WO2015107581A1 - 非水電解質二次電池用負極材及び負極活物質粒子の製造方法 - Google Patents
非水電解質二次電池用負極材及び負極活物質粒子の製造方法 Download PDFInfo
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- 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
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Definitions
- the present invention relates to a negative electrode material for a non-aqueous electrolyte secondary battery, and relates to a method for producing negative electrode active material particles.
- the present invention also relates to a negative electrode for a non-aqueous electrolyte secondary battery using the negative electrode material and a non-aqueous electrolyte secondary battery using the negative electrode.
- This secondary battery is not limited to a small electronic device, but is also considered to be applied to a large-sized electronic device represented by an automobile or the like, or an electric power storage system represented by a house.
- lithium ion secondary batteries are highly expected because they are small in size and easy to increase in capacity, and can obtain higher energy density than lead batteries and nickel cadmium batteries.
- the lithium ion secondary battery includes an electrolyte solution together with a positive electrode, a negative electrode, and a separator.
- This negative electrode contains a negative electrode active material involved in the charge / discharge reaction.
- the negative electrode active material when silicon is used as the negative electrode active material as the main raw material, the negative electrode active material expands and contracts during charge and discharge, so that it tends to break mainly near the surface layer of the negative electrode active material particles. Further, an ionic material is generated inside the active material, and the negative electrode active material particles are easily broken. When the negative electrode active material surface layer is cracked, a new surface is generated and the reaction area of the active material is increased. At this time, a decomposition reaction of the electrolytic solution occurs on the new surface, and a coating film that is a decomposition product of the electrolytic solution is formed on the new surface, so that the electrolytic solution is consumed. For this reason, the cycle characteristics are likely to deteriorate.
- silicon and amorphous silicon dioxide are simultaneously deposited using a vapor phase method (see, for example, Patent Document 1). Further, in order to obtain a high battery capacity and safety, a carbon material (electron conductive material) is provided on the surface layer of the silicon oxide particles (see, for example, Patent Document 2). Furthermore, in order to improve cycle characteristics and obtain high input / output characteristics, an active material containing silicon and oxygen is produced, and an active material layer having a high oxygen ratio in the vicinity of the current collector is formed (for example, (See Patent Document 3). Further, in order to improve the cycle characteristics, oxygen is contained in the silicon active material, the average oxygen content is 40 at% or less, and the oxygen content is increased at a location close to the current collector. (For example, see Patent Document 4).
- Si phase (for example, see Patent Document 5) by using a nanocomposite containing SiO 2, M y O metal oxide in order to improve the initial charge and discharge efficiency.
- a Li-containing material is added to the negative electrode, and pre-doping is performed to decompose Li and return Li to the positive electrode when the negative electrode potential is high (see, for example, Patent Document 6).
- the molar ratio of oxygen to silicon in the negative electrode active material is set to 0.1 to 1.2, and the molar ratio of oxygen amount to silicon amount in the vicinity of the interface between the active material and the current collector The active material is controlled in a range where the difference between the maximum value and the minimum value is 0.4 or less (see, for example, Patent Document 8).
- a metal oxide containing lithium is used (see, for example, Patent Document 9).
- a hydrophobic layer such as a silane compound is formed on the surface of the siliceous material (see, for example, Patent Document 10).
- Patent Document 11 silicon oxide is used and conductivity is imparted by forming a graphite film on the surface layer (see, for example, Patent Document 11).
- Patent Document 11 with respect to the shift value obtained from the Raman spectra for graphite coating, with broad peaks appearing at 1330 cm -1 and 1580 cm -1, their intensity ratio I 1330 / I 1580 is 1.5 ⁇ I 1330 / I 1580 ⁇ 3.
- particles having a silicon microcrystalline phase dispersed in silicon dioxide are used to improve high battery capacity and cycle characteristics (see, for example, Patent Document 12). Further, in order to improve overcharge and overdischarge characteristics, silicon oxide in which the atomic ratio of silicon and oxygen is controlled to 1: y (0 ⁇ y ⁇ 2) is used (for example, see Patent Document 13). .
- non-aqueous electrolyte secondary batteries particularly lithium ion secondary batteries, which are the main power source
- development of a non-aqueous electrolyte secondary battery including a negative electrode using a siliceous material as a main material is desired.
- non-aqueous electrolyte secondary batteries using a siliceous material are desired to have cycle characteristics close to those of a non-aqueous electrolyte secondary battery using a carbon material.
- the present invention has been made in view of such problems, and an object thereof is to provide a negative electrode material for a non-aqueous electrolyte secondary battery that can increase battery capacity and improve cycle characteristics and battery initial efficiency. It is. Another object of the present invention is to provide a negative electrode for a non-aqueous electrolyte secondary battery using the negative electrode material, and a non-aqueous electrolyte secondary battery using the negative electrode. Another object of the present invention is to provide a method for producing negative electrode active material particles that can be used for the negative electrode material.
- the present invention provides a negative electrode material for a nonaqueous electrolyte secondary battery having negative electrode active material particles, wherein the negative electrode active material particles are SiO x (0.5 ⁇ x ⁇ 1.6). Characterized in that the silicon compound contains a Li compound on the surface or inside thereof, and the negative electrode active material particles have a coating layer made of an organic polymer that covers the surface of the silicon compound.
- a negative electrode material for a nonaqueous electrolyte secondary battery is provided.
- the negative electrode material having such negative electrode active material particles is a material in which the SiO 2 component part that is destabilized when lithium is inserted or desorbed is modified in advance to another Li compound, the irreversible capacity generated during charging Can be reduced. Moreover, it has the outstanding tolerance with respect to the organic solvent and the water solvent by having the film layer which consists of an organic polymer which coat
- the organic polymer preferably contains at least one of a fluoroethylene group, a carboxyl group, a hydroxy group, and a carbonate group in the molecule. Further, the organic polymer contains at least one of polyacrylic acid and its alkali metal salt, carboxymethylcellulose and its alkali metal salt, polyvinyl alcohol, polycarbonate, polyvinylidene fluoride, and polyvinylidene fluoride. Is preferred.
- the content of the organic polymer with respect to the whole of the negative electrode active material particles is 0.01% by mass or more and less than 5% by mass.
- the organic polymer has an island-like structure at least partially.
- the organic polymer have an island-like structure, the decrease in electrical conductivity and ion conductivity of the negative electrode active material particles due to the coating of the organic polymer is minimized, and the coating film It is possible to impart resistance to aqueous solvents.
- At least one Li compound of Li 2 CO 3 , Li 2 O and LiF exists on the surface of the silicon compound.
- at least one Li compound among Li 4 SiO 4 , Li 6 Si 2 O 7 , and Li 2 SiO 3 exists in the silicon compound.
- the compound existing on the surface or inside of the silicon compound is any of these compounds, the effects of the present invention can be exhibited more effectively.
- the silicon compound is coated with a carbon-based compound.
- the coating amount of the carbon-based compound is 15% by mass or less with respect to the total of the silicon compound and the carbon-based compound.
- the peak area A in the vicinity of C1s binding energy 287.5 ⁇ 1.0 eV and the peak area B in the vicinity of 284.0 ⁇ 1.0 eV were 0.05 ⁇ It is preferable to satisfy the relationship of A / B ⁇ 3.00, and it is more preferable to satisfy the relationship of 0.10 ⁇ A / B ⁇ 1.00.
- the peak area A near a bond energy of 287.5 ⁇ 1.0 eV mainly derived from a carboxy group is compared with the peak area B near a bond energy of 284.0 ⁇ 1.0 eV derived from a single carbon.
- the carboxy group on the surface of the silicon compound can improve the adhesion between the organic polymer and the binder in the negative electrode, thereby further improving the battery characteristics.
- the coating layer made of the organic polymer contains a particulate carbonaceous material having a median diameter smaller than that of the silicon compound.
- the coating layer contains a carbon-based material having a median diameter smaller than that of the silicon compound, electrical conductivity between the particles of the silicon compound can be improved.
- the half-value width (2 ⁇ ) of a diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction of the silicon compound is 1.2 ° or more, and the crystallite size attributed to the crystal plane is 7.5 nm. The following is preferable.
- a silicon compound having such a half width and crystallite size has low crystallinity.
- a silicon compound having low crystallinity and a small amount of Si crystals battery characteristics can be improved.
- the silicon compound containing the Li compound is produced by a process including an electrochemical method.
- the present invention also provides a negative electrode for a non-aqueous electrolyte secondary battery using any one of the negative electrode materials for a non-aqueous electrolyte secondary battery described above.
- the negative electrode using the negative electrode material of the present invention can improve cycle characteristics and initial charge / discharge characteristics when used in a non-aqueous electrolyte secondary battery.
- the negative electrode for a nonaqueous electrolyte secondary battery further includes a carbon-based negative electrode material.
- the median diameter Y of the silicon compound and the median diameter X of the carbon-based negative electrode material satisfy the relationship of X / Y ⁇ 1.
- the negative electrode can be prevented from being destroyed due to volume change.
- this effect is effectively exhibited when the carbon-based negative electrode material is equal to or larger than the silicon compound.
- the present invention also provides a non-aqueous electrolyte secondary battery using any one of the negative electrodes described above.
- the nonaqueous electrolyte secondary battery using the negative electrode of the present invention can improve cycle characteristics and initial charge / discharge characteristics.
- the present invention also relates to a method for producing negative electrode active material particles contained in a negative electrode material for a non-aqueous electrolyte secondary battery, wherein a silicon compound represented by SiO x (0.5 ⁇ x ⁇ 1.6) is produced.
- a step of modifying the silicon compound by forming Li on the surface of the silicon compound and / or both by inserting Li into the silicon compound; and
- a method for producing negative electrode active material particles wherein the negative electrode active material particles are produced by a step of coating with a film layer comprising molecules.
- the SiO 2 component part contained in the negative electrode material for a non-aqueous electrolyte secondary battery of the present invention is modified in advance to another Li compound, and an organic polymer is obtained.
- Negative electrode active material particles having a coating layer made of can be produced.
- the negative electrode material for a non-aqueous electrolyte secondary battery according to the present invention is an irreversible capacity generated during charging because the SiO 2 component part, which is destabilized when lithium is inserted or desorbed, is previously modified into another compound. Can be reduced. Moreover, it has the outstanding tolerance with respect to the organic solvent and the water solvent by having the film layer which consists of an organic polymer which coat
- the negative electrode for a non-aqueous electrolyte secondary battery using the negative electrode material of the present invention and the non-aqueous electrolyte secondary battery using this negative electrode can improve cycle characteristics and initial charge / discharge characteristics. Moreover, the same effect can be acquired also in the electronic device, electric tool, electric vehicle, electric power storage system, etc. which used the secondary battery of this invention.
- the negative electrode active material particles contained in such a negative electrode material for a non-aqueous electrolyte secondary battery can be manufactured by the method for manufacturing negative electrode active material particles of the present invention.
- the non-aqueous electrolyte secondary battery using this siliceous material is expected to have cycle characteristics similar to those of the non-aqueous electrolyte secondary battery using the carbon material, but the non-aqueous electrolyte secondary battery using the carbon material and A negative electrode material exhibiting equivalent cycle stability has not been proposed.
- the inventors have intensively studied a negative electrode active material that can obtain good cycle characteristics when used in a negative electrode of a nonaqueous electrolyte secondary battery, and have reached the present invention.
- the negative electrode material for a non-aqueous electrolyte secondary battery of the present invention has negative electrode active material particles, and the negative electrode active material particles have a silicon compound represented by SiO x (0.5 ⁇ x ⁇ 1.6).
- the silicon compound includes a Li compound on the surface or inside, and the negative electrode active material particles have a coating layer made of an organic polymer that covers the surface of the silicon compound.
- FIG. 1 shows a cross-sectional configuration of a negative electrode for a nonaqueous electrolyte secondary battery (hereinafter sometimes simply referred to as “negative electrode”) according to an embodiment of the present invention.
- the negative electrode 10 is configured to have a negative electrode active material layer 12 on a negative electrode current collector 11.
- the negative electrode active material layer 12 may be provided on both surfaces or only one surface of the negative electrode current collector 11. Furthermore, the negative electrode current collector 11 may be omitted as long as the negative electrode active material of the present invention is used.
- the negative electrode current collector 11 is an excellent conductive material and is made of a material that is excellent in mechanical strength.
- Examples of the conductive material that can be used for the negative electrode current collector 11 include copper (Cu) and nickel (Ni). This conductive material is preferably a material that does not form an intermetallic compound with lithium (Li).
- the negative electrode current collector 11 preferably contains carbon (C) or sulfur (S) in addition to the main element. This is because the physical strength of the negative electrode current collector is improved.
- the current collector contains the above-described element, there is an effect of suppressing electrode deformation including the current collector.
- content of said content element is not specifically limited, Especially, it is preferable that it is 100 ppm or less. This is because a higher deformation suppressing effect can be obtained.
- the surface of the negative electrode current collector 11 may be roughened or not roughened.
- the roughened negative electrode current collector is, for example, a metal foil subjected to electrolytic treatment, embossing treatment, or chemical etching.
- the non-roughened negative electrode current collector is, for example, a rolled metal foil.
- the negative electrode active material layer 12 includes a plurality of particulate negative electrode active materials (hereinafter referred to as negative electrode active material particles) that can occlude and release lithium ions. Further, in terms of battery design, the negative electrode binder and the conductive auxiliary agent are further included. Other materials may be included.
- the negative electrode material for a nonaqueous electrolyte secondary battery of the present invention is a material constituting the negative electrode active material layer 12.
- the negative electrode active material particles used in the negative electrode material of the present invention contain a Li compound in the portion (surface or inside) of a silicon compound capable of occluding and releasing lithium ions, and a coating layer made of an organic polymer is further formed on the surface.
- a Li compound in the portion (surface or inside) of a silicon compound capable of occluding and releasing lithium ions, and a coating layer made of an organic polymer is further formed on the surface.
- TEM-EDX Transmission Electron Microscopy-Energy Dispersive X-ray Spectroscopy
- the negative electrode active material particles used for the negative electrode material of the present invention is a silicon oxide material containing a silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6), and x is 1 as the composition of the silicon compound. The closer one is preferable. This is because high cycle characteristics can be obtained.
- the siliceous material composition in the present invention does not necessarily mean 100% purity, and may contain a trace amount of impurity elements.
- Such negative electrode active material particles can be obtained by selectively changing a part of the SiO 2 component generated inside the silicon compound to a Li compound.
- a Li compound inside the silicon compound Li 4 SiO 4 , Li 6 Si 2 O 7 and Li 2 SiO 3 exhibit particularly good characteristics.
- Li compounds can be quantified by NMR (nuclear magnetic resonance) and XPS (X-ray photoelectron spectroscopy).
- the XPS and NMR measurements can be performed, for example, under the following conditions.
- Ar ion gun sputtering conditions 0.5 kV 2 mm x 2 mm 29 Si MAS NMR (magic angle rotating nuclear magnetic resonance)
- Device 700 NMR spectrometer manufactured by Bruker ⁇ Probe: 4 mmHR-MAS rotor 50 ⁇ L ⁇ Sample rotation speed: 10 kHz ⁇ Measurement environment temperature: 25 °C
- the method for producing the selective compound, that is, the modification of the silicon compound is preferably performed by an electrochemical method.
- negative electrode active material particles By producing negative electrode active material particles using such a modification (in-bulk modification) method, it is possible to reduce or avoid the formation of Li compounds in the Si region. In the atmosphere or in an aqueous slurry, It becomes a stable substance in the solvent slurry. Further, by performing the modification by an electrochemical method, it is possible to make a more stable substance with respect to the thermal modification (thermal doping method) in which the compound is randomly formed.
- Li 4 SiO 4 , Li 6 Si 2 O 7 , and Li 2 SiO 3 generated in the bulk of the silicon compound improves the characteristics. However, two or more kinds of characteristics are improved more. Coexistence state.
- At least one Li compound of Li 2 CO 3 , Li 2 O and LiF exists on the surface of the silicon compound.
- the storage characteristics of the powder are dramatically improved by generating a fluorine compound such as LiF on the outermost layer of the silicon compound.
- a fluorine compound such as LiF
- the method is not particularly limited, but the electrochemical method is most preferable.
- the negative electrode active material particles have a coating layer made of an organic polymer that covers the surface of the silicon compound.
- those having at least one of a fluoroethylene group, a carboxyl group, a hydroxy group, and a carbonate group in the skeleton exhibit particularly good characteristics.
- methods for producing the coating layer methods such as immersion / drying, mixing / melting of an organic polymer and a silicon compound, and fusion using a ball mill can be used.
- the organic polymer used as the coating layer is at least one of polyacrylic acid and its alkali metal salt, carboxymethylcellulose and its alkali metal salt, polyvinyl alcohol, polycarbonate, polyvinylidene fluoride, and polyvinylidene fluoride. It is preferable to contain.
- the particles of the above-mentioned silicon compound have a coating layer made of an organic polymer, thereby improving the resistance to organic solvents and water solvents while having a compound in which a part of the SiO 2 component is changed to a Li compound. it can.
- the content of the organic polymer constituting the coating layer of the silicon compound particles with the organic polymer is preferably 0.01% by mass or more and less than 5% by mass. More preferably, the content is 0.05% by mass or more and less than 3% by mass.
- the content of the organic polymer is 0.01% by mass or more, the effect of the coating layer can be more reliably exhibited, and the resistance to organic solvents and water solvents can be improved.
- content is less than 5 mass%, the electrical conductivity of the surface of a negative electrode active material particle and ion conductivity can be maintained in a favorable state, and it does not lead to deterioration of a battery characteristic.
- the amount of coating by this coating layer can be calculated by comparing the mass of the negative electrode active material particles before and after the formation of the coating, or by elemental analysis or the like.
- the organic polymer serving as the coating layer has an island-like structure at least partially.
- the silicon compound is coated with a carbon-based compound.
- the coating amount of the carbon compound is desirably 15% by mass or less with respect to the total of the silicon compound and the carbon compound.
- the electrical conductivity can be improved.
- the amount of the carbon-based compound exceeds 15% by mass, the battery characteristics are not deteriorated.
- the content is preferably 15% by mass or less.
- the coating method of these carbon compounds is not particularly limited, a sugar carbonization method and a thermal decomposition method of hydrocarbon gas are preferable. This is because the coverage can be improved.
- the peak area A in the vicinity of C1s binding energy 287.5 ⁇ 1.0 eV and the peak area B in the vicinity of 284.0 ⁇ 1.0 eV were 0.05 ⁇ A It is preferable to satisfy the relationship /B ⁇ 3.00, and it is more preferable to satisfy the relationship 0.10 ⁇ A / B ⁇ 1.00.
- the coating layer made of an organic polymer contains a particulate carbonaceous material having a median diameter smaller than that of the silicon compound, that is, a particulate carbonaceous material having a median diameter smaller than that of the silicon compound around the silicon compound. It is desirable to include a compound. This can improve the electrical conductivity between the silicon compound particles.
- the carbon-based compound can be present around the negative electrode active material particles by, for example, physical mixing with the negative electrode active material particles.
- the median diameter of the silicon compound is not particularly limited, but is preferably 0.5 ⁇ m to 20 ⁇ m. This is because, within this range, lithium ions are easily occluded and released during charging and discharging, and the particles are difficult to break. If the median diameter is 0.5 ⁇ m, the surface area is not too large, so that the battery irreversible capacity can be reduced. On the other hand, a median diameter of 20 ⁇ m or less is preferable because the particles are difficult to break and a new surface is difficult to appear.
- Examples of the negative electrode binder include one or more of polymer materials and synthetic rubbers.
- Examples of the polymer material include polyvinylidene fluoride, polyimide, polyamideimide, aramid, polyacrylic acid, lithium polyacrylate, and carboxymethylcellulose.
- the synthetic rubber is, for example, styrene butadiene rubber, fluorine rubber, or ethylene propylene diene.
- Examples of the negative electrode conductive assistant include one or more carbon materials such as carbon black, acetylene black, graphite, ketjen black, carbon nanotube, and carbon nanofiber.
- a negative electrode material silicon-based negative electrode material
- a carbon material carbon-based negative electrode material
- the electrical resistance of the negative electrode active material layer 12 can be reduced and the expansion stress associated with charging can be reduced.
- the carbon-based negative electrode material include pyrolytic carbons, cokes, glassy carbon fibers, organic polymer compound fired bodies, and carbon blacks.
- the negative electrode active material layer 12 is formed by, for example, a coating method.
- the coating method is a method in which a negative electrode active material particle and the above-described binder, and the like, and a conductive additive and a carbon material are mixed as necessary, and then dispersed and coated in an organic solvent or water.
- the manufacturing method of the negative electrode active material particle contained in the negative electrode material for nonaqueous electrolyte secondary batteries of this invention is demonstrated.
- a silicon compound represented by SiO x (0.5 ⁇ x ⁇ 1.6) is produced.
- the Li compound is generated on the surface or inside of the silicon compound, or both, thereby modifying the silicon compound.
- the surface of the silicon compound is covered with a coating layer made of an organic polymer.
- the negative electrode active material particles are produced, for example, by the following procedure.
- a raw material that generates silicon oxide gas is heated in a temperature range of 900 ° C. to 1600 ° C. in the presence of an inert gas or under reduced pressure to generate silicon oxide gas.
- the raw material is a mixture of metal silicon powder and silicon dioxide powder, and considering the surface oxygen of the metal silicon powder and the presence of trace amounts of oxygen in the reactor, the mixing molar ratio is 0.8 ⁇ metal silicon powder / It is desirable that the silicon dioxide powder is in the range of ⁇ 1.3.
- the Si crystallites in the particles are controlled by changing the preparation range and vaporization temperature, and by heat treatment after generation.
- the generated gas is deposited on the adsorption plate. The deposit is taken out with the temperature in the reactor lowered to 100 ° C. or lower, and pulverized and powdered using a ball mill, a jet mill or the like.
- a carbon layer can be formed on the surface layer of the obtained powder material, but this step is not essential.
- pyrolysis CVD As a method for generating a carbon layer on the surface layer of the obtained powder material, pyrolysis CVD is desirable.
- Thermal decomposition CVD fills the silicon oxide powder set in the furnace and the hydrocarbon gas into the furnace to raise the temperature in the furnace.
- the decomposition temperature is not particularly limited, but is particularly preferably 1200 ° C. or lower. More desirably, the temperature is 950 ° C. or lower, and disproportionation of the active material particles can be suppressed.
- the hydrocarbon gas is not particularly limited, but 3 ⁇ n is desirable in the CnHm composition. This is because the low production cost and the physical properties of the decomposition products are good.
- the reforming in the bulk can electrochemically insert and desorb Li.
- the apparatus structure is not particularly limited, for example, the bulk reforming can be performed using the bulk reforming apparatus 20 shown in FIG.
- the reformer 20 in the bulk is disposed in the bathtub 27 filled with the organic solvent 23, the positive electrode (lithium source) 21 disposed in the bathtub 27 and connected to one of the power sources 26, and the bathtub 27. It has a powder storage container 25 connected to the other side of the power source 26 and a separator 24 provided between the positive electrode 21 and the powder storage container 25.
- the powder storage container 25 stores a silicon compound powder 22.
- the modified silicon compound powder 22 is then immersed in a solution in which the organic polymer is dissolved, and then dried to produce a coating layer of the organic polymer.
- the obtained modified particles may not contain a carbon layer.
- organic solvent 23 in the bathtub 27 ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, or the like can be used.
- electrolyte salt contained in the organic solvent 23 lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), or the like can be used.
- the positive electrode 21 may use a Li foil or a Li-containing compound.
- the Li-containing compound include lithium carbonate and lithium oxide.
- the negative electrode active material particles are mixed with other materials such as a negative electrode binder and a conductive additive to form a negative electrode mixture, and then an organic solvent or water is added to form a slurry.
- the mixture slurry is applied to the surface of the negative electrode current collector and dried to form the negative electrode active material layer 12 shown in FIG. At this time, a heating press or the like may be performed as necessary.
- the initial efficiency of the battery and the stability of the active material accompanying the cycle characteristics are improved by changing the SiO 2 component present in the bulk to a stable Li compound. In that case, a higher effect can be obtained when Li silicate is generated inside the bulk.
- the negative electrode current collector contains carbon and sulfur of 90 ppm or less, higher effects can be obtained.
- Lithium ion secondary battery> a lithium ion secondary battery will be described as a specific example of a non-aqueous electrolyte secondary battery using the above-described negative electrode.
- a laminated film type secondary battery 30 shown in FIG. 3 is one in which a wound electrode body 31 is accommodated mainly in a sheet-like exterior member 35. This wound body has a separator between a positive electrode and a negative electrode and is wound. There is also a case where a separator is provided between the positive electrode and the negative electrode and a laminate is accommodated.
- the positive electrode lead 32 is attached to the positive electrode
- the negative electrode lead 33 is attached to the negative electrode.
- the outermost peripheral part of the electrode body is protected by a protective tape.
- the positive and negative electrode leads are led out in one direction from the inside of the exterior member 35 to the outside, for example.
- the positive electrode lead 32 is formed of a conductive material such as aluminum
- the negative electrode lead 33 is formed of a conductive material such as nickel or copper.
- the exterior member 35 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order.
- This laminate film is formed of two films so that the fusion layer faces the electrode body 31.
- the outer peripheral edges of the fusion layer are bonded together with an adhesive or an adhesive.
- the fused part is, for example, a film such as polyethylene or polypropylene, and the metal part is aluminum foil or the like.
- the protective layer is, for example, nylon.
- An adhesion film 34 is inserted between the exterior member 35 and the positive and negative electrode leads to prevent intrusion of outside air.
- This material is, for example, polyethylene, polypropylene, or polyolefin resin.
- the positive electrode has, for example, a positive electrode active material layer on both sides or one side of the positive electrode current collector, similarly to the negative electrode 10 of FIG.
- the positive electrode current collector is made of, for example, a conductive material such as aluminum.
- the positive electrode active material layer includes one or more positive electrode materials capable of occluding and releasing lithium ions, and includes other materials such as a binder, a conductive additive, and a dispersant depending on the design. You can leave. In this case, details regarding the binder and the conductive additive are the same as, for example, the negative electrode binder and the negative electrode conductive additive already described.
- a lithium-containing compound is desirable.
- the lithium-containing compound include a composite oxide composed of lithium and a transition metal element, or a phosphate compound having lithium and a transition metal element.
- compounds having at least one of nickel, iron, manganese, and cobalt are preferable.
- These chemical formulas are represented by, for example, Li x M 1 O 2 or Li y M 2 PO 4 .
- M 1 and M 2 represent at least one transition metal element.
- the values of x and y differ depending on the battery charge / discharge state, but are generally expressed as 0.05x ⁇ 1.10 and 0.05 ⁇ y ⁇ 1.10.
- Examples of the composite oxide having lithium and a transition metal element include lithium cobalt composite oxide (Li x CoO 2 ) and lithium nickel composite oxide (Li x NiO 2 ).
- Examples of the phosphate compound having lithium and a transition metal element include a lithium iron phosphate compound (LiFePO 4 ) or a lithium iron manganese phosphate compound (LiFe 1-u Mn u PO 4 (u ⁇ 1)). It is done. This is because, when these positive electrode materials are used, a high battery capacity can be obtained and excellent cycle characteristics can be obtained.
- the negative electrode has the same configuration as the above-described negative electrode 10 for a lithium ion secondary battery in FIG. 1.
- the negative electrode has negative electrode active material layers 12 on both surfaces of the current collector 11.
- the negative electrode preferably has a negative electrode charge capacity larger than the electric capacity (charge capacity as a battery) obtained from the positive electrode active material agent. This is because the deposition of lithium metal on the negative electrode can be suppressed.
- the positive electrode active material layer is provided on a part of both surfaces of the positive electrode current collector, and the negative electrode active material layer is also provided on a part of both surfaces of the negative electrode current collector.
- the negative electrode active material layer provided on the negative electrode current collector is provided with a region where there is no opposing positive electrode active material layer. This is for a stable battery design.
- the non-opposing region that is, the region where the negative electrode active material layer and the positive electrode active material layer are not opposed to each other, there is almost no influence of charge / discharge. Therefore, the state of the negative electrode active material layer is maintained as it is immediately after formation. This makes it possible to accurately examine the composition with good reproducibility without depending on the presence or absence of charge / discharge, such as the composition of the negative electrode active material.
- the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass through while preventing current short-circuiting due to bipolar contact.
- This separator is formed of, for example, a porous film made of synthetic resin or ceramic, and may have a laminated structure in which two or more kinds of porous films are laminated.
- the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.
- Electrode At least a part of the active material layer or the separator is impregnated with a liquid electrolyte (electrolytic solution).
- This electrolytic solution has an electrolyte salt dissolved in a solvent, and may contain other materials such as additives.
- a non-aqueous solvent for example, a non-aqueous solvent can be used.
- the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2-dimethoxyethane, and tetrahydrofuran.
- a high viscosity solvent such as ethylene carbonate or propylene carbonate
- a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. This is because the dissociation property and ion mobility of the electrolyte salt are improved.
- a halogenated chain carbonate ester or a halogenated cyclic carbonate ester is contained as a solvent. This is because a stable coating is formed on the surface of the negative electrode active material during charging / discharging, particularly during charging.
- the halogenated chain carbonate is a chain carbonate having halogen as a constituent element (at least one hydrogen is replaced by a halogen).
- the halogenated cyclic carbonate is a cyclic carbonate having halogen as a constituent element (at least one hydrogen is replaced by halogen).
- the kind of halogen is not particularly limited, but fluorine is more preferable. This is because a film having a higher quality than other halogens is formed. Also, the larger the number of halogens, the better. This is because the resulting coating is more stable and the decomposition reaction of the electrolytic solution is reduced.
- halogenated chain carbonate ester examples include fluoromethyl methyl carbonate and difluoromethyl methyl carbonate.
- halogenated cyclic carbonate examples include 4-fluoro-1,3-dioxolane-2-one and 4,5-difluoro-1,3-dioxolane-2-one.
- the solvent additive contains an unsaturated carbon bond cyclic carbonate. This is because a stable film is formed on the surface of the negative electrode during charging and discharging, and the decomposition reaction of the electrolytic solution can be suppressed.
- unsaturated carbon bond cyclic ester carbonate include vinylene carbonate and vinyl ethylene carbonate.
- sultone cyclic sulfonic acid ester
- solvent additive examples include propane sultone and propene sultone.
- the solvent preferably contains an acid anhydride. This is because the chemical stability of the electrolytic solution is improved.
- the acid anhydride include propanedisulfonic acid anhydride.
- the electrolyte salt can contain, for example, any one or more of light metal salts such as lithium salts.
- the lithium salt include lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ).
- the content of the electrolyte salt is preferably 0.5 mol / kg or more and 2.5 mol / kg or less with respect to the solvent. This is because high ionic conductivity is obtained.
- a positive electrode is produced using the positive electrode material described above.
- a positive electrode active material and, if necessary, a binder, a conductive additive and the like are mixed to form a positive electrode mixture, and then dispersed in an organic solvent to form a positive electrode mixture slurry.
- the mixture slurry is applied to the positive electrode current collector with a coating apparatus such as a die coater having a knife roll or a die head, and dried with hot air to obtain a positive electrode active material layer.
- the positive electrode active material layer is compression molded with a roll press or the like. At this time, it may be heated or repeated a plurality of times.
- a negative electrode is produced by forming a negative electrode active material layer on the negative electrode current collector using the same operating procedure as the production of the negative electrode 10 for lithium ion secondary batteries described above.
- the positive electrode lead 32 is attached to the positive electrode current collector and the negative electrode lead 33 is attached to the negative electrode current collector by ultrasonic welding or the like.
- the positive electrode and the negative electrode are laminated or wound via a separator to produce a wound electrode body 31, and a protective tape is bonded to the outermost periphery.
- the wound body is molded so as to have a flat shape.
- the insulating portions of the exterior member are bonded to each other by a thermal fusion method, and the wound electrode body is released in only one direction. Enclose.
- An adhesion film is inserted between the positive electrode lead and the negative electrode lead and the exterior member.
- a predetermined amount of the adjusted electrolytic solution is introduced from the release portion, and vacuum impregnation is performed. After impregnation, the release part is bonded by a vacuum heat fusion method.
- the laminated film type secondary battery 30 can be manufactured as described above.
- Example 1-1 The laminate film type secondary battery 30 shown in FIG. 3 was produced by the following procedure.
- the positive electrode active material is a mixture of 95 parts by mass of LiCoO 2 which is a lithium cobalt composite oxide, 2.5 parts by mass of a positive electrode conductive additive, and 2.5 parts by mass of a positive electrode binder (polyvinylidene fluoride, PVdF).
- a positive electrode mixture was obtained.
- the positive electrode mixture was dispersed in an organic solvent (N-methyl-2-pyrrolidone, NMP) to obtain a paste slurry.
- NMP N-methyl-2-pyrrolidone
- the slurry was applied to both surfaces of the positive electrode current collector with a coating apparatus having a die head, and dried with a hot air drying apparatus. At this time, the positive electrode current collector had a thickness of 15 ⁇ m.
- compression molding was performed with a roll press.
- the negative electrode active material is a mixture of metal silicon and silicon dioxide, placed in a reactor, and vaporized in a 10 Pa vacuum atmosphere is deposited on the adsorption plate. After cooling sufficiently, the deposit is taken out. It grind
- the produced powder was subjected to bulk modification using an electrochemical method in a 1: 1 mixed solvent of propylene carbonate and ethylene carbonate (containing an electrolyte salt at a concentration of 1.3 mol / kg). The obtained material was immersed in an NMP solution of polyvinylidene fluoride and then subjected to a drying treatment.
- the powder surface was coated with a coating layer made of polyvinylidene fluoride, which is an organic polymer.
- the negative electrode active material particles and the negative electrode binder, the conductive auxiliary agent 1 and the conductive auxiliary agent 2 are mixed at a dry mass ratio of 80: 8: 10: 2, and then diluted with water to obtain a paste-like negative electrode composition.
- An agent slurry was obtained.
- water was used as a solvent for polyacrylic acid, which is a negative electrode binder.
- the negative electrode mixture slurry was applied to both surfaces of the negative electrode current collector with a coating apparatus and then dried.
- a solvent (4-fluoro-1,3-dioxolan-2-one (FEC), ethylene carbonate (EC) and dimethyl carbonate (DMC)) is mixed, and then an electrolyte salt (lithium hexafluorophosphate: LiPF) is mixed. 6 ) was dissolved to prepare an electrolytic solution.
- a secondary battery was assembled as follows. First, an aluminum lead was ultrasonically welded to one end of the positive electrode current collector, and a nickel lead was welded to the negative electrode current collector. Subsequently, a positive electrode, a separator, a negative electrode, and a separator were laminated in this order and wound in the longitudinal direction to obtain a wound electrode body. The end portion was fixed with a PET protective tape. As the separator, a laminated film of 12 ⁇ m sandwiched between a film mainly composed of porous polyethylene and a film mainly composed of porous polypropylene was used.
- the outer peripheral edges except for one side were heat-sealed, and the electrode body was housed inside.
- the exterior member a nylon film, an aluminum foil, and an aluminum laminate film in which a polypropylene film was laminated were used.
- the prepared electrolyte was injected from the opening, impregnated in a vacuum atmosphere, and then heat-sealed and sealed.
- Example 1-2 to Example 1--7 A secondary battery was produced in the same manner as in Example 1-1, but the type of organic polymer in the coating layer covering the powder surface of the silicon compound in the negative electrode material was changed.
- Polypropylene carbonate and polyethylene in Examples 1-7 were used as the organic polymer for the coating layer, respectively.
- Comparative Example 1-1 A secondary battery was fabricated in the same manner as in Example 1-1 except that the coating layer covering the powder surface of the silicon compound in the negative electrode material was not formed.
- the silicon compounds in Examples 1-1 to 1-7 and Comparative Example 1 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- the silicon compound represented by SiOx the value of x was 0.9.
- LiF, Li 2 CO 3 , and Li 2 O are formed as inclusions on the surface, and Li 4 SiO 4 , Li 6 Si 2 O 7 , and Li 2 SiO 3 are formed as inclusions in the active material. It was.
- Example 1-1 to 1-7 and Comparative Example 1-1 the carbon coating amount was 5.0% by mass. In all of Examples 1-1 to 1-7, the content of the organic polymer with respect to the whole negative electrode active material particles was 1%.
- the cycle characteristics were examined as follows. First, in order to stabilize the battery, charge / discharge was performed for 2 cycles in an atmosphere at 25 ° C., and the discharge capacity at the second cycle was measured. Subsequently, charge and discharge were performed until the total number of cycles reached 100, and the discharge capacity was measured each time. Finally, the discharge capacity at the 100th cycle was divided by the discharge capacity at the 2nd cycle, and multiplied by 100 for% display to calculate the capacity maintenance rate.
- a constant current density until reaching 4.2V and charged at 2.5 mA / cm 2
- the current density at 4.2V constant voltage at the stage of reaching the voltage charged to reach 0.25 mA / cm 2 During discharging, discharging was performed at a constant current density of 2.5 mA / cm 2 until the voltage reached 2.5V.
- the initial efficiency (%) (initial discharge capacity / initial charge capacity) ⁇ 100 was calculated.
- the ambient temperature was the same as when the cycle characteristics were examined.
- the charge / discharge conditions were 0.2 times the cycle characteristics.
- polyvinylidene fluoride was used as the organic polymer.
- Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2 A secondary battery was manufactured in the same manner as in Example 1-1, except that the amount of oxygen in the bulk of the silicon compound at the time of manufacturing the negative electrode material was adjusted. In this case, the amount of oxygen deposited was adjusted by changing the ratio and temperature of the vaporized starting material.
- Table 2 shows the value of x of the silicon compound represented by SiO x in Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2.
- the silicon compounds in Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- LiF, Li 2 CO 3 , and Li 2 O are formed as inclusions on the surface, and Li 4 SiO 4 , Li 6 Si 2 O 7 , and Li 2 SiO 3 are formed as inclusions in the active material. It was.
- the carbon coating amount was 5.0% by mass, and the organic polymer (polyvinylidene fluoride) with respect to the whole negative electrode active material particles The content was 1%.
- Examples 3-1 and 3-2 A secondary battery was manufactured basically in the same manner as in Example 1-1, but the potential, current amount, and insertion / extraction method of Li during the bulk modification of the silicon compound were controlled. The state of inclusions produced in the compound was changed. When electrochemically modified, LiF, Li 2 CO 3 and Li 2 O are generated on the surface, and Li 2 SiO 3 , Li 6 Si 2 O 7 and Li 4 SiO 4 are generated inside. Moreover, the Li compound on the surface can be removed by washing with water. Thus, in Example 3-1, LiF, Li 2 CO 3 and Li 2 O were formed on the surface of the silicon compound, and Li 2 SiO 3 , Li 6 Si 2 O 7 and Li 4 SiO 4 were formed inside. . In Example 3-2, the Li compound on the surface of the silicon compound was removed, and Li 2 SiO 3 , Li 6 Si 2 O 7 , and Li 4 SiO 4 were present inside.
- the obtained Li compound can be confirmed by XPS.
- Li 4 SiO 4 is given by a binding energy around 532 eV
- Li 2 SiO 3 is given by a binding energy around 530 eV.
- the obtained Li compound can also be confirmed by 29 Si-MAS-NMR spectrum.
- the silicon compounds in Examples 3-1 and 3-2 and Comparative Example 3-1 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- the carbon coating amount was 5.0% by mass, and the content of the organic polymer (polyvinylidene fluoride) with respect to the whole of the negative electrode active material particles was 1. %Met.
- the silicon compound when the silicon compound is electrochemically modified, LiF, Li 2 CO 3 and Li 2 O are formed on the surface, and Li 2 SiO 3 , Li 6 Si 2 O 7 and Li 4 SiO 4 are generated inside. To do. Moreover, the Li compound on the surface can be removed by washing with water. Incorporating these reactions and the like, particularly in Example 3-1, the capacity retention ratio and the initial efficiency were improved by realizing an optimum bulk state. That is, the surface layer of the silicon compound preferably contains LiF, Li 2 CO 3 , and Li 2 O, and the active material contains Li 2 SiO 3 , Li 6 Si 2 O 7 , and Li 4 SiO 4 . It is desirable.
- Examples 4-1 to 4-3 A secondary battery was manufactured basically in the same manner as in Example 1-1. However, when an organic polymer (polyvinylidene fluoride) coating layer was formed on the silicon compound particles, the amount of the organic polymer was adjusted. did. Specifically, the step of immersing the negative electrode active material particles in the polyvinylidene fluoride NMP solution and drying was repeated until the predetermined content was reached. Specific contents of polyvinylidene fluoride are shown in Table 4.
- Example 4-1 A secondary battery was manufactured in the same manner as in Example 1-1 except that the organic polymer (polyvinylidene fluoride) coating layer was not formed on the silicon compound particles.
- the silicon compounds in Examples 4-1 to 4-3 and Comparative Example 4-1 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- the content of the organic polymer is preferably 0.01% by mass or more and less than 5% by mass.
- the battery characteristics are deteriorated due to poor resistance to an aqueous solvent. If the content of the organic polymer is less than 5%, the electrical conductivity and ionic conductivity of the negative electrode active material particles are not deteriorated, so that deterioration of battery characteristics can be prevented.
- the content of the organic polymer was 1% by mass.
- Example 5-1 to 5-4 the secondary battery was manufactured basically in the same manner as in Example 1-1. However, the surface layer portion of the silicon compound (silicon oxide material particles) was formed using the thermal decomposition CVD method. The amount of carbon when the carbon layer was formed was adjusted. In Example 5-4, a secondary battery was manufactured in the same manner as Example 1-1 except that no carbon layer was formed on the surface of the silicon compound.
- the silicon compounds in Examples 5-1 to 5-4 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- Example 6-1 to 6-4 a secondary battery was basically manufactured in the same manner as in Example 1-1. However, by changing the treatment temperature when performing the electrochemical reforming method, silicon was produced. When the compound surface layer was measured by XPS, the relationship A / B between the peak area A in the vicinity of C1s binding energy of 287.5 ⁇ 1.0 eV and the peak area B in the vicinity of 284.0 ⁇ 1.0 eV was changed.
- the silicon compounds in Examples 6-1 to 6-4 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- Examples 7-1 to 7-5 A secondary battery was manufactured in the same manner as in Example 1-1 except that a negative electrode containing a carbon-based material was prepared as follows. The median diameter of the silicon compound and the carbon-based material was adjusted and mixed with a shaker, and then converted into an electrode, thereby creating a negative electrode in which the carbon-based material was present around the silicon compound. The median diameter of each silicon compound of Examples 7-1 to 7-5, and the median diameter and the mixing amount of the carbon-based material are as shown in Table 7.
- the half-value width (2 ⁇ ) of the diffraction peak due to the (111) crystal plane obtained by X-ray diffraction is 1.22 °
- the crystal plane ( 111) was a crystallite size of 7.21 nm.
- the mixing amount is preferably 5% by mass or less in consideration of battery capacity and characteristics.
- Example 8-1 to 8-8 A secondary battery was manufactured in the same manner as in Example 1-1 except that the crystallinity of the silicon compound was changed.
- the change in crystallinity can be controlled by heat treatment in a non-atmospheric atmosphere after Li insertion and desorption.
- the full widths at half maximum of the silicon compounds of Examples 8-1 to 8-8 are shown in Table 8.
- the crystallite size is calculated to be 1.542 nm, but this is the result of fitting using analysis software, and no substantial peak is obtained. Therefore, it can be said that the silicon compound of Example 8-1 is substantially amorphous.
- Silicon compounds in Examples 8-1 to 8-8 are all median diameter D 50 was 5 [mu] m.
- Example 9-1 to 9-4 A secondary battery was manufactured in the same manner as in Example 1-1 except that the median diameter of the silicon compound was changed.
- the median diameters of the silicon compounds of Examples 9-1 to 9-4 are shown in Table 9.
- the half-width (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction is 1.22 °
- the crystal plane ( 111) was a crystallite size of 7.21 nm.
- Example 10-1 In the same manner as in Example 1-1, the silicon compound was modified by an electrochemical method to manufacture a secondary battery.
- Example 10-2 A secondary battery was manufactured in the same manner as in Example 1-1 except that the silicon compound was modified by the Li thermal doping method.
- Example 10-1 A secondary battery was manufactured in the same manner as in Example 1-1 except that Li was not introduced into the silicon compound and no modification was performed.
- the silicon compounds in Examples 10-1 and 10-2 and Comparative Example 10-1 all had the following physical properties.
- the median diameter D 50 of the silicon compound was 5 ⁇ m.
- the full width at half maximum (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction was 1.22 °, and the crystallite size attributed to the crystal plane (111) was 7.21 nm.
- an electrochemical method is desirable as a method for modifying the silicon compound.
- the thermal doping method is a technique in which a silicon material and Li metal or a Li compound are mixed and heat-treated, and does not improve the quality of the active material.
- Example 11-1 to 11-8 A secondary battery was manufactured in the same manner as in Example 1-1 except that a negative electrode containing a carbon-based negative electrode material was prepared in addition to the negative electrode material having negative electrode active material particles containing a silicon compound.
- Median diameter D 50 of the silicon compound (Y), shown in Table 11 the value of the carbonaceous negative electrode material median diameter D 50 of (X), and X / Y.
- the half width (2 ⁇ ) of the diffraction peak attributed to the (111) crystal plane obtained by X-ray diffraction is 1.22 °, and the crystal plane (111) The crystallite size attributed to was 7.21 nm.
- the carbon material in the negative electrode active material layer has a size equal to or greater than that of the silicon compound.
- the silicon compound that expands and contracts is equal to or smaller than that of the carbon-based negative electrode material, the composite material layer can be prevented from being broken.
- the carbon-based negative electrode material is larger than the silicon compound, the negative electrode volume density and initial efficiency during charging are improved, and the battery energy density is improved.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
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Abstract
Description
本発明の非水電解質二次電池用負極材を用いた非水電解質二次電池用負極について説明する。図1は、本発明の一実施形態における非水電解質二次電池用負極(以下、単に「負極」と称することがある。)の断面構成を表している。
図1に示したように、負極10は、負極集電体11の上に負極活物質層12を有する構成になっている。この負極活物質層12は負極集電体11の両面、又は、片面だけに設けられていても良い。さらに、本発明の負極活物質が用いられたものであれば、負極集電体11はなくてもよい。
負極集電体11は、優れた導電性材料であり、かつ、機械的な強度に長けた物で構成される。負極集電体11に用いることができる導電性材料として、例えば銅(Cu)やニッケル(Ni)があげられる。この導電性材料は、リチウム(Li)と金属間化合物を形成しない材料であることが好ましい。
負極活物質層12は、リチウムイオンを吸蔵、放出可能な複数の粒子状負極活物質(以下、負極活物質粒子と称する)を含んでおり、電池設計上、さらに負極結着剤や導電助剤など、他の材料を含んでいても良い。本発明の非水電解質二次電池用負極材は、この負極活物質層12を構成する材料となる。
XPS
・装置: X線光電子分光装置
・X線源: 単色化Al Kα線
・X線スポット径: 100μm
・Arイオン銃スパッタ条件: 0.5kV 2mm×2mm
29Si MAS NMR(マジック角回転核磁気共鳴)
・装置: Bruker社製700NMR分光器
・プローブ: 4mmHR-MASローター 50μL
・試料回転速度: 10kHz
・測定環境温度: 25℃
次に、上記した負極を用いた非水電解質二次電池の具体例として、リチウムイオン二次電池について説明する。
図3に示すラミネートフィルム型二次電池30は、主にシート状の外装部材35の内部に巻回電極体31が収納されたものである。この巻回体は正極、負極間にセパレータを有し、巻回されたものである。また正極、負極間にセパレータを有し積層体を収納した場合も存在する。どちらの電極体においても、正極に正極リード32が取り付けられ、負極に負極リード33が取り付けられている。電極体の最外周部は保護テープにより保護されている。
正極は、例えば、図1の負極10と同様に、正極集電体の両面又は片面に正極活物質層を有している。
負極は、上記した図1のリチウムイオン二次電池用負極10と同様の構成を有し、例えば、集電体11の両面に負極活物質層12を有している。この負極は、正極活物質剤から得られる電気容量(電池として充電容量)に対して、負極充電容量が大きくなることが好ましい。負極上でのリチウム金属の析出を抑制することができるためである。
セパレータは正極、負極を隔離し、両極接触に伴う電流短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータは、例えば合成樹脂、あるいはセラミックからなる多孔質膜により形成されており、2種以上の多孔質膜が積層された積層構造を有しても良い。合成樹脂として例えば、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレンなどが挙げられる。
活物質層の少なくとも一部、又は、セパレータには、液状の電解質(電解液)が含浸されている。この電解液は、溶媒中に電解質塩が溶解されており、添加剤など他の材料を含んでいても良い。
以下の手順により、図3に示したラミネートフィルム型の二次電池30を作製した。
実施例1-1と同様に、二次電池を作製したが、負極材中のケイ素化合物の粉末表面を被覆する被膜層の有機高分子の種類を変更した。実施例1-2ではポリアクリル酸を、実施例1-3ではポリアクリル酸ナトリウムを、実施例1-4ではポリプロピレンカーボネートを、実施例1-5ではカルボキシメチルセルロースナトリウムを、実施例1-6ではポリプロピレンカーボネートを、実施例1-7ではポリエチレンを、それぞれ被膜層用有機高分子として用いた。
(比較例1-1)
負極材中のケイ素化合物の粉末表面を被覆する被膜層を形成しないことを除き、実施例1-1と同様に、二次電池を作製した。
負極材を製造する際のケイ素化合物のバルク内酸素量を調整したことを除き、実施例1-1と同様に、二次電池の製造を行った。この場合、気化出発材の比率や温度を変化させ堆積される酸素量を調整した。実施例2-1~2-5、比較例2-1、2-2における、SiOxで表されるケイ素化合物のxの値を表2中に示した。
基本的に実施例1-1と同様に二次電池の製造を行ったが、ケイ素化合物のバルク改質時の、Li化合物作製時の電位、電流量、Liの挿入離脱手法を制御し、ケイ素化合物に生成される含有物の状態を変化させた。電気化学的に改質すると、LiF、Li2CO3、Li2Oが表面に、内部にLi2SiO3、Li6Si2O7、Li4SiO4が生成する。また、水洗することで表面のLi化合物を除去することができる。これにより、実施例3-1では、ケイ素化合物表面にLiF、Li2CO3、Li2Oが、内部にLi2SiO3、Li6Si2O7、Li4SiO4が生成した状態とした。実施例3-2では、ケイ素化合物の表面のLi化合物を除去し、内部にLi2SiO3、Li6Si2O7、Li4SiO4が存在する状態とした。
基本的に実施例1-1と同様に二次電池の製造を行ったが、ケイ素化合物のバルク改質を行わなかった。
基本的に実施例1-1と同様に二次電池の製造を行ったが、ケイ素化合物粒子に有機高分子(ポリフッ化ビニリデン)の被膜層を作製する際に、その有機高分子の量を調節した。具体的には、負極活物質粒子をポリフッ化ビニリデンNMP溶液に浸し、乾燥させる工程を、所定の含有量となるまで繰り返した。具体的なポリフッ化ビニリデンの含有量を表4中に示した。
ケイ素化合物粒子に有機高分子(ポリフッ化ビニリデン)の被膜層を形成しないことを除き、実施例1-1と同様に二次電池の製造を行った。
実施例5-1~5-3では、基本的に実施例1-1と同様に二次電池の製造を行ったが、熱分解CVD法を用いて、ケイ素化合物(酸化ケイ素材粒子)表層部に炭素層を成膜する際の炭素量を調整した。実施例5-4では、ケイ素化合物表面への炭素層の成膜を行わないことの他は実施例1-1と同様に二次電池の製造を行った。
実施例6-1~6-4では、基本的に実施例1-1と同様に二次電池の製造を行ったが、電気化学的改質法を行う際の処理温度を変えることによって、ケイ素化合物表層をXPSで測定した場合における、C1sの結合エネルギー287.5±1.0eV付近のピーク面積Aと、284.0±1.0eV付近のピーク面積Bの関係A/Bを変化させた。
以下のように炭素系材料を含む負極を作製したことの他は、実施例1-1と同様にして二次電池の製造を行った。ケイ素化合物と、炭素系材料のメディアン径を調節しシェイカーで混合後、電極化し、ケイ素化合物の周囲に炭素系材料を存在させた状態の負極を作成した。実施例7-1~7-5のそれぞれのケイ素化合物のメディアン径、並びに、炭素系材料のメディアン径及び混合量は、表7中に示した通りである。
ケイ素化合物の結晶性を変化させた他は、実施例1-1と同様に二次電池の製造を行った。結晶性の変化はLiの挿入、脱離後の非大気雰囲気下の熱処理で制御可能である。実施例8-1~8-8のケイ素化合物の半値幅を表8中に示した。実施例8-1では結晶子サイズを1.542nmと算出しているが、解析ソフトを用いフィッティングした結果であり、実質的にピークは得られていない。よって実施例8-1のケイ素化合物は実質的に非晶質であると言える。
ケイ素化合物のメディアン径を変化させた他は、実施例1-1と同様に二次電池の製造を行った。実施例9-1~9-4のケイ素化合物のメディアン径を表9中に示した。
実施例1-1と同様に、ケイ素化合物の改質を電気化学的手法により行い、二次電池を製造した。
ケイ素化合物の改質をLiの熱ドープ法により行った他は、実施例1-1と同様に二次電池を製造した。
ケイ素化合物へのLi導入をせず改質を行わないことの他は、実施例1-1と同様に二次電池を製造した。
ケイ素化合物を含む負極活物質粒子を有する負極材に加え、炭素系負極材を含む負極を作製したことの他は、実施例1-1と同様にして二次電池の製造を行った。ケイ素化合物のメディアン径D50(Y)、炭素系負極材のメディアン径D50(X)、及びX/Yの値を表11中に示す。
Claims (20)
- 負極活物質粒子を有する非水電解質二次電池用負極材であって、
前記負極活物質粒子がSiOx(0.5≦x≦1.6)で表されるケイ素化合物を有し、
前記ケイ素化合物が表面又は内部にLi化合物を含み、
前記負極活物質粒子が前記ケイ素化合物の表面を被覆する有機高分子からなる被膜層を有する
ことを特徴とする非水電解質二次電池用負極材。 - 前記有機高分子が、分子中にフルオロエチレン基、カルボキシル基、ヒドロキシ基及び炭酸エステル基のうちの少なくとも1つを含むことを特徴とする請求項1に記載の非水電解質二次電池用負極材。
- 前記有機高分子が、ポリアクリル酸及びそのアルカリ金属塩、カルボキシメチルセルロース及びそのアルカリ金属塩、ポリビニルアルコール、ポリカーボネート、ポリフッ化ビニリデン、並びに、ポリ四フッ化ビニリデンのうちの少なくとも1つを含むことを特徴とする請求項1又は請求項2に記載の非水電解質二次電池用負極材。
- 前記負極活物質粒子の全体に対する前記有機高分子の含有量が0.01質量%以上5質量%未満であることを特徴とする請求項1から請求項3のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記有機高分子が少なくとも一部に島状構造を有することを特徴とする請求項1から請求項4のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物の表面にLi2CO3、Li2O及びLiFのうちの少なくとも1つのLi化合物が存在することを特徴とする請求項1から請求項5のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物の内部にLi4SiO4、Li6Si2O7、Li2SiO3のうちの少なくとも1つのLi化合物が存在することを特徴とする請求項1から請求項6のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物の少なくとも一部が炭素系化合物で被覆されていることを特徴とする請求項1から請求項7のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記炭素系化合物の被覆量が、前記ケイ素化合物及び前記炭素系化合物の合計に対し15質量%以下であることを特徴とする請求項8に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物表層をXPSで測定した場合において、C1sの結合エネルギー287.5±1.0eV付近のピーク面積Aと、284.0±1.0eV付近のピーク面積Bが、0.05≦A/B≦3.00の関係を満たすことを特徴とする請求項8又は請求項9に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物表層をXPSで測定した場合において、C1sの結合エネルギー287.5±1.0eV付近のピーク面積Aと、284.0±1.0eV付近のピーク面積Bが、0.10≦A/B≦1.00の関係を満たすことを特徴とする請求項8又は請求項9に記載の非水電解質二次電池用負極材。
- 前記有機高分子からなる被膜層が、前記ケイ素化合物よりもメディアン径の小さい粒子状の炭素系材料を含有していることを特徴とする請求項1から請求項11のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記ケイ素化合物のX線回折により得られる(111)結晶面に起因する回折ピークの半値幅(2θ)が1.2°以上であり、その結晶面に起因する結晶子サイズが7.5nm以下であることを特徴とする請求項1から請求項12のいずれか1項に記載の非水電解質二次電池用負極材。
- 前記Li化合物が含まれるケイ素化合物が、電気化学的手法を含む工程で作製されたものであることを特徴とする請求項1から請求項13のいずれか1項に記載の非水電解質二次電池用負極材。
- 請求項1から請求項14のいずれか1項に記載の非水電解質二次電池用負極材を用いたことを特徴とする非水電解質二次電池用負極。
- さらに炭素系負極材を含むことを特徴とする請求項15に記載の非水電解質二次電池用負極。
- 前記ケイ素化合物のメディアン径Yと前記炭素系負極材のメディアン径XがX/Y≧1の関係を満たすことを特徴とする請求項16に記載の負非水電解質二次電池用負極。
- 請求項15から請求項17のいずれか1項に記載の負極を用いたことを特徴とする非水電解質二次電池。
- 非水電解質二次電池用負極材に含まれる負極活物質粒子の製造方法であって、
SiOx(0.5≦x≦1.6)で表されるケイ素化合物を作製する工程と、
前記ケイ素化合物にLiを挿入することにより、該ケイ素化合物の表面若しくは内部又はその両方にLi化合物を生成させて該ケイ素化合物を改質する工程と、
前記ケイ素化合物の表面を有機高分子からなる被膜層で被覆する工程と
により前記負極活物質粒子を製造することを特徴とする負極活物質粒子の製造方法。 - 前記ケイ素化合物を改質する工程を電気化学的手法により行うことを特徴とする請求項19に記載の負極活物質粒子の製造方法。
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CN105917499B (zh) | 2019-05-07 |
JP6474548B2 (ja) | 2019-02-27 |
JP2015156328A (ja) | 2015-08-27 |
KR102473873B1 (ko) | 2022-12-06 |
EP3096379A4 (en) | 2017-07-19 |
KR102309192B1 (ko) | 2021-10-06 |
KR20210124504A (ko) | 2021-10-14 |
US20190334167A1 (en) | 2019-10-31 |
EP3096379B1 (en) | 2020-02-26 |
EP3096379A1 (en) | 2016-11-23 |
US20170040599A1 (en) | 2017-02-09 |
CN105917499A (zh) | 2016-08-31 |
US10396351B2 (en) | 2019-08-27 |
KR20160110380A (ko) | 2016-09-21 |
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