WO2017047030A1 - Procédé de production de matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux - Google Patents

Procédé de production de matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux Download PDF

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WO2017047030A1
WO2017047030A1 PCT/JP2016/004004 JP2016004004W WO2017047030A1 WO 2017047030 A1 WO2017047030 A1 WO 2017047030A1 JP 2016004004 W JP2016004004 W JP 2016004004W WO 2017047030 A1 WO2017047030 A1 WO 2017047030A1
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negative electrode
active material
electrolyte secondary
silicon compound
secondary battery
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PCT/JP2016/004004
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English (en)
Japanese (ja)
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博道 加茂
貴一 廣瀬
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信越化学工業株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery and a method for producing a non-aqueous 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 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.
  • a negative electrode active material As a negative electrode active material, while carbon materials are widely used, further improvement in battery capacity is required due to recent market demands.
  • silicon As an element for improving battery capacity, the 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 alone but also for compounds represented by alloys and oxides. The shape of the active material is studied from a standard coating type of carbon material to an integrated type directly deposited on a current collector.
  • the negative electrode active material particles expand and contract during charge and discharge, and therefore the surface layer of the negative electrode active material particles mainly tends to break. Further, an ionic material is generated inside the active material, and the negative electrode active material particles are easily broken. When the surface layer of the negative electrode active material particles breaks, a new surface is generated, and the reaction area of the negative electrode active material particles increases. 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 of the battery 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). .
  • the alloy-based negative electrode is pre-doped with lithium by an electrochemical method (for example, see Patent Document 14).
  • non-aqueous electrolyte secondary batteries particularly lithium ion secondary batteries, which are the main power sources thereof. Is required to increase battery capacity.
  • 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.
  • Patent Document 14 the cycle maintenance rate and the initial efficiency of the battery have been improved by using, as the negative electrode active material, silicon oxide modified by inserting Li through electrolysis.
  • the negative electrode active material silicon oxide modified by inserting Li through electrolysis.
  • lithium is electrolyzed while refluxing lithium halide in a solution composed of ⁇ -butyrolactone to insert Li, but in order to advance the insertion of Li efficiently. Electrolysis was required while the solution used for electrolysis was at a high temperature (around 204 ° C., the boiling point of ⁇ -butyrolactone).
  • the present invention has been made in view of the above-described problems, and it is possible to increase the battery capacity of a nonaqueous electrolyte secondary battery and improve the cycle characteristics and the initial efficiency. It is an object of the present invention to provide a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery and a method for producing a non-aqueous electrolyte secondary battery, in which the substance can be produced with a simple device while reducing energy consumption.
  • the present invention provides a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery comprising a silicon compound containing lithium (SiO x : 0.5 ⁇ x ⁇ 1.6), A step of producing a silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6), and the silicon compound and the counter electrode are immersed in a non-aqueous solution containing at least lithium nitrate and / or lithium nitrite, and the silicon Provided is a method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery including a step of inserting lithium into the silicon compound by causing a potential difference between a compound and the counter electrode to perform electrolysis.
  • a secondary battery using a silicon-based active material into which Li has been inserted by electrolysis has improved initial efficiency by suppressing Li consumption at the negative electrode during the first charge / discharge, and the amount of Li extracted from the positive electrode accordingly. It is suppressed and the use range of the positive electrode is reduced, so that the battery maintenance rate is improved. Furthermore, when the non-aqueous solution used for electrolysis contains lithium nitrate or lithium nitrite, lithium can be inserted into the silicon compound at a relatively low temperature. This is because lithium nitrate and lithium nitrite have high solubility in non-aqueous solutions such as organic solvents, and can be highly concentrated even in relatively low temperature solutions.
  • lithium can be inserted into the silicon compound at a relatively low temperature, a simple apparatus can be used and energy consumption can be reduced.
  • lithium nitrate or lithium nitrite when used as in the present invention, it is NO x gas that is by-produced during electrolysis, so that damage to the current collector and silicon compound can be kept small.
  • a metal material can be used for the electrolysis section and the piping.
  • lithium nitrate and lithium nitrite are inexpensive and easy to use.
  • a non-aqueous solution containing at least lithium nitrate it is preferable to use a non-aqueous solution containing at least lithium nitrate.
  • lithium nitrate is a cheaper and more commonly used substance, it can be suitably used in the present invention.
  • the temperature of the non-aqueous solution is preferably 80 ° C. or higher.
  • lithium can be inserted into a silicon compound by electrolysis at a relatively low temperature range as described above.
  • the temperature of the non-aqueous solution is 80 ° C. or higher in the low temperature range, non-aqueous solution can be obtained.
  • the saturation concentration of the lithium salt increases in the aqueous solution, and the movement of ions becomes active, improving the ionic conductivity. Thereby, the insertion of lithium proceeds more efficiently.
  • the method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery of the present invention includes a step of forming an electrode containing the silicon compound before the electrolysis step, and the silicon compound contained in the electrode The electrolysis can be performed by creating a potential difference between the electrode and the counter electrode.
  • lithium may be inserted into the silicon compound contained in the electrode by electrolysis.
  • the electrode in the step of forming the electrode, at least one of the particulate silicon compound or the particulate silicon compound mixed with the carbon compound is mixed with a binder and applied to the current collector.
  • the electrode can be formed.
  • an electrode containing a silicon compound can be produced by the coating method as described above.
  • the silicon compound in the step of producing the silicon compound, is formed on a current collector having at least irregularities on the surface using a vapor phase method.
  • the electrolysis can be carried out by causing a potential difference between the silicon compound supported on the current collector and the counter electrode.
  • the silicon compound may be particulate.
  • a particulate silicon compound may be used.
  • the present invention provides a negative electrode for a nonaqueous electrolyte secondary battery containing a negative electrode active material for a nonaqueous electrolyte secondary battery by any one of the above-described manufacturing methods.
  • a method for producing a non-aqueous electrolyte secondary battery wherein a non-aqueous electrolyte secondary battery is produced using a negative electrode for a water electrolyte secondary battery.
  • the negative electrode active material production method and the negative electrode production method of the present invention include a negative electrode active material and a negative electrode that have high capacity and good cycle characteristics and initial charge / discharge characteristics when used in a non-aqueous electrolyte secondary battery. Simple equipment can be manufactured with reduced energy consumption.
  • 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 silicon compound containing oxygen has a lower initial efficiency than the carbon material, so that the battery capacity has been limited to that extent.
  • the cycle maintenance rate and initial efficiency of the battery have been improved.
  • the electrolysis for modifying the silicon compound causes damage to the current collector or silicon compound, and the non-aqueous electrolyte secondary battery using such a current collector or silicon compound for the negative electrode is a cycle.
  • battery characteristics such as characteristics and initial efficiency deteriorated.
  • electrolysis at a high temperature is required, there is a problem that energy consumption is large and a large-scale device is required.
  • the inventors have intensively studied a method for producing a negative electrode active material capable of obtaining good cycle characteristics and initial efficiency when used for a negative electrode of a non-aqueous electrolyte secondary battery, and reached the present invention.
  • the method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery according to the present invention includes a step of producing a silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6), a silicon compound and a counter electrode comprising at least lithium nitrate or And a step of inserting lithium into the silicon compound by immersing in a non-aqueous solution containing lithium nitrate or both and generating an electric potential difference between the silicon compound and the counter electrode to perform electrolysis.
  • an electrode containing a silicon compound may be prepared, and then the silicon compound contained in the electrode may be electrolyzed to insert lithium into the silicon compound. .
  • the silicon-based active material particles produced by the production method according to the present invention contain Li, so that the irreversible capacity is reduced during the first charge / discharge.
  • a non-aqueous solution containing lithium nitrate or lithium nitrite having high solubility in an organic solvent efficient lithium insertion with low energy consumption by electrolysis at a relatively low temperature is possible.
  • the electrolysis at a relatively low temperature is possible, the evaporation amount of the solution can be reduced. Therefore, the electrolysis can be performed even in an open system, and the apparatus used for the electrolysis can be simple.
  • the silicon-based active material particles in the present invention are a negative electrode active material mainly composed of a silicon compound, the battery capacity can be increased.
  • a silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6) is prepared.
  • Such a silicon compound represented by the general formula SiO x (where 0.5 ⁇ x ⁇ 1.6) can be produced, for example, by the following method.
  • a raw material for generating 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.
  • a mixture of metal silicon powder and silicon dioxide powder can be used as the raw material, 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.
  • Silicon dioxide powder ⁇ 1.3 is desirable.
  • 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.
  • x is preferably close to 1. 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.
  • lithium is inserted into the particulate silicon compound before being used as an electrode, and the silicon compound is modified. May be performed.
  • the modification of the particulate silicon compound before forming the electrode can be performed using, for example, a reformer 10 as shown in FIG.
  • the reformer 10 is disposed in the bathtub 17 filled with the non-aqueous solution 13, the counter electrode 11 disposed in the bathtub 17 and connected to one of the power sources 16, and the bathtub 17. It has a powder storage container 15 connected to the other side of the power source 16 and a separator 14 provided between the counter electrode 11 and the powder storage container 15.
  • the non-aqueous solution 13 contains at least lithium nitrate and / or lithium nitrite. These salts have high solubility in organic solvents and are inexpensive. In particular, lithium nitrate is preferred because it is more common.
  • the solvent of the non-aqueous solution 13 preferably includes an ether solvent. This is because the potential window of the ether solvent is wide, so that side reactions are unlikely to occur during the lithium insertion reaction into a silicon compound having a low potential.
  • these solvents for example, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (tetraglyme), or a mixed solvent thereof can be used.
  • Diethylene glycol dimethyl ether It is preferable to use triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
  • the solvent may contain a solvent other than the ether type.
  • the temperature of the non-aqueous solution is 80 ° C. or higher.
  • lithium can be inserted into a silicon compound by electrolysis at a relatively low temperature range as described above. However, if the temperature of the non-aqueous solution is 80 ° C. or higher in the low temperature range, non-aqueous solution can be obtained. The saturation concentration of the lithium salt increases in the aqueous solution, and the movement of ions becomes active, improving the ionic conductivity. Thereby, the insertion of lithium proceeds more efficiently.
  • the powder storage container 15 stores the particulate silicon compound 12.
  • a silicon compound is stored in the powder storage container 15, and a voltage is applied to the powder storage container 15 storing the silicon compound and the counter electrode 11 by a power source.
  • a potential difference is generated between the silicon compound 12 and the counter electrode 11 to perform electrolysis, and lithium can be inserted into the silicon compound 12.
  • lithium can be desorbed from the silicon compound 12 by applying an electric field opposite to that at the time of insertion of lithium.
  • a part of the SiO 2 component generated inside the silicon compound can be selectively modified into a Li compound by modification by electrolysis, and a silicon compound containing lithium can be produced.
  • the Li compound is contained on the surface, inside, or both of the silicon compound.
  • Selective reforming can be achieved by performing potential control during electrolysis. By controlling the potential, it is possible to select a site into which Li is inserted during electrolysis, thereby suppressing the generation of an active Li compound and improving the handleability of the electrode in the atmosphere.
  • a carbon film may be formed on the surface of the silicon compound before modifying the particulate silicon compound.
  • Thermal CVD is desirable as a method for generating the carbon film.
  • the silicon oxide powder set in the furnace and the furnace are filled with hydrocarbon gas to raise the temperature in the furnace.
  • the decomposition temperature is not particularly limited, but is particularly preferably 1200 ° C. or lower, and more preferably 950 ° C. or lower. This is because unintended disproportionation of the silicon compound can be suppressed.
  • the carbon film When the carbon film is generated by thermal CVD, for example, the carbon film can be formed on the surface layer of the powder material while adjusting the coverage and thickness of the carbon film by adjusting the pressure and temperature in the furnace.
  • the hydrocarbon gas used in the thermal decomposition CVD is not particularly limited, but 3 ⁇ n is desirable in the C n H m composition. This is because the manufacturing cost can be lowered and the physical properties of the decomposition product are good.
  • a step of forming an electrode containing a silicon compound may be included before the step of performing electrolysis.
  • electrolysis can be performed by generating a potential difference between the silicon compound contained in the electrode and the counter electrode.
  • the electrode can be configured as shown in FIG. 2, for example.
  • the electrode 20 is configured to have an active material layer 22 on a current collector 21.
  • the active material layer 22 may be provided on both surfaces or only one surface of the current collector 21.
  • the active material layer 22 contains a silicon compound.
  • the current collector 21 is an excellent conductive material and is made of a material having excellent mechanical strength.
  • Examples of the conductive material that can be used for the current collector 21 include copper (Cu), nickel (Ni), and iron (Fe).
  • This conductive material is preferably a material that does not form an intermetallic compound with lithium (Li).
  • the current collector 21 preferably contains carbon (C) and sulfur (S) in addition to the main element. This is because the physical strength of the current collector 21 is improved. This is because, in particular, when the active material layer 22 containing a silicon compound that expands during charging is included, if the current collector 21 contains the above-described element, there is an effect of suppressing electrode deformation including the current collector 21.
  • 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 current collector 21 may be roughened or not roughened.
  • the roughened current collector for example, electrolytic treatment, embossing treatment, or chemically etched metal foil can be used.
  • the current collector that is not roughened for example, a rolled metal foil or the like can be used.
  • the active material layer 22 In addition to the silicon compound (SiO x : 0.5 ⁇ x ⁇ 1.6), the active material layer 22 further includes other materials such as a binder, a conductive additive, and a carbon-based active material in terms of battery design. You can leave.
  • the surface of the silicon compound may be covered with a carbon film. In order to coat the surface of the silicon compound with the carbon film, the above-described thermal CVD may be used.
  • binder for example, polyimide, carboxymethyl cellulose, styrene butadiene rubber or the like can be used.
  • Examples of the conductive assistant include at least one of graphite such as carbon black, acetylene black, and scaly graphite, ketjen black, carbon nanotube, and carbon nanofiber. These conductive assistants are preferably in the form of particles having a median diameter smaller than that of silicon compound particles.
  • Examples of the carbon-based active material include pyrolytic carbons, cokes, glassy carbon fibers, organic polymer compound fired bodies, carbon blacks, and the like. By including the carbon-based active material, it is possible to reduce the electrical resistance of the active material layer 22 and relieve the expansion stress accompanying charging.
  • the electrode 20 can be formed by mixing at least one of a particulate silicon compound or a particulate silicon compound mixed with a carbon material with a binder and applying the mixture to a current collector. (This method is hereinafter referred to as a coating method). In the coating method, silicon compound particles and a binder, and the like, and if necessary, the above-mentioned conductive assistant and carbon-based active material are mixed and then dispersed in an organic solvent or water. For example, the electrode 20 can be produced by the following procedure.
  • the produced silicon compound particles are mixed with a conductive additive, a binder, a solvent, and the like to obtain a slurry.
  • a carbon-based active material may be mixed as necessary.
  • the conductive assistant a carbon-based material having a median diameter smaller than that of the silicon compound particles can be added as a conductive assistant. In that case, for example, acetylene black can be selected and added.
  • the slurry is applied to the surface of the current collector 21 and dried to form the active material layer 22.
  • an electrode can be produced by a coating method.
  • the silicon compound in the step of producing the silicon compound, may be directly supported on a current collector having at least unevenness on the surface by using a vapor phase method.
  • the vapor phase method is a method in which a raw material is vaporized and the vaporized raw material is directly deposited on the current collector 21.
  • the electrode can be fabricated as follows using a vapor phase method.
  • a vapor deposition material in which metal silicon powder and silicon dioxide powder are mixed at a mixing molar ratio is put into a carbon crucible.
  • the mixing molar ratio is preferably in the range of 0.8 ⁇ metal silicon powder / silicon dioxide powder ⁇ 1.3.
  • a current collector is disposed above the carbon crucible.
  • silicon monoxide gas is generated by heating the vapor deposition material using induction heating or resistance heating.
  • the degree of vacuum in the reaction furnace can be 10 ⁇ 2 Pa or less. In this way, the silicon compound can be deposited directly on the current collector.
  • the current collector used in the vapor phase method is preferably one having irregularities on the surface.
  • a metal foil subjected to electrolytic treatment, embossing treatment, or chemical etching can be used.
  • the current collector preferably has a surface roughness Ra value of 0.2 ⁇ m or more.
  • surface roughness Ra value in this specification is centerline average roughness Ra prescribed
  • a film-like electrolytic copper foil or the like is preferably used.
  • an electrode can be manufactured by a vapor phase method.
  • an electrode 31 produced by a coating method or a vapor phase method is placed on a roll 35 and is opposed to the counter electrode 32 to be a predetermined temperature, such as lithium nitrate, lithium nitrite, or these Immerse in a non-aqueous solution 33 containing both.
  • the counter electrode 32 can be a carbon electrode, for example.
  • the power source 34 causes the potential difference between the silicon compound contained in the electrode 31 and the counter electrode 32 to perform electrolysis, and lithium can be inserted into the silicon compound 12.
  • lithium can be desorbed from the silicon compound 12 by applying an electric field opposite to that at the time of insertion of lithium.
  • a negative electrode active material for a non-aqueous electrolyte secondary battery is produced.
  • Lithium ion secondary battery> The method for producing a non-aqueous electrolyte secondary battery of the present invention produced a negative electrode for a non-aqueous electrolyte secondary battery containing a negative electrode active material for a non-aqueous electrolyte secondary battery by the above-described method for producing a negative electrode active material.
  • a nonaqueous electrolyte secondary battery is manufactured using the negative electrode for a nonaqueous electrolyte secondary battery.
  • the method for producing a nonaqueous electrolyte secondary battery of the present invention will be described by taking as an example the case of producing a laminate film type secondary battery.
  • a laminated film type secondary battery 40 shown in FIG. 4 is one in which a wound electrode body 41 is accommodated mainly in a sheet-like exterior member 45.
  • This wound electrode body 41 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.
  • a positive electrode lead 42 is attached to the positive electrode
  • a negative electrode lead 43 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 45 to the outside, for example.
  • the positive electrode lead 42 is formed of a conductive material such as aluminum
  • the negative electrode lead 43 is formed of a conductive material such as nickel and copper.
  • the exterior member 45 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 wound electrode body 41.
  • the outer peripheral edge portions of the fused layer are bonded together with an adhesive or the like.
  • 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 44 is inserted between the exterior member 45 and the positive and negative electrode leads to prevent outside air from entering.
  • This material is, for example, polyethylene, polypropylene, or polyolefin resin.
  • the positive electrode has, for example, a positive electrode active material layer on both surfaces or one surface of the positive electrode current collector, similarly to the electrode 20 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 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 phosphoric acid having lithium and a transition metal element.
  • Examples of the compound include a lithium iron phosphate compound (LiFePO 4 ) and a lithium iron manganese phosphate compound (LiFe 1-u Mn u PO 4 (0 ⁇ u ⁇ 1)). 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 electrode 20 of FIG. 2 described above, and has, for example, a negative electrode active material layer on both surfaces of the negative electrode current collector.
  • 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 lithium metal deposition 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 to perform 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. Thus, the composition and the like of the negative electrode active material can be accurately examined with good reproducibility without depending on the presence or absence of charge / discharge.
  • 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 nonaqueous solvent for example, a nonaqueous 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, or tetrahydrofuran.
  • ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate it is desirable to use at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. This is because better characteristics can be obtained. In this case, more advantageous characteristics can be obtained by combining a high viscosity solvent such as ethylene carbonate or propylene carbonate and 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 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 the following materials. Examples thereof 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 manufactured 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, heating may be performed. Further, compression and heating 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 operation procedure as that for producing the electrode 20 described above.
  • the silicon compound may be modified before forming the negative electrode, or the silicon compound contained in the negative electrode may be modified after forming the negative electrode.
  • each active material layer can be formed on both surfaces of the positive electrode current collector and the negative electrode current collector. At this time, the active material application length of both surface portions may be shifted in either electrode (see FIG. 2).
  • an electrolyte solution is prepared.
  • the positive electrode lead 42 is attached to the positive electrode current collector by ultrasonic welding or the like, and the negative electrode lead 43 is attached to the negative electrode current collector (see FIG. 4).
  • a positive electrode and a negative electrode are laminated
  • 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 opened in only one direction.
  • the adhesion film 44 is inserted between the positive electrode lead 42 and the negative electrode lead 43 and the exterior member 45.
  • a predetermined amount of the prepared electrolytic solution is introduced from the open portion, and vacuum impregnation is performed. After impregnation, the open part is bonded by a vacuum heat fusion method.
  • the laminated film type secondary battery 40 can be manufactured as described above.
  • Example 1 an electrode containing a silicon compound (silicon-based active material) was produced by a vapor phase method as described below.
  • a raw material mixed with metallic silicon and silicon dioxide also referred to as a vaporization starting material
  • a silicon compound was deposited on the substrate, and this was performed on both sides to obtain a negative electrode having a negative electrode active material layer having a thickness of about 7 ⁇ m.
  • the value of x of SiOx was 1.
  • electrolysis was performed.
  • an electrode containing the silicon compound (silicon-based active material) prepared above was used as a cathode, a carbon plate was opposed to a part of the length direction as an anode, and heated to 120 ° C. while feeding the electrode by a roll, 2 mol / The lithium lithium nitrate / diglyme solution was impregnated and continuously electrolyzed.
  • the solvent was connected to the gas removing device, placed in the gas removing device, and circulated while removing the gas using ultrasonic waves.
  • the obtained negative electrode was rinsed with a diglyme solution and then vacuum-dried at 100 ° C.
  • test cell composed of an electrode containing a silicon compound and counter electrode lithium was prepared, and the initial charge / discharge characteristics were examined.
  • a 2032 type coin cell was used as this test cell.
  • FEC solvent
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a metal lithium foil having a thickness of 0.5 mm was used as the counter electrode for the electrode containing a silicon compound in the test cell. Further, polyethylene having a thickness of 20 ⁇ m was used as a separator.
  • the bottom pig of the 2032 type coin battery, the lithium foil, and the separator are stacked, and 150 mL of the electrolytic solution is injected, and subsequently, the negative electrode and the spacer (thickness: 1.0 mm) are stacked, and 150 mL of the electrolytic solution is injected.
  • a 2032 type coin battery was manufactured by lifting up the spring and the upper lid of the coin battery in this order and caulking with an automatic coin cell caulking machine.
  • the produced 2032 type coin battery was charged at a constant current density of 0.2 mA / cm 2 until reaching 0.0 V, and when the voltage reached 0.0 V, the current density was at 0.0 V constant voltage. It was charged to reach 0.02 mA / cm 2, when the discharge was discharged until the voltage reached 1.2V at a constant current density of 0.2 mA / cm 2. And the first time charge / discharge characteristic in this first time charge / discharge was investigated.
  • a laminate film type secondary battery 40 as shown in FIG. was made.
  • the positive electrode active material is 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 (acetylene black), and 2.5 parts by mass of a positive electrode binder (polyvinylidene fluoride: Pvdf).
  • a 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 a negative electrode produced in the same procedure as the electrode containing the silicon compound in the test cell was used.
  • electrolytic solution one prepared in the same procedure as the electrolytic solution of the above test cell was used.
  • a laminated film type lithium ion 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 12 ⁇ m in which a film mainly composed of porous polyethylene was sandwiched between films 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.
  • an electrolyte prepared from the opening was injected, 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 / 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 (because it is expressed in% ⁇ 100), and the capacity maintenance rate was calculated. As cycling conditions, a constant current density until reaching 4.3V, and charged at 2.5 mA / cm 2, current density reached 0.25 mA / cm 2 at 4.3V constant voltage at the stage of reaching the voltage 4.3V Until charged. During discharging, discharging was performed at a constant current density of 2.5 mA / cm 2 until the voltage reached 3.0V.
  • Examples 2 to 10, Comparative Examples 1 to 3 A test cell and a laminate film type secondary battery were prepared in the same manner as in Example 1 except that the composition of the non-aqueous solution used in the electrolysis step and the electrolysis temperature were changed as shown in Table 1. And cycle characteristics were evaluated. In Comparative Example 1, the step of electrolysis was not performed.
  • the initial efficiency and the battery maintenance rate are improved by inserting lithium into the silicon compound by electrolysis. This is because the battery is produced in a state where Li is inserted into the silicon compound contained in the negative electrode, so that the consumption of Li at the negative electrode during the initial charge / discharge is suppressed, the initial efficiency is improved, and the battery is extracted from the positive electrode accordingly. This is because the amount of Li is suppressed and the use range of the positive electrode is reduced, so that the battery retention rate is improved.
  • the battery characteristics are improved by using a non-aqueous solution containing lithium nitrate or lithium nitrite for electrolysis as compared with the case of using a solution containing lithium chloride or the like.
  • lithium nitrate and lithium nitrite are highly soluble even in non-aqueous solvents at relatively low temperatures, so that lithium can be inserted efficiently and chlorine that reacts with the copper of the current collector or silicon of the active material.
  • the nitrate produced as a by-product of NO x gas causes less damage to the electrode than the case where the halogen is produced as a by-product (Comparative Examples 2 and 3).
  • the concentration of the solution is preferably higher, and more preferably 1 mol / L or more. This is because the higher the solution concentration, the higher the ion concentration in the solution, thereby improving the ionic conductivity of the solution.
  • the solution temperature is preferably 100 ° C. or higher, and preferably around 120 ° C. This is also because the ionic conductivity of the solution is improved.
  • the silicon compound can be sufficiently modified even when electrolysis is performed at a relatively low temperature of 120 ° C., and energy consumption is reduced compared to the electrolysis performed at 204 ° C. as in Comparative Example 2. I was able to.
  • the boiling point of diglyme used as a solvent here is 162 ° C.
  • electrolysis could be performed at a temperature lower by about 40 ° C. than the boiling point of the solvent. That is, in the present invention, it was confirmed that an open system simple apparatus can be used because the evaporation amount of the solvent can be reduced.
  • the solvent is preferably an ether solvent, and a solvent containing three or more ether bonds such as diglyme and tetraglyme in the molecule is preferable. This is because such a solvent has high polarity and can further increase the concentration of the solute in the solution.
  • Example 11 and 12 A test cell and a laminate film type secondary battery were produced in the same manner as in Example 1 except that the electrode production method was changed to the coating method, and the initial charge / discharge characteristics and cycle characteristics were evaluated.
  • a silicon compound was used as the active material, and polyimide was used as the binder during electrode production.
  • a silicon compound and graphite were used as the active material at a mass ratio of 10:90, and carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) were used as the binder during electrode production.
  • CMC carboxymethyl cellulose
  • SBR styrene butadiene rubber
  • Comparative Examples 4 and 5 A test cell and a laminate film type secondary battery were produced in the same manner as in Example 1 except that the electrode production method was changed to the coating method and the electrolysis step was not carried out. Characteristics and cycle characteristics were evaluated.
  • a silicon compound was used as the active material, and polyimide was used as the binder during electrode production.
  • a silicon compound and graphite were used as the active material at a mass ratio of 10:90, and CMC and SBR were used as the binder during electrode production. Further, in the same manner as in Examples 11 and 12, the capacity per unit volume of the negative electrode was examined, and the relative value of the capacity per unit volume of the negative electrode based on Example 12 was calculated.
  • Table 2 shows the initial efficiency of the test cells of Examples 11 and 12 and Comparative Examples 4 and 5, the capacity retention rate of the laminated film type secondary battery, and the relative value of the capacity per unit volume of the negative electrode.
  • an electrode whose active material is SiO prepared by a vapor phase method is preferable in terms of battery retention rate, initial efficiency of the battery, and relative volume capacity of the negative electrode. This is because there are fewer voids between the active materials than in the coating method, and a substance such as a binder is not necessary.
  • the electrode of SiO / graphite (10/90 mass%) produced by the coating method is superior to the other examples in terms of the battery maintenance rate and the initial efficiency of the battery, the relative volume capacity of the negative electrode is inferior. This is because it contains a large amount of graphite as an active material. In Comparative Examples 1, 4 to 5 that have not undergone the electrolysis process, the initial efficiency of the battery is low.
  • 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

La présente invention concerne un procédé de production d'un matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux contenant un composé de silicium (SiOx où 0,5 ≤ x ≤ 1,6) qui contient du lithium. Ce procédé de production d'un matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux comprend : une étape dans laquelle est préparé un composé de silicium (SiOx où 0,5 ≤ x ≤ 1,6) ; et une étape dans laquelle le lithium est intercalé dans le composé de silicium au moyen d'une électrolyse qui est provoquée par la production d'une différence de potentiels entre le composé de silicium et une contre-électrode par immersion du composé de silicium et de la contre-électrode dans une solution non aqueuse qui contient au moins du nitrate de lithium et/ou du nitrite de lithium. Par conséquent, la présente invention concerne un procédé de production d'un matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux, ledit matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux permettant d'augmenter la capacité de la batterie, tout en permettant également d'améliorer les caractéristiques de cycle et l'efficacité initiale.
PCT/JP2016/004004 2015-09-16 2016-09-02 Procédé de production de matériau actif d'électrode négative pour batteries secondaires à électrolyte non aqueux et procédé de fabrication de batterie secondaire à électrolyte non aqueux WO2017047030A1 (fr)

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WO2020003687A1 (fr) * 2018-06-25 2020-01-02 信越化学工業株式会社 Procédé de fabrication de matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux, matériau actif d'électrode négative pour batterie secondaire à électrolyte non aqueux, électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
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CN111453713A (zh) * 2020-04-08 2020-07-28 合肥国轩高科动力能源有限公司 一种氧化亚硅/碳材料及其制备方法和应用

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