WO2016203696A1 - 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、並びに非水電解質二次電池用負極材の製造方法 - Google Patents
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、並びに非水電解質二次電池用負極材の製造方法 Download PDFInfo
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Definitions
- the present invention relates to a negative electrode active material for a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery, and a method for producing a negative electrode material for a nonaqueous electrolyte secondary battery.
- 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 above lithium ion secondary battery includes a positive electrode, a negative electrode, and a separator together with an electrolyte, and the negative electrode includes a negative electrode active material involved in a charge / discharge reaction.
- the negative electrode active material As the negative electrode active material, a carbon material is widely used, but further improvement in battery capacity is required due to recent market demand.
- silicon As a negative electrode active material, use of silicon as a negative electrode active material has been studied. This is because the theoretical capacity of silicon (4199 mAh / g) is 10 times or more larger than the theoretical capacity of graphite (372 mAh / g), so that significant improvement in battery capacity can be expected.
- the development of a siliceous material as a negative electrode active material has been examined not only for silicon itself but also for compounds represented by alloys and oxides.
- the shape of the active material has been studied from a standard coating type for carbon materials to an integrated type directly deposited on a current collector.
- 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 of the negative electrode active material. Further, an ionic material is generated inside the active material, and the negative electrode active material is easily broken. When the negative electrode active material surface layer is cracked, a new surface is generated thereby increasing the reaction area of the active material. At this time, a decomposition reaction of the electrolytic solution occurs on the new surface, and a coating 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, refer to 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.
- the molar ratio of oxygen to silicon in the negative electrode active material is set to 0.1 to 1.2, and the difference between the maximum and minimum molar ratios in the vicinity of the active material and current collector interface The active material is controlled within a range of 0.4 or less (see, for example, Patent Document 7).
- a metal oxide containing lithium is used (see, for example, Patent Document 8).
- a hydrophobic layer such as a silane compound is formed on the surface layer of the siliceous material (see, for example, Patent Document 9).
- Patent Document 10 conductivity is imparted by using silicon oxide and forming a graphite film on the surface layer.
- Patent Document 10 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 in order to improve high battery capacity and cycle characteristics (see, for example, Patent Document 11).
- silicon oxide in which the atomic ratio of silicon and oxygen is controlled to 1: y (0 ⁇ y ⁇ 2) is used (see, for example, Patent Document 12).
- a mixed electrode of silicon and carbon is prepared and the silicon ratio is designed to be 5 wt% or more and 13 wt% or less (see, for example, Patent Document 13).
- lithium ion secondary battery As described above, in recent years, small electronic devices typified by mobile terminals and the like have been improved in performance and multifunction, and the lithium ion secondary battery as the main power source is required to increase the battery capacity. ing. As one method for solving this problem, development of a lithium ion secondary battery composed of a negative electrode using a siliceous material as a main material is desired.
- a lithium ion secondary battery using a siliceous material is desired to have battery characteristics close to those of a lithium ion secondary battery using a carbon material.
- the use of silicon oxide modified by insertion and partial desorption of Li as the negative electrode active material has improved the cycle retention rate and initial efficiency of the battery.
- the modified silicon oxide since the modified silicon oxide has been modified using Li, its water resistance is relatively low. For this reason, the slurry containing the modified silicon oxide prepared during the production of the negative electrode is not sufficiently stabilized, and gas may be generated due to aging of the slurry. In some cases, it is difficult to use a device or the like that is used in general, or it is difficult to use.
- the present invention has been made in view of the above problems, and provides a negative electrode active material for a non-aqueous electrolyte secondary battery that has high stability with respect to an aqueous slurry, high capacity, and good cycle characteristics and initial efficiency.
- the purpose is to do.
- the present invention has negative electrode active material particles, and the negative electrode active material particles contain a silicon compound containing a Li compound (SiO x : 0.5 ⁇ x ⁇ 1.6).
- a negative electrode active material for a non-aqueous electrolyte secondary battery wherein at least part of the surface of the silicon compound is coated with a carbon coating, or the surface of the silicon compound or the surface of the carbon coating, or
- a negative electrode active for a non-aqueous electrolyte secondary battery wherein at least a part of both of them is coated with a composite layer containing a composite made of an amorphous metal oxide and a metal hydroxide.
- negative electrode active material particles containing a silicon compound are composed of amorphous metal oxide and metal hydroxide on the outermost surface. Since the composite layer containing the composite is included, the water resistance against the aqueous slurry is high. Further, when the composite is amorphous, Li is easily exchanged. Further, the present invention is excellent in conductivity because at least a part of the surface of the silicon compound is coated with a carbon film. Therefore, if the negative electrode active material of the present invention is used, a non-aqueous electrolyte secondary battery having a high battery capacity and a good cycle maintenance ratio utilizing the original characteristics of silicon oxide modified with Li can be industrially produced. Manufacturing in an advantageous production.
- the metal oxide and the metal hydroxide contain at least one element selected from aluminum, magnesium, titanium, and zirconium.
- the slurry becomes more stable at the time of electrode preparation.
- the thickness of the composite layer is preferably 10 nm or less. Moreover, it is particularly preferable that the thickness of the composite layer is 5 nm or less.
- the thickness of the composite layer is 10 nm or less, particularly 5 nm or less, the resistance of the silicon-based active material particles does not become excessively high, and good battery characteristics can be obtained.
- the silicon compound preferably contains Li 2 SiO 3 as the Li compound.
- Li silicate such as Li 2 SiO 3 is relatively stable as a Li compound, better battery characteristics can be obtained.
- the silicon compound has a peak derived from a SiO 2 region given to -95 to -150 ppm as a chemical shift value obtained from a 29 Si-MAS-NMR spectrum.
- the amount of Li compound such as Li silicate in the silicon compound is not excessive, and the SiO 2 component remains to some extent, so that the stability to the slurry during electrode preparation is further improved. .
- the silicon compound has a peak intensity A derived from Li 2 SiO 3 given in the vicinity of ⁇ 75 ppm as a chemical shift value obtained from the 29 Si-MAS-NMR spectrum, and SiO given to ⁇ 95 to ⁇ 150 ppm.
- the intensity B of the peak derived from the two regions preferably satisfies the relationship A> B.
- the silicon compound if the amount of Li 2 SiO 3 is larger with respect to the SiO 2 component, it becomes a negative electrode active material that can sufficiently obtain the effect of improving battery characteristics by inserting Li.
- a test cell comprising a negative electrode and a counter electrode lithium prepared by using a negative electrode active material obtained by mixing the negative electrode active material for a nonaqueous electrolyte secondary battery and a carbon-based active material is charged and discharged, and a discharge capacity is obtained.
- the negative electrode active material for a non-aqueous electrolyte secondary battery It is preferable that the potential V of the negative electrode has a peak in the range of 0.40 V to 0.55 V at the time of discharging in which a current flows so as to desorb lithium.
- the above-mentioned peak in the V-dQ / dV curve is similar to the peak of the siliceous material, and the discharge curve on the higher potential side rises sharply, so that the capacity is easily developed when designing the battery.
- the half width (2 ⁇ ) of the diffraction peak attributed to the Si (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 preferably 7.5 nm or less.
- the silicon-based active material having such a half width and crystallite size has low crystallinity and a small amount of Si crystals, the battery characteristics can be improved.
- the median diameter of the silicon compound is preferably 0.5 ⁇ m or more and 15 ⁇ m or less.
- the median diameter is 0.5 ⁇ m or more, the area where a side reaction occurs on the surface of the silicon compound is small, and therefore, Li is not consumed excessively and the cycle maintenance rate of the battery can be maintained high. Further, if the median diameter is 15 ⁇ m or less, the expansion at the time of inserting Li is small, it is difficult to crack, and cracks are hardly generated. Furthermore, since the expansion of the silicon compound is small, for example, a negative electrode active material layer in which a carbon active material is mixed with a commonly used silicon-based active material is not easily destroyed.
- the present invention provides a nonaqueous electrolyte secondary battery comprising any one of the above negative electrode active materials for nonaqueous electrolyte secondary batteries.
- Such a secondary battery has a high cycle maintenance ratio and initial efficiency, and can be manufactured industrially.
- the present invention provides a method for producing a negative electrode material for a non-aqueous electrolyte secondary battery including negative electrode active material particles, which has a general formula SiO x (0.5 ⁇ x ⁇ 1.6). ), A step of forming a carbon film on the surface of the silicon oxide particles, and insertion and desorption of Li from the silicon oxide particles coated with the carbon film. A step of modifying the silicon oxide particles, and a step of forming a composite layer including a composite of an amorphous metal oxide and a metal hydroxide on the surface of the modified silicon oxide particles.
- a negative electrode material for a non-aqueous electrolyte secondary battery is manufactured using the silicon oxide particles having the composite layer and having the composite layer formed therein.
- the nonaqueous negative electrode which has the high battery capacity and the favorable cycle maintenance factor which utilized the original characteristic of the silicon oxide modified using Li A material can be obtained. Furthermore, since the negative electrode material manufactured in this way contains the silicon-based active material particles having the composite layer as described above, the slurry produced at the time of manufacturing the negative electrode becomes stable. That is, a negative electrode material capable of industrially producing a secondary battery can be obtained.
- the composite layer forming step it is preferable to form the composite layer on the surface of the modified silicon oxide particles by hydrolysis and dehydration condensation of metal alkoxide.
- the negative electrode active material of the present invention can improve the stability of the slurry produced during the production of the secondary battery, and if this slurry is used, an industrially usable coating film can be formed. Capacity, cycle characteristics, and initial charge / discharge characteristics can be improved. Moreover, the secondary battery of the present invention containing this negative electrode active material can be produced industrially superiorly, and the battery capacity, cycle characteristics, and initial charge / discharge characteristics are good. 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 method for producing a negative electrode material of the present invention provides a negative electrode material that can improve the stability of a slurry produced during the production of a secondary battery and can improve battery capacity, cycle characteristics, and initial charge / discharge characteristics. Can be manufactured.
- Lithium ion secondary batteries using silicon-based active materials as the main material are expected to have cycle characteristics and initial efficiency close to those of lithium ion secondary batteries using carbon materials.
- silicon-based active material modified with Li in order to obtain cycle characteristics and initial efficiency close to those of a secondary battery, it is difficult to produce a stable slurry, and it is difficult to produce a good quality negative electrode.
- the present inventors have made extensive studies in order to obtain a negative electrode active material capable of easily producing a nonaqueous electrolyte secondary battery having a high battery capacity and good cycle characteristics and initial efficiency.
- the present invention has been reached.
- the negative electrode active material of the present invention includes silicon-based active material particles having a silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6) containing a Li compound.
- the negative electrode active material has a carbon film formed on at least a part of the surface of the silicon compound.
- the negative electrode active material is coated with a composite layer including a composite composed of an amorphous metal oxide and a metal hydroxide, at least a part of the surface of the silicon compound or the surface of the carbon film, or both of them. Has been.
- FIG. 1 shows an outline of the vicinity of the surface layer portion of the silicon compound 1.
- a carbon film 2 is formed on the surface of the silicon compound 1.
- the carbon film is formed on a part of the surface of the silicon compound.
- the carbon film may be formed on the entire surface of the silicon compound.
- a composite layer 3 including a composite made of amorphous aluminum oxide and aluminum hydroxide is formed on the surface of the silicon compound 1 and the surface of the carbon coating 2.
- FIG. 1 illustrates the case where the composite of the composite layer 3 contains an aluminum element, it is not particularly limited to this and may contain other metal elements.
- the composite layer 3 has an aluminum oxide region 3a and an aluminum hydroxide region 3b as shown in FIG.
- the silicon-based active material particles have a composite layer containing a composite composed of an amorphous metal oxide and a metal hydroxide on the outermost surface, In contrast, the water resistance is high. Conventionally, an aqueous slurry containing a silicon oxide modified by insertion and desorption of Li changes with time and gas is generated, which is not suitable for mass production.
- the silicon-based active material particles since the silicon-based active material particles have the composite layer as described above, it is difficult for gas generation due to aging of the slurry to occur, and a stable coating film can be obtained. Can be secured sufficiently. Further, when the composite is amorphous, Li is easily exchanged.
- the present invention is excellent in conductivity because at least a part of the surface of the silicon compound is coated with a carbon film. Therefore, if the negative electrode active material of the present invention is used, a non-aqueous electrolyte secondary battery having a high battery capacity and a good cycle maintenance ratio utilizing the original characteristics of silicon oxide modified with Li can be industrially produced. Manufacturing in an advantageous production.
- FIG. 2 shows a cross-sectional view of a negative electrode containing the negative electrode active material 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.
- the negative electrode current collector 11 may not be provided in the negative electrode of the nonaqueous electrolyte secondary battery of the present invention.
- 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 may not be 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 may contain a plurality of types of negative electrode active materials such as carbon-based active materials in addition to silicon-based active material particles. Furthermore, other materials such as a thickener (also referred to as “binder” or “binder”) or a conductive aid may be included in battery design. The shape of the negative electrode active material may be particulate.
- the negative electrode active material of the present invention includes silicon-based active material particles made of SiO x (0.5 ⁇ x ⁇ 1.6).
- the silicon-based active material particles are a silicon oxide material (SiO x : 0.5 ⁇ x ⁇ 1.6), and the composition is preferably such that x is close to 1. This is because high cycle characteristics can be obtained.
- the composition of the silicon oxide material in the present invention does not necessarily mean 100% purity, and may contain a small amount of impurity elements and Li.
- the lower the crystallinity of the silicon compound the better.
- the half-value width (2 ⁇ ) of a diffraction peak caused by the (111) crystal plane obtained by X-ray diffraction of a silicon-based active material using Cu—K ⁇ rays is 1.2 ° or more, and It is desirable that the crystallite size resulting from the crystal plane is 7.5 nm or less.
- the median diameter of the silicon compound is not particularly limited, but is preferably 0.5 ⁇ m or more and 15 ⁇ m or less. This is because, within this range, it is easy to occlude and release lithium ions during charging and discharging, and the silicon-based active material particles are difficult to break. If the median diameter is 0.5 ⁇ m or more, the surface area is not too large, so that side reactions are unlikely to occur during charging and discharging, and the battery irreversible capacity can be reduced. On the other hand, a median diameter of 15 ⁇ m or less is preferable because the silicon-based active material particles are difficult to break and a new surface is difficult to appear.
- the silicon-based active material includes Li 2 SiO 3 as a Li compound contained in the silicon compound. Since Li silicate such as Li 2 SiO 3 is relatively more stable than other Li compounds, a silicon-based active material containing these Li compounds can obtain more stable battery characteristics. These Li compounds can be obtained by selectively changing a part of the SiO 2 component generated inside the silicon compound to the Li compound and modifying the silicon compound.
- the Li compound inside the silicon compound 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.
- XPS ⁇ Device X-ray photoelectron spectrometer, ⁇ X-ray source: Monochromatic Al K ⁇ ray, ⁇ X-ray spot diameter: 100 ⁇ m, Ar ion gun sputtering conditions: 0.5 kV 2 mm ⁇ 2 mm.
- 29 Si MAS NMR (magic angle rotating nuclear magnetic resonance) Apparatus 700 NMR spectrometer manufactured by Bruker, ⁇ Probe: 4mmHR-MAS rotor 50 ⁇ L, Sample rotation speed: 10 kHz, -Measurement environment temperature: 25 ° C.
- an electrochemical method when modifying the silicon compound, an electrochemical method, a modification by oxidation-reduction reaction, and a physical method such as thermal doping can be used.
- the silicon compound when modified using an electrochemical technique and oxidation-reduction modification, the battery characteristics of the negative electrode active material are improved.
- the modification may be performed not only by inserting Li into the silicon compound but also by detaching Li from the silicon compound. Thereby, stability with respect to slurry, such as water resistance of a negative electrode active material, improves more.
- the silicon compound has a peak derived from the SiO 2 region given as -95 to -150 ppm as a chemical shift value obtained from the 29 Si-MAS-NMR spectrum. In this way, the stability to the slurry is further improved by leaving the SiO 2 region to some extent without changing all the SiO 2 regions in the silicon compound to the Li compound by the modification.
- the peak intensity A derived from Li 2 SiO 3 given in the vicinity of ⁇ 75 ppm as a chemical shift value obtained from the 29 Si—MAS-NMR spectrum of the silicon compound is ⁇ 95 to It is preferable that the intensity B of the peak derived from the SiO 2 region given at ⁇ 150 ppm satisfies the relationship of A> B.
- the silicon compound if the amount of Li 2 SiO 3 is relatively large when the SiO 2 component is used as a reference, the effect of improving battery characteristics by inserting Li can be sufficiently obtained.
- the silicon-based active material particles have a composite layer containing a composite made of an amorphous metal oxide and a metal hydroxide on the surface of the silicon compound or the surface of the carbon coating.
- the composite composed of the metal oxide and the metal hydroxide is preferably produced by hydrolysis and dehydration condensation of a metal alkoxide. This is because the metal oxide region and the hydroxide region are compatible in the composite layer.
- the metal oxide and metal hydroxide preferably contain at least one element selected from aluminum, magnesium, titanium, and zirconium.
- the outermost layer portion of the composite layer has a structure close to Al (OH) 3 . This is because the slurry becomes more stable during the production of the negative electrode.
- a composite layer by sol-gel reaction treatment of aluminum isopropoxide.
- a thin composite layer including a composite composed of amorphous aluminum oxide and aluminum hydroxide can be formed on the surface layer of the silicon-based active material.
- the thickness of the composite layer is preferably 10 nm or less, and more preferably 5 nm or less. If the thickness of the composite layer is 10 nm or less, although it depends on the composition of the mixture, the electric resistance does not become too high, so the battery characteristics are improved. Further, when the film thickness is about 2 to 3 nm, it is possible to further improve the stability to the slurry while suppressing an increase in electrical resistance.
- the film thickness of the composite layer can be confirmed with a TEM (transmission electron microscope).
- a test cell composed of a negative electrode and a counter electrode lithium prepared by using the negative electrode active material obtained by mixing the negative electrode active material and the carbon-based active material of the present invention was charged and discharged, and the discharge capacity Q
- the negative electrode at the time of discharge in which a current flows so that the negative electrode active material desorbs lithium It is preferable that the potential V has a peak in the range of 0.40V to 0.55V.
- the above-mentioned peak in the V-dQ / dV curve is similar to the peak of the siliceous material, and the discharge curve on the higher potential side rises sharply, so that the capacity is easily developed when designing the battery.
- silicon oxide particles represented by SiO x (0.5 ⁇ x ⁇ 1.6) are produced.
- a carbon film is formed on the surface of the silicon oxide particles.
- the silicon oxide particles are modified by inserting and removing Li from the silicon oxide particles.
- a Li compound can be generated inside or on the surface of the silicon oxide particles.
- a composite layer including a composite made of an amorphous metal oxide and a metal hydroxide is formed on the surface of the modified silicon oxide particles.
- a negative electrode material and a negative electrode can be produced by mixing with a conductive additive or a binder.
- the negative electrode material is manufactured by the following procedure, for example.
- 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 film is formed on the surface layer of the obtained powder material (silicon compound).
- the carbon coating is effective for further improving the battery characteristics of the negative electrode active material.
- Pyrolysis CVD is desirable as a method for forming a carbon film on the surface layer of the powder material.
- silicon oxide powder is set in a furnace, the furnace is filled with hydrocarbon gas, and the temperature in the furnace is raised.
- 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 unintended disproportionation of silicon oxide can be suppressed.
- Hydrocarbon gas is not particularly limited, 3 ⁇ n of C n H m composition it is desirable. This is because the low production cost and the physical properties of the decomposition products are good.
- the in-bulk reformer 20 includes a bathtub 27 filled with an organic solvent 23, a positive electrode (lithium source, reforming source) 21 disposed in the bathtub 27 and connected to one of the power sources 26, And a separator 24 provided between the positive electrode 21 and the powder storage container 25.
- the powder storage container 25 is connected to the other side of the power source 26.
- the powder storage container 25 stores silicon oxide powder 22.
- a silicon compound (silicon oxide particles) is stored in the powder storage container, and a voltage is applied to the powder storage container and the positive electrode (lithium source) storing the silicon oxide particles by a power source. Thereby, since lithium can be inserted into and desorbed from the silicon oxide particles, the silicon oxide powder 22 can be modified.
- 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, lithium oxide, lithium cobaltate, lithium olivine, lithium nickelate, and lithium vanadium phosphate.
- the modification may be performed using a thermal dope method.
- the powder material can be modified by mixing with LiH powder or Li powder and heating in a non-oxidizing atmosphere.
- a non-oxidizing atmosphere for example, an Ar atmosphere can be used as the non-oxidizing atmosphere.
- LiH powder or Li powder and silicon oxide powder are sufficiently mixed in an Ar atmosphere, sealed, and homogenized by stirring the sealed container. Thereafter, heating is performed in the range of 700 ° C. to 750 ° C. for reforming.
- a method of sufficiently cooling the heated powder and then washing with alcohol, alkaline water, weak acid or pure water can be used.
- a composite layer including a composite made of an amorphous metal oxide and a metal hydroxide is formed on the surface of the modified silicon oxide particles.
- the composite layer is preferably formed by hydrolysis and dehydration condensation of a metal alkoxide. If it does in this way, a hydrolysis and dehydration condensation of a metal alkoxide will occur continuously, and a complex can be efficiently generated so that a metal oxide field and a metal hydroxide field may be compatible. More specifically, for example, the composite layer can be formed by the following procedure.
- dehydrated ethanol, a silicon compound after modification of a mass of a quarter of the mass of dehydrated ethanol, and Al isopropoxide equivalent to 1.5% by mass of the modified silicon compound are put into a container, Stir for 3.5 hours. After stirring, ethanol is removed by suction filtration, and the silicon compound is vacuum-dried at 120 ° C. for 12 hours. At this time, the film thickness of the composite layer can be controlled by changing the mass of Al isopropoxide added simultaneously with the modifier.
- a silicon-based active material containing silicon oxide particles having the above composite layer and, if necessary, a carbon-based active material are mixed, and these negative electrode active materials are mixed with other materials such as a binder and a conductive additive.
- an organic solvent or water is added to form a slurry.
- the negative electrode mixture slurry is applied to the surface of the negative electrode current collector 11 and dried to form the negative electrode active material layer 12. At this time, a heating press or the like may be performed as necessary. As described above, the negative electrode of the nonaqueous electrolyte secondary battery of the present invention can be produced.
- Lithium ion secondary battery a laminated film type lithium ion secondary battery will be described as a specific example of the nonaqueous electrolyte secondary battery of the present invention.
- a laminated film type lithium ion secondary battery 30 shown in FIG. 4 is one in which a wound electrode body 31 is accommodated mainly in a sheet-like exterior member 35.
- the wound electrode body 31 has a separator between a positive electrode and a negative electrode, and is wound.
- 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 32 and 33 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 any one or more of positive electrode materials capable of occluding and releasing lithium ions, and other materials such as a positive electrode binder, a positive electrode conductive additive, and a dispersant depending on the design. May be included. In this case, details regarding the positive electrode binder and the positive electrode conductive additive are the same as, for example, the negative electrode binder and 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 vary depending on the battery charge / discharge state, but are generally expressed as 0.05 ⁇ x ⁇ 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 ), lithium nickel composite oxide (Li x NiO 2 ), and lithium nickel cobalt composite oxide.
- Examples of the lithium nickel cobalt composite oxide include lithium nickel cobalt aluminum composite oxide (NCA) and lithium nickel cobalt manganese composite oxide (NCM).
- 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 (0 ⁇ u ⁇ 1)). Is mentioned. If these positive electrode materials are used, a high battery capacity can be obtained, and excellent cycle characteristics can also be obtained.
- the negative electrode has the same configuration as the negative electrode 10 for lithium ion secondary battery in FIG. 2 described above, and has, for example, a negative electrode active material layer on both surfaces of the current collector.
- This 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. Thereby, precipitation 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 similarly, the negative electrode active material layer is 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 to perform a stable battery design.
- the separator separates the positive electrode and the negative electrode, and allows lithium ions to pass through while preventing a short circuit due to contact between the two electrodes.
- 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.
- 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 electrolyte 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 include, for example, one or more light metal salts such as a lithium salt.
- the lithium salt include lithium hexafluorophosphate (LiPF6) and lithium tetrafluoroborate (LiBF4).
- 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 ion conductivity is obtained.
- a positive electrode is manufactured using the positive electrode material described above.
- a positive electrode active material and, if necessary, a positive electrode binder and a positive electrode conductive additive are mixed to form a positive electrode mixture, which is 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, heating may be performed or compression may be 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.
- the laminated film type secondary battery 30 can be manufactured as described above.
- the negative electrode utilization rate during charge / discharge is preferably 93% or more and 99% or less. If the negative electrode utilization rate is in the range of 93% or more, the initial charge efficiency does not decrease, and the battery capacity can be greatly improved. Moreover, if the negative electrode utilization rate is in the range of 99% or less, Li is not precipitated and safety can be ensured.
- Example 1-1 The laminate film type secondary battery 30 shown in FIG. 4 was produced by the following procedure.
- the positive electrode active material is 95 parts by mass of lithium nickel cobalt aluminum composite oxide (LiNi 0.7 Co 0.25 Al 0.05 O), 2.5 parts by mass of positive electrode conductive additive (acetylene black), and a positive electrode binder. (Polyvinylidene fluoride, PVDF) 2.5 parts by mass were mixed to obtain a positive electrode mixture.
- the positive electrode mixture was dispersed in an organic solvent (N-methyl-2-pyrrolidone, NMP) to obtain a paste slurry.
- 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, a positive electrode current collector having a thickness of 15 ⁇ m was used. Finally, compression molding was performed with a roll press.
- a negative electrode was produced.
- a silicon-based active material was prepared as follows. A raw material (vaporization starting material) mixed with metallic silicon and silicon dioxide is placed in a reactor, and the vaporized material in a vacuum atmosphere of 10 Pa is deposited on an adsorption plate and cooled sufficiently. It was pulverized with a take-out ball mill. After adjusting the particle size, the carbon film was coated by performing thermal CVD. Subsequently, LiH powder having a mass corresponding to 4% by mass with respect to the silicon compound coated with the carbon coating was mixed in an argon atmosphere and stirred with a shaker. Thereafter, the agitated powder was modified by heat treatment at 740 ° C. in an atmosphere control furnace.
- the modified silicon oxide particles were put into a mixed solution of dehydrated ethanol and Al isopropoxide, stirred, filtered and dried to remove ethanol. Thereby, a composite layer containing a composite of aluminum oxide and aluminum hydroxide was formed.
- the film thickness of the composite layer was 3 nm. Here, the film thickness was calculated from the amount of aluminum remaining in the filtrate after filtration.
- the negative electrode active material was prepared by blending the silicon-based active material prepared as described above and the carbon-based active material in a mass ratio of 1: 9.
- the carbon-based active material a mixture of natural graphite and artificial graphite coated with a pitch layer at a mass ratio of 5: 5 was used.
- the median diameter of the carbon-based active material was 20 ⁇ m.
- the produced negative electrode active material conductive additive 1 (carbon nanotube, CNT), conductive additive 2 (carbon fine particles having a median diameter of about 50 nm), styrene butadiene rubber (styrene butadiene copolymer, hereinafter referred to as SBR), Carboxymethylcellulose (hereinafter referred to as CMC) was mixed at a dry mass ratio of 92.5: 1: 1: 2.5: 3, and then diluted with pure water to obtain a negative electrode mixture slurry.
- SBR and CMC are negative electrode binders (negative electrode binder).
- the negative electrode current collector an electrolytic copper foil (thickness 15 ⁇ m) was used. Finally, the negative electrode mixture slurry was applied to the negative electrode current collector and dried in a vacuum atmosphere at 100 ° C. for 1 hour. The amount of deposition (also referred to as area density) of the negative electrode active material layer per unit area on one side of the negative electrode after drying was 5 mg / cm 2 .
- an electrolyte salt lithium hexafluorophosphate: LiPF 6
- FEC fluoroethylene carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- an electrolyte salt lithium hexafluorophosphate: LiPF 6
- the content of the electrolyte salt was 1.0 mol / kg with respect to the solvent.
- 1.5% by mass of vinylene carbonate (VC) was added to the obtained 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.
- the cycle characteristics were examined as follows. First, in order to stabilize the battery, charge and discharge was performed for 2 cycles at 0.2 C 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 499 cycles, and the discharge capacity was measured each time. Finally, the discharge capacity at the 500th cycle obtained by 0.2 C charge / discharge was divided by the discharge capacity at the second cycle to calculate a capacity retention rate (hereinafter also simply referred to as a maintenance rate). In the normal cycle, that is, from the 3rd cycle to the 499th cycle, charging and discharging were performed with a charge of 0.7 C and a discharge of 0.5 C.
- initial efficiency (initial discharge capacity / initial charge capacity) ⁇ 100.
- the ambient temperature was the same as when the cycle characteristics were examined.
- Example 1-2 to Example 1-4 A secondary battery was manufactured in the same manner as in Example 1-1, except that the metal oxide species and metal hydroxide species in the composite layer were changed to those containing the elements shown in Table 1.
- the metal oxide species and the metal hydroxide species can be changed by changing the type of metal alkoxide used for the sol-gel reaction when forming the composite layer.
- Example 1-1 A secondary battery was manufactured in the same manner as in Example 1-1, except that the steps of forming the carbon coating, modifying the silicon compound, and forming the composite layer were not performed after the production of the silicon compound.
- Example 1-3 After the formation of the silicon compound, a secondary battery was manufactured in the same manner as in Example 1-1 except that the carbon film was formed and the silicon compound was modified, but the composite layer was not formed. .
- the physical properties of the silicon compounds in the above Examples and Comparative Examples are as follows.
- the value x of the silicon compound represented by SiO x was 1.0, and the median diameter D 50 of the silicon compound was 4 ⁇ m.
- the half-value width (2 ⁇ ) of the diffraction peak caused by the Si (111) crystal plane obtained by X-ray diffraction of the unmodified silicon compound as in Comparative Example 1-1 and Comparative Example 1-2 is 2.
- the crystallite size attributable to the crystal plane Si (111) was 3.29 nm.
- the half-value width (2 ⁇ ) of the diffraction peak due to the Si (111) crystal plane obtained by X-ray diffraction of the modified silicon compound is 2.257.
- the crystallite size attributable to the crystal plane Si (111) was 3.77 nm. This is because part of the silicon compound was disproportionated and crystallization progressed because the thermal doping method was used for the modification.
- the silicon compound after modification contained Li 2 SiO 3 .
- Example 1-1 to 1-4 and Comparative Examples 1-2 and 1-3 the coating amount of the carbon coating was 5% by mass with respect to the total of the silicon compound and the carbon coating. Further, in all the above Examples and Comparative Examples, a peak derived from the SiO 2 region given as -95 to -150 ppm as a chemical shift value obtained from the 29 Si-MAS-NMR spectrum appeared.
- Comparative Example 1-1 and Comparative Example 1-2 the peak intensity A derived from Li 2 SiO 3 given in the vicinity of ⁇ 75 ppm as the chemical shift value obtained from the 29 Si-MAS-NMR spectrum and the above SiO 2
- the relationship with the intensity B of the peak derived from the region was A ⁇ B. In other examples and comparative examples, the above relationship was A> B.
- the 29 Si-MAS-NMR spectrum obtained in Example 1-1 is shown in FIG.
- a 2032 size coin cell type test cell was prepared from the negative electrode and the counter electrode lithium prepared as described above, and the discharge behavior was evaluated. More specifically, first, constant current and constant voltage charging was performed up to 0 V with the counter electrode Li, and the charging was terminated when the current density reached 0.05 mA / cm 2 . Then, constant current discharge was performed to 1.2V. The current density at this time was 0.2 mA / cm 2 . From the data obtained by such charging and discharging, a graph is drawn with the vertical axis representing the rate of change in capacity (dQ / dV) and the horizontal axis representing the voltage (V), where V is 0.4 to 0.55 (V). It was confirmed whether a peak was obtained in the range. As a result, peaks were confirmed in all Examples and Comparative Examples other than Comparative Examples 1-1 and 1-2.
- Table 1 shows the evaluation results of Examples 1-1 to 1-4 and Comparative Examples 1-1, 1-2, and 1-3.
- Example 1-1 to Example 1-4 in Table 1 in the secondary battery using the negative electrode active material of the present invention, battery characteristics such as cycle characteristics and initial efficiency are improved by reforming with Li. In addition to obtaining the effect, the generation of gas could be greatly suppressed. In particular, in Example 1-1, the generation of gas was confirmed only after a lapse of one week from the preparation of the slurry.
- Comparative Example 1-3 in which the composite layer was not formed on the modified silicon-based active material particles, gas was generated when 6 hours had elapsed since the slurry was created.
- gas was generated within 6 hours after slurry preparation. I can say that.
- the slurry after gas generation is difficult to handle because the peel strength from the copper foil (current collector) decreases.
- the pot life of the slurry is required to be at least 6 hours. Therefore, the negative electrode active material of Comparative Example 1-3 cannot be used for industrial production. I can say that.
- Example 2-1 and 2-2 Comparative Examples 2-1 and 2-2
- a secondary battery was manufactured in the same manner as Example 1-1 except that the amount of oxygen in the bulk of the silicon compound was adjusted. In this case, the amount of oxygen was adjusted by changing the ratio and temperature of the vaporized starting material.
- Table 2 shows the values of x of the silicon compounds represented by SiO x in Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2.
- Examples 3-1 to 3-6 A secondary battery was manufactured in the same manner as in Example 1-1, except that the thickness of the composite layer was changed as shown in Table 3.
- the film thickness was adjusted by changing the mass ratio of Al isopropoxide to dehydrated ethanol and the modified silicon compound.
- the film thickness can also be measured by TEM, but here the film thickness was calculated from the amount of aluminum remaining in the filtrate after filtration.
- the film thickness (3 nm) in Example 3-3 the image was confirmed by TEM, and it was confirmed that the calculated value of the film thickness obtained by the above calculation method substantially coincided with the film thickness value measured by TEM. .
- Example 4-1 to Example 4-5 A secondary battery was manufactured in the same manner as in Example 1-1 except that the film thickness of the composite layer was changed as shown in Table 4 and the modification method was an electrochemical method. More specifically, the reforming includes a mixed solvent having a volume ratio of ethylene carbonate and dimethyl carbonate of 3: 7 (electrolyte salt at a concentration of 1.3 mol / kg) in the apparatus shown in FIG. ) was subjected to bulk modification using an electrochemical method.
- the reforming includes a mixed solvent having a volume ratio of ethylene carbonate and dimethyl carbonate of 3: 7 (electrolyte salt at a concentration of 1.3 mol / kg) in the apparatus shown in FIG. ) was subjected to bulk modification using an electrochemical method.
- the composite layer thickness is 10 nm or less, and in addition to the effect of suppressing gas generation, the effect of improving battery characteristics is more sufficiently achieved. It turns out that it is obtained. Also in this case, it has been found that particularly good battery characteristic improvement effects can be obtained when the thickness of the composite layer is 5 nm or less, particularly 2 to 3 nm.
- Example 5-1 and 5-2 Except that the silicon compound does not have a peak derived from the SiO 2 region given to -95 to -150 ppm as the chemical shift value obtained from the 29 Si-MAS-NMR spectrum, it is the same as in Example 1-1. A secondary battery was produced. By increasing the amount of Li during the modification, the intensity of the peak derived from the SiO 2 region was greatly reduced. Thereafter, Li was desorbed from the silicon compound to the extent that it can withstand the aqueous slurry, thereby producing a silicon-based active material having no SiO 2 region that can be confirmed by NMR.
- Example 5-2 the reforming method was changed to an electrochemical method.
- Example 5-1 and 5-2 generation of gas was confirmed after 24 hours and 48 hours, respectively.
- Example 1-1 in which a slurry was prepared under the same conditions as in Example 5-1, or Example 5-2 and the presence or absence of the above peak
- Example 3-3 in which the slurry was produced under the same conditions, gas generation was confirmed after one week as described above. From this, it was found that the effect of suppressing the generation of gas is higher when the silicon-based active material contains a SiO 2 region that can be confirmed by NMR.
- Example 6-1 In the same manner as in Example 1-1, except that the silicon compound was such that the relationship between the peak intensity A derived from Li 2 SiO 3 and the peak intensity B derived from the SiO 2 region was A ⁇ B. A battery was produced. In this case, the amount of Li 2 SiO 3 was reduced by reducing the amount of Li during the modification, and the peak intensity A derived from Li 2 SiO 3 was reduced.
- Example 6-1 When a silicon dioxide region that can be confirmed by NMR is strongly left in the silicon compound, the direction is mild to gas generation (a direction in which gas generation is suppressed).
- the time until gas generation was evaluated to be the same one week as Example 1-1 satisfying the relationship A> B of peak intensity, but in actuality, the gas of Example 6-1 was evaluated. The time until generation is considered to be longer than the time until gas generation in Example 1-1. However, the initial efficiency in Example 6-1 was slightly lower than that in Example 1-1.
- Example 7-1 A secondary battery was fabricated in the same manner as in Example 1-1, except that the silicon-based active material had no peak in the V-dQ / dV curve where V was in the range of 0.40 V to 0.55 V. .
- the silicon compound (SiOx) In order for the discharge curve shape to rise sharper, the silicon compound (SiOx) needs to exhibit a discharge behavior similar to that of silicon (Si). When there is no peak in the above range, the silicon compound has a relatively gentle discharge curve. Therefore, when the assembled cell is used, the initial efficiency slightly decreases.
- Examples 8-1 to 8-9 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 of the silicon compound can be controlled by heat treatment in a non-air atmosphere after the silicon compound is produced. In the modification by the thermal doping method, a certain amount of heat is applied to the silicon compound. Therefore, in Examples 8-8 and 8-9, the material close to amorphous is modified by an electrochemical method in order to maintain low crystallinity.
- a high retention rate was obtained with a low crystalline material having a half width (2 ⁇ ) of 1.2 ° or more and a crystallite size attributable to the Si (111) plane of 7.5 nm or less.
- Example 9-1 to Example 9-6 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 as shown in Table 9.
- the maintenance rate was improved. This is presumably because the surface area of the silicon compound was not too large and the area where the side reaction occurred could be reduced.
- the median diameter is 15 ⁇ m or less, the particles are difficult to break during charging, and SEI (solid electrolyte interface) due to the new surface is difficult to be generated during charging and discharging, so that loss of reversible Li can be suppressed.
- 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
続いて、このような本発明の負極活物質を含む二次電池の負極の構成について説明する。
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、ケイ素系活物質粒子の他に炭素系活物質などの複数の種類の負極活物質を含んでいて良い。さらに、電池設計上、増粘剤(「結着剤」、「バインダー」とも呼称する)や導電助剤等の他の材料を含んでいても良い。また、負極活物質の形状は粒子状であって良い。
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℃。
続いて、本発明の非水電解質二次電池の負極の製造方法の一例を説明する。
次に、上記した本発明の非水電解質二次電池の具体例として、ラミネートフィルム型のリチウムイオン二次電池について説明する。
図4に示すラミネートフィルム型のリチウムイオン二次電池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。この巻回電極体31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。
負極は、上記した図2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、集電体の両面に負極活物質層を有している。この負極は、正極活物質剤から得られる電気容量(電池としての充電容量)に対して、負極充電容量が大きくなることが好ましい。これにより、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。
セパレータは正極と負極を隔離し、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。
最初に上記した正極材を用い正極電極を作製する。まず、正極活物質と、必要に応じて正極結着剤、正極導電助剤などを混合し正極合剤としたのち、有機溶剤に分散させ正極合剤スラリーとする。続いて、ナイフロール又はダイヘッドを有するダイコーターなどのコーティング装置で正極集電体に合剤スラリーを塗布し、熱風乾燥させて正極活物質層を得る。最後に、ロールプレス機などで正極活物質層を圧縮成型する。この時、加熱しても良く、また圧縮を複数回繰り返しても良い。
以下の手順により、図4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。
複合層における金属酸化物種及び金属水酸化物種を表1に示すような元素を含むものに変更したこと以外、実施例1-1と同様に、二次電池の製造を行った。金属酸化物種及び金属水酸化物種の変更は、複合層形成時のゾルゲル反応に使用する金属アルコキシドの種類を変更することで可能である。
ケイ素化合物の作製後に、炭素被膜の形成、ケイ素化合物の改質、及び複合層の形成のいずれの工程も行わなかった以外、実施例1-1と同様に、二次電池の製造を行った。
ケイ素化合物の作製後に、炭素被膜の形成を行ったが、ケイ素化合物の改質、及び複合層の形成は行わなかったこと以外、実施例1-1と同様に、二次電池の製造を行った。
ケイ素化合物の作製後に、炭素被膜の形成、及びケイ素化合物の改質を行ったが、複合層の形成は行わなかったこと以外、実施例1-1と同様に、二次電池の製造を行った。
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ることで、酸素量を調整した。実施例2-1、2-2、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。
複合層の膜厚を表3に示すように変更したこと以外、実施例1-1と同様に、二次電池の製造を行った。膜厚は、脱水エタノールと改質後のケイ素化合物に対するAlイソプロポキシドの質量比を変化させることで調整した。なお、膜厚はTEMでも測定可能であるが、ここでは濾過後の濾過液に残ったアルミニウム量から、膜厚を計算した。また、実施例3-3における膜厚(3nm)に関しては、TEMで画像を確認し、上記計算法で得た膜厚の算出値がTEMで測定する膜厚値とほぼ一致することを確認した。
複合層の膜厚を表4に示すように変更したことと、改質方法を電気化学的手法としたこと以外、実施例1-1と同様に、二次電池の製造を行った。より具体的には、改質は、図3に示した装置内で、エチレンカーボネート及びジメチルカーボネートの体積比が3:7の混合溶媒(電解質塩を1.3mol/kgの濃度で含んでいる。)中で電気化学法を用いバルク改質を行った。
ケイ素化合物を29Si-MAS-NMR スペクトルから得られるケミカルシフト値として-95~-150ppmに与えられるSiO2領域に由来するピークを持たないものとしたこと以外、実施例1-1と同様に二次電池を作製した。改質時にLi量を増加させることで、SiO2領域に由来するピークの強度を大幅に低減した。そして、その後、水系スラリーに耐えられる程度にまでケイ素化合物からLiを脱離することで、NMRで確認可能なSiO2領域が無いケイ素系活物質を作製した。
ケイ素化合物をLi2SiO3に由来するピークの強度Aと上記SiO2領域に由来するピークの強度Bとの関係がA<Bのものとしたこと以外、実施例1-1と同様に二次電池を作製した。この場合、改質時にLi量を減らすことで、Li2SiO3の量を減らし、Li2SiO3に由来するピークの強度Aを小さくした。
ケイ素系活物質をV-dQ/dV曲線において、Vが0.40V~0.55Vの範囲にピークが得られないものとしたこと以外、実施例1-1と同様に二次電池を作製した。
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。ケイ素化合物の結晶性の変化は、ケイ素化合物の作製後に非大気雰囲気下で熱処理することで制御可能である。なお、熱ドープ法による改質では、ケイ素化合物に一定以上の熱がかかる。そこで、実施例8-8、8-9では、より非晶質に近い材料において、低結晶性を維持するために電気化学法で改質を行っている。
ケイ素化合物のメディアン径を表9のように変化させたこと以外、実施例1-1と同様に二次電池の製造を行った。
Claims (13)
- 負極活物質粒子を有し、該負極活物質粒子はLi化合物が含まれるケイ素化合物(SiOx:0.5≦x≦1.6)を含有するものである非水電解質二次電池用負極活物質であって、
前記ケイ素化合物の表面の少なくとも一部が炭素被膜で被覆されたものであり、
前記ケイ素化合物の表面若しくは前記炭素被膜の表面、又はこれらの両方の少なくとも一部が、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層で被覆されたものであることを特徴とする非水電解質二次電池用負極活物質。 - 前記金属酸化物及び金属水酸化物は、アルミニウム、マグネシウム、チタニウム、及びジルコニウムのうち少なくとも1種の元素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活物質。
- 前記複合層の厚さが10nm以下である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活物質。
- 前記複合層の厚さが5nm以下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活物質。
- 前記ケイ素化合物は、前記Li化合物としてLi2SiO3を含む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活物質。
- 前記ケイ素化合物が、29Si-MAS-NMR スペクトルから得られるケミカルシフト値として-95~-150ppmに与えられるSiO2領域に由来するピークを持つ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負極活物質。
- 前記ケイ素化合物が、29Si-MAS-NMR スペクトルから得られるケミカルシフト値として-75ppm付近に与えられるLi2SiO3に由来するピークの強度Aと、-95~-150ppmに与えられるSiO2領域に由来するピークの強度Bとが、A>Bの関係を満たす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負極活物質。
- 前記非水電解質二次電池用負極活物質と炭素系活物質とを混合した負極活物質を使用して作製した負極電極と対極リチウムとから成る試験セルを充放電し、放電容量Qを前記対極リチウムを基準とする前記負極電極の電位Vで微分した微分値dQ/dVと前記電位Vとの関係を示すグラフを描いた場合に、前記非水電解質二次電池用負極活物質がリチウムを脱離するよう電流を流す放電時における、前記負極電極の電位Vが0.40V~0.55Vの範囲にピークを有するものであ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活物質。
- 前記ケイ素化合物が、X線回折により得られるSi(111)結晶面に起因する回折ピークの半値幅(2θ)が1.2°以上であると共に、その結晶面に起因する結晶子サイズが7.5nm以下のものであることを特徴とする請求項1から請求項8のいずれか1項に記載の非水電解質二次電池用負極活物質。
- 前記ケイ素化合物のメディアン径が0.5μm以上15μm以下のものであることを特徴とする請求項1から請求項9のいずれか1項に記載の非水電解質二次電池用負極活物質。
- 請求項1から請求項10のいずれか1項に記載の非水電解質二次電池用負極活物質を含むことを特徴とする非水電解質二次電池。
- 負極活物質粒子を含む非水電解質二次電池用負極材の製造方法であって、
一般式SiOx(0.5≦x≦1.6)で表される酸化珪素粒子を作製する工程と、
前記酸化珪素粒子の表面に炭素被膜を形成する工程と、
前記炭素被膜が被覆された酸化珪素粒子に、Liを挿入、脱離することで、前記酸化珪素粒子を改質する工程と、
前記改質後の酸化珪素粒子の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を形成する工程とを有し、前記複合層を形成された酸化珪素粒子を用いて、非水電解質二次電池用負極材を製造することを特徴とする非水電解質二次電池用負極材の製造方法。 - 前記複合層形成工程において、金属アルコキシドの加水分解及び脱水縮合によって前記改質後の酸化珪素粒子の表面に前記複合層を形成することを特徴とする請求項12に記載の非水電解質二次電池用負極材の製造方法。
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KR102633418B1 (ko) | 2024-02-06 |
JP6407804B2 (ja) | 2018-10-17 |
CN107710466B (zh) | 2020-11-03 |
KR20180019569A (ko) | 2018-02-26 |
US10418627B2 (en) | 2019-09-17 |
JP2017010645A (ja) | 2017-01-12 |
US20180175377A1 (en) | 2018-06-21 |
TWI709273B (zh) | 2020-11-01 |
EP3312916A4 (en) | 2019-03-20 |
EP3312916A1 (en) | 2018-04-25 |
TW201717457A (zh) | 2017-05-16 |
EP3312916B1 (en) | 2024-03-20 |
CN107710466A (zh) | 2018-02-16 |
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