WO2004027902A1 - リチウムポリマー電池及びその製造方法 - Google Patents
リチウムポリマー電池及びその製造方法 Download PDFInfo
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- WO2004027902A1 WO2004027902A1 PCT/JP2003/011231 JP0311231W WO2004027902A1 WO 2004027902 A1 WO2004027902 A1 WO 2004027902A1 JP 0311231 W JP0311231 W JP 0311231W WO 2004027902 A1 WO2004027902 A1 WO 2004027902A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/22—Immobilising of electrolyte
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a lithium polymer battery and a method for producing the same. More specifically, the present invention uses a negative electrode containing, as an active material, a composite carbon material powder composed of two or more types of graphite material powder obtained by adhering a low-crystalline carbon material to the surface of a highly crystalline graphite powder.
- the present invention relates to a lithium polymer battery and a method for manufacturing the same. Background art
- the carbon material has a potential of absorbing and releasing lithium closer to that of lithium than that of other materials.
- graphite material can incorporate lithium into its crystal lattice theoretically at a ratio of one lithium atom to six carbon atoms. Therefore, the graphite material is a carbon material having a high capacity per unit weight and unit volume. Furthermore, since the graphite material has a flat lithium-in / out potential and is chemically stable, a battery having good cycle stability can be obtained by using it.
- JP-A-4-115457, JP-A-11115458, JP-A-237971 and others disclose a battery using a graphite-based carbon material as a negative electrode active material.
- -114421 discloses a battery using a surface-treated graphite-based carbon material as a negative electrode active material.
- Graphite-based carbon material is an organic electrolyte mainly composed of ethylene carbonate (EC) By using, a discharge capacity almost equal to the theoretical capacity can be obtained. In addition, the charge / discharge potential is slightly higher than the potential of lithium dissolution, and is very flat. Therefore, when a battery is manufactured using a graphite-based carbon material as a negative electrode active material, a secondary battery having high capacity and high flatness of battery voltage can be realized, and a high capacity battery can be achieved.
- EC ethylene carbonate
- graphite-based carbon materials have a problem that they cause decomposition of the organic electrolyte due to high crystallinity.
- PC propylene carbonate
- It is widely used as a solvent for electrolytes.
- graphite-based carbon material is used as the negative electrode active material, the decomposition reaction of PC occurs remarkably, and the negative electrode composed of graphite-based carbon material cannot be charged / discharged because only 10% of PC exists in the electrolyte. This is reported in J. Electroch em. Soc., Vol. 142, 1746 (1995).
- the solution is as follows: (1) Add an additive such as vinylene carbonate to the electrolyte and form a film on the graphite-based carbon material, which is the negative electrode active material. (2) A method of covering the surface of a highly crystalline graphite-based carbon material with a low-crystalline carbon material has been proposed. In the latter method, a composite graphite material having both the high capacity characteristic of a highly crystalline graphite-based carbon material and the lack of electrolyte selectivity, which is a characteristic of a low-crystalline carbon material, can be obtained.
- ion-conductive polymers having high ion conductivity 14 have been proposed and is being practically put into practical use.
- Batteries using the above-mentioned ion conductive polymer are widely described in patent documents and the like.
- U.S. Pat. No. 4,303,748 to Armand et al. U.S. Pat. No. 4,589,197 to North and U.S. Pat. , 547, 440 and the like.
- One of the features of these batteries is that an ion conductive polymer containing a solution in which an electrolyte salt is dissolved in a polymer material having a polyether structure is used.
- ionic conductive polymers have low ionic conductivity at room temperature or lower, so that it is not possible to realize a small size, light weight, and high energy density required for a battery for a drive power supply of a portable electronic device or a memory backup power supply.
- a monomer, an organic solvent (particularly, a high dielectric constant organic solvent such as EC or PC) and an electrolytic solution comprising an electrolyte salt are used as a method for further improving the ion conductivity compared to the above-described ion conductive polymer.
- a method of mixing and polymerizing a monomer has been proposed. By this method, the electrolyte solution is held in the polymer network, and a gel-like polymer electrolyte (hereinafter, referred to as a chemically crosslinked gel) that is kept in a solid state can be obtained.
- Chemically crosslinked gels have a high retention of electrolytes and do not melt even at high temperatures (for example, about 100 ° C), which is effective from the viewpoint of preventing liquid leakage in abnormal situations.
- high temperatures for example, about 100 ° C
- An object of the present invention is to provide a lithium polymer battery.
- a positive electrode a negative electrode containing a negative electrode active material composed of a carbon material powder, and an electrolyte using a chemically crosslinked gel, wherein the carbon material powder has a low crystalline carbon material on the surface of the highly crystalline graphite powder.
- a lithium polymer battery comprising a mixture of at least two types of composite graphite material powders having different physical property values adhered to each other.
- the carbon material powder as the negative electrode active material at least two or more kinds of carbon materials having a low crystalline carbon material attached to the surface of the highly crystalline graphite powder and having different physical property values from each other.
- a method for producing a lithium polymer battery including a step of impregnating a negative electrode containing a composite graphite material powder with a precursor of a chemically crosslinked gel, and a step of gelling the precursor to obtain an electrolyte is provided.
- FIG. 1 is a cross-sectional view showing an example of the composite graphite material powder of the present invention.
- the composite graphite material powder is excellent as a negative electrode active material
- the lubricity inherent in the highly crystalline graphite powder (hereinafter, also referred to as graphite powder) is hindered by the low crystalline carbon material on the surface. Therefore, the filling property is poor, and a high-density negative electrode may not be obtained.
- the inventors of the present invention have found that the filling property is greatly affected by the physical properties of the composite graphite material powder, such as the coating ratio or the type of core material. .
- the inventors of the present invention have proposed that the use of two or more kinds of composite graphite material powders having different physical property values as the negative electrode active material makes it possible to form a chemically crosslinked gel precursor.
- Radicals generated by means such as UV are consumed at their active sites and inhibit polymerization reactions.
- By coating the surface with a low-crystalline carbon material it is thought that the consumption of radicals by the graphite powder is suppressed, and the generated radicals are efficiently used for the polymerization reaction.
- containing at least two or more types of composite graphite material powders having different physical property values means that at least the composite graphite material powder as the main active material and the composite graphite material powder for improving the filling property thereof Includes types.
- the composite graphite material powder is an aggregate of powders. Strictly speaking, it is difficult to obtain a completely uniform aggregate of the powder. Therefore, the physical property value of each particle and the physical property value of the particle aggregate ( Average).
- two or more types mean that there are two or more types of composite graphite material powder having different physical property values as the latter aggregate.
- the physical property values include crystallinity (plane spacing, crystallite size, etc.), specific surface area, particle size distribution, covering ratio, Raman intensity ratio, true density, bulk density, purity, shape, and the like.
- the difference in the coating ratio means that the average value of the amount of the low-crystalline carbon material / (the amount of the high-crystalline graphite powder + the amount of the low-crystalline carbon material) (hereinafter referred to as the coating ratio) is different.
- the coating ratio Means By making the covering ratio different, it is possible to manufacture a high-performance secondary battery with higher capacity density.
- the coating ratio does not mean a value for each particle but a value as an aggregate of the composite graphite material powder, that is, an average value. This value is calculated based on the weight of the graphite powder in the manufacturing process and the weight change of the composite graphite material powder finally obtained.
- the coating ratio of the composite graphite material powder having the larger coating ratio is preferably in the range of 0.03 to 0.3, and more preferably 0.1 to 0.25. If the coating ratio is larger than 0.3, the low crystal part becomes too large, and the charge / discharge capacity becomes low, which is not preferable. In addition, when it is less than 0.03, the control effect on the decomposition of the electrolytic solution is reduced. Therefore, it is not preferable.
- the coating ratio of the composite graphite material powder having the smaller coating ratio is preferably 0.1 or less, more preferably 0.01 to 0.10. More preferably, it is 0.01 to 0.05.
- a material less than 0.01 is not sufficient to suppress the above-mentioned inhibition factors of polymerization, and a coating ratio greater than 0.1 is not preferable because it is difficult to obtain a negative electrode having excellent performance and high packing density.
- the amount of the composite graphite material powder having a small coating ratio with respect to the amount of the composite graphite material powder having a large coating ratio is preferably 50% or less by weight, more preferably about 10 to 30%. If the amount added is too large, the properties of the material will dominate, and the effect of suppressing the factors that inhibit polymerization will not be sufficiently obtained, or the material itself will not be oriented.
- the load characteristics, etc. may deteriorate due to reasons such as worsening of the electrolyte penetration. If the added amount is not sufficient, there is a problem that the effect of improving the filling property cannot be sufficiently obtained.
- the type of graphite powder By changing the type of graphite powder instead of varying the coating ratio, it is possible to obtain high-capacity density and high-performance batteries. Even when two or more types of graphite powders with different crystallinity evaluations defined by X-ray diffraction, Raman spectroscopy, true density, etc. are used and the low-crystalline carbon material is coated with the same coating ratio, It became clear that the filling 14 differs depending on the type of graphite powder. This is due to the difference in fillability due to differences in the average fine structure that cannot be determined by evaluation means such as X-ray diffraction, the shape of the composite graphite powder derived from the shape of the core material, and the balance of the particle size. It is presumed to occur.
- the coating ratio when the graphite powders are different is not particularly limited, but the coating ratio of the composite graphite material powder having a large coating ratio is preferably in the range of 0.3 to 0.3 in order to further enhance the filling property.
- the coating ratio of the composite graphite material powder is preferably from 0.01 to 0.10. A more preferred latter coating ratio is from 0.01 to 0.05.
- the amount of the composite graphite material powder having a small coating ratio with respect to the amount of the composite graphite material powder having a large coating ratio is preferably 50% or less by weight, more preferably 10% or less.
- a parameter called a compression ratio is defined as an index indicating the degree of filling, and the physical properties of the composite graphite material powder are defined.
- the compression ratio is defined as adding 7.5 parts by weight (based on 100 parts by weight of composite graphite material powder) of PVDF (polyvinylidene fluoride) as a binder to the target composite graphite material powder, It means the change in thickness when the slurry obtained by mixing with the solvent is applied to a copper foil and pressed at a linear pressure of 300 kg / cm.
- Compression ratio thickness of coating film after pressing Z thickness of coating film before pressing
- the density of the coating when the coating is prepared is also important. That is, the higher the coating film density before pressing and the lower the compression ratio, the higher the density of the negative electrode can be obtained. Even if the compression ratio is sufficiently low, if the coating density before pressing is too low, the graphite powder is likely to be oriented when pressed to obtain a high-density negative electrode, resulting in a negative electrode with poor load characteristics. May be. Further, even for a material having a sufficiently high coating density before pressing, it is not preferable since a negative electrode having a high energy density cannot be obtained if the compression ratio is large. In the present invention, the coating density before pressing is 0.7. g Z cm 3 or more, the compression ratio is 0.4-0.
- the coating film density after pressing is 1.5 g / cm 3 or more.
- the higher the coating density after pressing the higher the capacity of the negative electrode.
- the high-density negative electrode obtained when the coating density before pressing is low and the compression ratio is low is not preferable because the load characteristics may be deteriorated due to the orientation of the material and the like.
- the composite graphite material powder in the present invention is obtained by a method such as a gas phase method, a liquid phase method, and a solid phase method.
- FIG. 1 it can be obtained by attaching a low-crystalline carbon material 2 to the surface of a highly crystalline graphite powder 1.
- the graphite powder used for the core material may be natural graphite, particulate graphite (scale-like, lump, fibrous, whisker-like, spherical, crushed, etc.), or mesocarbon micro beads, mesophase pitch powder, isotropic
- One or more graphite daggers such as conductive pitch powder can be used.
- the average spacing (d 002) of the (002) plane is 0.335 to 0.340 nm by X-ray wide-angle diffraction, and the (002) plane
- the crystallite thickness (Lc) is 10 nm or more (more preferably, 40 nm or more)
- the crystallite thickness (La) in the (110) plane direction is 1 Onm or more (more preferably, 5 Onm or more)
- argon laser Raman The peak intensity ratio around 1360 cm- 1 to the peak intensity ratio around 1580 cm- 1 (hereinafter referred to as R value) is preferably 0.5 or less (more preferably, 0.4 or less).
- the crystallinity of the graphite powder is not sufficient. Therefore, when the composite graphite material powder is produced, the capacity of a low potential portion (0 to 300 mV based on the potential of Li) close to dissolution precipitation of lithium is not sufficient, which is not preferable.
- the particle size distribution of the graphite powder used as the core material is preferably about 0.1 to 150 ⁇ m.
- the particle size of the composite graphite material powder with the low crystalline carbon material attached to the surface of the graphite powder is
- the particle size of the final product will be almost specified. If the particle size of the core material is smaller than 0.1 jum, there is a high risk of causing an internal short circuit through the pores of the battery separator, which is not preferable. If it is larger than 150 m, it is not preferable because the uniformity of the negative electrode, the packing density of the active material, the handling property in the process of producing the negative electrode and the like are reduced.
- the particle size here is the average value of the powder and is measured by a laser diffraction particle size distribution meter. In the specified particle size distribution, the value showing the peak is defined as the particle size.
- the gas phase method is a method in which a gaseous raw material or a liquid raw material is transported into a reaction system by a method such as spraying or publishing.
- This is a method in which carbon is formed from the gas phase on the surface of graphite powder by thermal decomposition of raw materials.
- the thermal decomposition can be performed in a temperature range of about 450 to 150 ° C.
- raw materials include aliphatic saturated hydrocarbons such as methane, ethane, and propane; aliphatic unsaturated hydrocarbons such as propylene; and aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and perylene.
- an inert gas such as argon or nitrogen can be used as a carrier gas as appropriate.
- a method of adding hydrogen to suppress the generation of soot in the gas phase can be considered.
- the liquid phase method is to attach a raw material to be carbonized by a carbon precursor via a liquid phase to the surface of black and sinter them. Is to form carbon on the surface.
- the raw materials include aromatic hydrocarbons such as naphthalene, phenanthrene, acenaphthylene, anthracene, triphenylene, pyrene, thalicene, and perylene; tars or pitches obtained by polycondensation of these under heat and pressure; or aromatics thereof. Tar, pitch, asphalt, and oils mainly composed of a mixture of aromatic hydrocarbons.
- the origin of these raw materials may be petroleum-based or coal-based.
- the graphite powder coated with the carbon precursor may be subjected to a washing step.
- a washing step By adding a washing step, the low molecular components of the carbon precursor can be removed, the carbonization rate from the carbon precursor can be improved, and the particles can be fused or aggregated during firing. The effect is that it can be suppressed.
- the organic solvent used for washing include toluene, quinoline, acetone, hexane, benzene, xylene, methylnaphthalene, alcohols, coal-based oil, and petroleum-based oil.
- toluene, quinoline, acetone, benzene, xylene, methanol, coal-based light oil “medium oil, petroleum-based light oil” medium oil and the like are more preferable.
- the solid-phase method In the method of forming a low-crystalline carbon material on the surface of graphite powder, the solid-phase method In this method, a carbon precursor is carbonized via a solid phase, and the raw material is attached to the surface of graphite, and the carbon is formed on the surface by firing. Generally, a resin undergoes carbonization via a solid phase.However, in order to attach such a resin to the surface of graphite powder, the resin is dissolved in a solvent, or heated to a temperature equal to or higher than the melting point. However, there is a method of mixing and adhering to the surface by the method described in the description of the liquid phase method. It is also possible to mix the resin and black powder by mixing them and keeping them near the melting point during firing.
- Specific raw materials include: polyamideimide resin; polyamide resin; conjugated resin such as polyacetylene, poly (p-phenylene), poly (p-phenylenevinylene); phenolic resin; furfuryl alcohol resin; Cellulose; acrylic resins such as polyatarilonitrile and poly ( ⁇ -halogenated acrylonitrile); halogenated vinyl resins such as polychlorinated vinyl, polyvinylidene chloride, and chlorinated polychlorinated vinyl; and the like.
- the firing conditions the firing method and firing atmosphere described in the above liquid layer method can be applied.
- the low crystalline carbon material obtained by the above method is more preferably an X-ray wide angle diffraction method in which the average plane spacing (d002) of the (002) plane is larger than 340 nm.
- the crystallite thickness (L c) in the (002) plane direction is smaller than 40 nm (more preferably, smaller than 10 nm), and the crystallite thickness (L a) in the (110) plane direction Is smaller than 50 nm (more preferably smaller than 1 O nm), and the R value is larger than 0.4 (more preferably larger than 0.5).
- a negative electrode is formed by mixing 1 to 30 parts by weight of a binder with 100 parts by weight of the active material.
- Fluoropolymers such as polytetrafluoroethylene and polyvinylidene fluoride, polyolefin polymers such as polyethylene and polypropylene, and synthetic rubbers can be used as the binder, but are not limited thereto. is not . If the amount of the binder is more than 30 parts by weight, a practical lithium polymer battery cannot be produced because the resistance or polarization of the negative electrode increases and the discharge capacity decreases. On the other hand, if the amount of the binder is less than 1 part by weight, the binding ability is lost, which is not practical.
- a heat treatment can be performed at a temperature around the melting point of the binder in order to improve the binding property.
- synthetic rubbers as the binder among the binders.
- a negative electrode having the above compression ratio and a physical property of a coated film density of 1.5 g / cc or more after pressing may be liable to cycle deterioration due to repeated expansion and contraction of the negative electrode due to charge and discharge. . Since the rubber-based binder has strong binding ability and rubber elasticity, it is thought that it is possible to follow the expansion and contraction of the active material and suppress cycle deterioration of the negative electrode.
- the polymerizable monomer used as a raw material of the chemically crosslinked gel in the present invention is not particularly limited as long as it has affinity with a solvent solution of an electrolyte and has a polymerizable functional group.
- examples thereof include those having a polyether structure and an unsaturated double bond group, and polymerizable monomers for providing polymers such as oligoester acrylate, polyester, polyimine, polythioether, and polysulfane, alone or in combination of two or more.
- those having a polyether structure and an unsaturated double bond group are preferable from the viewpoint of affinity with a solvent.
- polyether structural unit examples include ethylene oxide, propylene oxide, butylene oxide, glycidyl ethers, and the like, and a single or a combination of two or more of them can be used. In the case of a combination of two or more, the form can be appropriately selected regardless of block or random. Among them, the use of an acrylate-based polymerizable monomer composed of a polyfunctional monomer and a monofunctional monomer is preferable because it gives a gel having strength and elasticity that can follow the volume change of the negative electrode.
- the acrylate ester-based monomer one obtained by esterifying a terminal hydroxyl group of polyether polyol with acrylic acid can be suitably used.
- the polyfunctional monomer is a polyether obtained by using polyhydric alcohols such as ethylene glycol, glycerin, and trimethylolpropane as initiators, and adding ethylene oxide (EO) alone or by adding EO and propylene oxide (PO) to addition polymerization. It is obtained by esterifying the terminal hydroxyl groups of the polyol with acrylic acid.
- the monofunctional monomer is a polyhydric alcohol obtained by addition polymerization of ethylene oxide (EO) alone or EO with propylene oxide (PO) using a monovalent alcohol such as methanol, ethanol, or propanol as an initiator. It is obtained by esterifying the terminal hydroxyl group of the ether polyol with acrylic acid.
- the polyfunctional monomer plays an important role in the liquid retention of the electrolyte of the gel electrolyte, and the average molecular weight is more preferably in the range of 5,000 to 10,000. When a polyfunctional monomer within the above range is employed, it can be easily dissolved in the electrolyte when adjusting the precursor, and has excellent liquid retaining properties when the gel electrolyte is prepared.
- a monofunctional monomer having a smaller average molecular weight can improve the flexibility of the gel electrolyte, and a monofunctional monomer having an average molecular weight of about 200 to 3,000 is preferably used.
- Examples of the electrolytic solution used for the electrolyte include cyclic carbonates such as PC, EC, and butylene carbonate; chain carbonates such as dimethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate; ⁇ -butyrolactone; Ratatones such as ⁇ -valerolatatatone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, ethyl ether, ethers such as 1,2-dimethoxetane, 1,2-diethoxetane, ethoxymethoxetane, dioxane, dimethyl sulfoxide, sulfolane, Examples thereof include methylsulfolane, acetonitrile, methyl formate, and methyl acetate, and these can be used.
- lithium perchlorate Li i C 10 4
- lithium Hofujidani Li i BF 4
- lithium phosphofluoride Li i PF 6
- lithium hexafluoroarsenate Li i As F 6
- 6 lithium fluoride antimonate Li i SbF 6
- triflumizole Ruo b lithium methanesulfonate Li i CF 3 S0 3)
- Torifuruoro lithium acetate Li i CF 3 COO
- triflumizole Ruo b methanesulfonic acid imide lithium Li iN ( Lithium salts such as CF 3 SO 2 ) 2
- LiN Lithium salts such as CF 3 SO 2 ) 2
- the electrolyte is obtained by dissolving the electrolyte salt in the solvent selected above to prepare an electrolyte solution, mixing with the polymerizable monomer, and polymerizing.
- the ratio of the polymerizable monomer and the electrolyte is as follows: from the viewpoint of the performance comparable to the electrolyte and the retention of the electrolyte that does not cause the electrolyte leakage, the electrolyte: the monomer is 70:30 to 99:
- 1 is preferred, and more preferably 80:20 to 97: 3.
- the ratio is preferably such that the polyfunctional monomer: monofunctional monomer is mixed in the range of 4: 6 to 9: 1.
- a method for crosslinking the solid polymer electrolyte a method using photoenergy such as ultraviolet light, an electron beam, and visible light, and a method using heating can be used. It is also important to use a polymerization initiator if necessary. In particular, in a crosslinking method using ultraviolet rays or heating, it is preferable to add a few percent or less of a polymerization initiator.
- the polymerization initiator include photopolymerization initiators such as trimethylsilyl benzophenone, benzoin, 2-methylbenzoin, 4-methoxybenzophenone, benzoin methinoleate> ⁇ leanthraquinone, benzyl ⁇ / dimethyl ketal and the like.
- a polymerization initiator such as benzoyl oxide, methylethylketone peroxide, ⁇ , ⁇ '-azobisisobutyronitrile may be added.
- the wavelength of UV polymerization and UV light is suitably from 250 to 360 nm. According to the present invention, even when an initiator is used, a good polymer can be obtained with a small amount of initiator. Residual polymerization initiators and by-products due to the polymerization initiator may adversely affect battery characteristics, and are therefore preferably minimized.
- the amount of the initiator depends on the type of the initiator, it is usually preferable to keep the amount of the initiator at 300 ppm or less with respect to the precursor composed of the polymerizable monomer and the electrolytic solution.
- an oxide containing lithium can be used as the positive electrode active material.
- L i C o 0 2 Specific examples of the cathode active material, L i N i 0 2, L i F e 0 2, L i Mn 0 2, L i Mn a O 4 or their transition metal, A partially substituted material may be used. This is mixed with a conductive material, a binder, and in some cases, a solid electrolyte or the like to form a positive electrode. The mixing ratio can be 5 to 50 parts by weight of the conductive material and 1 to 30 parts by weight of the binder with respect to 100 parts by weight of the active material.
- the conductive material carbons such as carbon black (acetylene black, thermal black, channel black, etc.), graphite powder, metal powder and the like can be used, but are not limited thereto.
- binder examples include fluorine polymers such as polytetrafluoroethylene and polyvinylidene fluoride, and polyolefin polymers such as polyethylene and polypropylene.
- the amount of the conductive material is less than 5 parts by weight or the amount of the binder is more than 30 parts by weight, the resistance or the polarization of the positive electrode increases and the discharge capacity decreases, so that a practical lithium polymer battery cannot be manufactured. If the conductive material is more than 50 parts by weight (parts by weight vary depending on the type of conductive material mixed), the amount of active material contained in the positive electrode decreases, and the discharge capacity of the positive electrode decreases. If the amount of the binder is less than 1 part by weight, the binding ability is lost.
- the amount of the active material contained in the positive electrode decreases as in the case of the conductive material, and further, as described above, the resistance or polarization of the positive electrode increases and the discharge capacity decreases. Not practical.
- a 1: 1 mixed solvent of EC and ⁇ _butyrolataton in which 1 liter of lmo Li BF 4 was dissolved was used as an electrolyte.
- a monomer having a weight ratio of 7: 3 was mixed with the electrolyte so that the ratio of the electrolyte to the monomer was 95: 5.
- To the solution was added 200 ppm of a thermal polymerization initiator based on the total weight to prepare a precursor.
- the thermal polymerization initiator used is t-butyl peroxyneodecanate.
- the graphite powder and the precursor were mixed so that the ratio by weight was 1:10, and the mixture was kept in a constant temperature bath at 80 ° C. for 24 hours to check the curing state of the precursor.
- Example 1 The amount of low crystalline carbon material / (the amount of high crystalline graphite powder + (the amount of high crystalline graphite powder + A hardening experiment was conducted using an average value of the amount of the low-crystalline carbon material) (Example 1). In addition, Comparative Example 1 was a case where the low-crystalline carbon material was not coated. Table 1 shows the results. In Table 1, ⁇ is sufficiently cured and there is no liquid part ⁇ means that the gel is slightly soft but no liquid part remains, and X means that the liquid part is not fully cured and a liquid part is observed.
- Table 1 shows that the higher the coating ratio, the better the curing condition.
- the composite graphite material powder hardened regardless of the initiator concentration, and was particularly more effective in the region where the initiator was 5000 ppm or less than when only the core material was used.
- lithium cobaltate Li Co0 2
- a positive electrode active material Using lithium cobaltate (L i Co0 2) as a positive electrode active material.
- a binder solution obtained by dissolving vinylidene polyfluoride as a binder in a solvent N-methyl-12-pyrrolidone in a mortar. A paste was made.
- the paste thus obtained was applied on an aluminum foil current collector, which was temporarily dried at 60 ° C., heat-treated at 150 ° C., and pressed.
- the negative electrode size was 3.5 x 3 cm (coated area 3 x 3 cm), and aluminum foil (50 zni) was welded to the uncoated area. Furthermore, what was dried at 180 ° C. under reduced pressure to remove water was used as a positive electrode for testing.
- the coating density was 2.9 g / cm 3 .
- a 1: 1 mixed solvent of E C and ⁇ _butyrolactone in which 8 mol / liter of LiB F4 was dissolved was used as an electrolyte.
- a tetrafunctional acrylate monomer having an average molecular weight of 750 to 9000 containing a copolymer of ethylene oxide and propylene oxide and a monofunctional acrylate monomer having an average molecular weight of 200 to 300 are in a weight ratio of 7: 3.
- a thermal polymerization initiator was added to the solution at 200 ppm based on the total weight to form a precursor.
- the electrodes obtained as described above were overlapped so as to face each other, and inserted into a bag-shaped aluminum laminate bag.
- the above precursor was put therein, and heat sealing was performed under reduced pressure. Next, it was kept at 80 ° C. for 4 hours to carry out thermal polymerization, thereby producing a polymer battery.
- the obtained battery is charged at a current value of 4 mA, charged at 4.1 V-CCCV (constant current and voltage), and discharged at 2.75.
- V-CC constant current
- Table 2 shows the materials used, mixing ratios, etc., coating density (before pressing), compression ratio, coating density (after pressing), volume energy density per negative electrode active material layer, and capacity retention during cycling.
- Table 3 shows the rates.
- the coating density of the obtained negative electrode was 1.65 gZcm 3 .
- a battery was prepared in the same manner as in Example 2 except that the negative electrode thus obtained was used, and a charge / discharge test was performed.
- Table 2 shows the materials used, mixing ratios, etc.
- Table 3 shows the coating density (before pressing), compression ratio, coating density (after pressing), volume energy density per negative electrode active material layer, and capacity retention during cycling. Shown in
- a negative electrode and a battery were produced in the same manner as in Example 2 except that the graphite material powder shown in Table 2 was used as an active material as a carbon material. Result (coating density (before pressing), compression ratio
- Table 3 shows the coating density (after pressing), the volume energy density per negative electrode active material layer, and the capacity retention during cycling.
- MCMB is an abbreviation for mesocarbon microbeads, which is a pitch-based spherical carbon material.
- a positive electrode and a negative electrode were produced in the same manner as in Example 2 except that the composite graphite material powder shown in Table 4 was used.
- a tetrafunctional acrylate monomer having an average molecular weight of 7500 to 9000 containing a copolymer of ethylene oxide and propylene oxide and a monofunctional acrylate monomer having an average molecular weight of 200 to 300 have a weight ratio of 9: 1.
- the monomer was mixed with the electrolyte so that the ratio of the electroless drought to the monomer was 97: 3.
- a UV initiator was added to the solution at 2000 ppm based on the total weight to form a precursor.
- a non-woven fabric made of polyester is placed on the positive electrode as a separator, impregnated with a precursor for the positive electrode, sandwiched between quartz plates, and irradiated with 3 OmW / cm 2 UV light.
- the negative electrode was impregnated with a precursor for the negative electrode, and was similarly irradiated with UV light to integrate the negative electrode and the electrolyte layer.
- the obtained electrodes were bonded together so that the active material layers faced each other, inserted into a bag-shaped aluminum laminate, and heat-sealed under reduced pressure to produce a lithium polymer battery. Charge the obtained battery with a current value of 4 mA.4.IV
- a lithium polymer battery was prepared in the same manner as in Example 6, except that 2 parts of SBR (styrene butadiene rubber) and 2 parts of CMC—NH 4 were used as a binder for the negative electrode, and water was used as a dispersion medium. An evaluation was performed. Table 4 shows the mixing ratio, etc., and Table 5 shows the coating density (before pressing), compression ratio, coating density (after pressing), volume energy density per negative electrode active material layer, and capacity retention during cycling.
- SBR styrene butadiene rubber
- CMC—NH 4 styrene butadiene rubber
- Table 4 shows the mixing ratio, etc.
- Table 5 shows the coating density (before pressing), compression ratio, coating density (after pressing), volume energy density per negative electrode active material layer, and capacity retention during cycling.
- a polymer battery was produced in the same manner as in Example 6, except that the composite graphite material powder shown in Table 4 was used. Table 5 shows the results.
- the lithium polymer battery provided by the present invention uses a chemically crosslinked gel, the gel does not dissolve and become liquefied even when the battery is exposed to high temperatures. Therefore, a highly reliable battery in which swelling of the battery is unlikely to occur can be obtained.
- the feature of the lithium polymer battery is that it can be made thinner and can be freely shaped. By using it inside a gap between electronic devices, the feature can be used more effectively. In applications where the user cannot easily replace the battery, long-term reliability and battery swelling are extremely important, and its industrial significance is significant.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
Description
Claims
Priority Applications (1)
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AU2003261897A AU2003261897A1 (en) | 2002-09-19 | 2003-09-03 | Lithium polymer battery and method for manufacturing same |
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JP2002-273688 | 2002-09-19 | ||
JP2002273688A JP4336087B2 (ja) | 2002-09-19 | 2002-09-19 | リチウムポリマー電池及びその製造方法 |
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PCT/JP2003/011231 WO2004027902A1 (ja) | 2002-09-19 | 2003-09-03 | リチウムポリマー電池及びその製造方法 |
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JP (1) | JP4336087B2 (ja) |
KR (1) | KR100656848B1 (ja) |
CN (1) | CN100355117C (ja) |
AU (1) | AU2003261897A1 (ja) |
TW (1) | TWI266444B (ja) |
WO (1) | WO2004027902A1 (ja) |
Cited By (3)
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---|---|---|---|---|
CN1331253C (zh) * | 2004-04-29 | 2007-08-08 | 宁波杉杉新材料科技有限公司 | 人造石墨锂离子电池负极材料制造方法 |
CN100341173C (zh) * | 2004-04-29 | 2007-10-03 | 宁波杉杉新材料科技有限公司 | 天然石墨锂离子电池负极材料制造方法 |
WO2021260175A1 (fr) * | 2020-06-26 | 2021-12-30 | Saft | Electrode négative hybride graphite/lithium |
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JP5623686B2 (ja) | 2007-06-01 | 2014-11-12 | パナソニック株式会社 | 複合負極活物質および非水電解質二次電池 |
JP5131913B2 (ja) * | 2008-03-31 | 2013-01-30 | 三井造船株式会社 | 電極材料に用いる粒子の炭素コーティング方法および二次電池 |
KR101319676B1 (ko) * | 2009-03-30 | 2013-10-17 | 쥬오 덴끼 고교 가부시키가이샤 | 혼합 탄소 재료 및 비수계 이차 전지용 음극 |
US9412235B2 (en) | 2009-05-08 | 2016-08-09 | Aristocrat Technologies Australia Pty Limited | Gaming system, a method of gaming and a linked game controller |
WO2012127548A1 (ja) * | 2011-03-18 | 2012-09-27 | パナソニック株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
JP2014067625A (ja) * | 2012-09-26 | 2014-04-17 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
KR102236913B1 (ko) | 2014-08-28 | 2021-04-05 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 음극 및 이를 포함하는 리튬 이차 전지 |
JP6240586B2 (ja) * | 2014-10-28 | 2017-11-29 | Jfeケミカル株式会社 | リチウムイオン二次電池負極材料用黒鉛質粒子、リチウムイオン二次電池負極およびリチウムイオン二次電池 |
CN105633356B (zh) * | 2014-11-06 | 2020-07-28 | 中国电子科技集团公司第十八研究所 | 安全高比能量锂离子电池正极材料的制备方法 |
WO2017057123A1 (ja) * | 2015-09-30 | 2017-04-06 | Necエナジーデバイス株式会社 | リチウムイオン二次電池用負極及びリチウムイオン二次電池 |
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- 2002-09-19 JP JP2002273688A patent/JP4336087B2/ja not_active Expired - Fee Related
-
2003
- 2003-09-03 AU AU2003261897A patent/AU2003261897A1/en not_active Abandoned
- 2003-09-03 WO PCT/JP2003/011231 patent/WO2004027902A1/ja active Application Filing
- 2003-09-03 CN CNB038222345A patent/CN100355117C/zh not_active Expired - Fee Related
- 2003-09-03 KR KR1020057004776A patent/KR100656848B1/ko active IP Right Grant
- 2003-09-12 TW TW092125192A patent/TWI266444B/zh not_active IP Right Cessation
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CN1331253C (zh) * | 2004-04-29 | 2007-08-08 | 宁波杉杉新材料科技有限公司 | 人造石墨锂离子电池负极材料制造方法 |
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Also Published As
Publication number | Publication date |
---|---|
CN1682392A (zh) | 2005-10-12 |
AU2003261897A1 (en) | 2004-04-08 |
KR20050057491A (ko) | 2005-06-16 |
CN100355117C (zh) | 2007-12-12 |
KR100656848B1 (ko) | 2006-12-13 |
TWI266444B (en) | 2006-11-11 |
JP2004111272A (ja) | 2004-04-08 |
TW200408154A (en) | 2004-05-16 |
JP4336087B2 (ja) | 2009-09-30 |
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