WO2006100794A1 - Electrode negative pour batterie rechargeable a electrolyte non aqueux - Google Patents

Electrode negative pour batterie rechargeable a electrolyte non aqueux Download PDF

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Publication number
WO2006100794A1
WO2006100794A1 PCT/JP2005/017380 JP2005017380W WO2006100794A1 WO 2006100794 A1 WO2006100794 A1 WO 2006100794A1 JP 2005017380 W JP2005017380 W JP 2005017380W WO 2006100794 A1 WO2006100794 A1 WO 2006100794A1
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WIPO (PCT)
Prior art keywords
negative electrode
lithium
particles
active material
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2005/017380
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English (en)
Japanese (ja)
Inventor
Hitohiko Honda
Kiyotaka Yasuda
Yoshiki Sakaguchi
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Publication of WO2006100794A1 publication Critical patent/WO2006100794A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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 negative electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery having the negative electrode.
  • a negative electrode of a lithium secondary battery As a negative electrode of a lithium secondary battery, a material in which a mixture containing a carbon-based material such as graphite is applied to a current collector such as an aluminum foil is widely used.
  • the lithium storage performance of carbon-based materials has reached a level close to the theoretical value, and the development of a new negative electrode active material has been demanded in order to significantly improve the capacity of lithium secondary batteries.
  • Silicon-based materials and tin-based materials have been proposed as such negative electrode active materials.
  • silicon particles in which lithium is occluded by an electrochemical reaction are used as a negative electrode active material. It has been proposed to be used as (see JP-A-7-29602). Silicon particles are pressed to form pellets, and a lithium foil is pressed onto them to obtain a negative electrode. The negative electrode is incorporated in a battery, and lithium is occluded in silicon particles by utilizing a local battery reaction formed between lithium and silicon particles in the presence of a non-aqueous electrolyte.
  • the silicon particles are finely pulverized by the stress generated due to expansion and contraction due to charge and discharge, and the negative electrode force is also dropped. There is also the inconvenience that the warpage is remarkable. Since the lithium foil is positioned between the separator and the pellet of silicon particles, lithium dendrite is generated due to the remaining lithium, which may cause a short circuit. Therefore, it is difficult to manufacture batteries other than coin-type batteries, for example, cylindrical or square batteries.
  • the present invention includes particles of a silicon-based material in which lithium is occluded, and has an active material layer in which a metal material having a low ability to form a lithium compound penetrates between the particles.
  • the amount of lithium in the particles is 5 to 50% of the initial capacity of silicon.
  • a negative electrode for a non-aqueous electrolyte secondary battery is provided.
  • the present invention provides a method for producing the negative electrode as a preferred method.
  • a carrier foil having a layer containing silicon-based material particles has a low ability to form a lithium compound, and is immersed in a plating bath containing a metal material to perform electroplating, thereby forming a lithium compound between the particles. Low !, depositing metal materials,
  • the working electrode which is the carrier foil in which the metal material is deposited between the particles, and the counter electrode having metallic lithium are immersed in a non-aqueous electrolyte solution obtained by dissolving a lithium salt in an organic solvent. And a counter electrode are short-circuited to provide a method for producing a negative electrode for a non-aqueous electrolyte secondary battery in which lithium is occluded in the particles.
  • the present invention is preferably a manufacturing method of the negative electrode
  • a current collector having a layer containing particles of a silicon-based material has a low ability to form a lithium compound, and is immersed in a plating bath containing a metal material to perform electrolytic plating, thereby forming a lithium compound between the particles.
  • Low performance, deposit metal material
  • the layer in which the metal material is deposited between the particles is opposed to a metal lithium foil with a non-aqueous electrolyte interposed therebetween,
  • the present invention provides a method for producing a negative electrode for a non-aqueous electrolyte secondary battery in which lithium is occluded in the particles by heating in this state.
  • the present invention further provides a non-aqueous electrolyte secondary battery comprising the negative electrode.
  • FIG. 1 is a schematic diagram showing a cross-sectional structure of a negative electrode according to a first embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a process for manufacturing the negative electrode shown in FIG. 1.
  • FIG. 3 is a schematic diagram showing another process for manufacturing the negative electrode shown in FIG. 1.
  • FIG. 4 is a schematic view showing still another process for manufacturing the negative electrode shown in FIG. 1.
  • FIG. 4 is a schematic view showing still another process for manufacturing the negative electrode shown in FIG. 1.
  • FIG. 5 is a schematic diagram showing a cross-sectional structure of a negative electrode according to a second embodiment of the present invention.
  • FIG. 6 is a schematic view showing a process for manufacturing the negative electrode shown in FIG.
  • FIG. 7 is a graph showing a second-cycle charge / discharge curve of a secondary battery using the negative electrode obtained in Example 1.
  • FIG. 8 is a graph showing a second-cycle charge / discharge curve of a secondary battery using the negative electrode obtained in Example 2.
  • FIG. 9 is a graph showing a second-cycle charge / discharge curve of a secondary battery using the negative electrode obtained in Example 3.
  • FIG. 10 is a graph showing a second-cycle charge / discharge curve of a secondary battery using the negative electrode obtained in Comparative Example 1.
  • FIG. 11 is a graph showing a second-cycle charge / discharge curve of a secondary battery using the negative electrode obtained in Comparative Example 2.
  • FIG. 1 schematically shows a cross-sectional structure of a negative electrode according to an embodiment of the present invention.
  • the negative electrode 1 of the present embodiment has a current collector 2 as a core material in the central region in the thickness direction.
  • An active material layer 3 is formed on each surface of the current collector 2.
  • a surface layer 4 is formed on each active material layer 3.
  • the active material layer 3 includes particles 5 of a silicon-based material that occludes lithium.
  • the amount of lithium contained in the particles 5 is set to 5 to 50% with respect to the theoretical initial charge capacity of silicon contained in the particles 5.
  • the reason for setting the amount of lithium in this way is as follows. Compared to a negative electrode using graphite as an active material, a lithium secondary battery having a negative electrode using silicon as an active material has a general feature that the discharge voltage rapidly decreases at the end of discharge. This is because the potential of the negative electrode changes significantly in a region where there is little lithium present in the negative electrode using silicon as an active material.
  • the amount of lithium occluded by silicon and the potential of the negative electrode are not in a linear relationship, and the potential of the negative electrode varies greatly as the amount of silicon decreases.
  • the negative electrode potential of the negative electrode using silicon as the active material rises, the battery voltage becomes lower than the operating voltage (cut-off voltage) of the current electronic device product, Therefore, the design of electronic circuits of electronic products must be changed. Also improve battery energy density. I can't make it up.
  • the present invention intends to design a battery that can charge and discharge in a lithium amount region where the potential is stable while avoiding a significant portion of the potential change. From this viewpoint, the lower limit of the amount of lithium is determined.
  • the higher the amount the higher the capacity of the battery, the higher its energy density (Wh), and the higher the average discharge voltage of the battery.
  • the positive electrode material such as LiCoO.
  • the amount of lithium is limited and high capacity cannot be achieved. This viewpoint power determines the upper limit of the amount of lithium. By occluding lithium within the range determined in this way, the battery can be increased in capacity and energy density in the operating voltage range of current electronic equipment products.
  • the storage amount of lithium contained in the particles 5 is preferably 10 to 40 with respect to the theoretical initial charge capacity of silicon contained in the particles 5. %, More preferably 20 to 40%, more preferably 25 to 40%. Theoretically, silicon occludes lithium up to the state represented by the thread and the formula SiLi.
  • SiLi it is 100% of the initial charge theoretical capacity of silicon. This means that lithium is occluded by silicon until it is in a state.
  • Examples of silicon-based materials include silicon alone and silicon and metal compounds. These materials can be used alone or in combination.
  • Examples of the metal include one or more elements selected from the group force consisting of Cu, Ag, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. Of these metals, Cu, Ag, Ni, and Co are preferred. Cu, Ag, and Ni are preferably used because of their excellent electronic conductivity and low ability to form lithium compounds.
  • the size of the particles 5 is not critical in the present embodiment, but the maximum particle size is 0.01 to 30 ⁇ m, and particularly 0.01 to 10 m. From the viewpoint of preventing particle 5 from falling off. For the same reason, when the particle size of particle 5 is expressed by D value, 0.1 to 8 111
  • the particle size of the particle 5 is measured by laser diffraction scattering type particle size distribution measurement and electron microscope observation.
  • the following method may be used to occlude lithium in the silicon-based material particles.
  • a layer containing particles of a silicon-based material is formed on a conductive foil. This is used as the working electrode.
  • an electrode having metallic lithium is used as the counter electrode. Both electrodes are immersed in a nonaqueous electrolytic solution obtained by dissolving a lithium salt in an organic solvent. Under this condition, both electrodes are short-circuited. As a result, current flows due to the potential difference between the two electrodes. That is, lithium ions are eluted from the metal lithium at the counter electrode, and the eluted lithium ions are occluded by the particles of the silicon-based material at the working electrode.
  • Lithium can also be occluded by energizing with an external power supply instead of short-circuiting both electrodes, that is, without occluding lithium without using an external power supply.
  • the occlusion method is also effective from the viewpoint of reducing the amount of water and a small amount of oxygen contained in the negative electrode 1. That is, when water or oxygen is contained in the silicon-based material particles, the water reacts with the metallic lithium of the counter electrode and is removed from the system by performing the method described above. Ma Oxygen is trapped in lithium. As a result, the amount of water and oxygen contained in the silicon-based material particles are reduced. That is, the occlusion method is an effective method for dehydration treatment and deoxygenation treatment of particles of silicon-based material. The longer the short-circuit time, the more the moisture content and oxygen content of the silicon-based material particles tend to decrease.
  • propylene carbonate for example, a solution having a concentration of lmolZD can be used.
  • the metal material 6 having a low ability to form a lithium compound penetrates between the particles 5 in the active material layer 3.
  • “Lithium compound forming ability is low!” Means that lithium does not form an intermetallic compound or solid solution, or even if lithium is formed, the lithium has a very small force or is very unstable.
  • the metal material 6 is preferably deposited between the particles by electrolytic plating. It is preferable that the metal material 6 penetrates over the entire thickness direction of the active material layer 3. And it is preferable that the particles 5 exist in the infiltrated metal material 6. That is, it is preferable that the particles 5 are not substantially exposed on the surface of the negative electrode 1 and are embedded in the surface layer 4.
  • the adhesion between the active material layer 3 and the surface layer 4 becomes strong, and the particles 5 are prevented from falling off.
  • the generation of electrically isolated particles 5 is effectively prevented.
  • the current collecting function is maintained. As a result, functional degradation as a negative electrode is suppressed. In addition, the longevity of the negative electrode can be increased.
  • the metal material 6 having a low ability to form a lithium compound penetrating into the active material layer 3 has conductivity, and examples thereof include copper, nickel, iron, cobalt, and alloys of these metals. Etc.
  • the metal material 6 having a low lithium compound-forming ability penetrating into the active material layer 3 penetrates the active material layer 3 in the thickness direction.
  • the particles 5 and the current collector 2 are electrically and reliably conducted through the metal material 6, and the electron conductivity of the negative electrode as a whole is further increased.
  • the penetration of the metal material 6 over the entire thickness direction of the active material layer 3 can be confirmed by electron microscope mapping using the metal material 6 as a measurement target.
  • the void ratio in the active material layer 3 is preferably about 0.1 to 30% by volume, and more preferably about 0.5 to 5% by volume.
  • the void ratio can be determined by electron microscope mapping. Since the active material layer 3 is preferably formed by applying a conductive slurry containing particles 5 and drying it, voids are naturally formed in the active material layer 3.
  • the composition of the conductive slurry, and the application conditions of the slurry may be appropriately selected.
  • the ratio of the voids may be adjusted by pressing the coating film under appropriate conditions.
  • the volume of the void does not include the volume of the hole (through hole) described later.
  • the active material layer can also be formed using a gas deposition method described later.
  • the active material layer 3 may contain a conductive carbon material in addition to the particles 5. This further imparts electron conductivity to the negative electrode 1.
  • the amount of the conductive carbon material contained in the active material layer 3 is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. It is.
  • These particles preferably have a particle size of 40 ⁇ m or less, particularly 20 ⁇ m or less, from the viewpoint of further imparting electron conductivity.
  • the lower limit of the particle size of the particles is not particularly limited and is preferably smaller. In view of the method for producing the particles, the lower limit is about 0.01 m.
  • the thickness of the active material layer 3 can be appropriately adjusted according to the ratio of the amount of the particles 5 to the whole negative electrode and the particle size of the particles 5, and is not particularly critical in the present embodiment. Generally 1 to: L00 ⁇ m, especially about 3 to 60 ⁇ m.
  • the active material layer 3 is continuously covered with a pair of surface layers 4 formed on each surface of the layer 3.
  • the main role of the surface layer 4 is to prevent (i) particles 5 contained in the active material layer 3 from falling out due to stress caused by charge / discharge, and (mouth) the negative electrode. Is to give strength.
  • the implementation shown in Figure 5 below In the case of a negative electrode in a form, that is, a negative electrode that does not have a current collector, the role of (mouth) becomes more prominent than in this embodiment.
  • Each surface layer 4 is thinner than the current collector 2. Specifically, a thin layer of about 0.3 to 10 m, particularly about 0.4 to 8 / ⁇ ⁇ , particularly about 0.5 to 5 m is preferable. As a result, the active material layer 3 can be coated almost uniformly and continuously with the minimum necessary thickness. As a result, it is possible to prevent the fine particles 5 from falling off. Moreover, by using such a thin layer, the proportion of the particles 5 in the entire negative electrode becomes relatively high, and the energy density per unit volume and unit weight can be increased.
  • the surface layer 4 is preferably formed by electrolytic plating as described later. The two surface layers 4 may have the same thickness or different thicknesses.
  • the surface layer 4 is made of a metal that can be a current collector of the non-aqueous electrolyte secondary battery.
  • it is preferably composed of a metal that can be a current collector of a lithium secondary battery.
  • An example of such a metal is a metal material having a low ability to form a lithium compound. Examples of such metal materials are as described above.
  • it is particularly preferable to use copper or nickel or an alloy thereof.
  • it is preferable to use a nickel-tandasten alloy because the surface layer 4 can have high strength.
  • the two surface layers 4 may have the same constituent material or different ones.
  • the material may be the same as or different from the metal material penetrating into the active material layer 3.
  • the surface layer 4 preferably has a large number of fine voids (not shown) that are open in the surface and communicate with the active material layer 3.
  • the fine voids exist in the surface layer 4 so as to extend in the thickness direction of the surface layer 4.
  • the fine voids are fine with a width of about 0.1 ⁇ m and a force of about 10 m.
  • the fine voids have a width that allows the nonaqueous electrolyte to penetrate.
  • the non-aqueous electrolyte has a smaller surface tension than the aqueous electrolyte, it can penetrate sufficiently even if the width of the fine voids is small.
  • the fine voids preferably electrolyze the surface layer 4 It is formed simultaneously with the formation by plating.
  • the average pore area of the fine voids is 0.1 to 50 111 2 , and preferably 0.1 to 20 111 2 , more preferably [or 0.5 5: 2 about LO / zm.
  • the average pore area is preferably 0.1 to 50%, more preferably 0.1 to 20% of the maximum cross-sectional area of the particles 5.
  • the maximum cross-sectional area of particle 5 is the particle size (D value) of particle 5 measured.
  • the maximum cross-sectional area when 5 is regarded as a sphere having a diameter of D value.
  • the ratio of the total area of the microvoids to the area of the observation field (this ratio is referred to as the area ratio) is 0.1. -20%, particularly preferably 0.5-10%.
  • the reason for this is the same as that for setting the aperture area of the fine gap 6 within the above range.
  • the surface of the surface layer 4 is viewed in plan by electron microscope observation, no matter what observation field of view is taken, one is within a square field of view of 100 ⁇ m X lOO / zm. It is preferable that 20,000, especially 10 to 1,000, especially 50 to 500 fine voids are present.
  • the negative electrode 1 has a large number of holes 7 formed therein.
  • the hole 7 is open on each surface of the negative electrode 1 and extends in the thickness direction of the active material layer 3 and the surface layer 4.
  • the hole 7 has a sufficiently large size compared to the fine voids described above.
  • the active material layer 3 is exposed on the wall surface of the hole 7.
  • the role of hole 7 is as follows.
  • the other is the role of relieving stress caused by the volume change when the volume of the particles 5 in the active material layer 3 changes due to charge / discharge. Stress is mainly in the plane direction of negative electrode 1. Occur. Therefore, even if the volume of the particles 5 increases due to charging and stress occurs, the stress is absorbed by the holes 7 that are spaces. As a result, significant deformation of the negative electrode 1 is effectively prevented.
  • Another role of the hole 7 is that the gas generated in the negative electrode can be released to the outside. Specifically, H, CO, CO, etc. due to moisture contained in trace amounts in the negative electrode
  • the opening of the holes 7 formed on the surface of the negative electrode 1 is opened.
  • the value obtained by dividing the porosity, that is, the total area of the holes 7 by the apparent area of the surface of the negative electrode 1 and multiplying by 100 is preferably 0.3 to 30%, particularly 2 to 15%.
  • the hole diameter of the hole 7 opened on the surface of the negative electrode 1 is preferably 5 to 500 m, particularly 20 to LOO m.
  • the electrolyte can be sufficiently supplied into the active material layer, and the stress due to the volume change of the particles 5 can be increased. Can be effectively mitigated.
  • an average of 100 to 2500, particularly 1000 to 40,000, especially 5000 to 20000, is applied in the lcm x 1 cm square observation field. It is preferable to be open.
  • the hole 7 may penetrate the negative electrode 1 in the thickness direction. However, considering the role of the pores 7 to sufficiently supply the electrolyte solution into the active material layer and relieve the stress caused by the volume change of the particles 5, the holes 7 extend in the thickness direction of the negative electrode 1.
  • the negative electrode 1 does not need to penetrate as shown in Figure 1. It suffices if the surface is open and has at least the active material layer 3 extending in the thickness direction.
  • the current collector 2 located in the central region in the thickness direction of the negative electrode 1 can be the same as that used conventionally as the current collector of the negative electrode for a non-aqueous electrolyte secondary battery.
  • the current collector is preferably composed of a metal material having a low lithium compound-forming ability as described above. Examples of such metallic materials are as already described. In particular, it is preferable that copper, nickel, stainless steel, and the like be used.
  • the thickness of the current collector 2 is not critical in the present embodiment, but is preferably 10-30 m in consideration of the balance between maintaining the strength of the negative electrode 1 and improving the energy density.
  • carrier foil 11 is prepared as shown in FIG.
  • the carrier foil 11 is used as a support for producing the negative electrode 1.
  • the manufactured negative electrode 1 is supported before use or during the battery assembling power, and is used to improve the handleability of the negative electrode 1.
  • the carrier foil 11 has such a strength that no distortion or the like occurs in the manufacturing process of the negative electrode 1 and in the transporting process and the battery assembling process after manufacturing. Therefore, the carrier foil 11 preferably has a thickness of about 10 to 50 m.
  • the important role of the carrier foil 11 is a support for manufacturing the negative electrode 1. Therefore, when the strength of the negative electrode 1 is sufficient, it is not always necessary to manufacture the negative electrode 1 using the carrier foil.
  • the carrier foil 11 it is preferable to use a conductive foil.
  • the carrier foil 11 may not be made of metal as long as it has conductivity.
  • the use of the metal carrier foil 11 has the advantage that the carrier foil 11 can be melted and made after the negative electrode 1 is manufactured and recycled.
  • the carrier foil 11 is configured to include at least one metal of Cu, Ni, Co, Fe, Cr, Sn, Zn, In, Ag, Au, Al, and Ti. It is preferable.
  • a foil manufactured by various methods such as a rolled foil and an electrolytic foil can be used without particular limitation.
  • a release agent 12 is applied to one surface of the carrier foil 11 to perform a release treatment.
  • the release agent is preferably applied to the rough surface of the carrier foil 11.
  • the release agent 12 is described later. Used to successfully peel the negative electrode 1 from the carrier foil 11
  • Nitrogen-containing compounds include, for example, benzotriazole (BTA), carboxybenzotriazole (CBTA), tolyltriazole (TTA), N ′, ⁇ ′-bis (benzotriazolylmethyl) urea (BTD— Triazole compounds such as U) and 3-amino-1H-1, 2,4-triazole ( ⁇ ) are preferably used.
  • BTA benzotriazole
  • CBTA carboxybenzotriazole
  • TTA tolyltriazole
  • BTD ⁇ ′-bis (benzotriazolylmethyl) urea
  • BTD Triazole compounds such as U
  • ⁇ 3-amino-1H-1, 2,4-triazole
  • sulfur-containing compounds include mercaptobenzothiazole ( ⁇ ), thiocyanouric acid (TCA), and 2-benzimidazolethiol (BIT).
  • organic compounds are used by being dissolved in alcohol, water, acidic solvent, alkaline solvent or the like.
  • concentration is preferably 2 to 5 gZl.
  • the peelability can be controlled by the concentration of the release agent and the coating amount.
  • inorganic release agents such as chromium, lead, and chromate instead of release agents that also have organic compound strength.
  • the step of applying the release agent is only performed in order to successfully release the negative electrode 1 from the carrier foil 11 in the release step described later.
  • the carrier foil 11 on which the release agent 12 is formed is subjected to an electrolytic plating process, and the surface layer 4 is formed on the release agent 12 as shown in FIG. 2 (c).
  • the plating bath and the plating conditions for forming the surface layer 4 are appropriately selected according to the constituent material of the surface layer 4.
  • a copper sulfate bath or a copper pyrophosphate bath having the following composition can be used as a plating bath.
  • the bath temperature is preferably about 40 to 70 ° C.
  • the current density is preferably about 0.5 to 50 AZdm 2 . If electrolysis is performed under these conditions, many fine voids (not shown) extending in the thickness direction from the surface of the negative electrode 1 to the active material layer 3 are formed in the surface layer 4.
  • a conductive slurry containing silicon-based material particles is applied on the surface layer 4 to form a coating film 3 ′.
  • the slurry contains conductive carbon material particles, a binder, a diluting solvent, and the like in addition to the silicon-based material particles.
  • the silicon-based material particles and the conductive carbon material particles are as described above.
  • the binder polyvinylidene fluoride (PVDF), polyethylene (PE), ethylene propylene monomer (EPDM), styrene butadiene rubber (SBR) and the like are used.
  • PVDF polyvinylidene fluoride
  • PE polyethylene
  • EPDM ethylene propylene monomer
  • SBR styrene butadiene rubber
  • a diluting solvent N-methylpyrrolidone, cyclohexane or the like is used.
  • the amount of silicon material particles in the slurry is preferably about 14 to 40% by weight.
  • the amount of the conductive carbon material particles is preferably about 0.4 to 4% by weight.
  • the amount of the binder is preferably about 0.4 to 4% by weight.
  • a slurry is prepared by adding a diluting solvent to these components.
  • a layer containing silicon-based material particles may be formed on the surface layer 4 by using a gas deposition method.
  • active material particle powder Si, etc.
  • a carrier gas nitrogen, argon, etc.
  • aerosol aerosolized in a state of being aerosolized, and then the substrate (current collection).
  • Foil This is a technique of forming a film on the surface by pressure bonding. Compared to CVD, PVD, sputtering, and other thin film formation methods, the composition change is small even when using multi-component active material powder! Have.
  • an active material film layer having a large number of voids can be formed by adjusting the injection conditions (active material particle diameter, gas pressure, etc.) of the same method.
  • the carrier foil 11 on which the coating film 3 'is formed is immersed in a plating bath containing a metal material having a low ability to form a lithium compound to perform electroplating. Since the coating film 3 ′ has a large number of minute spaces between the particles, the plating solution enters the minute space in the coating film 3 ′ by immersion in the plating bath, and the coating film 3 ′ and the surface layer 4 Reach up to the interface. Under this condition, electrolytic plating is performed (hereinafter, this plating is also referred to as penetration plating).
  • a metal material having a low lithium compound forming ability on the inside of the coating film 3 ′ and (b) on the inner surface side of the coating film 3 ′ (ie, the surface side facing the surface layer 4) 6 Precipitates between the particles 5, and the metal material 6 penetrates over the entire thickness direction of the coating film 3 '.
  • the penetration condition is low in terms of the ability to form a lithium compound, and is important for allowing the metal material 6 to be deposited in the coating film 3 '.
  • the copper concentration should be 30 to: LOOgZl, the sulfuric acid concentration 50 to 200 gZl, and the chlorine concentration 30 ppm or less.
  • the liquid temperature should be 30 to 80 ° C and the current density should be 1 to: LOOAZdm 2 .
  • the metal material 6 having a low lithium compound forming ability is deposited over the entire thickness direction of the coating film 3 ′.
  • a particularly important condition is the current density during electrolysis. If the current density is too high, precipitation does not occur inside the coating film 3 ′, but only on the surface of the coating film 3 ′.
  • a hole 7 penetrating the coating film 3 ′ and the surface layer 4 is formed by a predetermined drilling process.
  • the hole 7 can be formed by laser processing.
  • mechanical drilling can be performed with a needle or punch.
  • the laser may be irradiated toward the coating film 3 ′.
  • a forming method using a sandblasting process or a photoresist technique can be used as another forming means of the hole 7, a forming method using a sandblasting process or a photoresist technique can be used as another forming means of the hole 7, a forming method using a sandblasting process or a photoresist technique can be used.
  • the holes 7 are preferably formed so as to exist at substantially equal intervals. This is because the whole negative electrode can react uniformly.
  • the carrier foil in a state where the punching force is applied is used as a working electrode.
  • an electrode containing metallic lithium is used, and both electrodes immersed in the non-aqueous electrolyte are short-circuited by the method described above, so that the silicon-based material particles in the coating film 3 'occlude lithium.
  • the active material layer 3 is formed as shown in FIG.
  • the laminate of the surface layer 4 and the active material layer 3 thus obtained is also referred to as the negative electrode precursor 13.
  • the order of the lithium occlusion operation and the drilling operation described above may be reversed.
  • the current collector 2 is placed between the negative electrode precursors 13 so that the active material layers 3 in each negative electrode precursor 13 face each other. Sandwiched between.
  • the current collector 2 and both negative electrode precursors 13 are integrated by bonding.
  • the current collector 2 and both negative electrode precursors 13 are simply overlapped and pressure-bonded, and these three components are combined. Can be pasted together. If you want to strengthen the bonding, you can use a conductive adhesive material such as a conductive paste to bond the three.
  • each carrier foil 11 is peeled and separated from the surface layer 4.
  • the intended negative electrode 1 is obtained.
  • the force depicted so that the release agent 12 remains on the carrier foil 11 side may remain on the surface layer 4 side depending on the thickness type. It may remain on the side. Or it may remain in both.
  • the negative electrode 1 may be supported on the carrier foil 11 without being peeled off from the carrier foil 11 before use.
  • FIG. 1 As another method of the present production method, there is a method shown in FIG. In this method, the steps until the coating film 3 ′ is formed on the surface layer 4 are the same as the operations shown in FIG. 2 (a) to FIG. 2 (d). Next, the coating film 3 ′ formed in FIG. 2 (d) is infiltrated to form a plating layer 3 ′′ as shown in FIG. 3 (a). Lithium has not yet been occluded in the silicon-based material particles. In the following description, the thus obtained laminate of the surface layer 4 and the adhesive layer 3 ′′ is also referred to as the negative electrode precursor 14. Next, as shown in FIG. 3 (b), the negative electrode precursor 14 A hole is drilled to form hole 7.
  • a current collector 2 having a metal lithium layer 15 formed on each surface is prepared.
  • the metallic lithium layer 15 can be formed by a known thin film forming means such as a vacuum deposition method.
  • the conductive foil 2 on which the metal lithium layer 15 is formed is sandwiched between a pair of negative electrode precursors 14 as shown in FIG. 3 (c).
  • the negative electrode precursor 14 is supported by the carrier foil 11.
  • the plating layers 3 "of each negative electrode precursor 14 face each other and the surface layer 4 faces outward.
  • the negative electrode 1 ′ thus obtained, lithium is not yet occluded in the silicon-based material particles contained in the plating layer 3 ′′. Lithium is occluded in the silicon-based material particles. Therefore, in this method, the negative electrode 1 ′ is used together with the positive electrode to form a non-aqueous electrolyte secondary battery.
  • the metallic lithium layer 15 in the negative electrode 1 ′ is a silicon-based material in the presence of the non-aqueous electrolyte.
  • a local battery is formed between the material particles and the metallic lithium layer 15 Lithium is electrochemically occluded by nearby particles. Alternatively, lithium is occluded by the particles due to the lithium concentration gradient.
  • the negative electrode 1 shown in FIG. 1 is obtained. In other words, in this method, after the battery is assembled, lithium is occluded in the silicon-based material particles in the battery.
  • FIG. 4 As another method of this production method, there is a method shown in FIG. This method begins with Fig. 4.
  • a slurry containing silicon-based material particles is applied to each surface of the current collector 2 to form a coating film 3 ′.
  • the formed coating 3 ' is permeated to form a tacking layer 3mm and a surface layer 4.
  • the material having the penetration and the material of the surface layer 4 are the same. If you want to make these materials different, after penetrating the top surface of the coating film 3 ', replace the plating bath and use a plating bath containing a metal of another material. If the surface layer 4 is formed, it is necessary.
  • the metal lithium foil 15 is opposed to each of the plating layers 3 ".
  • a non-aqueous solution is provided between the plating layer 3" and the metal lithium foil 15. Keep it wet with electrolyte.
  • the non-aqueous electrolyte for example, propylene carbonate, ethylene carbonate Z dimethyl carbonate mixed solution, or the like can be used.
  • a lithium salt such as LiPF or LiCIO in the non-aqueous electrolyte.
  • the lithium power plating layer 3 "in the metal lithium foil 15 occludes the silicon-based material particles.
  • the heating means There is no particular limitation on the heating means.
  • the heating temperature of the metal lithium foil 15 is adjusted so that lithium is sufficiently occluded, and 30 to 160 ° C, particularly 60 to 150 ° C. It is preferable that
  • the negative electrode 1 obtained by each of the above methods is used with a known positive electrode, separator, and non-aqueous electrolyte to form a non-aqueous electrolyte secondary battery.
  • the positive electrode is prepared by suspending a positive electrode active material and, if necessary, a conductive agent and a binder in an appropriate solvent to produce a positive electrode mixture, coating the collector, drying it, and then rolling and pressing. Obtained by cutting and punching.
  • As the positive electrode active material lithium cobalt composite oxide (LiCoO), lithium nickel composite
  • the non-aqueous electrolyte also has a solution power obtained by dissolving a lithium salt as a supporting electrolyte in an organic solvent.
  • lithium salts include LiCIO, LiBF, LiAlCl, LiPF, LiAsF, LiSbF, LiSCN ⁇ LiCl, LiBr ⁇ Lil, Li
  • a battery configured by combining the negative electrode 1 of the present embodiment with a positive electrode containing a current positive electrode active material, for example, a lithium cobalt composite oxide, the voltage drop of the battery is small even at the end of discharge.
  • a current positive electrode active material for example, a lithium cobalt composite oxide
  • the form of the battery using the negative electrode 1 of the present embodiment may be, for example, a coin type, a cylindrical type, or a square type.
  • the metal material 6 with a low lithium compound forming capacity penetrates between the silicon-based material particles 5 occluded with lithium, so that any form of battery can be formed. Even so, the falling off of the particles 5 is effectively prevented.
  • a cylindrical or prismatic battery is more likely to lose the active material than a coin-type battery.
  • the negative electrode of this embodiment is used, the negative electrode is used to form a cylindrical or rectangular battery. Even if a battery of the type is constructed, the particles 5 will fall off.
  • a separator is interposed between the negative electrode 1 and the positive electrode, and these three members are wound to form a wound body, and the wound body is accommodated in the battery container.
  • This is particularly effective when used in a uni roll type battery (cylindrical battery or prismatic battery).
  • the negative electrode 1 of the embodiment shown in FIG. 5 does not have one of the two active material layers 3 and 3 included in the negative electrode of the embodiment shown in FIG. Corresponds to what is not.
  • the structure of the active material layer 3 of the present embodiment is the same as that of the active material layer of the embodiment shown in FIG. 1, and includes the silicon-based material particles 5 that occlude lithium.
  • the negative electrode 1 has an active material layer 3 and a pair of surface layers 4 formed on each surface thereof, and in the central region in the thickness direction. It does not have a current collector as a core material.
  • a metal material 6 having a low ability to form a lithium compound penetrates between the particles 5 of the silicon-based material that occludes lithium.
  • the surface layer 4 is composed of a metal material having a low lithium compound forming ability. This metal material may be the same material as the metal material 6 penetrating between the particles 5 of the active material layer 3 or a different material.
  • the negative electrode 1 is formed with a large number of holes 7 penetrating in the thickness direction. Hole 7 is open on the surface of negative electrode 1.
  • the function of the hole 7 is the same as that of the embodiment shown in FIG.
  • the diameter and pitch of the holes 7 and the hole area ratio on the negative electrode surface can be the same as those in the embodiment shown in FIG.
  • the negative electrode 1 of the present embodiment does not have a current collector.
  • the surface layer 4 has a current collecting function. That is, in the negative electrode 1 of the present embodiment, the surface layer 4 has both a current collecting function and a function of preventing the fine particles 5 from falling off.
  • the surface layer 4 a large number of fine voids (not shown) extending in the thickness direction and reaching the active material layer 3 are formed.
  • the function of the fine gap is the same as that of the embodiment shown in FIG.
  • the negative electrode of the embodiment shown in FIG. 1 in the case where the negative electrode 1 has holes, it is not necessary to form fine voids in the surface layer 4.
  • the negative electrode of the present embodiment also has the same effects as the negative electrode of the embodiment shown in FIG. Furthermore, according to the negative electrode 1 of the present embodiment, due to having no current collector, FIG. There is also an advantage that the energy density can be increased as compared with the negative electrode of the embodiment shown in FIG.
  • FIG. 1 A suitable example of the method for producing the negative electrode 1 of the present embodiment is shown in FIG.
  • the process up to the step of forming the active material layer 3 by impregnating the coating film containing the silicon-based material particles 5 in which lithium is occluded is the same as in FIGS. 2 (a) to 2 (e).
  • the carrier foil 11 formed up to the active material layer 3 is immersed in a plating bath containing a metal material having a low ability to form a lithium compound, and electrolytic plating is performed.
  • the surface layer 4 is formed on the active material layer 3 as shown in FIG.
  • the conditions for electrolytic plating for forming the surface layer 4 can be the same as the electrolytic plating conditions for the surface layer 4 already formed on the carrier foil 11. Further, by using the conditions, a large number of fine voids (not shown) extending in the thickness direction can be formed in the surface layer 4 formed on the active material layer 3.
  • a laminate is formed on the carrier foil 11 by laminating the surface layer 4, the active material layer 3, and the other surface layer 4 in this order.
  • the laminated body is drilled to form a large number of holes 7 penetrating the laminated body in the thickness direction, as shown in FIG. 6 (b). Specific examples of the drilling force are as already described with respect to the embodiment shown in FIG.
  • the present invention has been described based on the preferred embodiments, the present invention is not limited to the above-described embodiments, and various modifications can be made.
  • the surface layer 4 is formed on the active material layer 3, but the surface layer 4 is not formed within a range in which the strength of the negative electrode 1 can be sufficiently maintained. Also good.
  • the force in which a large number of holes 7 are formed on the surface of the negative electrode and extend in the thickness direction of the active material layer 3 may not be formed.
  • the holes 7 are not formed, it is preferable to form fine voids in the surface layer 4.
  • the negative electrode of each of the embodiments described above can be used alone, or a plurality of the negative electrodes can be used in an overlapping manner.
  • a conductive foil for example, a metal foil
  • a core material can be interposed between adjacent negative electrodes.
  • the surface layer 4 has a single-layer structure.
  • at least one of the surface layers may have a multilayer structure of two or more layers.
  • at least one surface layer is formed of nickel (low lithium compound formation ability! Metal material) and a lithium compound high formation ability, metal material strength lower layer and copper (low lithium compound formation ability, gold
  • the lithium compound forming ability of the surface layer 4 is low, and the lithium compound forming ability of at least one metal material penetrating the active material layer 3 is low! It can be a different material from material 6.
  • all the metal materials having a low lithium compound forming ability contained in each surface layer have a low ability to form a lithium compound penetrating into the active material layer 3, and may be a material different from the metal material 6.
  • the metal material 6 penetrating into the active material layer 3 is the active material. It may exist up to the boundary between layer 3 and surface layer 4. Alternatively, the metal material 6 penetrating into the active material layer 3 may constitute a part of the surface layer 4 beyond the boundary portion. Conversely, the constituent material of the surface layer 4 may exist in the active material layer 3 beyond the boundary.
  • the operation of precipitating the metal material 6 having a low ability to form a lithium compound in the active material layer 3 is performed in two or more different plating baths, thereby precipitating in the active material layer 3.
  • the metal material 6 to be formed can have two or more different multilayer structures.
  • the negative electrode shown in FIG. 1 was manufactured according to the process shown in FIG. A copper carrier foil (thickness 35 m) obtained by electrolysis was acid-washed at room temperature for 30 seconds (Fig. 2 (a)). The carrier foil was immersed for 3 seconds in a 3 g / l CBTA solution kept at 40 ° C. In this way, treatment with a release agent was performed (Fig. 2 (b)). After the treatment, the solution power was also raised and washed with pure water for 15 seconds.
  • the carrier foil was immersed in an H 2 SO 4 / CuSO plating bath and electroplated.
  • the surface layer was formed to a thickness of 5 m. After lifting from the plating bath, it was washed with pure water for 30 seconds and dried in the atmosphere.
  • a slurry containing Si particles was applied to the surface layer to a thickness of 20 m to form a coating film (Fig. 2 (d)).
  • the composition of the slurry is grain
  • the carrier foil on which the coating film was formed was immersed in a Watt bath having the following bath composition, and nickel was infiltrated into the coating film by electrolysis.
  • the current density was 5AZdm 2
  • the bath temperature was 50 ° C
  • the pH was 5.
  • a nickel electrode was used as the anode.
  • a DC power source was used as the power source. After raising the plating bath power, it was washed with pure water for 30 seconds and dried in the air.
  • a YAG laser was irradiated toward the carrier foil having the coating film on which penetration was applied. Irradiation also performed the side force of the coating. As a result, holes that penetrate the coating film and surface layer were regularly formed (Fig. 2 (e)).
  • the hole diameter was 24 ⁇ m
  • the pitch was 100 / ⁇ ⁇ (10000 holes Zcm 2 )
  • the hole area ratio was 4.5%.
  • a two-electrode cell was manufactured using a carrier foil with a permeation plating as a working electrode and a metal lithium foil as a counter electrode.
  • the electrolyte is LiPF ethylene carbonate: Dimethi
  • Carbonate 1: 1 (volume ratio) solution (concentration lmolZD was used. Both electrodes were connected to an external power source and energized, and the lithium of the counter electrode was occluded in the Si particles of the working electrode. The current density was 1. OmA / cm The energization time was 192 minutes, and the amount of occluded lithium was 40% of the initial capacity of Si. The amount of water in the Si particles before and after occlusion of lithium was curled. Measurement by the Fischer method revealed that it was 386.3 ppm before occlusion and 33.9 ppm after occlusion, thus obtaining a negative electrode precursor supported by the carrier foil (FIG. 2 (f)).
  • a current collector made of a rolled copper foil having a thickness of 10 m prepared separately from the negative electrode precursor was sandwiched between a pair of negative electrode precursors (FIG. 2 (g)).
  • the sandwiching was performed so that the active material layers in each negative electrode precursor face each other.
  • each negative electrode precursor and current collector They were pasted and integrated.
  • the carrier foil and the surface layer were peeled off to obtain the desired negative electrode (Fig. 2 (h)).
  • Example 2 Other than setting the energization time in the 2-electrode cell to 96 minutes and 120 minutes and setting the lithium storage amount to 20% (Example 2) and 25% (Example 3) of the initial charge capacity of Si.
  • the moisture content of the Si particles before and after occlusion of lithium was measured by the force Fischer method, in Example 2, it was 386.3 ppm before occlusion and 47.4 ppm after occlusion.
  • Example 3 it was 386.3 ppm before occlusion and 40.2 ppm after occlusion.
  • a cylindrical nonaqueous electrolyte secondary battery was produced using the obtained negative electrode as a working electrode.
  • LiCoO was used as the counter electrode.
  • the counter electrode is 4mAhZcm 2 and LiCoO is 20 mm thick.
  • FIG. 7 also shows the results when carbon powder coated on the surface of copper foil to a thickness of 80 m is used as the working electrode.
  • the capacity of the battery can be improved without changing the type of the positive electrode active material used in the current nonaqueous electrolyte secondary battery. it can. This is technically significant in that the battery capacity can be improved within the operating voltage of current electronic equipment products.
  • the negative electrode of the present invention when a minute amount of moisture or oxygen, which is a substance that increases the initial irreversible capacity, is contained in the constituent members of the battery including the negative electrode. However, since the moisture and oxygen react with the metal lithium and are consumed, the moisture and oxygen in the battery are reduced. As a result, the initial irreversible capacity can be reduced, and the charge / discharge efficiency (cycle characteristics) in each charge / discharge cycle is improved.

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Abstract

La présente invention concerne une électrode négative pour batterie rechargeable à électrolyte non aqueux. L’électrode négative comprend des particules d’un matériau en silicium à absorption de lithium et une couche de matériau actif en métal, qui présente un faible pouvoir de formation de composé de lithium, insérée entre les particules. La teneur en lithium des particules est de 5 à 50 % en fonction de la capacité théorique de charge initiale du silicium. L’électrode négative permet d’améliorer la capacité de la batterie sans modifier le type du matériau actif de cathode utilisé dans la batterie rechargeable à électrolyte non aqueux et, même lorsque les particules de matériau actif sont réduites en fine poudre suite à la charge/décharge, les propriétés de conduction des électrons et la fonction de captage du courant peuvent être assurées et conservées.
PCT/JP2005/017380 2005-03-23 2005-09-21 Electrode negative pour batterie rechargeable a electrolyte non aqueux Ceased WO2006100794A1 (fr)

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CN110571489A (zh) * 2019-10-14 2019-12-13 钱起 一种锂离子电池的分步化成方法
CN110707389A (zh) * 2019-10-14 2020-01-17 钱起 一种具有镍钴锰酸锂正极的锂离子电池的化成方法

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JP2009110798A (ja) * 2007-10-30 2009-05-21 Sony Corp 電池
JP5470696B2 (ja) 2007-10-31 2014-04-16 ソニー株式会社 リチウムイオン二次電池用負極およびリチウムイオン二次電池
WO2010071166A1 (fr) * 2008-12-19 2010-06-24 Ｎｅｃトーキン株式会社 Electrode négative pour pile secondaire à solution électrolytique non aqueuse et pile secondaire à solution électrolytique non aqueuse l'utilisant, et procédé de fabrication d'une électrode négative pour une pile secondaire à solution électrolytique non aqueuse
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JP5511604B2 (ja) * 2010-09-17 2014-06-04 日東電工株式会社 リチウム二次電池およびその負極
JP5551101B2 (ja) * 2011-03-30 2014-07-16 株式会社クラレ リチウムイオン二次電池用の負極およびリチウムイオン二次電池
GB2492167C (en) 2011-06-24 2018-12-05 Nexeon Ltd Structured particles
JP2015510666A (ja) 2012-01-30 2015-04-09 ネクソン リミテッドＮｅｘｅｏｎ Ｌｉｍｉｔｅｄ Ｓｉ／Ｃ電気活性材料組成物
GB2499984B (en) 2012-02-28 2014-08-06 Nexeon Ltd Composite particles comprising a removable filler
US9478800B2 (en) 2012-05-15 2016-10-25 Mitsui Mining & Smelting Co., Ltd. Negative electrode active material for nonaqueous electrolyte secondary batteries
GB2502625B (en) 2012-06-06 2015-07-29 Nexeon Ltd Method of forming silicon
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