WO2007055007A1 - Particule de matiere active d’electrode negative pour une batterie secondaire au lithium, electrode negative l’utilisant et procede pour les fabriquer - Google Patents

Particule de matiere active d’electrode negative pour une batterie secondaire au lithium, electrode negative l’utilisant et procede pour les fabriquer Download PDF

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WO2007055007A1
WO2007055007A1 PCT/JP2005/020586 JP2005020586W WO2007055007A1 WO 2007055007 A1 WO2007055007 A1 WO 2007055007A1 JP 2005020586 W JP2005020586 W JP 2005020586W WO 2007055007 A1 WO2007055007 A1 WO 2007055007A1
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negative electrode
particles
active material
electrode active
alloy
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PCT/JP2005/020586
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English (en)
Japanese (ja)
Inventor
Hiroshi Kagawa
Tsutomu Sada
Kanae Hashimoto
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Pionics Co., Ltd.
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Priority to PCT/JP2005/020586 priority Critical patent/WO2007055007A1/fr
Publication of WO2007055007A1 publication Critical patent/WO2007055007A1/fr

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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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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 novel high-capacity negative electrode active material particle for a lithium secondary battery and a method for producing the same, and in particular, mainly silicon and / or tin having an amorphous region in whole or in part.
  • the present invention relates to a negative electrode for a secondary battery, active material particles, a negative electrode for a lithium secondary battery, a lithium secondary battery, and a method for producing them.
  • Lithium secondary batteries are used in particular for portable devices. Batteries that are used with many functions added to mobile phones and portable electronic devices such as portable devices such as recent portable devices, personal computers, and PDAs have an output voltage corresponding to the operating voltage of the device and the usage time. There is a demand to increase the battery capacity to be affected. In particular, regarding the increase in battery capacity to extend the usage time, the capacity of the battery cannot be increased in a limited battery space other than increasing the energy density of the active material that stores electrical energy.
  • the positive electrode active material of a typical lithium secondary battery conventionally used is lithium cobaltate, and the negative electrode active material is graphite. It is difficult to achieve a volumetric energy efficiency of 400 Wh / L or more with such a battery material configuration.
  • the theoretical energy amount of graphite as a negative electrode active material is 372 mAh / g, there is a limit to further improving battery capacity, and the use of other types of negative electrode active materials is not limited to each research institution or Researched and developed by battery manufacturers.
  • silicon and tin are listed as negative electrode active materials capable of occluding and releasing lithium, similar to graphite. It is explained that when these metals are used alone, the volume expands due to the occlusion of lithium (during charging), and conversely the volume shrinks during the release of lithium (during discharging).
  • Silicon and tin as negative electrode active materials have a large volume expansion / contraction ratio associated with insertion / desorption of lithium ions, and particles are likely to be finely divided. There is a problem that the charge / discharge performance deteriorates with the charge / discharge cycle.
  • the negative electrode active material is a force that covers the surface of the negative electrode current collector by sputtering, vacuum deposition, plating, or the like.
  • the thickness of the coating layer that can be formed by such a surface treatment method is at most about several ⁇ m. However, if the thickness of the coating layer is too thick, there is a problem in that the coating layer cracks due to a change in volume when lithium is occluded and released, resulting in pulverization.
  • the present invention was developed for the purpose of solving the above problems, and the main purpose thereof is (1) particles associated with insertion and extraction of lithium in the anode active material particles. (2) Retains the electrical connection between the finely divided fine particles even when the fine particles of the negative electrode active material particles are occluded / released Formation of an electrical connection network that can be used, (3) reduction in volume change during lithium insertion and extraction, and (4) surface treatment while increasing the amount of negative electrode active material coating on the negative electrode current collector
  • An object of the present invention is to provide negative electrode active material particles for a lithium secondary battery, a negative electrode for a lithium secondary battery, a lithium secondary battery, and a method for producing them, capable of reducing the load.
  • one of the negative electrode active material particles and the method for producing the same according to the present invention is an alloy mainly composed of silicon and / or tin having an amorphous region in whole or in part.
  • Particles, low-melting-point metal particles made of a low-melting-point metal element or an alloy containing them, and a carbon material fired at a low temperature, and the low-melting-point metal particles and the carbon material are all or part of the surface of the alloy particles Is fixed (or coated), or the low melting point gold Negative electrode active material particles for lithium secondary batteries that electrochemically occlude and release lithium, characterized in that alloy particles and carbon materials are fixed (or coated) on all or part of the surface of the metal particles And a method for manufacturing the same.
  • the alloy particles mainly containing silicon and / or tin having an amorphous region in whole or in part are used as a base material.
  • the low melting point metal particles and the carbon material are fixed (or coated) on all or part of the surface, or the low melting point metal particles are used as a base material, and silicon having an amorphous region on the surface or part thereof and / or Alternatively, it is possible to provide negative electrode active material particles having a complicated shape by adhering (or coating) the alloy particles mainly containing tin and the carbon material.
  • the negative electrode active material particle force S accompanies insertion and extraction of lithium.
  • the low melting point metal particles and the carbon material fill the gaps formed between the respective particles and the negative electrode current collector so as to maintain the electrical connection. Therefore, it is possible to expand the electrical tolerance for the volume change of the coating layer that causes the negative electrode short circuit.
  • the alloy particles having an amorphous region and the carbon material are fixed to all or a part of the surface of the low melting point metal particle, silicon and / or tin coated on the surface of the negative electrode active material particle
  • the low melting point metal particles serving as the core of each are the negative electrode current collector and the negative electrode active material particles adjacent thereto.
  • the conductive material such as carbon fiber existing around them serves to guarantee direct contact with the negative electrode current collector and the negative electrode active material particles adjacent thereto. To do.
  • the alloy particles themselves are refined from strain fatigue due to structural changes due to volume changes due to insertion and extraction of lithium, resulting in a decrease in electrical contact due to isolation.
  • a low melting point on the surface of the alloy particles When the metal particles and the carbon material are fixed, the low-melting-point metal particles and the carbon material function to secure an electrical connection ⁇ between the particles after the miniaturization by the volume change proceeds. Therefore, it is possible to provide a lithium secondary battery having excellent charge / discharge cycle characteristics regardless of the miniaturization of silicon and z or tin.
  • the negative electrode active material particles when the low melting point metal particles are combined with the alloy particles mainly composed of silicon and Z or tin as the negative electrode active material, the negative electrode active material particles have a predetermined thickness on the negative electrode current collector. In addition to forming an appropriate void between each particle and the negative electrode current collector, the low melting point metal particles are easily deformed, and combined with the lithium occlusion 'release of the coating layer.
  • the negative electrode active material particles according to the present invention act to absorb the volume change, and as a result, the volume change of the coating layer itself accompanying charge / discharge can be reduced.
  • the porosity of the coating layer formed on the negative electrode surface by the negative electrode active material particles according to the present invention is preferably in the range of 30 to 85%, preferably in the range of 30 to 65%. More preferred.
  • the porosity is less than 30%, it is difficult for the electrolytic solution to penetrate into the coating layer formed of the negative electrode active material particles, and a large amount of time is required for vacuum impregnation of the electrolytic solution. The battery performance is deteriorated due to the need for the amount of impregnation and the impregnation amount is insufficient, and the internal short circuit is likely to occur due to the movement of the electrode within the limited volume.
  • the porosity is higher than 65%, a predetermined amount of the negative electrode active material cannot be disposed within the limited volume, and the battery capacity is reduced. Particularly, when the porosity is higher than 85%, it becomes a serious problem. .
  • the average particle diameter of the produced negative electrode active material particles is 25 ⁇ m or less. More preferably, it effectively prevents the generation of stress strain against the volume change during insertion and extraction of negative electrode active material particles having an average particle size of 5 xm or less. Miniaturization can be suppressed.
  • the average particle diameter of the negative electrode active material particles is larger than 25 ⁇ m, irregularities are generated on the surface of the negative electrode coating layer, and in particular, a negative electrode current collector partially having a corner is formed into a negative electrode active material having such a large particle diameter.
  • a lithium secondary battery incorporating this negative electrode may cause an internal short circuit at a rate of about 23% and damage the separator. This was confirmed by dismantling the secondary battery.
  • the alloy particles mainly containing silicon and / or tin having an amorphous region used in the present invention preferably have a flat and fibrous shape such as a flat shape and a fibrous shape rather than a spherical shape. It was found that particles having such a shape are more difficult to refine.
  • the average particle diameter of the alloy particles themselves is 5 ⁇ m or less. More preferably, the use of alloy particles having an average particle size of 2 xm or less effectively suppresses stress strain in response to volume changes when lithium is absorbed and released, and is fine. Can be suppressed. In addition, if the average particle diameter of the low melting point metal particles themselves, which are the cores to be combined at this time, is suppressed to the following, the generation of stress strain can be effectively prevented and miniaturization can be suppressed.
  • the average particle diameter of the negative electrode active material particles is around the low melting point metal particles.
  • the average particle size of the particles as a whole is preferably 35 ⁇ or less, more preferably 15 / im or less.
  • the current collector can be uniformly coated, and electrical contact can be maintained with respect to the volume change of the particles during the insertion and extraction of lithium.
  • the average particle diameter of the alloy particles containing silicon and / or tin as the main component is larger than 5 ⁇ m, irregularities are generated on the surface of the negative electrode coating layer, and the average of the low melting point metal particles as the core
  • the particle diameter is larger than 15 ⁇ m, the thickness of the coating layer coated on the negative electrode current collector becomes larger than necessary.
  • the lithium secondary battery in which the negative electrode is incorporated has about 16%. It was confirmed by dismantling the damaged lithium-ion battery that the separator was damaged by causing internal short circuit at a rate.
  • the average particle diameter of the produced negative electrode active material particles is 3 If it exceeds 5 ⁇ m, the bonding thickness of the alloy particles mainly composed of silicon and / or tin fixed to the outer surface becomes too large, and the alloy particles become a low melting point metal as the charge / discharge cycle elapses. It peels off from the particle surface and becomes isolated.
  • the average particle diameter of the negative electrode active material particles in which the alloy particles mainly composed of silicon and iron or tin are fixed to all or a part of the surface of the low melting point metal particles is suppressed to 15 ⁇ m or less.
  • the alloy particles are fixed to the outer surface of the low-melting-point metal particles in a state of being stacked in a maximum of 3 to 4 layers, and resist the expansion and contraction of the alloy particles, so that the shape does not easily collapse.
  • the average particle size of the negative electrode active material particles when the core diameter is 7 ⁇ m or less, the stability of the composite negative electrode active material particles is further increased.
  • the shape of the alloy particles mainly composed of silicon and / or tin when fixed to the surface of the low-melting-point metal particles relaxes the uneven distribution of stress strain generated during insertion and extraction of lithium and makes it uniform.
  • the particle shape closer to the sphere is preferable, and the particle shape closer to the sphere is more difficult to proceed.
  • the alloy particles mainly composed of silicon and Z or tin used in the present invention preferably have an amorphous region in whole or in part.
  • the alloy particles mainly composed of silicon and Z or tin have an amorphous region in the whole or a part thereof, and other metal elements to be added are silicon and silicon. It may not be necessary to be alloyed with all of Z or tin, but may be alloyed with part of silicon and / or tin.
  • This amorphous region is generated by the method described below.
  • the other metal added to amorphize silicon and / or tin is to promote the amorphization of silicon and / or tin depending on the purpose and process of addition. It is roughly divided into a first other metal added to the metal and a second other metal added to make silicon and / or tin amorphous to form an alloy.
  • the first other metal added by using a general alloy production method is added to the total weight of the final negative electrode active material particles.
  • Pre-silicon and / or tin alloy particles are produced so as to be 0.1 wt% or less.
  • pre-silicon and / or tin alloy particles are prepared by adding about 0.1 wt% of the first other metal to silicon and / or tin in advance, the subsequent planets In the amorphization process using a ball mill or the like, if the first other metal is not added, the amorphization process time, which was about 30 to 48 hours without the addition of the first other metal, is about several hours. Short time and time can be greatly reduced.
  • the composition of the alloy particles after the above-mentioned pre-silicon and Z or tin alloy particles and the second other metal described later are amorphized and alloyed is the second other
  • the first metal has a lower rate than 0.1 wt% with respect to the total weight of the alloy particles. It will be contained in the amorphous alloy particles.
  • iron when iron is used as the first other metal in the silicon alloy particles, iron may be contained with a content of 0.1 wt% or more because iron contains a small amount of silicon.
  • suitable first other metals to be added in advance in order to promote the amorphization of silicon and / or tin include iron, ano-remium, chromium, antimony and magnesium.
  • pre-silicon and / or tin alloy particles in which silicon and Z or tin and a first other metal are alloyed can be obtained by adding silicon and Z or tin and a plurality of different first other metals. It may be alloyed.
  • the above pre-silicon and / or tin alloy particles are mixed with a second other metal and selected from at least a mechanical alloying method, a mechanical gliding method, a liquid quenching method, and a gas quenching method.
  • Alloy particles made mainly of silicon and Z or tin having amorphous regions in whole or in part are produced by the above manufacturing method 1.
  • the generated alloy particles containing silicon and / or tin as a main component may have an amorphous region in whole or in part
  • the other metal added is silicon and It may also be alloyed with silicon and / or part of tin that does not have to be alloyed with all of tin.
  • a mixed powder of alloy particles mainly composed of silicon and / or tin produced by the different production methods described above should be used. You can also.
  • the second other metal mixed with the pre-silicon and / or tin alloy particles includes iron, aluminum, cobalt, copper, There are nickel, chromium, magnesium, lead, zinc, bismuth and antimony, and tin is an effective metal for making amorphous silicon amorphous.
  • the alloy particles mainly composed of silicon and / or tin to be amorphized are amorphized by mixing the second other metal which is the same as or different from the first other metal. It may be a
  • the first and second other metals contained in the amorphous alloy particles mainly composed of amorphous silicon and / or tin are 10 to 83 wt% with respect to the total weight of the alloy particles. It is preferably included.
  • the first and second other metals contained in the amorphized alloy particles are less than 10 wt%, from strain fatigue due to structural changes accompanying volume expansion and contraction during lithium insertion and release, As alloy particles become finer, electrical contact between particles due to isolation tends to be poor.
  • silicon having an amorphous region manufactured by the above-described manufacturing method includes amorphous silicon, microcrystalline silicon, polycrystalline silicon, and single crystal silicon due to the difference in the crystal structure of silicon.
  • silicon having a microcrystalline region is included in addition to silicon having an amorphous region.
  • Microcrystalline silicon is a material in which both a peak near 520 cm 1 corresponding to a crystalline region and a peak near 480 cm 1 corresponding to an amorphous region are substantially detected in Raman spectroscopic analysis. Microcrystalline silicon is substantially composed of a crystalline region and an amorphous region.
  • the reason for using amorphous silicon and / or tin as the negative electrode active material is that, in the case of negative electrode active materials such as silicon and / or tin, which have been regarded as promising conventionally, lithium
  • One of the disadvantages is that the volume expansion change when occlusion or release is very large, 3 times the force, 4 times, and as a result, the crystals cannot withstand the volume change and become finely pulverized. As a result, the electrical connection path in the negative electrode is interrupted and does not contribute to the electrochemical reaction.
  • the durability against the expansion / contraction is due to the strong bonding force between the metals by being compounded with other metals.
  • the volume change of the particles themselves can be reduced by amorphization.
  • the electrical connection path in the negative electrode is prevented from being interrupted by the finely pulverized particles. This is because it can function extremely effectively.
  • the component contained in the electrolyte is composed of negative electrode active material particles. It is also considered that the adhesion between the negative electrode coated with the negative electrode active material particles and the solid electrolyte is improved as a result of diffusing into the layer and forming a solid solution.
  • the durability of the negative electrode active material in the negative electrode is enhanced with respect to expansion and contraction, the pulverization is suppressed, and further, the adhesion between the negative electrode and the solid electrolyte is improved, thereby charging the lithium secondary battery.
  • the proportion of the amorphous region in the total weight of the alloy particles containing silicon and / or tin as a main component is 80 wt% or more, the structural breakdown due to volume expansion / contraction of the alloy particles is suppressed, thereby reducing lithium.
  • Charge / discharge of secondary battery The capacity decay rate after 50 cycles is improved to about 1/20, and the capacity of lithium secondary battery is attenuated compared to the case of using silicon alloy particles that have not become amorphous. The suppression effect can be further enhanced.
  • each of the alloy particles serves as a nucleus thereof. It works to efficiently support the voids formed between the melting point metal particles while maintaining a constant contact, and furthermore, silicon that does not change the relative position of the low melting point metal particles during the insertion and extraction of lithium. Only alloy particles mainly composed of Z or tin have voids formed between the particles. The volume will expand and contract in it.
  • pre-silicon and / or tin alloy particles are made amorphous or amorphous.
  • the adhesion between the alloy particles mainly composed of silicon and Z or tin and the low melting point metal particles is preferably carried out in an inert gas or reducing gas atmosphere.
  • the proportion of the metal oxide generated at this time in the total weight of the negative electrode active material particles is greater than lwt%, the utilization factor of the initial negative electrode active material particles becomes 90% or less due to a synergistic effect. Therefore, the ratio of the metal oxide to the total weight of the negative electrode active material particles is preferably suppressed to 1 wt% or less.
  • the negative electrode active material particles according to the present invention have low melting point metal particles and a carbon material fixed (or coated, adhered, or bonded) to all or part of the surface of alloy particles mainly composed of silicon and / or tin. , Fusing, bonding, crimping, etc.), or adhering the alloy particles and the carbon material to all or a part of the surface of the low melting point metal particles (or coating, bonding, bonding, fusing, bonding)
  • the surface of the negative electrode active material particles has a very complicated shape.
  • the shape of the composite negative electrode active material particles is such that after the surface treatment is performed on the negative electrode current collector, appropriate voids are formed between the particles in the negative electrode coating layer to change the volume accompanying charge / discharge. Even when a volume change occurs, the gap between each particle generated thereby is ensured to ensure electrical connection between each particle. State Many additional effects are obtained.
  • the packing density of the negative electrode active material composite particles can be increased by the amount that the binder can be omitted.
  • the omitted binder does not contribute to the electrochemical reaction at all, and as a result, the battery capacity of the lithium secondary battery can be increased.
  • the lithium secondary battery to which the negative electrode according to the present invention is applied can be charged and discharged with extremely high efficiency.
  • the network conductive network formed between the low melting point metal particles and the carbon material activates and promotes the function as the negative electrode active material. Therefore, the conductivity and battery capacity of the lithium secondary battery are further improved.
  • the low-melting-point metal particles and the carbon material forming the network conductive network have a volume expansion of the negative electrode active material that accompanies charging / discharging of the lithium secondary battery. ⁇ Stabilizes the charge / discharge cycle characteristics of lithium secondary batteries by adapting to the shrinkage in the negative electrode and maintaining the negative electrode shape without destroying the conductive network.
  • the core acts as a first effect.
  • the alloy particles mainly composed of silicon and / or tin having a relatively small particle size are fixed to the surface of the low melting point metal particles as a negative electrode active material for inserting and extracting lithium, the alloy particles As a result, it is possible to reduce the electrical resistance between the negative electrode active material particles and the negative electrode itself to which the negative electrode active material particles are applied.
  • a negative electrode active material particle according to the present invention and a carbon material such as ketjen black or a conductive material that is difficult to occlude lithium on the surface of a negative electrode current collector made of a copper-plated film.
  • the negative electrode active material particles according to the present invention have a large proportion of the total volume of the negative electrode active material particles of the low melting point metal particles exhibiting high conductivity and conductivity, the negative electrode active material particles
  • the electrical resistance of the negative electrode to which the negative electrode active material particles are applied depends on the physical properties of the low melting point metal particles.
  • the negative electrode active material particles according to the present invention are substantially unaffected by alloy particles mainly composed of silicon and / or tin having a smaller volume, and have a substantially uniform electric resistance. Obtainable.
  • ketjen black or acetylene having an ultrafine shape of nano units is used. While it is necessary to use a conductive material such as black, according to the negative electrode active material particles of the present invention, the conductive material having these ultrafine shapes is made of a relatively large particle size such as low-temperature calcined carbon or black ship. As a result, the negative electrode capacity can be increased and the electrical resistance can be reduced. In addition, the conductivity can be further improved if used in combination with conductive materials such as ketjen black and acetylene black.
  • the silica fixed to the surface of the low-melting-point metal particles serving as a nucleus is used. Since the alloy particles containing kon and / or tin as a main component increase with occlusion of lithium so as to fill the voids formed between the negative electrode active material particles, the electrical conductivity between the negative electrode active material particles is increased. Connection can be further strengthened.
  • the negative electrode active material pre-particles that have been surface-modified and composited in this way are obtained by sintering silicon having an amorphous region, alloy particles mainly composed of Z or tin, and low melting point metal particles by a sintering method, Modified compounding method (A method in which multiple types of powder collide with each other at high speed and circulate in the container to form an alloy and treat the surface. It is produced by surface treatment of the alloy particles or low-melting-point metal particles using a mechano-fusion manufacturing method in which alloying and surface treatment are performed using the grinding heat and pressure applied when the powder is pressed in the gap. . Further, the negative electrode active material particles according to the present invention may use a mixed powder of negative electrode active material pre-particles produced by these different production methods.
  • the carbon material fixed to the surface of the negative electrode active material pre-particles described above is preferably fired at a low temperature in a temperature range of 300 to 100 ° C, more preferably in a temperature range of 600 ° C to 800 ° C. It is preferable that one or more carbon materials selected from the group consisting of one bon, acetylene black, ketjen black, carbon fiber and graphite are included.
  • the carbon material is fixed by carbonizing or volatilizing the polymer organic material by coating the surface of the negative electrode active material pre-particles with the polymer organic material and firing it in an inert gas atmosphere. It may be generated.
  • the negative electrode active material particles according to the present invention are obtained by using these carbon materials and other metal particles as media. It becomes possible to maintain the electrical connection between the particles, and to suppress the decrease in the battery capacity of the lithium secondary battery.
  • the negative electrode surface resistance was 9 ⁇ cm when the negative electrode active material particles not subjected to such surface treatment were applied, whereas the negative electrode when the negative electrode active material particles according to the present invention were applied.
  • the surface resistance is 0.9 ⁇ cm or less when low melting point alloy particles or carbon materials are fixed to the surface of alloy particles mainly composed of silicon and / or tin, and silicon and Z or When alloy particles containing tin as a main component or carbon materials are fixed, the resistance can be reduced to 1.5 ⁇ cm or less.
  • the low melting point metal particles and the carbon material function to ensure the bonding to the negative electrode current collector and the conductivity between the particles as described above.
  • suitable low-melting-point metal particles that can be used are those in which the metal itself such as lead solder, lead-free solder, and conductor paste is soft and processed at a low temperature of about 850 ° C or less.
  • Is at least one or more metal elements selected from the group consisting of iron, aluminum, copper, nickel, lead, zinc, bismuth, indium, antimony and selenium, or at least silver solder, Sn-Pb alloy, Group strength consisting of Sn-Sb alloy, Sn-Ag alloy, Sn-Bi alloy, Sn-In alloy, Sn-Zn alloy and Sn-Ag-In-Bi alloy Includes one or more selected alloys It is preferable that
  • a carbon material that complements the function of the conductive network formed in a mesh shape and can function as a negative electrode active material itself the above-described temperature range of preferably 300 to 1000 ° C, More preferably, a carbon material such as carbon, acetylene black or ketjen black, which has been calcined at a low temperature in the temperature range of 600 ° C. to 800 ° C., is used for the composite and surface modification of the negative electrode active material particles. Can do.
  • the low melting point metal particles and the carbon material used in the present invention may be used in combination of a plurality of different metal particles or a plurality of different carbon materials.
  • the blending ratio (wt%) of the low melting point metal particles and the carbon material used for such surface modification to the whole negative electrode active material particles is not particularly limited, and charging / discharging of the battery is not limited.
  • Lithium secondary battery applications such as emphasizing cycle characteristics or battery (negative electrode) capacity, depending on the purpose, low melting point metal particles and carbon materials to be used.
  • the mixing ratio, the particle diameter, and the particle size distribution can also be selected as appropriate. Therefore, when the low melting point metal particles and the carbon material are adhered to the surface of the alloy particles mainly composed of silicon and / or tin, the selected low melting point metal particles and the carbon material have gaps between adjacent particles. It may be configured to be selectively thinly bonded so as to form a point contact.
  • the negative electrode active material particles according to the present invention are substantially composed of alloy particles mainly composed of silicon and / or tin that contribute to the absorption and release of lithium as negative electrode active material particles, and the particles thereof. Since metal particles with different melting points (or soft melting points) having different diameters are combined and fixed to each other, intermetallic bonding proceeds between the alloy particles and the low melting point metal particles. Therefore, it is possible to provide negative electrode active material particles that are easily fixed and firmly fixed (or coated).
  • the negative electrode active material particles of the present invention can be coated on the surface of the negative electrode current collector at a low temperature.
  • a strong electrical connection between the negative electrode current collector, the coating layer, and the negative electrode active material particles formed in the coating layer can form an electrical network having high conductivity. it can.
  • the negative electrode active material particles for a lithium secondary battery according to the present invention comprise silicon and / or tin as a main component by alloying all or part of silicon and / or tin with the first other metal.
  • the first step for producing alloy particles, and all or a part of the alloy particles are further alloyed and / or surface-treated with a second other metal to be modified into alloy particles having an amorphous region.
  • a low-melting-point metal particle and a low-temperature-fired carbon material are fixed to the surface of the alloy particles having the amorphous region, or the amorphous material is bonded to the surface of the low-melting-point metal particle.
  • a third step for forming a negative electrode active material particle by adhering an alloy particle having a region and a low-temperature fired carbon material wherein the third step includes at least a mechanical alloying method, Mechanical gliding method, Nofuyu John method, is produced by hybridizing methods and 1 of the process selected from sintering.
  • another negative electrode active material particle for a lithium secondary battery according to the present invention comprises silicon and / or tin by alloying all or part of silicon and / or tin with the first other metal.
  • a first step for producing alloy particles as a main component, and all or part of the alloy particles are further alloyed and / or surface-treated with a second other metal to have amorphous regions.
  • the negative electrode for a lithium secondary battery according to the present invention comprises silicon and / or tin as a main component by alloying all or part of silicon and / or tin with the first other metal.
  • the first step for producing alloy particles, and all or a part of the alloy particles are further alloyed and / or surface-treated with a second other metal to be modified into alloy particles having an amorphous region.
  • a low-melting-point metal particle and a low-temperature fired carbon material are fixed to the surface of the alloy particles having the amorphous region, or the amorphous material is adhered to the surface of the low-melting-point metal particle.
  • the third step is at least one manufacturing method selected from a mechanical alloying method, a mechanical two-force regridding method, a mechanofusion method, a hybridizing method, and a sintering method
  • the fourth step is selected from a cold rolling method, a coating method, a sintering method, a melt dropping method, a DLC method, a manufacturing method of pressing after plasma spraying by a plasma spraying method, and a manufacturing method of heating press. Manufactured by a manufacturing method.
  • the negative electrode for another lithium secondary battery according to the present invention includes all of silicon and Z or tin.
  • Mechanical gliding method, mechano-fusion method, hybridizing method and sintering method, and the fifth step is a cold rolling method, a coating method, a sintering method, a melt dropping method It is manufactured by one manufacturing method selected from the manufacturing method that presses after the thermal spraying method, the DLC method, the plasma spraying method, and the manufacturing method that performs hot pressing.
  • the first step is to use pre-silicon and / or tin alloy particles by using silicon and / or tin and the first other metal, for example, a general alloying method such as a melting method. Is to be made.
  • the pre-silicon and / or tin alloy particles are mixed with the second other metal, and at least a mechanical alloying method, a mechanical gliding method, a liquid quenching method, and a gas quenching method are used.
  • the pre-silicon and / or tin alloy particles are made amorphous by using the production method 1 selected from the above method, and silicon and / or tin having an amorphous region in the whole or a part thereof are the main components. Alloy particles are produced.
  • the alloy particles mainly composed of silicon and / or tin need only have an amorphous region in all or a part thereof, the other metal added is silicon and It may not be alloyed with all of tin and / or silicon and part of Z or tin. Furthermore, in a third step of surface-modifying amorphous alloy particles, which will be described later, silicon produced by the different manufacturing method and It is also possible to use a mixed powder of alloy particles mainly composed of tin.
  • amorphized silicon and / or tin-based alloy particles and low-melting-point alloy particles, and a low-temperature-fired carbon material such as carbon, acetylene black, and ketchin black are used.
  • the carbon material is added to the mechanical alloying method using a planetary ball mill, the sintering method, and other surface modification compounding methods (inside the container, while multiple types of powder collide with each other at high speed).
  • a hybridizing method and alloying using frictional heat and pressure when the powder is pressed in the gap between the inner wall of the container and the central axis
  • mechanical gliding method or mechano-fusion method.
  • the negative electrode active material particles according to the present invention to be described later can use a mixed powder of negative electrode active material particles produced by these different production methods.
  • the alloy particles having an amorphous region mainly composed of silicon and / or tin used in the third step and the low melting point metal particles are combined with a specific fixing method such as a mechanical alloying method.
  • a specific fixing method such as a mechanical alloying method.
  • the carbon material to be fixed to the negative electrode active material pre-particles is replaced with a carbon material such as carbon, acetylene black, or ketchin black that has been fired at a low temperature, and the surface of the negative electrode active material pre-particles is coated with a polymer organic material. Then, the macromolecular organic matter may be fixed by carbonization or volatilization by firing in an inert gas atmosphere (see step 4 according to claims 31 and 33).
  • carbon materials and other metal particles adhering to the surface of the negative electrode active material particles form irregularities on the surface of the negative electrode active material particles.
  • a conductive network that remains and is formed in a mesh is maintained. Therefore, the negative electrode active material particles according to the present invention can maintain the electrical connection between the particles using these carbon materials and other metal particles as a medium, and the battery capacity of the lithium secondary battery can be maintained. Reduction can be suppressed.
  • the pre-silicon and / or tin alloy particles in the second step are made amorphous.
  • the surface-modified composite treatment of the amorphized silicon and / or tin-based alloy particles and low melting point metal particles is performed in an inert gas or reducing gas atmosphere. I prefer it.
  • the ratio of the metal oxide to the total weight of the negative electrode active material particles is preferably suppressed to 1 wt% or less.
  • a negative electrode for a lithium secondary battery according to the present invention comprises a negative electrode active material particle according to the present invention and an iron, aluminum, copper, nickel, chromium, lead, tin, zinc, One or more conductive materials selected from the group consisting of conductive carbon materials, and A coating material containing an inner layer is coated, heat-dried, and roll-pressed to a predetermined thickness to produce a coating layer having a predetermined porosity (claim 32). See step 4 and step 5 in claim 33).
  • Such a coating method on the negative electrode current collector is performed by roughening the surface of the negative electrode current collector, ion-sputtering columnar silicon, and PVD as described in other patent documents.
  • the coating layer can be made thicker, and a porous coating layer can be formed. Therefore, it is possible to increase the electrode capacity and increase the volume efficiency.
  • the negative electrode for a lithium secondary battery according to the present invention is formed on the surface of a negative electrode current collector made of a copper foil or a resin film plated with copper without using a conductive material and a binder.
  • the negative electrode active material particles are directly arranged, and the surface of the negative electrode current collector is subjected to a surface treatment by a cold rolling method, a coating method, a sintering method, a melt dropping method, or a thermal spraying method, or a heating force is applied. It can also be produced by carrying out the press treatment (heat press method) simultaneously.
  • the method of coating the negative electrode current collector is a porous material having a predetermined void capable of effectively absorbing the volume change of the negative electrode active material particles accompanying the occlusion and release of lithium.
  • This is particularly useful for forming a covering layer, and can be applied to a coating method in which a solution in which a binder and a conductive material are mixed and dried. Since the packing density of the material particles can be increased, the battery capacity per unit volume can be increased.
  • the electrical connection between the negative electrode active material particles is only an indirect connection due to the contact between the particles in the conventional negative electrode active material particles, whereas the negative electrode active material particles according to the present invention are electrically connected.
  • substance particles in addition to the conventional connection between each particle, it also forms a direct connection in which the low melting point metal particles or each particle via the carbon material are bonded.
  • the electrical resistance of the electrode is reduced to 1/10 or less compared to
  • the fixing of the carbon material to the negative electrode active material pre-particles using the polymer organic material is performed by using a heating press method in the negative electrode manufacturing process, which is a coating material containing the negative electrode active material pre-particles and the polymer organic material.
  • a heating press method in the negative electrode manufacturing process which is a coating material containing the negative electrode active material pre-particles and the polymer organic material.
  • the polymer organic material is carbonized or volatilized on the surface of the negative electrode active material pre-particles simultaneously with the formation of the negative electrode. May be.
  • the lithium secondary battery according to the present invention has a high charge rate when negative electrode active material particles in which low melting point metal particles are fixed to the surface of alloy particles mainly composed of silicon and / or tin are applied.
  • up to 2C shows approximately the same battery capacity as 0.2C, and alloy particles mainly composed of silicon and iron or tin on the surface of the low melting point alloy particles
  • the battery capacity is almost the same as that of 0.2C up to 5C, so the lithium secondary battery according to the present invention is applied to a small electric device. It is also possible.
  • the porosity of the coating layer formed on the negative electrode surface is preferably in the range of 37% to 65% of the porosity in the state where the front and back surfaces of the negative electrode current collector are coated with the negative electrode active material particles.
  • the expansion of the negative electrode thickness can be suppressed by absorbing the volume expansion associated with the insertion and extraction of lithium in the negative electrode active material particles, and the negative electrode is incorporated as a whole.
  • the change in the shape of the lithium secondary battery can be minimized. More preferably, when the occlusion of lithium during charging is completed, the porosity of the coating layer is reduced to about 30%, more preferably about 10%, so that the shape change of the lithium secondary battery is further suppressed. be able to. Therefore, the particle size, filling amount, and filling density of the negative electrode active material particles used at the time of preparing the negative electrode may be appropriately selected according to the thickness of the negative electrode coating layer (electrode thickness) to be set.
  • the negative electrode active material particles of the present invention alloy particles mainly composed of silicon and / or tin, low-melting-point metal particles, and a low-temperature-fired carbon material are fixed so as to form a complex shape. Therefore, when a conductive material such as carbon or a binder is added to this and the coating material is coated on the surface of the negative electrode current collector, a network-like conductive network having a strong electrical connection in the negative electrode coating layer is formed. It is formed. For this reason, it is possible to suppress particle shape collapse due to volume expansion / contraction associated with charge / discharge cycles of lithium secondary batteries, and to maintain electrical connection even when the particles are miniaturized. Cycle characteristics can be improved.
  • the negative electrode active material particles according to the present invention are (1) suppression of lithium occlusion of negative electrode active material particles and (2) occlusion of lithium of negative electrode active material particles. To release Even when the accompanying particle refinement occurs, the electrical connection of the refined fine particles can be maintained.
  • the negative electrode according to the present invention constructs a network-like conductive network bonded to the surface of the negative electrode current collector, (3) even when the anode active material particles are finely divided, The presence of the conductive network ensures electrical conductivity between the particles and does not hinder the electrochemical reaction of lithium.
  • the negative electrode according to the present invention can be manufactured by a relatively simple process in which the negative electrode active material particles are heated to melt or soften the low melting point metal particles and press-bond on the negative electrode current collector surface.
  • (4) negative electrode active material particles for lithium secondary battery with reduced volume change at the time of occlusion and release of lithium, negative electrode for lithium secondary battery, lithium secondary battery, and production methods thereof can be provided.
  • a lithium secondary battery can be provided in which the charge / discharge efficiency is high, the cycle life and energy density are not reduced, and the internal resistance is not increased.
  • the individual compounding ratio of other metals the particle size of the raw material, the particle size of the alloy particles having an amorphized region and the low melting point metal particles, the ratio of the particle size, etc. It is not particularly limited as long as it follows the technical idea. Therefore, for example, the low melting point alloy particles are not limited to solder and the like, and it is also possible to use metal elements or other conductive pastes that can be melted and bonded to each other at a temperature that does not alter the negative electrode active material particles. Can be appropriately selected according to the use, capacity, and form of the lithium secondary battery, such as being usable for a positive electrode active material with poor conductivity.
  • FIG. 1 is a perspective view of a thin pack battery using a negative electrode active material according to the present invention.
  • FIG. 2 is a perspective view of a negative electrode coated with a negative electrode active material according to the present invention.
  • FIG. 3 An enlarged model cross-sectional view of the negative electrode cross-section according to the present invention (particle surface morphology) is shown.
  • FIG. 4 shows charge / discharge cycle characteristics of a lithium secondary battery to which a negative electrode according to the present invention is applied and a comparative example.
  • FIG. 5 An enlarged model cross-sectional view of the negative electrode cross-section according to the present invention (particle surface morphology)
  • FIG. 6 shows charge / discharge cycle characteristics of a lithium secondary battery to which a negative electrode according to the present invention is applied and a comparative example.
  • FIG. 1 shows an external perspective view of a thin lithium secondary pack battery 1 using negative electrode active material particles 5 according to the present invention, and the battery 1 is provided with a positive electrode terminal 2 and a negative electrode terminal 3, respectively. .
  • FIG. 2 shows a perspective view of the negative electrode used in FIG. 1.
  • the negative electrode according to the present invention is formed on the front and back surfaces of the negative electrode current collector 4 having a copper foil force of about 8 zm in thickness.
  • the active material particles 5 are hot press-molded so that the thickness of each of the active material particles 5 is approximately 40 ⁇ m, with their positions slightly shifted on the front and back surfaces.
  • the negative electrode active material particles 5 were prepared by the usual melt alloying method, with an average particle size of 2 ⁇ m in which 0.07% aluminum, 0.01% chromium, 0.1% iron and 0.01% magnesium were added in advance to silicon. Pre-silicon alloy powder particles were prepared and used.
  • the pre-silicon alloy particles, the nickel powder particles having an average particle diameter of 5 ⁇ m, and the magnesium powder particles having an average particle diameter of 6 ⁇ m were added to 0.6: 0.3: 0.1 Mix in a weight ratio, store in a planetary ball mill container in an argon gas atmosphere, seal the container, and rotate at high speed for about 3 hours (mechanical alloying method). Alloy particles, nickel powder particles, and magnesium powder particles were alloyed and made amorphous.
  • the classified powder of negative electrode active material particles 5 according to the present invention was made into a paste by mixing an appropriate amount of a 5% solution of PVA (polyvinyl alcohol) as an organic polymer with stirring and mixing.
  • the negative electrode active material particles 5 are applied to the front and back surfaces of the negative electrode current collector 4 preheated to about 130 ° C so as to have a certain thickness, and then heated with a roll heated to about 210 ° C. After fixing (or covering) the anode current collector 4 to the front and back surfaces, heat treatment was performed at 750 ° C for 2 hours in a mixed gas atmosphere furnace of argon gas and 5% hydrogen gas, and the PVA was cooled at a low temperature.
  • a negative electrode for a lithium battery according to the present invention was produced by calcination.
  • Fig. 3 shows an enlarged schematic diagram of the cross section of the negative electrode according to the present invention (particle surface morphology) produced at this time.
  • Sn-Zn-A1 is a low melting point metal particle fixed on the surface of the silicon alloy particle 6 constituting the negative electrode active material particle 5 by the surface modification composite treatment. Alloy 7 and vapor-grown carbon fiber 9 and force Network conductivity in the state where negative electrode active material particles 5 and negative electrode current collector 4 are bonded to each other through Sn-Zn-A1 alloy 8 melted together. A network is formed. Further, the PVA solution as an organic polymer is carbonized by heat treatment under an inert gas atmosphere, and is deposited as low-temperature fired carbon 10 on the surface of the silicon alloy particles 6 to coat the silicon alloy particles 6.
  • the negative electrode covering layer to which the negative electrode active material particles 5 according to the present invention having such a structure were applied was pressed to a predetermined thickness so that the porosity was 53%.
  • the negative electrode coating layer to which the negative electrode active material particles 5 according to the present invention are applied is similar to the structure of the sintered body, and carbon fibers 9 and Sn_Zn_Al alloys 7 and carbon 10 fixed on the surface of each silicon alloy particle 6 are formed. Adjacent silicon alloy particles 6 are electrically connected to each other, and their surface area is increased, and then the Sn_Zn_Al alloy 8 that is melted and bonded to form a skeleton-like conductivity Form a network.
  • the adhesive film is thermally bonded.
  • the negative electrode terminal 2 is ultrasonically welded to the uncoated part of the end of the negative electrode current collector 4 and, after vacuum drying, is rolled up in a flat shape while being superimposed via the positive electrode current collector and the separator, Then, it is sealed in a battery pack that has been molded with an anoremi laminate film, heat sealed with one side remaining, and vacuum-impregnated with electrolyte from the unsealed portion, and then heat-sealed under vacuum to seal the unsealed portion.
  • a lithium secondary battery 1 was produced (see FIG. 1).
  • the theoretical battery capacity in design of the thin pack battery incorporating the negative electrode coated with the negative electrode active material particles according to the present invention produced in this way is about 2,020 mAh.
  • low-melting-point metal particles made of Sn—Pb alloy were added to amorphous silicon alloy powder particles classified so that the same average particle diameter as in Example 1 was 2 / m. Ar mixed in an inert gas atmosphere and sealed in a container. This was set in a hybridizing machine and operated for about 5 minutes to perform a surface modification composite treatment of silicon alloy particles 6. It was observed that the negative electrode active material particles 5 thus produced were bonded to the surface of the silicon alloy powder particles 6 by interspersed with small Sn_Pb alloy particles.
  • the produced negative electrode active material particles 5 were classified so as to have an average particle diameter of 5 ⁇ m, and then coated and bonded to the front and back surfaces of the negative electrode current collector 4 made of copper foil by a thermal spraying method. Thereafter, in order to make the sprayed surface of the negative electrode current collector 4 smooth, it was roll-pressed with a rolling roll having a constant roll gap to produce a negative electrode to which the negative electrode active material particles 5 according to the present invention were applied (FIG. 2). See). It was observed that the negative electrode produced in this way was slightly denser than the negative electrode active material particles 5 of Example 1 shown in FIG. 3, and the negative electrode active material particles 5 were bonded and connected by the Sn_Pb alloy. It was done.
  • a lithium secondary battery 1 was produced in the same manner as in Example 1 (see FIG. 1).
  • the theoretical battery capacity of the design at that time was 1,950 mAh.
  • the coating was performed so that O z m was obtained.
  • a multilayer polyethylene film having a thickness of about 20 ⁇ m was used.
  • Positive electrode active material 90wt% consisting of lithium cobaltate 40wt%, lithium iron phosphate 10wt%, nickel-lithium cobaltate 40wt%, conductive agent (ketine black) 5wt% and binder one (polyvinylidene fluoride) 5wt% Are mixed and dissolved in a suitable amount of solvent (N-methylpyrrolidone) to form a paste, which is then applied to the positive electrode current collector (aluminum foil with a thickness of about 15 zm) and the dried coating film after pressing. The coating was performed so that the specific gravity was 3 and the thickness was about 60 xm.
  • Fig. 4 shows the results of charge / discharge cycles at a 5-hour rate of a lithium secondary battery to which the negative electrode active material particles and the negative electrode according to the present invention are applied, and a low melting point metal as a comparative example.
  • the surface-modified composite treatment is applied to the particles and carbon material, and a solution containing a mixture of conductive material and binder made of silicon alloy particles and ketjen black is applied to a specified thickness using a coating machine.
  • the characteristics of the battery when it is charged and discharged at a 5-hour rate are shown for a lithium secondary battery that uses a negative electrode made by drying after about 10 minutes of drying at about 150 ° C.
  • the curves indicated by A1 and A2 in FIG. 4 are the charge characteristics and discharge characteristics at the fifth cycle of the lithium secondary battery in Example 1 according to the present invention, and are indicated by A3 and A4.
  • the curve shown is the charge and discharge characteristics of the 45th cycle.
  • B1 and B2 are the charge characteristics and discharge characteristics at the fifth cycle of the lithium secondary battery in Example 2 according to the present invention
  • the curves indicated by B3 and B4 are the charge characteristics and discharge characteristics at the 45th cycle.
  • the curves indicated by C1 and C2 indicate the fifth cycle of the lithium secondary battery of Comparative Example 2.
  • the curves indicated by C3 and C4 show the charge and discharge characteristics of the 45th cycle.
  • the lithium secondary battery of Example 1 according to the present invention had a battery capacity of 2,020 mAh as originally designed due to the characteristic A.
  • the battery capacity of about 2, OlOmAh is shown even after the 45th cycle, the battery capacity of about 99.5% of the initial design value can be maintained even after the 45th cycle. It was.
  • the lithium secondary battery of Example 2 according to the present invention had a battery capacity of 1,950 mAh as originally designed due to the characteristic B. Furthermore, since the battery capacity of about 1,900 mAh is exhibited even after the 45th cycle, it is proved that the battery capacity of about 97.4% of the initially measured value can be maintained even after the 45th cycle. It was.
  • the battery capacity of the lithium secondary battery of Example 2 was less than that of Example 1 and the battery capacity was greatly reduced even after the charge / discharge cycle.
  • the negative electrode of Example 2 was coated with negative electrode active material particles using a thermal spraying method, so that an oxide was generated in the negative electrode, and lithium was consumed by reducing this oxide during charge and discharge, and was used as lithium carbonate. As a result of the passivation, it is presumed that the battery capacity of the lithium secondary battery of Example 2 was reduced.
  • a negative electrode to which negative electrode active material particles mainly composed of tin were applied was manufactured.
  • the device was sealed and applied with an acceleration of about 150 G, and the device was operated for about 70 minutes to perform mechanical alloying (MA).
  • the obtained amorphous alloy particles made of tin were classified so as to have an average particle size of 7 zm, and then Sn- ⁇ having an average particle size of 3 ⁇ m as a low melting point metal.
  • the alloy particles were mixed and surface-modified with a planetary ball mill at 200 rpm for 20 minutes to fix Sn—Zn alloy particles to the surface of the alloy particles made of tin.
  • a negative electrode active material particles produced is 6 beta m After that, it is placed on the surface of the negative electrode current collector made of copper foil having a thickness of 10 ⁇ m without using a binder, heated to about 280 ° C. and fixed to the surface of the negative electrode current collector, and further, with a pressure roll.
  • a negative electrode to which the negative electrode active material particles according to the present invention were applied was prepared with a smooth surface (see FIG. 2).
  • a lithium secondary battery having a theoretical battery capacity of about 1,800 mAh was fabricated using a positive electrode, a separator, and an electrolyte prepared using the same conditions as in the above-described example (see FIG. 1).
  • the initial battery capacity, 790mAh was about 1,710mAh at the 45th cycle, about 95% ⁇ IJ rate. (Not shown).
  • the characteristic C of the lithium secondary battery according to the comparative example is approximately 1,970 mAh at the initial charge, compared to the initial design battery capacity value of approximately 2, OOOmAh.
  • the battery capacity was shown to be about 1,750mAh at the 5th cycle and about 950mAh at the 45th cycle, and the battery capacity was found to be significantly attenuated. This is because a resistance layer is formed on the surface of the negative electrode active material particles along with the charge / discharge cycle of the lithium secondary battery, and the electrical connection between each particle is destroyed and repeatedly destroyed while it is repeatedly expanded and contracted. it is conceivable that.
  • the decrease in the battery capacity after the charge / discharge cycle of the lithium secondary battery according to the present invention is small. This is because the lithium occlusion of the coating layer made of the negative electrode active material particles according to the present invention in the negative electrode is performed. ⁇ It is considered that the change in volume expansion and contraction due to release is small and the coating layer has a strength capable of resisting stress strain due to the volume change.
  • Examples 1 to 3 What is more important in Examples 1 to 3 is that the low-melting-point alloy particles and the low-temperature fired carbon material are fixed to all or a part of the surface of the negative electrode active material particles to form a network-like conductive network. And the connection between the individual particles and the negative electrode current collector could be strengthened by the low melting point metal particles and the carbon material. As a result, even when the negative electrode active material particles are further refined by repeated expansion and contraction associated with the charge / discharge cycle, the surface of the negative electrode active material particles formed into a complicated shape due to the effect of the surface modification composite treatment is electrically conductive. The function can be maintained, and even if the negative electrode active material particles are detached from the negative electrode current collector, an electrical connection network within the negative electrode is secured, and sufficient electron transfer during charge / discharge is possible. can do.
  • Example 4 Nigative electrode active material particles in which alloy particles mainly composed of silicon and / or tin are fixed to the surface of low melting point metal particles.
  • Negative electrode active material particles 5 are average particles in which 0.07% of aluminum, 0.01% of chromium, 0.1% of iron and 0.01% of magnesium are added to silicon by the usual melt alloying method. Pre-silicon alloy powder particles having a diameter of 2 ⁇ m were prepared and used.
  • the pre-silicon alloy particles, nickel powder particles having an average particle diameter of 5 ⁇ m, and magnesium powder particles were mixed at a weight ratio of 0.6: 0.3: 0.1. Then, in a planetary ball mill container in an argon gas atmosphere, the container is sealed and rotated at high speed for about 10 hours (mechanical alloying method), so that pre-silicon alloy particles, nickel particles, and magnesium powder are obtained. The particles were alloyed and made amorphous.
  • the weight ratio of the amorphized silicon alloy powder particles 6 ′ having an average particle diameter of 2 ⁇ and Zn powder particles 7 ′ having an average particle diameter of 8 / im is 16: 1.
  • the mixture was then mixed and subjected to a surface modification composite treatment for 15 minutes using a mechanofusion device, so that the negative electrode active material pre-coated with the silicon powder particles 6 'fixed on the surface with the Zn powder particles 7' as the core. Particles prepared and classified at 25 ⁇ m or less were used as raw material powder in the next step.
  • the negative electrode active material particles 5 thus produced have a weight ratio of 92: 4: ketjen black 10 'as a conductive material for further increasing the conductivity and a binder for binding them.
  • the resulting solution was applied to the surface of the negative electrode current collector 4 made of copper foil with a thickness of 8 ⁇ m and dried at about 140 ° C.
  • a negative electrode to which the negative electrode active material particles 5 according to the present invention were applied was produced (see FIG. 2).
  • FIG. 5 shows the formula (particle surface morphology).
  • negative electrode active material particles 5 in which silicon powder particles 6 ′ and low-temperature calcined carbon 9 ′ are fixed on the surface with the Zn powder particles 7 ′ as nuclei in this way are electrically conductive materials. Together with 10 ', it is connected by a binder to form a conductive network.
  • the conductive material 10 ′ also serves to electrically and structurally connect the negative electrode active material particles 5 together.
  • the negative electrode coating layer to which the negative electrode active material particles 5 having the above-described structure according to the present invention were applied was pressed to a thickness of 77 ⁇ m, so that the porosity of the negative electrode coating layer was 53 ⁇ m.
  • a negative electrode according to the present invention having a% content was prepared.
  • the negative electrode terminal 2 to which the adhesive film is thermally bonded is connected to the negative electrode current collector 4.
  • the theoretical battery capacity in design of the thin pack battery having the negative electrode coated with the negative electrode active material particles 5 according to the present invention thus produced is about 1,900 mAh.
  • the negative electrode active material particles 5 were added by adding 0.1% iron and 0.1% aluminum to tin by the melt alloying method as in Example 4. Next, after pulverization, pre-tin alloy particles with an average particle size of 4 ⁇ m and cobalt particles with an average particle size of 6 ⁇ m are mixed at a weight ratio of 80:20 and placed in a planetary ball mill container under an argon gas atmosphere. After storing and sealing, it was made amorphous by rotating at high speed with 150G applied for about 90 minutes (mechanical alloying method). XRD analysis of the obtained alloy particles revealed that no tin element and cobalt element peaks were detected, indicating that all tin had become amorphous.
  • the pulverized tin-cobalt alloy powder particles 6 ' were mixed with low melting point alloy particles 7' made of Zn-Sn alloy in an inert Ar gas atmosphere and sealed in a container. This is set in a hybridizing machine and is operated for about 4 minutes to perform a surface modification composite treatment of tin-cobalt alloy particles 6 '. I gave it. It was observed that the negative electrode active material particles 5 thus produced were bound to the surface of the Zn—Sn alloy particles 7 ′ with the tin cobalt alloy particles 6 ′ having an average particle diameter of 2 ⁇ m being scattered. It was. Furthermore, in order to prevent unevenness of the surface when applied to the negative electrode current collector, the particles were classified so that the maximum particle size was 12 ⁇ m or less.
  • the classified negative electrode active material particles 5 are discharged from a slit nozzle having a certain gap from the surface of the negative electrode current collector 4 made of copper foil so that the surface of the negative electrode current collector 4 has a certain thickness. Then, it was further roll-pressed with a rolling roll heated to about 170 ° C. to produce a negative electrode to which the negative electrode active material particles 5 according to the present invention were applied (see FIG. 2).
  • the negative electrode produced in this way is a portion of the core Zn_Sn alloy particles 7 'being crushed by other particles, and thus, from the negative electrode active material particles 5 of Example 4 shown in FIG. It was observed that the negative electrode active material particles 5 were connected and bonded to the negative electrode current collector 4 and other particles in a slightly dense state.
  • a lithium secondary battery 1 was produced in the same manner as in Example 4 (see Fig. 1).
  • the theoretical battery capacity of the design at that time was 1,950 mAh.
  • Example 4 an appropriate amount of a solvent (N-methylpyrrolidone) was added to a negative electrode mixture consisting of 88 wt% of a negative electrode active material, 4 wt% of a conductive agent (Ketjen black), and 8 wt% of a binder (polyvinylidene fluoride). The solution was dissolved to form a solution, and this was applied to the negative electrode current collector 4 (copper foil having a thickness of 8 ⁇ ) so that the dry coating film had a thickness of about 60 ⁇ .
  • a solvent N-methylpyrrolidone
  • Example 5 a negative electrode active material 100 wt% was dissolved in a solvent by adding an appropriate amount of a solvent (N-methylpyrrolidone), and this was dissolved into a negative electrode current collector 4 (thickness 8 am). The thickness of the dry coating film was about 60 ⁇ m.
  • a multilayer polyethylene film having a thickness of about 20 ⁇ m was used.
  • Lithium cobaltate 40wt%, lithium iron phosphate 10wt%, nickel-lithium cobaltate Mix by mixing 90 wt% of positive electrode active material consisting of 40 wt%, 5 wt% of conductive agent (Ketjen Black) and 5 wt% of binder (polyvinylidene fluoride), and dissolving it by calcining an appropriate amount of solvent (N-methylpyrrolidone)
  • solvent N-methylpyrrolidone
  • FIG. 6 shows a result of a charge / discharge cycle at a 5-hour rate of a lithium secondary battery to which the negative electrode active material particles and the negative electrode according to the present invention are applied, and as a comparative example, as a nucleus.
  • a solution in which a conductive material and a binder are mixed with negative electrode active material particles composed of only silicon alloy particles having amorphous regions that do not have low-melting-point metal particles is applied to a predetermined thickness with a coating machine.
  • the characteristics of the battery when it is charged and discharged at a 5-hour rate are shown for a lithium secondary battery that uses a negative electrode that is dried at about 150 ° C for about 10 minutes and then pressed.
  • the curves indicated by A1 and A2 in FIG. 6 are the charge characteristics and discharge characteristics at the fifth cycle of the lithium secondary battery in Example 4 according to the present invention, and are indicated by A3 and A4.
  • the curves shown are the charge and discharge characteristics at the 45th cycle.
  • B1 and B2 are the charge characteristics and discharge characteristics at the fifth cycle of the lithium secondary battery in Example 5 according to the present invention
  • the curves indicated by B3 and B4 are the charge characteristics and discharge characteristics at the 45th cycle.
  • the curves shown by C1 and C2 are the charge characteristics and discharge characteristics of the 5th cycle of the lithium secondary battery of Comparative Example 2
  • the curves shown by C3 and C4 are the charge characteristics of the 45th cycle. Characteristics and discharge characteristics.
  • the lithium secondary battery of Example 4 according to the present invention obtained a battery capacity of 1,900 mAh according to the initial design value by the characteristic A.
  • the battery capacity of about 1,840 mAh was exhibited even after the 45th cycle, so it was proved that the battery capacity of about 96.8% of the initial design value could be maintained even after the 45th cycle. It was.
  • the lithium secondary battery of Example 5 according to the present invention has an originally designed value due to the characteristic B. It was found that a battery capacity of 1,950 mAh was obtained. Furthermore, since the battery capacity of about 1,900 mAh is exhibited even after the 45th cycle, it is proved that the battery capacity of about 97.4% of the initially measured value can be maintained even after the 45th cycle. It was.
  • the characteristic C of the lithium secondary battery according to the comparative example is approximately 1,950 mAh at the first charge, compared to the originally designed battery capacity value of about 2, OOOmAh.
  • the battery capacity was shown to be about 1,740 mAh at the 5th cycle, and about 940mAh at the 45th cycle, and the battery capacity was found to be significantly attenuated. This is because a resistance layer is formed on the surface of the negative electrode active material particles along with the charge / discharge cycle of the lithium secondary battery, and the electrical connection between each particle is destroyed and repeatedly destroyed while it is repeatedly expanded and contracted. it is conceivable that.
  • the decrease in the battery capacity after the charging / discharging cycle of the lithium secondary battery according to the present invention is small. This is because lithium is occluded in the coating layer composed of the negative electrode active material particles according to the present invention in the negative electrode. ⁇ Volume expansion due to release 'It is considered that the change in shrinkage is small and the coating layer has a strength capable of resisting stress strain due to the volume change.
  • an alloy particle mainly composed of silicon and / or tin and a low-temperature fired carbon material are fixed to all or a part of the surface of the low-melting-point metal particle to form a network-like conductive network.
  • the connection between the individual particles and the negative electrode current collector could be strengthened by the alloy particles mainly composed of silicon and / or tin and the carbon material.
  • the surface of the negative electrode active material particles formed into a complicated shape due to the effect of the surface modification composite treatment is electrically conductive. The function can be maintained, and even if the negative electrode active material particles are detached from the negative electrode current collector, an electrical connection network within the negative electrode is secured, and sufficient movement of electrons during charging and discharging is possible. be able to.
  • the negative electrode active material particles in the case where silicon and Z or tin are mixed with other metals and all or a part thereof is alloyed and adjusted, a plurality of other types of metals are mixed. Thus, it was found that there are other optimal metal combinations that can achieve higher charge / discharge efficiency.
  • aluminum, copper, and tin are easily alloyed with other metals, such as lead and antimony, promote alloying with other metals, and magnesium and cobalt are lithium occlusions. • It is possible to suppress the deterioration of charge / discharge cycles by maintaining the conduction mechanism by suppressing the refinement of alloy particles mainly composed of silicon and / or tin against volume expansion / contraction caused by release. found.
  • lithium secondary batteries since aluminum, iron, magnesium and nickel are very active metals, oxidation, unless attention is paid to the atmosphere, especially when alloying with silicon and / or tin. Heat generation occurs, and as a result, the charge / discharge efficiency of the lithium secondary battery is reduced. If even part of the metal oxide is present in the alloy particles containing silicon and / or tin as a main component, when lithium is occluded, the lithium is oxidized and deactivated. The capacity of the secondary battery will be reduced. It was found that the lifetime of lithium secondary batteries can be improved by setting the moisture content of all materials used in lithium secondary batteries to 10 ppm or less.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne des particules de matière active d’électrode négative pour une batterie secondaire au lithium pouvant réaliser une occlusion et une libération de lithium électrochimique. L’invention est caractérisée en ce que les particules sont composées de particules d’un alliage composé principalement d’étain et/ou de silicium doté en totalité ou en partie d’une région amorphe, des particules métalliques à faible point de fusion d’un élément métallique à faible point de fusion ou d’un alliage le contenant, et d’un matériau carboné cuit à basse température, et en ce que soit les particules métalliques à faible point de fusion et le matériau carboné sont fixés rapidement sur la totalité ou une partie de la surface des particules d’alliage, soit les particules d’alliage et le matériau carboné sont fixés rapidement à la totalité ou une partie de la surface des particules métalliques à faible point de fusion. En outre, l’invention concerne une électrode négative pour une batterie secondaire au lithium et une batterie secondaire au lithium les utilisant, ainsi qu’un procédé de fabrication. Une quelconque isolation attribuée à la miniaturisation des particules de la matière active d’électrode négative est supprimée par la formation d’un réseau de connexion électrique, de sorte qu’un quelconque changement de volume peut être réduit et que la quantité des particules de la matière active d’électrode négative utilisée pour recouvrir les collecteurs d’électrode négative peut être augmentée.
PCT/JP2005/020586 2005-11-10 2005-11-10 Particule de matiere active d’electrode negative pour une batterie secondaire au lithium, electrode negative l’utilisant et procede pour les fabriquer WO2007055007A1 (fr)

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JP2010244727A (ja) * 2009-04-01 2010-10-28 Namics Corp 電極材料とその製造方法、及び、リチウムイオン二次電池
KR101063239B1 (ko) * 2008-11-28 2011-09-07 금호석유화학 주식회사 실리콘계 리튬이차전지용 음극활물질
WO2011122671A1 (fr) * 2010-03-30 2011-10-06 大日本印刷株式会社 Electrode plane négative destinée à une batterie rechargeable au lithium-ion, batterie rechargeable au lithium-ion, bloc de batteries et procédé de fabrication de batterie rechargeable au lithium-ion
CN101882677B (zh) * 2009-05-08 2012-08-01 复旦大学 用于锂离子电池的硒化锂-三硒化二锑阴极材料及制备方法
CN101882678B (zh) * 2009-05-08 2012-08-01 复旦大学 用于锂离子电池的硒化锂-二硒化三铜阴极材料及制备方法
JPWO2017082369A1 (ja) * 2015-11-10 2018-10-18 日産自動車株式会社 電気デバイス用負極活物質、およびこれを用いた電気デバイス
EP3483959A1 (fr) * 2017-11-08 2019-05-15 Samsung SDI Co., Ltd Matériau actif négatif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant
CN111430684A (zh) * 2020-01-19 2020-07-17 蜂巢能源科技有限公司 复合负极及其制备方法和应用

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KR101063239B1 (ko) * 2008-11-28 2011-09-07 금호석유화학 주식회사 실리콘계 리튬이차전지용 음극활물질
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CN101882677B (zh) * 2009-05-08 2012-08-01 复旦大学 用于锂离子电池的硒化锂-三硒化二锑阴极材料及制备方法
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JPWO2017082369A1 (ja) * 2015-11-10 2018-10-18 日産自動車株式会社 電気デバイス用負極活物質、およびこれを用いた電気デバイス
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EP3483959A1 (fr) * 2017-11-08 2019-05-15 Samsung SDI Co., Ltd Matériau actif négatif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant
US10991939B2 (en) 2017-11-08 2021-04-27 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery and rechargeable lithium battery including same
CN111430684A (zh) * 2020-01-19 2020-07-17 蜂巢能源科技有限公司 复合负极及其制备方法和应用
CN111430684B (zh) * 2020-01-19 2022-02-25 蜂巢能源科技有限公司 复合负极及其制备方法和应用

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