WO2005082783A1 - Oxyhydroxyde de fer contenant du lithium et procédé de fabrication d’une cellule électrochimique électrolytique non aqueuse contenant ledit oxyhydroxyde - Google Patents

Oxyhydroxyde de fer contenant du lithium et procédé de fabrication d’une cellule électrochimique électrolytique non aqueuse contenant ledit oxyhydroxyde Download PDF

Info

Publication number
WO2005082783A1
WO2005082783A1 PCT/JP2005/003685 JP2005003685W WO2005082783A1 WO 2005082783 A1 WO2005082783 A1 WO 2005082783A1 JP 2005003685 W JP2005003685 W JP 2005003685W WO 2005082783 A1 WO2005082783 A1 WO 2005082783A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
electrode
iron oxyhydroxide
oxyhydroxide
producing
Prior art date
Application number
PCT/JP2005/003685
Other languages
English (en)
Japanese (ja)
Inventor
Miki Yasutomi
Toru Tabuchi
Original Assignee
Japan Storage Battery Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Storage Battery Co., Ltd. filed Critical Japan Storage Battery Co., Ltd.
Publication of WO2005082783A1 publication Critical patent/WO2005082783A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a lithium-containing iron oxyhydroxide and a nonaqueous electrolyte electrochemical cell containing the same.
  • lithium-ion secondary batteries have been widely used as power sources for electronic devices such as mobile phones and digital cameras.
  • the multifunctionality of such electronic devices is remarkably progressing, and the emergence of batteries having a high energy density in place of the currently used lithium ion secondary batteries is expected.
  • lithium that contributes to the redox reaction was not included. Therefore, the negative electrode active material combined with this was limited to metallic lithium and lithium alloy.
  • electrodes using these metallic lithium-lithium alloys could not be used due to poor thermal stability and cycle performance.
  • the Mn0 2 and V 2 0 5 of the positive electrode active material had to be containing lithium.
  • a conventional electrochemical method in which a force electrode is applied to electrodes using these active materials in a lithium ion-containing electrolyte using a counter electrode such as lithium metal.
  • an electrochemical control device is required and the manufacturing process becomes complicated.
  • lithium butyl lithium containing material such as LiCoO 2 and LiNi0 2, phenylalanine lithium, naphthyl lithium, there have the Li x Co0 2 ( ⁇ > 1 ) was immersed in a solution including lithium iodide and Li x Ni0
  • a method of synthesizing 2 ( ⁇ ⁇ > 1), which is described in Japanese Patent Application Laid-Open No. 05-135760.
  • a lithium-containing substance is immersed in a solution in which lithium ions and a polycyclic aromatic compound are dissolved to compensate for the irreversible capacity of the positive electrode, which is described in Japanese Patent Publication No. 3227771.
  • a first invention provides a method for producing lithium-containing iron oxyhydroxide, comprising: contacting a solution obtained by dissolving lithium metal and a polycyclic aromatic compound in a solvent with iron oxyhydroxide; In which lithium is absorbed.
  • the polycyclic aromatic compound is at least one of naphthalene, phenanthrene, and anthracene. Things.
  • the amount X of lithium stored in 1 mol of the oxyiron hydroxide is in the range of 0.5 mol ⁇ X ⁇ 2 mol. It is characterized by being within.
  • the oxyiron hydroxide is a J3 phase.
  • the fifth invention is directed to a method of manufacturing a nonaqueous electrolyte electrochemical cell, An electrode containing lithium-containing oxyiron hydroxide obtained by the method is used as a positive electrode.
  • a sixth invention is directed to a method for producing a nonaqueous electrolyte electrochemical cell, wherein the electrode containing lithium-containing oxyiron hydroxide obtained by the production method according to the second invention is used as a positive electrode. .
  • a seventh invention is a method for producing a nonaqueous electrolyte electrochemical cell, characterized in that the electrode containing lithium-containing oxyiron hydroxide obtained by the production method according to the third invention is used as a positive electrode. .
  • An eighth invention is directed to a method for producing a nonaqueous electrolyte electrochemical cell, wherein the electrode containing lithium-containing oxyiron hydroxide obtained by the production method according to the fourth invention is used as a positive electrode. .
  • a ninth invention is directed to a method for producing a nonaqueous electrolyte electrochemical cell, wherein the electrode containing lithium-containing oxyiron hydroxide obtained by the production method according to the first invention is used as a negative electrode. .
  • a tenth invention provides a method for producing a nonaqueous electrolyte electrochemical cell, characterized in that the electrode containing lithium-containing oxyiron hydroxide obtained by the production method according to the second invention is used as a negative electrode. is there.
  • FIG. 1 shows (a) FeOOH-Li lo 0 (b) FeOOH 'Li 0 of the present invention. 5 and (c) X-ray diffraction patterns of FeOOH.
  • FIG. 2 shows the electrochemical potential behavior of the lithium-containing oxyiron hydroxide electrode of Example 1.
  • FIG. 3 shows the electrochemical potential behavior of the iron oxyhydroxide electrode of Comparative Example 1.
  • FIG. 4 shows the electrochemical potential behavior of the electrode of Example 6.
  • FIG. 5 shows the electrochemical potential behavior of the electrode of Example 13.
  • FIG. 6 shows the charge / discharge characteristics of the non-aqueous electrolyte secondary battery of Example 14.
  • FIG. 7 shows the charge / discharge characteristics of the non-aqueous electrolyte secondary battery of Example 15.
  • trifluorene anthanthrene, acenaphthene, acenaphthylene, benzopyrene, benzophnoleolene, benzophenanthrene, benzophnoleroacene, benzoperylene, coronene, chrysene, hexabenzoperylene or derivatives thereof.
  • oxyiron hydroxide of the present invention a part of the iron is replaced with at least one element selected from Co, Ti, V, Cr, Mn, M, Cu and Zn. (0 ⁇ a ⁇ 0.5, M is at least one selected from Co, Ti, V, Cr, Mn, Ni, Cu and Zn).
  • These oxyiron hydroxides are prepared by adding Li, Na, K, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Zr, Pb and Sn in an aqueous solution in which iron salts are dissolved.
  • the compound can be synthesized by adding a salt containing at least one element selected from the group consisting of and then hydrolyzing.
  • the iron oxyhydroxide of the present invention can be used in any of the following phases.
  • the lithium-containing oxyhydroxide of the present invention is prepared by preparing a complex solution in which metallic lithium and a polycyclic aromatic compound are dissolved in an organic solvent, and contacting the complex solution with powder of oxyiron hydroxide. Can be obtained by Further, it can also be obtained by a method in which this complex solution is brought into contact with an electrode containing iron oxyhydroxide. It can also be obtained by contacting an organic solvent with oxyiron hydroxide or an electrode containing the same, and then dissolving lithium metal and the polycyclic aromatic compound in the solvent.
  • the complex solution contains lithium ions, polycyclic aromatic compound, polycyclic aromatic compound anion, and solvent.
  • the solution contains metallic lithium, lithium ion, polycyclic aromatic compound, anion of polycyclic aromatic compound, and solvent. Electrons are transferred from the anion of the polycyclic aromatic compound to the iron oxyhydroxide, and at the same time, lithium ions are absorbed into the iron oxyhydroxide. At this time, the polycyclic aromatic compound, ayuon, returns to the polycyclic aromatic compound, and thus has a catalytic role in the lithium storage reaction.
  • the concentration of lithium ions in this complex solution is preferably in the range from 0.07 g dm " 3 to saturation. If the concentration is less than 0.07 g dnf 3 , the occlusion time will be longer, and the occlusion time will be shorter. For this purpose, it is more preferable to make the lithium ion concentration saturated.
  • the concentration of the polycyclic aromatic compound in the complex solution is preferably from 0.005 to 2.0 mol dm- 3 . More favorable Mashiku is 0. 005 ⁇ 025 mol dnf 3, more preferably 0. 005 ⁇ 0. 01 mol dnf 3 der The If the concentration of the polycyclic aromatic compound is less than 0.005 mol dm- 3 , the occlusion time is prolonged, and if the concentration is greater than 2.0 mol dm- 3 , the polycyclic aromatic compound precipitates in the solution.
  • the time for bringing the complex solution into contact with the oxyiron hydroxide is not particularly limited, but in order to occlude lithium sufficiently in the oxyhydroxide, 0.1 to 240 hours is preferable, and 0.1 to 72 hours. Time is more preferred.
  • the lithium storage rate can be increased by stirring the solution.
  • the occlusion rate can be increased.
  • the temperature be equal to or lower than the boiling point of the solvent to be used. It is more preferable to set the range in consideration of workability.
  • Solvents used in the complex solution of the present invention include getyl ether, 1-methoxypropane, 1-methoxybutane, 2-methoxybutane, 1-methoxypentane, 2-methoxypentane, 1-methoxyhexane, 2-Methoxyhexane, 3-methoxyhexane, 1-ethoxypropane, 2-ethoxybutane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethyltetrahydrofuran, dimethylsulfoxide, etc. No.
  • the type of the solvent used for the complex solution is not particularly limited.
  • the lithium-containing oxyhydroxide obtained by the production method of the present invention is obtained by storing X moles of lithium with respect to 1 mole of oxyhydroxide.
  • the value of X can be controlled by the concentration of lithium ions and polycyclic aromatic compounds in the complex solution, reaction time, and temperature.
  • the molar number X of lithium can be determined by the amount of charge of the electrode containing the obtained lithium-containing oxyiron hydroxide.
  • the amount of charge electricity is defined as the electrode containing the lithium-containing oxyiron hydroxide as the working electrode, metallic lithium as the counter electrode and reference electrode, and ethylene carbonate (EC) and ethyl methyl carbonate (EMC) as the electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the polycyclic aromatic compound functions as a catalyst for the reaction of storing lithium. In the course of the reaction, the polycyclic aromatic compound does not extract H from the iron oxide hydroxide. Therefore, since no by-product is generated, the desired lithium-containing iron oxyhydroxide can be obtained.
  • the crystal structure of the lithium-containing oxyiron hydroxide of the present invention is preferably amorphous.
  • the term “amorphous” refers to the case where the half-width of the peak at around 36.8 ⁇ 0.5 ° of lithium-containing oxyiron hydroxide in X-ray diffraction using CuKa is 1.0 ° or more.
  • FIG. 1 shows a typical X-ray diffraction pattern of the lithium-containing iron oxyhydroxide obtained by the production method of the present invention.
  • (a) is FeOOH ⁇ Li L.
  • C) of Fig. 5 is the result of FeOOH.
  • Fig. 1 is FeOOH ⁇ Li L.
  • the symbol ⁇ indicates the peak of FeOOH in the ⁇ phase
  • the symbol port indicates the peak of the nickel substrate
  • the symbol ⁇ indicates the peak of polyethylene force.
  • the lithium-containing oxyhydroxide having an X value of 0.5 the half width was 1.0 ° or more. Therefore, it was found that when the value of X was 0.5 or more, the lithium-containing iron oxyhydroxide became amorphous. In addition, since no peaks other than iron oxyhydroxide, nickel on the substrate, and polyethylene cover were observed, it was found that no by-product was generated.
  • the lithium-containing oxyiron hydroxide of the present invention can be used for both positive and negative electrodes.
  • the negative electrode active material is not particularly limited.
  • carbon materials such as graphite and amorphous carbon, oxides, nitrides, and the like can be used. Among these, carbon materials and oxides such as graphite and amorphous carbon are preferably used because of their excellent capacity / charge / discharge cycle performance.
  • the positive electrode active material is not particularly limited.
  • transition metal compounds such as manganese dioxide and vanadium pentoxide, transition metal chalcogen compounds such as iron sulfide and titanium sulfide, and carbon materials such as activated carbon and graphite can be used.
  • Ethylene-propylene-diene terpolymer acrylonitrile-butadiene rubber, fluororubber, polyacetate
  • Polymethyl methacrylate Polyethylene, Nitrocellulose, Polyvinylidene fluoride, Polyethylene, Polypropylene, Polytetrafluoroethylene, Tetrafluoroethylene-Hexafluoropropylene copolymer, Polyvinylidene monochloride Trifluoroethylene copolymer
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • Either a non-aqueous solvent or an aqueous solution can be used as a solvent for mixing the binder.
  • Non-aqueous solvents include N-methyl- 2 -pyrrolidone, dimethyl'formamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, getyltriamine, N-N-dimethylamino Propylamine, ethylene oxide, tetrahydrofuran and the like can be used.
  • a dispersant, a thickener and the like can be added to the aqueous solution.
  • Iron, copper, stainless steel, nickel and aluminum can be used as current collectors for the electrodes. Further, as the shape, a sheet, a foam, a mesh, a porous expanded lattice, or the like can be used. Further, the current collector can be used with holes formed in any shape.
  • Organic solvents used for the electrolyte include ethylene carbonate, propylene carbonate, butylene carbonate, trifluoropropylene carbonate, ⁇ -butyrolactone, sulfolane, 1,2-dimethoxetane, 1,2-jetoxetane, tetrahydrofuran, and tetrahydrofuran.
  • carbonate compounds such as vinylene carbonate and butylene carbonate, benzene compounds such as biphenyl and cyclohexylbenzene, and sulfur compounds such as propane sultone can be used alone or in the electrolyte.
  • the electrolyte solution and the solid electrolyte can be used in combination.
  • the solid electrolyte a crystalline or amorphous inorganic solid electrolyte can be used.
  • Li 4 _ x G ei - x P x S 4 to be able to use typified by Chio LISICON, the latter Li l-Li 2 0-B 2 0 5 system, Li 2 0- Si0 2 system, Lil- Li 2 S- B 2 S 3 type, Lil - Li 2 S- SiS 2 system, Li 2 S- SiS 2 - Li 3 P0 4 A system can be used.
  • LiPF 6 LiC10 4, LiBF 4, LiAsF 6, LiPF (CF 3) 5, LiPF 2 (CF 3) 4, LiPF 3 (CF 3) 3, LiPF 4 (CF 3 ) 2 , LiPF 5 (CF 3 ), LiPF 3 (C 2 F 5 ) 3 , LiCF 3 S0 3 , LiN (S0 2 CF 3 ) 2 , LiN (S0 2 CF 2 CF 3 ) 2 , LiN (C0CF 3) ) 2, LiN (C0CF 2 CF 3) 2, LiC 4 B0 8 walking alone and can be used as a mixture.
  • LiPF 6 is preferable as the lithium salt because the cycle performance is improved.
  • Microporous membranes such as nylon, cellulose acetate, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride and polyolefin can be used as separators in non-aqueous electrolyte electrochemical cells.
  • the shape of the nonaqueous electrolyte electrochemical cell is not particularly limited, and may be a square, an ellipse, a coin, a button, a sheet, or the like.
  • this electrode as a working electrode, a metal lithium plate as the reference electrode contact Yopi counter, electrolytic EC and EMC and O volume ratio as solution 1: dissolve the LiC10 4 of 1 mol DNF 3 in a mixed solvent of 1
  • a three-electrode glass cell was fabricated using the above.
  • the electrochemical potential behavior of this electrode was investigated as follows. At 25 ° C, the battery was charged to 4.2 V vs. Li / Li + with a current of 0.01 CmA, and then discharged to 1.5 V vs. Li / Li +.
  • FIG. 2 shows the electrochemical potential behavior of this lithium-containing oxyiron hydroxide electrode. The potential of this electrode gradually shifted from 1.0 V vs. Li / Li + to 4.2 V vs.
  • Li / Li + Li / Li + . This is probably because lithium was electrochemically desorbed from lithium-containing iron oxyhydroxide by charging. It was found that a large value of 307 mAh g " 1 was obtained per unit mass of lithium-containing iron oxyhydroxide, and that the potential of the electrode during discharging was 4.2 V vs. Li I Li + Slowly shifted from 1.5 V to 1.5 V vs. Li I Li + , and the quantity of electricity (discharge capacity) was per unit mass of lithium-containing iron oxyhydroxide. A large capacity of 280 mAh g- 1 was obtained. This value was 93% of the theoretical capacity when 1 mol of Li was inserted into iron oxyhydroxide.
  • Example 1 As a reference example to prove the difficulty of the idea itself of the present invention, in Example 1, 1.0 ⁇ ⁇ phase was used. An electrode was prepared using a conventionally known 10 ⁇ m layered nickel oxyhydroxide instead of iron oxyhydroxide, and the electrochemical behavior was examined by applying the method of the present invention. The effect was investigated.
  • the values of the charge electricity and the discharge capacity of the obtained lithium-containing nickel oxyhydroxide electrode are the values described in the 44th Battery Symposium on Abstract No. 1C09 (2003), respectively. Since it was as small as 104 mAh g- 1 and 96 mAh g- 1, which are almost the same as above, it can not be foreseen that from this cited example, it is possible to obtain an actual capacity comparable to the theoretical capacity as in the present invention. Thus, in the case of nickel oxyhydroxide, the same effect as in the case of iron oxyhydroxide of the present invention cannot be obtained because the crystal structure of nickel oxyhydroxide is a layered structure.
  • lithium ion batteries is 2 V and a low operating voltage system as in the present invention
  • Lithium-containing oxyhydroxide / iron / C-based lithium-ion batteries practically require large capacities close to the theoretical capacities, so the effect of the present invention can be said to be remarkable.
  • a paste was prepared by mixing 80% by mass of the active material of the ⁇ -phase iron oxyhydroxide powder used in Example 1, 5% by mass of acetylene black, and 15% by mass of PVDF in a glass plate. This paste was applied on a 20-m-thick aluminum foil and dried under reduced pressure at 70. To evaporate the bandits P. This was pressurized with a roller, and then the size was adjusted to 10 mm WX 20 mmL X 100 ⁇ mT with a slitter to produce an electrode. The electrochemical potential behavior of this electrode was measured as follows.
  • a three-electrode glass cell was fabricated using this method.
  • the electrochemical potential behavior of this electrode was examined as follows. 4. At 25 ° C, current 0.01 C mA. After charging to 2 V vs. Li I Li + , the battery was discharged to 1.5 V vs. Li / Li +.
  • Figure 3 shows the electrochemical potential behavior of this oxyiron hydroxide electrode. Charging characteristics do not appear in the figure, the potential was immediately 4. Reached 2 V vs. Li I Li +.
  • the charged amount of electricity of this electrode was 0 niAh g- 1 per unit mass of iron oxyhydroxide.
  • the reason for this is that the electrochemical iron elimination reaction did not progress because the iron oxide hydroxide electrode did not contain lithium.
  • the potential of this electrode gradually shifted from 3.2 V vs. Li I Li + to 1.5 V vs. Li / Li + .
  • This electric quantity (discharge capacity) was 281 mAh per unit mass of iron oxyhydroxide.
  • lithium-containing oxyhydroxide prepared by a method in which conventional iron oxyhydroxide is brought into contact with a solution containing lithium metal and a polycyclic aromatic compound can be chemically synthesized and contained. That is, the electrode has a large charge amount and a large discharge capacity.
  • the amount of charge of the lithium-containing oxyiron hydroxide electrode of 307 mAh g— 1 means that x represented by the general formula Fe00H ′ Li x is a value of 1.
  • Example 2 a 1.6 mol dm- 3 n-butyllithium Jetyl ether solution was used, and a-phase oxyiron hydroxide powder was immersed in this solution. For 24 hours, filtered, and washed with dimethyl carbonate. This was dried under reduced pressure at room temperature to obtain a powder.
  • PVDF polyvinylidene fluoride
  • the NMP was evaporated by applying this paste on an aluminum foil having a thickness of 20 ⁇ and drying under reduced pressure at 70 ° C. This was pressurized with a roller, and then sized to 10 mmW ⁇ 20 mmL ⁇ 100 jumT with a slitter to produce an electrode.
  • this electrode as a working electrode, a metal lithium plate as the reference electrode contact Yopi counter, electrolytic volume ratio of EC and EMC as solution 1: dissolve LiC10 4 of 1 mol dm- 3 in a mixed solvent of 1
  • a three-electrode glass cell was fabricated using the resulting material.
  • the electrochemical potential behavior of this electrode was investigated as follows. At 25 ° C, charge up to 4.2 V vs. Li / Li + with a current of 0.01 C mA After charging, the battery was discharged to 1.5 V vs. Li I Li + . The charge and discharge capacity of the electrode in the first cycle were small, 72 mAh g- 1 and 65 mAh, respectively. The reason is considered to be that when n-butyllithium getyl ether solution was used, H was extracted from the oxyhydroxide and the crystal structure collapsed, and by-products such as iron oxide were generated. .
  • Example 1 the immersion time was changed to 30 minutes to obtain a lithium-containing oxyhydroxide powder according to the present invention.
  • an electrode B containing lithium-containing iron oxyhydroxide according to the present invention was obtained using the lithium-containing iron oxyhydroxide powder as an active material.
  • Example 1 the immersion time was changed to 1 hour to obtain a lithium-containing iron oxyhydroxide powder according to the present invention.
  • an electrode C containing lithium-containing iron oxyhydroxide according to the present invention was obtained by using the lithium-containing iron oxyhydroxide powder as an active material.
  • Example 1 the immersion time was set to 48 hours to obtain a lithium-containing oxyiron hydroxide powder according to the present invention.
  • an electrode D containing the lithium-containing iron oxyhydroxide according to the present invention was obtained by using the lithium-containing iron oxyhydroxide powder as an active material.
  • Example 1 the immersion time was set to 60 hours to obtain a lithium-containing oxyiron hydroxide powder according to the present invention.
  • the electrode E containing lithium-containing iron oxyhydroxide according to the present invention was obtained using the lithium-containing iron oxyhydroxide powder as the active material in Example 1.
  • Electrodes B, D and E containing these lithium-containing oxyiron hydroxides were examined for their electrochemical potential behavior as follows.
  • the lithium-containing iron oxyhydroxide electrode obtained as the working electrode, a metal lithium plate as the reference electrode and the counter electrode, and 1 mol dnf 3 in a 1: 1 mixed solvent of EC and EMC as the electrolyte solution. It used after dissolved LiC10 4 of 3 Gokukashoku shone ⁇ 1 ⁇ 1 ⁇ ! ⁇ We have manufactured a glass cell.
  • Example 1 the condition of standing for 24 hours was changed to stirring for 24 hours to obtain a lithium-containing oxyiron hydroxide powder according to the present invention.
  • the electrode F containing the lithium-containing iron oxyhydroxide according to the present invention was obtained using the lithium-containing iron oxyhydroxide powder as the active material.
  • the electrochemical potential behavior of this electrode was examined as follows. An electrode containing lithium-containing oxyhydroxide obtained as a working electrode, a metal lithium plate as a reference electrode and a counter electrode, and 1 mol in a mixed solvent of EC and EMC in a 1: 1 volume ratio of EC and EMC as an electrolyte. dm- 3 used after dissolved LiC10 4 of was fabricated glass cell three-electrode.
  • the battery was charged to 4.2 V vs. Li / Li + with a current of 0.01 CmA, and then discharged to 0.3 V vs. Li / Li + .
  • Figure 4 shows the electrochemical potential behavior of this electrode.
  • the amount of electricity charged per unit mass of the lithium-containing oxyiron hydroxide obtained by this method was 1210 mAh g- 1 .
  • the discharge capacity is 1112 mA. It has been found that the lithium-containing oxyiron hydroxide of the present invention can be charged and discharged even in a low potential region and can be used as a negative electrode active material of a nonaqueous electrolyte electrochemical cell.
  • Example 1 the solvent of the complex solution was 1-methoxybutane, and a lithium-containing oxyiron hydroxide powder according to the present invention was obtained.
  • An electrode G containing lithium-containing oxyiron hydroxide according to the present invention was obtained by using the lithium-containing oxyiron hydroxide powder as an active material in Example 1.
  • Example 1 the solvent of the complex solution was 1-methoxybutane, and the polycyclic aromatic compound was anthracene, whereby a lithium-containing oxyiron hydroxide powder according to the present invention was obtained.
  • the electrode H containing the lithium-containing oxyhydroxide according to the present invention was obtained using the lithium-containing oxyhydroxide as the active material.
  • Example 1 lithium-containing oxyiron hydroxide powder according to the present invention was obtained using 1-methoxybutane as the solvent of the complex solution and phenanthrene as the polycyclic aromatic compound.
  • Example 1 an electrode I containing the lithium-containing oxyhydroxide according to the present invention was obtained using the lithium-containing oxyhydroxide as the active material.
  • Example 1 a lithium-containing iron oxyhydroxide powder according to the present invention was obtained by using 1-methoxypropane as a solvent for the complex solution.
  • Example 1 an electrode J containing the lithium-containing iron oxyhydroxide according to the present invention was obtained by using the lithium-containing iron oxyhydroxide powder as the active material.
  • Example 1 a lithium-containing oxyiron hydroxide powder according to the present invention was obtained using 1-methoxypropane as the solvent of the complex solution and anthracene as the polycyclic aromatic compound.
  • an electrode ⁇ containing lithium-containing iron oxyhydroxide according to the present invention was obtained using the lithium-containing iron oxyhydroxide powder as an active material.
  • Example 1 a lithium-containing oxyiron hydroxide powder according to the present invention was obtained using 1-methoxypropane as the solvent of the complex solution and phenanthrene as the polycyclic aromatic compound.
  • the active material was the lithium-containing iron oxyhydroxide powder,
  • an electrode L containing a solution-containing oxyiron hydroxide was obtained.
  • - used after dissolved LiC10 4 of 3 were fabricated glass cell three-electrode.
  • the battery was charged to 4.2 V vs. Li I Li + with a current of 0.01 C mA, and then discharged to 1.5 V vs. Li I Li +.
  • Table 2 shows the values of the charge amount and the discharge capacity of the obtained electrode containing lithium-containing oxyiron hydroxide in the first cycle.
  • Example 1 By adding 0.033 mol of lithium sulfate to an aqueous solution in which 0.1 mol of ferric chloride was dissolved, an oxyiron hydroxide powder having an average particle size of 1.0 ⁇ m was synthesized. This
  • an electrode containing the lithium-containing oxyhydroxide according to the present invention was obtained by using the lithium-containing oxyhydroxide powder as the active material. This electrode was examined in the following manner.
  • the battery was charged to 4.2 V vs. Li / Li + with a current of 0.01 CmA, and then discharged to 1.5 V vs. Li / Li +.
  • Figure 5 shows its electrochemical potential behavior.
  • the amount of electricity charged per unit mass of the lithium-containing iron oxyhydroxide is 290 mAh g- 1 .
  • the discharge capacity was 351 mAh g- 1 . Therefore, it is preferable to use i3-phase iron oxyhydroxide powder.
  • a non-aqueous electrolyte secondary battery (Fe00H'Li / C system) using the lithium-containing oxyhydroxide obtained in Example 1 as a positive electrode active material and graphite as a negative electrode active material was produced.
  • the fabrication method is as follows. A paste was prepared by mixing 80% by mass of the lithium-containing oxyiron hydroxide powder obtained in Example 1, 5% by mass of acetylene black, and 15% by mass of PVDF in ⁇ P. This paste was applied on an aluminum foil having a thickness of 20 ⁇ and dried under reduced pressure at 70 ° C to evaporate NMP.
  • This battery was charged and discharged at 25 ° C. with a constant current of 0.1 C mA.
  • Figure 6 shows the charge / discharge characteristics.
  • This battery is capable of charging and discharging, the charge electrical quantity Contact Yopi discharge capacity was respectively 1 1. 3 mAh and I 5. 0 mAh.
  • the charge / discharge reaction of this battery is considered as in the following equation (1).
  • the right direction is the charging reaction, and the left direction is the discharging reaction.
  • the lithium-containing iron oxyhydroxide of the present invention is used as a positive electrode and contains no lithium.
  • a non-aqueous electrolyte electrochemical cell can be formed by combining with a carbon material such as graphite or amorphous carbon, and an anode such as an oxide or a nitride.
  • Vanadium pentoxide (V 2 0 5) as the positive electrode active material, to produce a nonaqueous electrolyte secondary battery using lithium-containing Okishi water iron oxide according to the present invention as a negative electrode active material (V ⁇ s / FeOOH 'Li system).
  • the fabrication method is as follows. V 2 0 5 powder 75 mass average particle diameter of 80 nm. /. And 5 mass of acetylene black. /. And PVDF20 mass ° /. And Paste were mixed in a corrupt P. The NMP was evaporated by applying this paste to aluminum foil ⁇ with a thickness of 20 ⁇ and drying under reduced pressure at ⁇ ° C.
  • the volume ratio of EC and EMC as the electrolytic solution using a 1: obtained by dissolving a LiC10 4 of 1 mol dm- 3 in a mixed solvent of 1 nominal capacity of Furaddeddo type 20 mAh Li-based non-aqueous electrolyte secondary batteries were fabricated.
  • This battery was charged and discharged at a constant current of 0.1 C mA at 25 ° C.
  • Fig. 7 shows the charge / discharge characteristics. This battery was chargeable and dischargeable, and the charged electricity and discharge capacity were 13.5 mAh and M. 7 mAh, respectively.
  • the charge / discharge reaction of this battery is considered as in the following equation (2). The right direction is the charging reaction, and the left direction is the discharging reaction.
  • a new secondary battery can be manufactured according to the present invention. Therefore, using the lithium-containing oxyhydroxide of the present invention as a negative electrode, a transition metal compound containing no lithium, such as manganese dioxide or vanadium pentoxide, or a transition metal chalcogen such as iron sulfide or titanium sulfide.
  • a non-aqueous electrolyte electrochemical cell can be obtained by combining the compound and a positive electrode such as activated carbon or graphite.

Abstract

Procédé de fabrication d’un oxyhydroxyde de fer contenant du lithium caractérisé en ce qu’une solution complexe dans laquelle du lithium métal et un composé aromatique polycyclique sont dissous dans un solvant, est mise au contact d’oxyhydroxyde de fer pour absorber le lithium dans l’oxyhydroxyde de fer. Il est également divulgué un procédé de production d’une cellule électrochimique électrolytique non aqueuse en utilisant une électrode contenant un oxyhydroxyde de fer contenant du lithium obtenu par un tel procédé. Ce procédé permet d’obtenir une batterie secondaire avec électrolyte non aqueux d’une forte capacité de décharge et de bonnes performances cycliques.
PCT/JP2005/003685 2004-03-01 2005-02-25 Oxyhydroxyde de fer contenant du lithium et procédé de fabrication d’une cellule électrochimique électrolytique non aqueuse contenant ledit oxyhydroxyde WO2005082783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-055705 2004-03-01
JP2004055705 2004-03-01

Publications (1)

Publication Number Publication Date
WO2005082783A1 true WO2005082783A1 (fr) 2005-09-09

Family

ID=34908878

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/003685 WO2005082783A1 (fr) 2004-03-01 2005-02-25 Oxyhydroxyde de fer contenant du lithium et procédé de fabrication d’une cellule électrochimique électrolytique non aqueuse contenant ledit oxyhydroxyde

Country Status (1)

Country Link
WO (1) WO2005082783A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160012973A1 (en) * 2013-03-29 2016-01-14 Panasonic Intellectual Property Management Co., Ltd. Conductive polymer particle dispersion, electrolytic capacitor using same, and method of producing these
CN110268555A (zh) * 2017-11-08 2019-09-20 株式会社Lg化学 包含磁赤铁矿的锂硫电池用正极和包含所述正极的锂硫电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05135760A (ja) * 1991-07-19 1993-06-01 Matsushita Electric Ind Co Ltd 非水電解液二次電池およびその製造法
JP2000095525A (ja) * 1998-06-12 2000-04-04 Japan Storage Battery Co Ltd リチウムニッケル含有化合物の製造方法
WO2001080337A1 (fr) * 2000-04-19 2001-10-25 Japan Storage Battery Co., Ltd. Matiere active d'electrode positive pour accumulateur, procede de production de ladite matiere et accumulateur electrolytique non aqueux comportant cette matiere

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05135760A (ja) * 1991-07-19 1993-06-01 Matsushita Electric Ind Co Ltd 非水電解液二次電池およびその製造法
JP2000095525A (ja) * 1998-06-12 2000-04-04 Japan Storage Battery Co Ltd リチウムニッケル含有化合物の製造方法
WO2001080337A1 (fr) * 2000-04-19 2001-10-25 Japan Storage Battery Co., Ltd. Matiere active d'electrode positive pour accumulateur, procede de production de ladite matiere et accumulateur electrolytique non aqueux comportant cette matiere

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160012973A1 (en) * 2013-03-29 2016-01-14 Panasonic Intellectual Property Management Co., Ltd. Conductive polymer particle dispersion, electrolytic capacitor using same, and method of producing these
US10147552B2 (en) * 2013-03-29 2018-12-04 Panasonic Intellectual Property Management Co., Ltd. Conductive polymer particle dispersion, electrolytic capacitor using same, and method of producing these
CN110268555A (zh) * 2017-11-08 2019-09-20 株式会社Lg化学 包含磁赤铁矿的锂硫电池用正极和包含所述正极的锂硫电池

Similar Documents

Publication Publication Date Title
KR101558535B1 (ko) 음극 활물질, 이를 포함하는 음극, 음극의 제조 방법 및 리튬 전지
KR101264332B1 (ko) 캐소드 활물질 및 이를 채용한 리튬 전지
JP5808073B2 (ja) 正極活物質及びこれを採用した正極とリチウム電池
KR101444189B1 (ko) 나트륨 이차전지용 음극활물질, 이를 이용한 전극의 제조방법 및 이를 포함하는 나트륨 이차전지
US11569492B2 (en) Positive-electrode active material and battery
US10854876B2 (en) Positive electrode active material and battery using positive electrode active material
JP5897971B2 (ja) 電極活物質、非水系二次電池用電極、非水系二次電池及び非水系二次電池用電極の製造方法
WO2014028219A1 (fr) Batteries au lithium-ion à densité d'énergie élevée, capacité de cyclage excellente et faible impédance interne
JP6394253B2 (ja) 非水系二次電池用電極、その製造方法及び非水系二次電池
JP2008091236A (ja) 非水電解質二次電池
KR20160081692A (ko) 실리콘계 음극 활물질, 이의 제조방법, 상기 실리콘계 음극 활물질을 포함하는 음극 및 상기 음극을 포함하는 리튬 이차전지
JP2005281128A (ja) リチウム含有オキシ水酸化鉄の製造方法およびその製造方法で得られたリチウム含有オキシ水酸化鉄を含む電極を用いた非水電解質電気化学セル
CN112313817A (zh) 正极材料和二次电池
JP2012181975A (ja) 非水二次電池
EP2607319B1 (fr) H4V3O8, nouveau matériau électroactif d'oxyde de vanadium (IV) pour batteries aqueuses et non aqueuses
JP2005108826A (ja) リチウム含有物質およびそれを含む非水電解質電気化学セルの製造方法
JP2012146650A (ja) 負極活物質組成物、それを利用した負極極板の製造方法及びリチウム二次電池
JP4447880B2 (ja) リチウム含有オキシ水酸化ニッケルの製造方法およびそれを含む電極を備えた非水電解質電気化学セル
WO2014073701A1 (fr) Matériau actif d'électrode positive, batterie au lithium-ion, et procédé pour la fabrication d'un matériau actif d'électrode positive
US10446834B2 (en) Positive active material, manufacturing method thereof, and positive electrode and lithium battery including the material
JP2002175836A (ja) 非水電解質電池
JP2015187929A (ja) 非水電解質二次電池
JP5360860B2 (ja) 非水電解液二次電池
WO2005082783A1 (fr) Oxyhydroxyde de fer contenant du lithium et procédé de fabrication d’une cellule électrochimique électrolytique non aqueuse contenant ledit oxyhydroxyde
US8741480B2 (en) Non-aqueous secondary battery comprising a polyvalent organic lithium salt

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase