電位範囲で安定な金属箔や合金箔、アルミニウムなどの金属表層を有するフィルムが用いられる。正極活物質層は、正極活物質の他に、導電材及び結着剤を含むことが好ましい。
図1に例示するように、負極10は、負極集電体11と、負極集電体11上に形成された負極活物質層12とを備えることが好適である。負極集電体11には、例えば、導電性を有する薄膜体、特に銅などの負極の電位範囲で安定な金属箔や合金箔、銅などの金属表層を有するフィルムが用いられる。負極活物質層12は、負極活物質13の他に、結着剤(図示せず)を含むことが好適である。結着剤としては、正極の場合と同様にポリテトラフルオロエチレン等を用いることもできるが、スチレン-ブタジエンゴム(SBR)やポリイミド等を用いることが好ましい。結着剤は、カルボキシメチルセルロース等の増粘剤と併用されてもよい。
非水電解質の電解質塩としては、例えばLiClO4、LiBF4、LiPF6、LiAlCl4、LiSbF6、LiSCN、LiCF3SO3、LiCF3CO2、LiAsF6、LiB10Cl10、低級脂肪族カルボン酸リチウム、LiCl、LiBr、LiI、クロロボランリチウム、ホウ酸塩類、イミド塩類などを用いることができる。この中でも、イオン伝導性と電気化学的安定性の観点から、LiPF6を用いることが好ましい。電解質塩は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。これら電解質塩は、非水電解質1Lに対し0.8~1.5molの割合で含まれていることが好ましい。
セパレータには、イオン透過性及び絶縁性を有する多孔性シートが用いられる。多孔性シートの具体例としては、微多孔薄膜、織布、不織布等が挙げられる。セパレータの材質としては、ポリエチレン、ポリプロピレン等のポリオレフィンが好適である。
〈実施例〉
〔負極の作製〕
表面を炭素で被覆したSiOX(X=0.93、平均一次粒子径:5.0μm)を準備した。尚、被覆はCVD法を用いて行い、また、SiOXに対する炭素の割合は10質量%、SiOX表面の炭素被覆率を100%とした。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)とを、体積比が3:7の割合となるように混合した混合溶媒に、六フッ化リン酸リチウム(LiPF6)を、1.0モル/リットル添加して非水電解液を調製した。
不活性雰囲気中で、外周にNiタブを取り付けた上記負極と、リチウム金属箔と、負極とリチウム金属箔との間に配置させたポリエチレン製セパレータとを用いて電極体を作製した。この電極体を、アルミニウムラミネートからなる電池外装体内に入れ、更に、非水電解液を電池外装体内に注入し、その後電池外装体を封止して電池A1を作製した。
熱処理後の放冷時間を1時間にしたこと以外は、上記の実験1と同様にして電池A2を作製した。熱処理及び水洗後のSiOX粒子の混相被覆の平均厚みは40nmであった。
熱処理後の放冷時間を5時間にしたこと以外は、上記の実験1と同様にして電池A3を作製した。熱処理及び水洗後のSiOX粒子の混相被覆の平均厚みは130nmであった。
負極活物質としてのSiOXとして、未処理のSiOXを用いた(即ち、混相被膜を有さないSiOXを用いた)こと以外は、上記の実験1と同様に電池Zを作製した。
上記各電池を、以下の条件で充放電し、下記(1)式で示す初回充放電効率と下記(2)式で示す10サイクル目の容量維持率とを調べたので、その結果を表1に示す。
0.2It(4mA)の電流で電圧が0Vになるまで定電流充電を行った後、0.05It(1mA)の電流で電圧が0Vになるまで定電流充電を行った。次に、10分間休止した後、0.2It(4mA)の電流で電圧が1.0Vになるまで定電流放電を行った。
初回充放電効率(%)
=(1サイクル目の放電容量/1サイクル目の充電容量)×100・・・(1)
〔10サイクル目の容量維持率の算出式〕
10サイクル目の容量維持率(%)
=(10サイクル目の放電容量/1サイクル目の放電容量)×100・・・(2)
Claims (7)
- 非水電解質二次電池に用いられる粒子状の負極活物質であって、
SiとSiO2を含む母粒子と、
前記母粒子の表面を覆う、SiO2と炭素を含む混相被膜と、
前記混相被膜の表面を覆う炭素被膜と、を備える非水電解質二次電池用負極活物質。 - 前記母粒子は、SiOX(0.5≦X≦1.5)である、請求項1に記載の非水電解質二次電池用負極活物質。
- 前記混相被膜は、SiO2からなる相に炭素が分散している、請求項1または請求項2に記載の非水電解質二次電池用負極活物質。
- 前記混相被膜は、SiO2と炭素のみから構成される、請求項1から請求項3のいずれかに記載の非水電解質二次電池用負極活物質。
- 前記混相被膜の平均厚みは、0.005μ~1μmである、請求項1から請求項4のいずれかに記載の非水電解質二次電池用負極活物質。
- 前記母粒子の表面は、前記混相被膜により100%被覆されている、請求項1から請求項5のいずれかに記載の非水電解質二次電池用負極活物質。
- 前記母粒子及び前記混相被膜を備える粒子の表面は、前記炭素被膜により50%以上100%以下被覆されている、請求項1から請求項6のいずれかに記載の非水電解質二次電池用負極活物質。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580046961.9A CN106797025B (zh) | 2014-09-01 | 2015-08-21 | 非水电解质二次电池用负极活性物质 |
JP2016546292A JP6477713B2 (ja) | 2014-09-01 | 2015-08-21 | 非水電解質二次電池用負極活物質 |
US15/318,884 US10062903B2 (en) | 2014-09-01 | 2015-08-21 | Negative electrode active material for nonaqueous electrolyte secondary battery |
US16/051,651 US10741833B2 (en) | 2014-09-01 | 2018-08-01 | Negative electrode active material for nonaqueous electrolyte secondary battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-176834 | 2014-09-01 | ||
JP2014176834 | 2014-09-01 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/318,884 A-371-Of-International US10062903B2 (en) | 2014-09-01 | 2015-08-21 | Negative electrode active material for nonaqueous electrolyte secondary battery |
US16/051,651 Continuation US10741833B2 (en) | 2014-09-01 | 2018-08-01 | Negative electrode active material for nonaqueous electrolyte secondary battery |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016035274A1 true WO2016035274A1 (ja) | 2016-03-10 |
Family
ID=55439363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/004186 WO2016035274A1 (ja) | 2014-09-01 | 2015-08-21 | 非水電解質二次電池用負極活物質 |
Country Status (4)
Country | Link |
---|---|
US (2) | US10062903B2 (ja) |
JP (1) | JP6477713B2 (ja) |
CN (1) | CN106797025B (ja) |
WO (1) | WO2016035274A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022514715A (ja) * | 2019-11-14 | 2022-02-14 | 寧徳新能源科技有限公司 | 負極材料、並びに、それを含む電気化学装置及び電子装置 |
JP2022514807A (ja) * | 2019-11-28 | 2022-02-16 | 寧徳新能源科技有限公司 | 負極、並びに、それを含む電気化学装置及び電子装置 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20210099888A (ko) * | 2020-02-05 | 2021-08-13 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005123175A (ja) * | 2003-09-26 | 2005-05-12 | Jfe Chemical Corp | 複合粒子およびその製造方法、リチウムイオン二次電池用負極材料および負極、ならびにリチウムイオン二次電池 |
JP2006092969A (ja) * | 2004-09-24 | 2006-04-06 | Toshiba Corp | 非水電解質二次電池用負極活物質及び非水電解質二次電池 |
JP2008153117A (ja) * | 2006-12-19 | 2008-07-03 | Nec Tokin Corp | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 |
JP2011060676A (ja) * | 2009-09-14 | 2011-03-24 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極及びリチウムイオン二次電池 |
WO2014119256A1 (ja) * | 2013-01-29 | 2014-08-07 | 三洋電機株式会社 | 非水電解質二次電池用負極活物質、当該負極活物質を用いた非水電解質二次電池用負極、及び当該負極を用いた非水電解質二次電池 |
WO2015098024A1 (ja) * | 2013-12-25 | 2015-07-02 | 三洋電機株式会社 | 非水電解質二次電池用負極活物質及びその負極活物質を用いた非水電解質二次電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004063433A (ja) * | 2001-12-26 | 2004-02-26 | Shin Etsu Chem Co Ltd | 導電性酸化珪素粉末、その製造方法及び該粉末を用いた非水電解質二次電池用負極材 |
TWI278429B (en) * | 2002-05-17 | 2007-04-11 | Shinetsu Chemical Co | Conductive silicon composite, preparation thereof, and negative electrode material for non-aqueous electrolyte secondary cell |
JP4868556B2 (ja) | 2010-04-23 | 2012-02-01 | 日立マクセルエナジー株式会社 | リチウム二次電池 |
US9431652B2 (en) * | 2012-12-21 | 2016-08-30 | Lg Chem, Ltd. | Anode active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including the anode active material |
EP2765636B1 (en) * | 2012-12-21 | 2018-02-21 | Lg Chem, Ltd. | Cathode material for lithium secondary battery, method for manufacturing same and lithium secondary battery comprising same |
-
2015
- 2015-08-21 CN CN201580046961.9A patent/CN106797025B/zh active Active
- 2015-08-21 WO PCT/JP2015/004186 patent/WO2016035274A1/ja active Application Filing
- 2015-08-21 JP JP2016546292A patent/JP6477713B2/ja active Active
- 2015-08-21 US US15/318,884 patent/US10062903B2/en active Active
-
2018
- 2018-08-01 US US16/051,651 patent/US10741833B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005123175A (ja) * | 2003-09-26 | 2005-05-12 | Jfe Chemical Corp | 複合粒子およびその製造方法、リチウムイオン二次電池用負極材料および負極、ならびにリチウムイオン二次電池 |
JP2006092969A (ja) * | 2004-09-24 | 2006-04-06 | Toshiba Corp | 非水電解質二次電池用負極活物質及び非水電解質二次電池 |
JP2008153117A (ja) * | 2006-12-19 | 2008-07-03 | Nec Tokin Corp | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 |
JP2011060676A (ja) * | 2009-09-14 | 2011-03-24 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極及びリチウムイオン二次電池 |
WO2014119256A1 (ja) * | 2013-01-29 | 2014-08-07 | 三洋電機株式会社 | 非水電解質二次電池用負極活物質、当該負極活物質を用いた非水電解質二次電池用負極、及び当該負極を用いた非水電解質二次電池 |
WO2015098024A1 (ja) * | 2013-12-25 | 2015-07-02 | 三洋電機株式会社 | 非水電解質二次電池用負極活物質及びその負極活物質を用いた非水電解質二次電池 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2022514715A (ja) * | 2019-11-14 | 2022-02-14 | 寧徳新能源科技有限公司 | 負極材料、並びに、それを含む電気化学装置及び電子装置 |
JP7349498B2 (ja) | 2019-11-14 | 2023-09-22 | 寧徳新能源科技有限公司 | 負極材料、並びに、それを含む電気化学装置及び電子装置 |
JP2022514807A (ja) * | 2019-11-28 | 2022-02-16 | 寧徳新能源科技有限公司 | 負極、並びに、それを含む電気化学装置及び電子装置 |
JP7178488B2 (ja) | 2019-11-28 | 2022-11-25 | 寧徳新能源科技有限公司 | 負極、並びに、それを含む電気化学装置及び電子装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016035274A1 (ja) | 2017-06-15 |
US20170117541A1 (en) | 2017-04-27 |
US10062903B2 (en) | 2018-08-28 |
CN106797025B (zh) | 2019-06-18 |
JP6477713B2 (ja) | 2019-03-06 |
CN106797025A (zh) | 2017-05-31 |
US10741833B2 (en) | 2020-08-11 |
US20190044131A1 (en) | 2019-02-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6314990B2 (ja) | 非水電解質二次電池用負極活物質及びその負極活物質を用いた非水電解質二次電池 | |
US20160329562A1 (en) | Negative electrode active material for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary battery containing negative electrode active material | |
WO2013018486A1 (ja) | 非水電解質二次電池用活物質及びその製造方法並びにそれを用いた負極 | |
WO2015129188A1 (ja) | 非水電解質二次電池 | |
WO2015098023A1 (ja) | 非水電解質二次電池用負極 | |
JP6394612B2 (ja) | 非水電解質二次電池用負極 | |
JP4798964B2 (ja) | 非水電解質二次電池 | |
WO2015136922A1 (ja) | 非水電解質二次電池 | |
WO2009116284A1 (ja) | 非水電解質二次電池 | |
WO2015098024A1 (ja) | 非水電解質二次電池用負極活物質及びその負極活物質を用いた非水電解質二次電池 | |
US20140065480A1 (en) | Positive-Electrode Active Material, Manufacturing Method Of The Same, And Nonaqueous Electrolyte Rechargeable Battery Having The Same | |
JP5783029B2 (ja) | 非水電解質二次電池用の負極とその製造方法、及び非水電解質二次電池 | |
JP2019530141A (ja) | リチウムイオン電池用複合正極活物質、その製造方法、及びそれを含む正極を含むリチウムイオン電池 | |
JP6509363B2 (ja) | 電気化学素子用電極、その製造方法、およびこれを含む電気化学素子 | |
US10741833B2 (en) | Negative electrode active material for nonaqueous electrolyte secondary battery | |
TW201318252A (zh) | 鋰離子二次電池用正極材料、鋰離子二次電池用正極構件、鋰離子二次電池、及鋰離子二次電池用正極材料之製造方法 | |
JPWO2015045314A1 (ja) | 非水電解質二次電池 | |
US20140065481A1 (en) | Positive-Electrode Active Material, Manufacturing Method Of The Same, And Nonaqueous Electrolyte Rechargeable Battery Having The Same | |
JP6459953B2 (ja) | リチウムイオン電池 | |
KR20240100228A (ko) | 리튬 이차전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15838812 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016546292 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15318884 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15838812 Country of ref document: EP Kind code of ref document: A1 |