WO2014013837A1 - Particules de matériau actif pour batteries secondaires au lithium-ion, et batterie secondaire au lithium-ion utilisant celles-ci - Google Patents

Particules de matériau actif pour batteries secondaires au lithium-ion, et batterie secondaire au lithium-ion utilisant celles-ci Download PDF

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WO2014013837A1
WO2014013837A1 PCT/JP2013/067027 JP2013067027W WO2014013837A1 WO 2014013837 A1 WO2014013837 A1 WO 2014013837A1 JP 2013067027 W JP2013067027 W JP 2013067027W WO 2014013837 A1 WO2014013837 A1 WO 2014013837A1
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lithium ion
active material
ion secondary
electrode active
secondary batteries
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PCT/JP2013/067027
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English (en)
Japanese (ja)
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良幸 高森
心 ▲高▼橋
正 藤枝
拓也 青柳
尚貴 木村
達哉 遠山
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株式会社 日立製作所
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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
    • H01M4/131—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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 ion secondary battery active material particle and a lithium ion secondary battery using the same.
  • a lithium ion secondary battery has a high atomic energy density and a high gravimetric energy density compared to other secondary batteries because of its low atomic weight and high ionization tendency. Therefore, it is widely used as a power source for portable devices such as mobile phones and notebook PCs. Furthermore, because of global warming prevention and fossil fuel exhaustion problems, application to power sources for power storage of power generation systems using renewable energy such as solar power generation and solar power generation and solar power generation is also promoted. ing. Most of lithium ion secondary batteries put to practical use at present use a flammable organic electrolyte solution as the electrolyte. Therefore, there is a risk such as liquid leakage and ignition, and the development of a highly safe lithium ion secondary battery free of these risks is desired.
  • Patent Document 1 a change in battery dimensions, an increase in internal resistance, and a charge / discharge performance at a large current due to expansion / contraction of an active material accompanying charge / discharge of a lithium secondary battery. It has been proposed to solve the deterioration of the above using active material particles coated with a covering layer containing a conductive agent and a lithium ion conductive inorganic solid electrolyte.
  • the surface of the active material of the all solid lithium ion secondary battery is covered with a layer mainly composed of a hard glassy solid electrolyte having lithium ion conductivity, so that it is active when lithium ions are inserted into the active material.
  • the expansion of the substance can be suppressed by the hard coating layer covering the active material.
  • the lithium ion secondary battery of the present invention for solving the above problems includes a positive electrode, a negative electrode, and a solid electrolyte, and at least one of a positive electrode active material and a negative electrode active material occludes and releases lithium ions to expand. It is characterized in that it is coated with a coating layer containing oxide glass having a shrinking property.
  • the positive electrode active material particles or the negative electrode active material particles according to the present invention for solving the above problems are a coating layer including an oxide glass having a property of absorbing and releasing lithium ions to expand and contract the surface of the active material. It is characterized by being covered.
  • the coating layer is preferably a low melting point oxide glass having lithium ion conductivity and containing vanadium and / or phosphorus or tellurium.
  • the above configuration it is possible to provide a highly safe and long life all solid lithium ion secondary battery.
  • the expansion and contraction of the positive and negative electrode active materials accompanying charge and discharge the contact surfaces of the positive and negative electrode active materials and the solid electrolyte are peeled off to prevent the lithium ion conductive network from being divided.
  • the lithium ion conductivity of the lithium ion secondary battery can be maintained, and the performance deterioration due to the repetition of charge and discharge cycles can be suppressed.
  • FIG. 2 is a schematic view of an all solid lithium ion secondary battery.
  • the solid electrolyte layer 4 is disposed between the positive electrode 5 and the negative electrode 7.
  • the all solid lithium ion secondary battery is highly safe because it uses a nonflammable solid electrolyte having lithium ion conductivity as an electrolyte.
  • the inventors of the present invention conducted intensive studies on reduction of lithium ion conduction resistance, which is a problem of all solid lithium ion secondary batteries. As a result, by providing a coating layer having a feature of expanding and contracting due to lithium ion absorption / desorption around the active material, deterioration in performance due to repeated charging and discharging was suppressed.
  • the covering layer can reduce the volume change of the active material, and can suppress the separation of the interface with the solid electrolyte.
  • the present inventors have led to the development of a low melting point oxide glass material having lithium ion conductivity.
  • the low melting point oxide glass containing at least one of vanadium oxide and tellurium or phosphorus has a feature of expansion and contraction due to absorption and release of lithium ions.
  • the oxide glass material used for the coating layer contains at least one of vanadium and tellurium or phosphorus, has lithium ion conductivity, and has a property of expanding and contracting due to absorption and release of lithium ions.
  • the positive and negative electrode active material particles and the solid electrolyte can be obtained by the expansion and contraction of the positive and negative electrode active materials during charge and discharge.
  • the contact surfaces of the particles peel off, preventing the lithium ion conducting network from breaking up. Thereby, the lithium ion conductivity can be maintained even when the charge and discharge cycle is repeated, and the battery performance can be suppressed from being deteriorated.
  • a conductive material powder such as acetylene black or a metal powder may be added to the covering layer in order to enhance the electron conductivity in the electrode, if necessary.
  • the oxide glass has a low melting point, specifically, a softening point of 500 ° C. or less.
  • the coating treatment is performed at a high temperature of 700 ° C. to 1200 ° C., but in the treatment at such a high temperature, the reaction of the active material and the solid electrolyte coating layer results in the active material particles and the coating layer An altered layer may occur at the layer interface.
  • the contact surface may peel off or a crack may occur in the coating layer at the time of temperature decrease after heat treatment at high temperature. is there.
  • the covering layer made of oxide glass may be provided on solid electrolyte particles in addition to the positive and negative electrode active material particles.
  • solid electrolyte particles are bound with each other by using a binder or hot pressed to form a solid electrolyte layer.
  • the binder does not have lithium ion conductivity, and thus solid electrolyte particles are bound to one another. Even if it is worn, that part does not contribute to lithium ion conduction. Therefore, there is a problem that a sufficient lithium ion conduction path is not formed, and the ion conduction resistance is increased.
  • a solid electrolyte particle is provided with a coating layer made of the oxide glass of the present invention
  • the coated solid electrolyte particle is dispersed in a solvent and coated in a sheet, and then the softening point of the oxide glass is obtained.
  • the solid electrolyte particles can be bound with a material having lithium ion conductivity, so the contact area between the solid electrolyte particles becomes wide, and the lithium ion conductivity is greatly improved.
  • the oxide glass coating layer according to the present invention has a low softening point of 500 ° C.
  • FIG. 1 is a view showing an example of a positive electrode active material particle having a covering layer 2 in which a positive electrode active material 1 is coated with an oxide glass.
  • the covering layer 2 made of oxide glass is characterized in that its volume expands and contracts due to the absorption and release of lithium ions 3.
  • the lithium ion 3 is released from the positive electrode active material 1 by charging and the positive electrode active material 1 contracts, the lithium ion 3 released from the positive electrode active material is inserted into the oxide glass coated with the positive electrode active material 1 Layer 2 expands. As a result, the volume change of the whole active material particle can be suppressed.
  • the oxide glass may be an amorphous so-called ordinary glass or a crystallized glass in which crystals are precipitated in an amorphous glass matrix.
  • amorphous oxide glass is superior in coverage to crystallized glass.
  • crystallized glass is more excellent in lithium ion conductivity. Therefore, when the periphery of the active material is coated with amorphous oxide glass, and active material particles having this coating layer are bonded with crystalline oxide glass, the lithium ion conductivity is particularly excellent. It becomes possible to form an electrode.
  • the oxide glass is characterized by containing vanadium as a main component and at least one selected from tellurium and phosphorus as another component.
  • iron, manganese, tungsten, molybdenum, barium, cobalt or the like can be added to the oxide glass to control crystallinity, a softening point, and a thermal expansion coefficient.
  • the softening point of the oxide glass is preferably 500 ° C. or less, and more preferably the softening point is 400 ° C. or less.
  • the softening point of the oxide glass forming the coating layer of the solid electrolyte is that of the oxide glass forming the coating layer of the active material. It is preferable to be higher than the softening point. In some cases, heating may be performed when the battery is manufactured by combining the positive electrode, the negative electrode, and the electrolyte, and by raising the softening point of the electrolyte, problems such as short circuit between the positive and negative electrodes are less likely to occur.
  • the amount of oxide glass to be coated is changed because the degree of expansion and contraction varies depending on the type of active material, but the amount of oxide glass added is 1% by volume or more and 30% by volume in terms of volume with respect to the active material It is desirable that If it is less than 1% by volume, the active material can not be sufficiently coated, and a sufficient effect of the covering layer can not be obtained. If it is more than 30% by volume, the lithium ion contributes to charge and discharge when forming the electrode. This is because the amount decreases and the capacity of the battery decreases.
  • a known positive electrode active material capable of inserting and extracting lithium ions can be used.
  • it can be represented by LiMO 2 (M is at least one transition metal), and M includes Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V and the like.
  • M is at least one transition metal
  • M includes Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V and the like.
  • a part of manganese or cobalt or nickel such as lithium manganate or lithium cobaltate or lithium nickelate represented by LiMO 2 may be substituted with one or two transition metals, or magnesium or aluminum. It can be used even if it substitutes with a metal element.
  • oxide glass containing vanadium as a main component is used as the covering material, if crystallized glass containing vanadium is used as the positive electrode active material, adhesion between the active material and the covering layer and transfer of lithium ions are further increased. It becomes good.
  • a known negative electrode active material capable of inserting and extracting lithium ions can be used as the negative electrode active material.
  • a carbon material typified by graphite an alloy material such as a TiSn alloy or a TiSi alloy, a nitride such as LiCoN, or an oxide such as Li 4 Ti 5 O 12 can be used.
  • lithium foil may be used.
  • the solid electrolyte material which conducts lithium ion can be used.
  • a nonflammable inorganic solid electrolyte is preferred.
  • a sulfide glass represented by lithium halides such as LiCl and LiI
  • Oxide glasses represented by Li 3.4 V 0.6 Si 0.4 O 4 , Li 2 P 2 O 6 and the like, and perovskite oxides represented by Li 0.34 La 0.51 TiO 2.94 and the like can be used.
  • the material of an oxide type has high stability with respect to water or oxygen rather than sulfide glass, and is preferable.
  • the method of coating oxide glass is not particularly limited.
  • a positive and negative electrode active material or a solid electrolyte and oxide glass are mixed at a predetermined ratio, coated by heat treatment at a temperature above the softening point of the oxide glass, and then crushed by a ball mill etc.
  • a method of coating the particles by heat treatment at a temperature above the softening point of the oxide glass, etc. may be mentioned.
  • the particle size of the oxide glass particles is smaller than the particle size of the particles to be coated Is desirable.
  • a present Example is an example which coat
  • an oxide glass coating material was produced.
  • As raw materials 255 g of vanadium pentoxide (V 2 O 5 ) powder, 30 g of phosphorus pentoxide (P 2 O 5 ) powder, and 15 g of cobalt oxide (CoO) powder are mixed, charged into a platinum crucible, and an electric furnace It was kept at 1100 ° C. for 2 hours. The temperature rising rate was 10 ° C./min. In addition, during heating, the material in the platinum crucible was stirred so as to be uniform. The sample after 2 hours passed was taken out of the electric furnace, poured on a stainless steel plate preheated to 300 ° C., and naturally cooled to obtain oxide glass (A). The softening point of the obtained glass measured by differential thermal analysis was 302 ° C., and the crystallization temperature was 369 ° C. The produced oxide glass (A) was crushed using a ball mill so that the average particle diameter was about 1 ⁇ m.
  • ⁇ Positive electrode active material particles LiCoO 2 powder with an average particle diameter of 10 ⁇ m was used as the positive electrode active material. Mix 95% by volume of LiCoO 2 powder and ketjen black as a conductive material, mix 85% by volume of the oxide glass (A) powder prepared with this mixture powder, and treat for 10 minutes using a ball mill By doing this, composite particles were produced.
  • the composite glass particles were treated for 30 minutes in dry air at 315 ° C., which is higher than the softening point of the oxide glass, to prepare oxide glass-coated active material particles.
  • a present Example is an example which produced the electrode for lithium ion secondary batteries using the positive electrode active material particle produced in Example 1.
  • FIG. 1 A present Example is an example which produced the electrode for lithium ion secondary batteries using the positive electrode active material particle produced in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode paste was applied to a 20 ⁇ m thick aluminum foil, dried and heat-formed at 315 ° C. higher than the melting point of the oxide glass (A) to obtain a 120 ⁇ m thick positive electrode sheet.
  • the resultant was punched into a disk shape having a diameter of 14 mm to form a positive electrode layer.
  • a present Example is an example which coat
  • ⁇ Anode active material particles As the negative electrode active material, Li 4 Ti 5 O 12 powder having an average particle diameter of 10 ⁇ m was used. Li 4 Ti 5 O 12 powder Ketjen black as a conductive material 95 was mixed with 5% by volume, mixing the same oxide glass (A) powder as that used in the mixture powder and the positive electrode in 85:15 volume% And treated for 10 minutes using a ball mill to produce composite particles.
  • the composite glass particles were treated for 30 minutes in dry air at 315 ° C., which is higher than the softening point of the oxide glass, to prepare oxide glass-coated active material particles.
  • a present Example is an example which produced the electrode for lithium ion secondary batteries using the negative electrode active material particle produced in Example 3.
  • FIG. 1 A present Example is an example which produced the electrode for lithium ion secondary batteries using the negative electrode active material particle produced in Example 3.
  • the negative electrode paste was applied to a 20 ⁇ m thick copper foil, dried and heat-formed at 315 ° C. higher than the melting point of the oxide glass (A) to obtain a 120 ⁇ m thick negative electrode sheet.
  • the resultant was punched into a disk shape having a diameter of 14 mm to form a negative electrode layer.
  • the present example is an example in which an all solid lithium ion secondary battery was produced using Example 2 and Example 4.
  • an oxide glass coating material for a solid electrolyte was produced.
  • As raw materials 240 g of vanadium pentoxide (V 2 O 5 ) powder, 30 g of phosphorus pentoxide (P 2 O 5 ) powder, and 30 g of ferric oxide (Fe 2 O 3 ) powder are mixed and charged into a platinum crucible And kept at 1100 ° C. for 2 hours using an electric furnace. The temperature rising rate was 10 ° C./min. In addition, during heating, the material in the platinum crucible was stirred so as to be uniform.
  • the sample after 2 hours passed was taken out of the electric furnace, poured on a stainless steel plate preheated to 300 ° C., and naturally cooled to obtain oxide glass (B).
  • the softening point of the obtained glass measured by differential thermal analysis was 352 ° C., and the crystallization temperature was 422 ° C.
  • the produced oxide glass (B) was ground using a ball mill so that the average particle size was about 1 ⁇ m.
  • LATP having an average particle size of 5 ⁇ m was used. 95 volume% of LATP powder and 5 volume% of oxide glass (B) powder were mixed, this was thrown into NMP, and the solid electrolyte paste which adjusted viscosity to 20 Pa.s was obtained.
  • the solid electrolyte paste is applied to a 50 ⁇ m thick polyimide sheet, and drying and thermoforming are performed at 365 ° C., which is a temperature higher than the softening point of the oxide glass (B), for the purpose of glass coating treatment of the solid electrolyte A solid electrolyte sheet with a thickness of 100 ⁇ m was obtained. The resultant was punched into a disk shape having a diameter of 15 mm and separated from the polyimide sheet to form a solid electrolyte layer.
  • LiCoO 2 powder with an average particle diameter of 10 ⁇ m was used as the positive electrode active material. 8 g of LiCoO 2 powder, 1.5 g of LATP having an average particle diameter of 5 ⁇ m as a lithium ion conductor in the positive electrode layer, and 0.5 g of ketjen black as a conductive material are mixed, and 10 g of this mixed powder is polyvinylidene fluoride 1.0 g of this was added to NMP to obtain a positive electrode paste whose viscosity was adjusted to 20 Pa ⁇ s.
  • the positive electrode paste was applied to a 20 ⁇ m-thick aluminum foil, subjected to heating and drying treatment, and a 120 ⁇ m-thick positive electrode sheet was obtained.
  • the resultant was punched into a disk shape having a diameter of 14 mm to form a positive electrode layer.
  • ⁇ Negative electrode layer> Li 4 Ti 5 O 12 powder having an average particle diameter of 10 ⁇ m was used. 8 g of Li 4 Ti 5 O 12 powder, 1.5 g of LATP having an average particle diameter of 5 ⁇ m as a lithium ion conductor in the negative electrode layer, and 0.5 g of ketjen black as a conductive material, and 10 g of this mixed powder Then, 0.5 g of polyvinylidene fluoride was added thereto, and this was charged into NMP to obtain a negative electrode paste whose viscosity was adjusted to 20 Pa ⁇ s.
  • the negative electrode paste was applied to a copper foil of 20 ⁇ m in thickness, subjected to heat molding and drying treatment, to obtain a negative electrode sheet of 120 ⁇ m in thickness.
  • the resultant was punched into a disk shape having a diameter of 14 mm to form a negative electrode layer.
  • Solid electrolyte layer For the solid electrolyte, LATP having an average particle size of 5 ⁇ m was used. A solid electrolyte paste having a viscosity adjusted to 20 Pa ⁇ s was obtained by mixing 9.5 g of LATP powder and 0.5 g of polyvinylidene fluoride and introducing this into NMP. This solid electrolyte paste was applied to a 50 ⁇ m thick polyimide sheet and dried to obtain a 100 ⁇ m thick solid electrolyte sheet. The resultant was punched into a disk shape having a diameter of 15 mm and separated from the polyimide sheet to form a solid electrolyte layer.
  • Example 5 (Evaluation) Initial capacity measurement, internal resistance measurement, and charge and discharge cycle tests were performed on the batteries produced in Example 5 and Comparative Example. As a result, no significant difference was found in the initial capacities of the batteries produced in Example 5 and Comparative Example. On the other hand, regarding the internal resistance, the value of Example 5 is about 40% smaller than the internal resistance of the comparative example, and it is clear that the all solid lithium ion secondary battery of the example is superior.
  • the positive and negative electrode active material particles are coated with oxide glass having lithium ion conductivity, and it is estimated that the resistance is the highest in the battery reaction, and the transfer of lithium ions at the interface between the active material particles and the solid electrolyte In the solid electrolyte layer, by covering the solid electrolyte particles with an oxide glass layer having lithium ion conductivity, lithium ion conduction is formed when the solid electrolyte layer is formed. It is considered to be due to the development of the path.
  • the life of the all-solid-state lithium ion secondary battery of this example was significantly improved. This is because, even if the volume change of the active material occurs due to the insertion and desorption of lithium ions during charge and discharge, the coating layer expands and contracts due to the insertion and detachment of lithium ions in the oxide glass, and the interface It is considered that the decrease in performance could be suppressed by relieving the stress and maintaining the lithium ion conduction path.
  • the all-solid-state lithium ion secondary battery of this example is superior to the comparative example and superiority is confirmed.
  • the all-solid-state lithium ion secondary battery which used the solid electrolyte for electrolyte as an example was described in the present Example, you may apply to the lithium ion secondary battery which uses a liquid electrolyte for electrolyte. This is usually because when the positive electrode or the negative electrode is formed using a binder, the portion of the surface of the active material in contact with the binder is not in direct contact with the electrolyte solution which is a lithium ion conductive material, It is difficult for lithium ion to occlude and release.
  • the electrode when the electrode is formed by providing the covering layer of oxide glass on the positive and negative electrode active materials, the electrode does not contain the binder having no ion conductivity in the electrode. It can be made. Since the entire surface of the active material is in contact with the lithium ion conductor, insertion and extraction of lithium ions from the entire surface easily proceeds, and capacity increase and charge / discharge at a high rate become possible.
  • It relates to a lithium ion secondary battery, and can be used for an all solid lithium ion secondary battery that does not use a liquid as an electrolyte.
  • positive electrode active material 2; low melting point glass coating layer, 3; lithium ion, 4; solid electrolyte layer, 5; positive electrode, 6; positive electrode current collector, 7; negative electrode, 8; negative electrode current collector.

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Abstract

L'invention concerne une batterie secondaire au lithium-ion entièrement à l'état solide hautement sûre qui maintient la conductivité des ions de lithium, supprime la détérioration des performances due à la répétition des cycles de charge/décharge, et possède une longue durée de vie en service. Afin de réaliser l'objectif susmentionné, une batterie secondaire au lithium-ion selon la présente invention comprend une électrode positive, une électrode négative et un électrolyte solide, et est caractérisée en ce qu'un matériau actif d'électrode positive et/ou un matériau actif d'électrode négative est recouvert d'une couche de revêtement qui est formée de verre contenant du vanadium et du phosphore et/ou du tellure. De plus, les particules de matériau actif d'électrode positive ou les particules de matériau actif d'électrode négative, qui permettent de réaliser l'objectif susmentionné, sont caractérisées en ce que la surface du matériau actif est recouverte d'une couche de revêtement qui est formée de verre contenant du vanadium et du phosphore et/ou du tellure.
PCT/JP2013/067027 2012-07-19 2013-06-21 Particules de matériau actif pour batteries secondaires au lithium-ion, et batterie secondaire au lithium-ion utilisant celles-ci WO2014013837A1 (fr)

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JP2012160100A JP2014022204A (ja) 2012-07-19 2012-07-19 リチウムイオン二次電池用活物質粒子およびそれを用いたリチウムイオン二次電池
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US11217785B2 (en) 2017-01-24 2022-01-04 Samsung Electronics Co., Ltd. Composite cathode active material and secondary battery including the same
US11532813B2 (en) 2020-02-20 2022-12-20 Samsung Electronics Co., Ltd. Composite cathode active material, preparation method thereof, cathode layer including the same, and all-solid secondary battery including the cathode layer

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JP2015005398A (ja) * 2013-06-20 2015-01-08 トヨタ自動車株式会社 全固体リチウムイオン電池用正極
JP6102615B2 (ja) * 2013-08-01 2017-03-29 日立金属株式会社 負極活物質及びそれを用いた二次電池
JP6494194B2 (ja) * 2014-07-04 2019-04-03 マクセルホールディングス株式会社 リチウム二次電池用被覆正極活物質、その製造方法及びそれを用いたリチウム二次電池
CN113571676A (zh) 2015-04-02 2021-10-29 松下知识产权经营株式会社 电池
JP7104877B2 (ja) * 2017-11-16 2022-07-22 トヨタ自動車株式会社 リチウム二次電池用の正極材料
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KR20200039260A (ko) 2018-10-05 2020-04-16 주식회사 엘지화학 리튬 이차전지용 양극 및 이의 제조 방법
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