WO2011039924A1 - Batterie primaire bisulfure de fer-lithium - Google Patents

Batterie primaire bisulfure de fer-lithium Download PDF

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WO2011039924A1
WO2011039924A1 PCT/JP2010/004884 JP2010004884W WO2011039924A1 WO 2011039924 A1 WO2011039924 A1 WO 2011039924A1 JP 2010004884 W JP2010004884 W JP 2010004884W WO 2011039924 A1 WO2011039924 A1 WO 2011039924A1
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positive electrode
electrode plate
iron disulfide
lithium
negative electrode
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PCT/JP2010/004884
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English (en)
Japanese (ja)
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加藤文生
森垣健一
福原佳樹
清水敏之
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パナソニック株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding

Definitions

  • the present invention relates to a non-aqueous electrolyte battery having a positive electrode containing iron disulfide as a main active material and a negative electrode containing lithium as a main active material and using an organic solvent as an electrolyte, that is, iron disulfide / lithium primary It relates to batteries.
  • the iron disulfide / lithium primary battery is composed of positive and negative electrode materials having a very high theoretical capacity of about 894 mAh / g for the positive electrode active material iron disulfide and about 3863 mAh / g for the negative electrode active material. It is a battery that is extremely excellent in terms of other characteristics such as low capacity and long-term reliability because of its capacity and light weight.
  • the iron disulfide / lithium primary battery has an initial open circuit voltage of 1.7 to 1.8 V and an average discharge voltage of around 1.5 V.
  • Other 1.5 V class primary batteries for example, aqueous solutions can be electrolyzed.
  • the practical value is also high from the viewpoint of compatibility with manganese batteries, alkaline manganese batteries, silver oxide batteries, air batteries and the like used for the liquid.
  • a cylindrical iron disulfide / lithium primary battery in practical use is an electrode group in which a strip-like positive electrode plate and a negative electrode plate are wound many times through a separator inside a hollow cylindrical battery case. It is stored in shape.
  • a positive electrode plate of this battery is made of an aluminum mixture mixed slurry (paint) obtained by mixing iron disulfide and a carbon conductive material / binder in a solvent. It is produced by coating and rolling on both sides of a flat foil.
  • the negative electrode plate is lithium or an aluminum alloyed lithium plate (foil), and the separator is a polyethylene microporous film.
  • the current collection between the electrode group and the battery case or sealing plate is performed by welding the lead wire taken out from the positive / negative electrode plate to the battery case / sealing plate, or by connecting the positive / negative electrode plate to the battery case / sealing plate. It is secured in the form of a contact system between.
  • iron disulfide / lithium primary batteries have high practical value, but the positive electrode active material, iron disulfide, expands in volume as it discharges, so the positive electrode active material is simply highly charged to increase battery capacity. Then, as the discharge progressed, the electrolyte solution in the positive electrode decreased, resulting in a phenomenon that the positive electrode active material could not be fully used.
  • the iron disulfide / lithium primary battery of the present invention includes a positive electrode plate using iron disulfide as a positive electrode active material, a negative electrode plate using metal lithium as a negative electrode active material, and a separator, and the positive electrode The separator is sandwiched between a plate and the negative electrode plate, and these are wound.
  • the positive electrode plate includes a positive electrode mixture in which iron disulfide, a carbon conductive material, and a binder are mixed, and an expanded metal.
  • the positive electrode mixture is filled in the opening of the expanded metal, and the positive metal mixture is held in the expanded metal, and the porosity of the positive electrode plate is 25% or more and 35% or less, and the negative electrode plate Is a lithium alloyed with one or more elements selected from Sn, Mg, Zn, Bi and Al.
  • the inventors of the present application also investigated other types of battery technologies when studying iron disulfide / lithium primary batteries.
  • a 3V-class manganese dioxide / lithium primary battery using baked manganese dioxide or the like as a positive electrode active material is also widely used.
  • the positive electrode is also formed inside the battery case. It has a configuration that houses a wound electrode group of a plate, a negative electrode plate, and a separator, but the positive electrode plate here is a mixture (granulated powder with low moisture content) consisting of manganese dioxide and a carbon conductive material / binder.
  • the mainstream method is to fill and roll into expanded metal.
  • the positive electrode plate of the expanded metal filling method as described above has an advantage that the productivity is higher than the method of applying slurry on both sides of the flat foil.
  • filling the expanded metal makes it easy to make the positive electrode plate thicker and shorter, so reducing the excess separator (shortening), etc., increasing the active material in the battery and increasing the capacity of the battery It is thought that it is suitable for doing.
  • the positive electrode plate is made thicker and shorter as the method of filling the iron disulfide positive electrode into expanded metal. It is considered advantageous to perform.
  • the positive electrode plate is simply made thicker and shorter, the area where the positive and negative electrode plates face each other is reduced, and the current density per unit area [mA / cm 2 ] during discharge is excessive. Since the conditions are severe, there arises a problem that sufficient high-load discharge characteristics cannot be secured.
  • the iron disulfide of the positive electrode active material expands in volume with discharge, the positive electrode active material particles can be impregnated and penetrated into the positive electrode at the end of discharge and the positive electrode active material particles at the end of discharge can be prevented from falling off.
  • the present inventors thought that it was necessary to consider how to fill the active material.
  • the known expanded metal filling type positive electrode plate handled manganese dioxide or the like having a relatively small volume expansion, it has not been studied how to cope with the volume expansion as described above. It was.
  • the inventors of the present application have conducted various experiments based on the above-described study, and as a result, have found that the porosity of the positive electrode plate is the key, and have come up with the present invention.
  • the positive electrode plate using iron disulfide as a positive electrode active material is a positive electrode plate in which the positive electrode active material is 90% or more of iron disulfide.
  • the negative electrode plate which uses metallic lithium as a negative electrode active material is a negative electrode plate whose negative electrode active material is 90% or more of metallic lithium.
  • Expanded metal is a metal plate that is stretched by making a number of cuts and forming a large number of openings.
  • the expanded metal mesh is a mesh.
  • the porosity of the positive electrode plate is the ratio of the void volume in the positive electrode to the total positive electrode plate (including the expanded metal) volume (%) with respect to the positive electrode plate in the initial state in which only the preliminary discharge immediately after battery preparation was performed. ).
  • the mass mixing ratio of iron disulfide and carbon conductive material in the positive electrode mixture is from 97/3 to 93/7. From the mixing ratio of 3 parts by mass of carbon conductive material to 97 parts by mass of iron disulfide, iron disulfide is mixed. This means a mixing ratio range up to 93 parts by mass with respect to a mixing ratio of 7 parts by mass of the carbon conductive material, and includes both ends of the range.
  • the theoretical capacity of the positive electrode plate is calculated based on the mass [g] of the iron disulfide material held on the positive electrode plate, assuming that the material is theoretically the maximum four-electron reaction (894 mAh / g) [ mAh], and the theoretical capacity per unit area is obtained by dividing this value by the area [cm 2 ] of the positive electrode plate.
  • the exemplary iron disulfide / lithium primary battery of the present invention employs an expanded metal filling method for the positive electrode plate, and the porosity is set in the range of 25% to 35% in consideration of the expansion of the iron disulfide material. .
  • the porosity of the positive electrode plate is less than 25%, the electrolyte impregnation / penetration into the positive electrode at the end of discharge is reduced, and conversely, the porosity is greater than 35%.
  • the porosity of the positive electrode is preferably in the range of 25% to 35%.
  • the exemplary iron disulfide / lithium primary battery can suppress the voltage drop phenomenon at the end of the high-load discharge.
  • lithium used for the negative electrode plate is alloyed with one or more elements of Sn, Mg, Zn, Bi, and Al.
  • membrane formed in the negative electrode surface within a battery decreases, and the polarization by the side of the negative electrode at the time of discharge is reduced significantly.
  • the polarization on the negative electrode side during discharge is greatly reduced. At the same time, it also has the following effects.
  • lithium alloyed with a different element as described above is, for example, a known manufacturing flow in which a metallic lithium ingot is melted and extruded to form a plate-like foil. It can be produced by a method such as adding.
  • the battery total The discharge voltage can be maintained at a high level.
  • the high load discharge characteristics of the battery can be sufficiently secured while taking advantage of the advantage of high capacity when the expanded metal type positive electrode is used.
  • the theoretical capacity per unit area of the positive electrode plate can be set to 35 mAh / cm 2 or more and 70 mAh / cm 2 or less. If the theoretical capacity per unit area is less than 35 mAh / cm 2, it is necessary to increase the positive electrode area (lengthening the positive electrode plate) in order to ensure battery capacity, and excess expanded metal or Since the separator is accommodated, it tends to be disadvantageous for high capacity and high output. On the other hand, if the theoretical capacity per unit area is larger than 70 mAh / cm 2 , the positive electrode plate can be shortened and it is advantageous for high capacity, but the positive electrode thickness is excessive and the facing area between the positive and negative electrodes becomes insufficient. It is easy to ensure high load discharge characteristics.
  • the total mass of elements to be alloyed with lithium in the negative electrode plate can be 0.1% or more and 3% or less with respect to the total mass of the negative electrode plate (the mass excluding leads for current collection). This is because if the total mass of the alloying elements is less than 0.1%, it is difficult to obtain the effect of reducing the coating on the negative electrode surface. Conversely, if the total mass of the alloying elements is greater than 3%, This is because the ratio of lithium as an active material is relatively low, which tends to be disadvantageous in increasing the capacity of the battery.
  • the carbon conductive material of the positive electrode can contain carbon powder having a BET specific surface area of 300 m 2 / g or more.
  • a carbon conductive material having a large specific surface area it is possible to improve the impregnation property of the electrolytic solution into the positive electrode that is made thicker and shorter, and it is easy to ensure high load discharge characteristics.
  • the mass mixing ratio in the positive electrode mixture of iron disulfide and carbon conductive material can be set in the range of 97/3 to 93/7. If the mixing ratio of the carbon conductive material is less than the above range, it is difficult to ensure sufficient high rate discharge characteristics. When the mixing ratio of the carbon conductive material is larger than the above range, that is, when the mixing ratio of the iron disulfide as the active material is smaller than the above range, it is difficult to ensure the absolute capacity of the battery.
  • the expanded metal of the positive electrode can be made of aluminum or stainless steel from the viewpoint of chemical stability to the electrolyte and low cost.
  • the skeleton shape is preferably a rhombus (diamond shape).
  • Fig. 1 shows a skeletal drawing of expanded metal with a diamond (diamond) mesh.
  • the plate thickness T directly reflects the plate thickness of the metal plate before processing.
  • a desirable plate thickness T that can impart appropriate flexibility to the positive electrode plate while suppressing breakage of the positive electrode plate during filling / compression and electrode group configuration is 0.1 mm or more and 0.15 mm or less.
  • the step width W is a parameter that determines the thickness of the skeleton together with the plate thickness T. From the viewpoint of suppressing the breakage of the positive electrode plate as described above and reducing the volume ratio of the core material, W is 0.2 mm or more. A range of 0.3 mm or less is preferred.
  • the center-to-center distance LW in the long direction and the center-to-center distance SW in the short direction of the mesh are parameters that define the size of the hole formed in the expanded metal. Suitable for LW and SW from the viewpoint of sufficiently maintaining the current collection from the active material particles at a position away from the skeleton and ensuring the tensile strength as the core material while reducing the volume ratio of the core material as much as possible. The range is determined. As a result of the study by the present inventors from the above viewpoint, a preferable range of the center-to-center distance LW in the long direction is 2 mm or more and 3 mm or less, and a preferable range of the center-to-center distance SW in the short direction is 0.8 mm or more. It is 1.8 mm or less.
  • FIG. 2 is a schematic cross-sectional view of an iron disulfide / lithium primary battery according to an embodiment of the present invention.
  • the iron disulfide / lithium primary battery has a positive electrode plate 1 using iron disulfide as an active material and a negative electrode plate 2 using lithium as an active material.
  • the electrode group is configured by winding the positive electrode plate 1, the negative electrode plate 2, and the separator 3 interposed therebetween in a spiral shape.
  • This electrode group is housed in a bottomed cylindrical case 9 together with a non-aqueous electrolyte (not shown).
  • a sealing plate 8 is attached to the opening of the case 9.
  • a lead 4 connected to the core material of the positive electrode plate 1 is connected to the sealing plate 8.
  • the lead 5 connected to the negative electrode plate 2 is coupled to the case 9.
  • an upper insulating plate 6 and a lower insulating plate 7 are respectively provided at the upper and lower portions of the electrode group to prevent internal short circuits.
  • the positive electrode plate 1 is manufactured as follows. After mixing iron disulfide and a conductive agent, a binder and water are added and kneaded to prepare a positive electrode mixture. Next, a predetermined amount of this positive electrode mixture is placed on the expanded metal, filled in the mesh, dried and compressed. Then, it cuts into a fixed size, peels a part of positive electrode mixture, welds the lead
  • the strip-shaped negative electrode plate 2 is composed of lithium (foil) alloyed with one or more elements of Sn, Mg, Zn, Bi, and Al.
  • the solvent used for the non-aqueous electrolyte is not particularly limited as long as it is an organic solvent used for a known non-aqueous electrolyte of a lithium primary battery.
  • ⁇ -Butyllactone, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane and the like can be used alone or in combination.
  • the supporting electrolyte constituting the non-aqueous electrolyte includes lithium perchlorate, lithium borofluoride, lithium hexafluorophosphate, lithium trifluoromethanesulfonate, lithium iodide, and LiN (CF that has an imide bond in the molecular structure.
  • 3 SO 2) 2, LiN ( C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) (C 4 F 9 SO 2) , or the like can be used.
  • Example 1 ⁇ Production of battery> 95 parts by mass of iron disulfide having an average particle size (particle size at a volume fraction of 50%: D 50 ) of 25 ⁇ m and Ketjen Black (EC300J manufactured by Lion Corporation, BET specific surface area: 800 m 2 / g) After 5 parts by mass of the mixture is dry-mixed, a suitable amount of water is added to and kneaded with PTFE disversion (Polyflon (registered trademark) D-1E manufactured by Daikin Industries, Ltd.), which is a binder. A positive electrode mixture was prepared. The solid content ratio of PTFE was adjusted to 5% by mass with respect to the total mass (total mass excluding moisture) of the positive electrode mixture after drying.
  • PTFE disversion Polyflon (registered trademark) D-1E manufactured by Daikin Industries, Ltd.
  • This positive electrode mixture was placed on an expanded metal, pushed into the mesh, filled, dried and compressed.
  • the porosity of the positive electrode plate (the ratio of the void volume in the positive electrode to the positive electrode volume including the expanded metal) was adjusted to 30%. After that, it is cut to a fixed size (length 200 mm, width 44 mm, theoretical capacity per unit area of positive electrode: 50 mAh / cm 2 ), a part of the positive electrode mixture is peeled off, and a lead is welded to the expanded metal of the part. I got a plate.
  • the expanded metal is made of aluminum and has a diamond-shaped mesh structure / skeleton shape as shown in FIG. The dimensions of the expanded metal are as follows: plate thickness T: 0.13 mm, step width W: 0.25 mm, center-to-center distance LW: 2.5 mm, center-to-center distance SW: 1.2 mm in the short direction. It was.
  • the negative electrode plate 2 was a strip-like lithium alloy containing five kinds of alloying elements shown in Table 1 and a strip-like metallic lithium.
  • the separator 3 is a polyolefin microporous membrane (Celgard Co., Ltd. # 2400), and the electrolyte is 1,3-dioxolane (DOL) and 1,2-dimethoxyethane.
  • DOL 1,3-dioxolane
  • DME 1,2-dimethoxyethane
  • Each battery is aged for 3 days in an atmosphere at 45 ° C. after assembly, and then corresponds to 5% of the positive electrode theoretical capacity (capacity calculated on the assumption that the discharge capacity of iron disulfide is 894 mAh / g).
  • a preliminary discharge was performed. The following evaluation was performed after preliminary discharge.
  • the batteries a1 to a5 using the alloyed lithium of Sn, Mg, Zn, Bi, and Al as the negative electrode plate have excellent DSC pulse discharge characteristics.
  • the batteries a1 to a5 had fewer films formed on the negative electrode plate surface than the battery a6, and the polarization on the negative electrode side during discharge was reduced.
  • the battery produced above has a length of the positive electrode plate of 200 mm, which is only 70% of the positive electrode plate length of a general iron disulfide / lithium primary battery. Even when combined with a positive electrode plate that has been made thicker and shorter with the expanded metal method, the polarization of the negative electrode side is significantly reduced in the batteries a1 to a5, so that the discharge performance of the battery as a whole can be improved. It is inferred that it was kept high.
  • Example 2 In Example 2, in order to obtain knowledge about the porosity of the positive electrode plate, only the compression conditions were changed in the same positive electrode plate production as in Example 1, and b1 to b1 having different porosity as shown in Table 3 were obtained. A positive electrode plate of b5 was prepared. Then, the battery constitution conditions were the same as in the case of the battery a1 of Example 1 (using Sn alloyed lithium as the negative electrode), and batteries b1 to b5 having respective positive electrode void ratios were produced.
  • Table 3 shows that unless the porosity of the positive electrode plate is set in the range of 25 to 35%, it is difficult to obtain excellent DSC pulse discharge characteristics. Since the iron disulfide particles expand in volume along with the discharge, the battery b1 having a porosity of less than 25% lacks the porosity and decreases the electrolyte impregnation and permeability into the positive electrode at the end of discharge. It is considered that the DSC pulse discharge characteristics become low. In addition, in the battery b5 in which the porosity is larger than 35%, it is difficult to collect current between the expanded metal and the active material particles, and it is considered that both 100 mA continuous discharge and DSC pulse discharge remain in low characteristics.
  • Example 3 In Example 3, an experiment was conducted to obtain knowledge about the theoretical capacity per unit area of the positive electrode plate. Units as shown in Table 4 were obtained by changing the theoretical capacity per unit area by changing both the length and thickness of the positive electrode plate while keeping the mass and porosity of the positive electrode mixture the same as in Example 1. A positive electrode plate having a theoretical capacity per area was produced. On the other hand, the alloyed lithium containing Sn: 1.5% by mass was also used for the negative electrode plate, and the entire mass was the same as that of the battery a1 of Example 1, while corresponding to the length of the positive electrode plate. Thus, the length and thickness were adjusted. In addition, the following procedure was the same as in Example 1, and batteries c1 to c6 corresponding to the respective positive electrodes were produced.
  • Table 4 shows that the theoretical capacity per unit area of the positive electrode plate is preferably 35 to 70 mAh / cm 2 .
  • the battery c1 having a theoretical capacity per unit area of 30 mAh / cm 2 , excess positive metal and separator are accommodated in the battery case due to the lengthening of the positive and negative electrode plates, and the amount of electrolyte solution injected We could not secure enough. As a result, the DSC pulse discharge characteristic is low.
  • the battery c6 in which the theoretical capacity per unit area was increased to 75 mAh / cm 2 , the thickness of the positive electrode was excessive, and the facing area between the positive and negative electrodes was insufficient. Yes.
  • Example 4 the mass ratio of elements to be alloyed with lithium of the negative electrode plate was examined. As shown in Table 5, Sn, Mg, Zn, Bi, and Al were used as alloying elements, and a negative electrode plate was prepared in which the addition ratio of each element with respect to the mass of the entire lithium alloy was changed. Then, the battery configuration conditions thereafter were all the same as in Example 1, and batteries d1 to d25 corresponding to the respective negative electrode plates were produced.
  • the mass ratio of the elements to be alloyed with lithium in the negative electrode plate is 0.1 to 3% with respect to the total mass of the negative electrode plate (the mass excluding leads for collecting current). .
  • batteries d1, d6, d11, d16, and d21 having a mass of alloying elements as small as 0.05% it is difficult to obtain the effect of reducing the coating on the negative electrode surface, and the DSC pulse discharge characteristics are poor.
  • batteries d5, d10, d15, d20, and d25 which have a large alloying element mass of 3.5%, also have a relatively low ratio of lithium as the negative electrode active material. As an absolute capacity).
  • Example 5 In Example 5, in order to obtain knowledge about the type of carbon conductive material, the carbon conductive material shown in Table 6 was used, and the other conditions were all the same as in the case of the battery a1 of Example 1 (Sn alloy for the negative electrode). Batteries e1 to e6 corresponding to the respective carbon conductive materials were produced.
  • Example 6 In Example 6, in order to obtain knowledge about the mass mixing ratio of iron disulfide and the carbon conductive material in the positive electrode mixture, the positive electrode mixture having the mass mixing ratio shown in Table 7 was used. As in the case of the battery a1 of Example 1 (using Sn alloyed lithium as the negative electrode), batteries f1 to f5 corresponding to the respective mass mixing ratios were produced.
  • Example 7 Here, the skeleton shape of the diamond (diamond) expanded metal was examined.
  • An expanded metal made of aluminum and having the shape parameters shown in Table 8 was prepared, and all other conditions were the same as in the case of the battery a1 of Example 1 (using Sn alloyed lithium for the negative electrode).
  • a battery corresponding to expanded metal was constructed.
  • the thickness T is 0.1 to 0.15 mm
  • the step width W is 0.2 to 0.3 mm
  • the center distance LW in the long direction is 2 to 3 mm
  • the center distance SW in the short direction is It can be seen that a range of 0.8 to 1.8 mm is desirable.
  • the active metal is located away from the skeleton because the expanded metal has a large pore diameter. It is assumed that it is difficult to maintain current collection from the particles and the discharge characteristics are not improved.
  • the expanded metal is made of aluminum, but the same discharge characteristics can be obtained by using stainless steel.
  • the expanded metal made of stainless steel stronger than aluminum Is done.
  • Example 5 ketjen black or specific carbon black was used as the carbon powder having a BET specific surface area of 300 m 2 / g or more.
  • the same effect can be obtained with carbon nanotubes, carbon nanofibers and the like having a specific surface area. It is done. Further, it is considered that a similar effect can be obtained even if a conductive material in a form mixed with other carbon powder is used mainly with carbon powder having a BET specific surface area of 300 m 2 / g or more (50% or more). .
  • the element to be alloyed with lithium of the negative electrode is not limited to one kind, and may be alloyed in addition to two or more kinds of lithium.
  • the AA size cylindrical battery is used, but the present invention itself is not limited to this, and is appropriately used for other sizes of cylindrical batteries, prismatic batteries, and the like. It is possible.
  • the iron disulfide / lithium primary battery according to the present invention has a high capacity and an excellent high-load discharge characteristic, and is used for electronic games, toys and the like including digital still cameras. It is optimal as a 1.5V class primary battery.

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  • Cell Electrode Carriers And Collectors (AREA)

Abstract

L'invention porte sur une batterie primaire bisulfure de fer-lithium qui possède à la fois une grande capacité et d'excellentes caractéristiques en termes de décharge de forte charge. L'invention porte plus précisément sur une batterie primaire au bisulfure de fer-lithium, dans laquelle une plaque d'électrode positive est obtenue en remplissant un métal allongé par un mélange d'électrode positive, le métal contenant celui-ci, dans lequel sont dispersés du bisulfure de fer, un agent conducteur en carbone et un liant, avec une fraction de vide dans la plage comprise entre 25 et 35 % et une plaque d'électrode négative est configurée de lithium allié avec un ou plusieurs éléments sélectionnés parmi l'étain, le magnésium, le zinc, le bismuth et l'aluminium. Il est souhaitable que la capacité théorique par unité de surface de la plaque d'électrode positive soit comprise entre 35 et 70 mAh/cm2 et que la masse totale des éléments utilisés pour l'alliage de la plaque d'électrode négative soit comprise entre 0,1 et 3 % de la masse totale de la plaque d'électrode négative.
PCT/JP2010/004884 2009-09-29 2010-08-03 Batterie primaire bisulfure de fer-lithium WO2011039924A1 (fr)

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JP2009223814A JP2012248280A (ja) 2009-09-29 2009-09-29 二硫化鉄・リチウム一次電池
JP2009-223814 2009-09-29

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WO2012066709A1 (fr) * 2010-11-15 2012-05-24 パナソニック株式会社 Batterie primaire au lithium
WO2022172750A1 (fr) * 2021-02-12 2022-08-18 パナソニックＩｐマネジメント株式会社 Batterie à électrolyte non aqueux

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JP7411942B2 (ja) 2020-05-29 2024-01-12 パナソニックＩｐマネジメント株式会社 非水電解質電池
JP7385611B2 (ja) * 2021-01-27 2023-11-22 プライムプラネットエナジー＆ソリューションズ株式会社 湿潤粉体からなる電極材料および電極とその製造方法ならびに該電極を備える二次電池

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WO2012066709A1 (fr) * 2010-11-15 2012-05-24 パナソニック株式会社 Batterie primaire au lithium
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WO2022172750A1 (fr) * 2021-02-12 2022-08-18 パナソニックＩｐマネジメント株式会社 Batterie à électrolyte non aqueux

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