JP3805053B2 - lithium secondary battery - Google Patents

lithium secondary battery Download PDF

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JP3805053B2
JP3805053B2 JP2663797A JP2663797A JP3805053B2 JP 3805053 B2 JP3805053 B2 JP 3805053B2 JP 2663797 A JP2663797 A JP 2663797A JP 2663797 A JP2663797 A JP 2663797A JP 3805053 B2 JP3805053 B2 JP 3805053B2
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intermetallic compound
negative electrode
secondary battery
active material
sn
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JPH10223221A (en
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直人 三宅
吉彦 森
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旭化成エレクトロニクス株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a positive electrode having an active material that occludes and releases lithium, a negative electrode, and a secondary battery having a lithium ion transfer medium.
[0002]
[Prior art]
  In recent years, electronic devices have been remarkably reduced in size and weight, and accordingly, a battery serving as a power source is desired to be small in size, light in weight, and high in energy density. In the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use. However, since these are primary batteries, they cannot be used repeatedly, and their application fields are limited. On the other hand, lead batteries and nickel-cadmium batteries have been used in the field of secondary batteries, but both have major problems in terms of size and weight reduction. From this point of view, non-aqueous electrolyte secondary batteries have attracted attention, and research and development of non-aqueous electrolyte secondary batteries using lithium as a negative electrode have been actively conducted. This battery has excellent characteristics such as high energy density, low self-discharge, and light weight. However, in this non-aqueous electrolyte secondary battery, as the charge / discharge cycle progresses, lithium has a dendrite-like crystal growth at the time of charge / discharge, and there is a disadvantage that the possibility of reaching the positive electrode and causing an internal short circuit increases. This is a major obstacle to commercialization.
[0003]
  Accordingly, various nonaqueous electrolyte secondary batteries using a carbon material intercalating or doping lithium as a negative electrode active material (hereinafter referred to as a carbon negative electrode) have been proposed. As for the carbon material, it is described in, for example, Japanese Patent Application Laid-Open No. 59-143280 that a graphite intercalation compound is used as a negative electrode using intercalation. Further, as a negative electrode material utilizing the doping phenomenon, it is possible to use a carbonaceous material such as a resin fired body or coke as disclosed in JP-A-58-35881, JP-A-58-209864, JP-A-59-173979. No. 6, JP-A 62-90863, JP-A 63-13282, JP-A 2-66856 and the like. Actually, secondary batteries using graphite or non-graphitizable carbon as a negative electrode active material have been put into practical use.
[0004]
  Further, it is publicly known that metals or semimetals such as Al, Ge, Si, Sn, Zn, and Pb are alloyed with lithium, and these alloyed negative electrode active materials (hereinafter referred to as alloy negative electrodes). The secondary battery used for this is being studied. Such a secondary battery has a high capacity and a high energy density, and can occlude and release more lithium ions than a carbon negative electrode. Therefore, the secondary battery has a higher capacity and a higher energy density than when a carbon negative electrode is used. Although a secondary battery can be obtained, it has not been put into practical use because of poor cycle characteristics.
[0005]
  Recently, the development of secondary batteries with higher capacity and longer cycle life than carbon anodes has been attempted, and those using iron silicide, nickel silicide, manganese silicide as the anode material are disclosed ( JP-A-5-159780, JP-A-8-153517, JP-A-8-153538). Mg2Ge or NiSi2CaF2The fact that the type structure intermetallic compound has a high capacity as a negative electrode material has been publicized at the 36th Battery Conference.
[0006]
[Problems to be solved by the invention]
  However, high performance and miniaturization of portable electronic devices are considered to continue in the future, and further increase in capacity and energy density of secondary batteries are desired.
  Accordingly, an object of the present invention is to provide a conventional carbon material having a capacity and energy density equivalent to those of a conventionally known lithium, or a secondary battery using a metal or metalloid alloyed with lithium as a negative electrode active material The present invention provides an excellent secondary battery having cycle characteristics equivalent to those of a secondary battery using as a negative electrode active material.
[0007]
[Means for Solving the Problems]
  The present invention has been made to solve the above problems.
  That is, the present inventionOneIs a secondary battery having a positive electrode, a negative electrode, and a lithium ion transfer medium using an active material capable of inserting and extracting lithium.As the positive electrode active material, the chemical composition formula Li x M y N z O 2 (M represents at least one selected from cobalt, nickel, manganese, and other transition metals, N represents at least one non-transition metal, and x, y, and z are each 0.05 <x <1.10. 0.85 ≦ y ≦ 1.00, 0 ≦ z <0.10) or Li (1 + x) Mn (2-x) O 4 Using a lithium-containing metal oxide represented by (0 ≦ X ≦ 1),As a negative electrode active material,Ge, Si, Sn, ZnAn intermetallic compound of at least one element selected from the group of elements and a metal or metalloid other than the above element group(However, the case where a coating layer is provided by plasma spraying or low-pressure plasma spraying or pulse plasma deposition method) and the half-width of the strongest peak in the X-ray diffraction method using CuKα ray is 0.2. Low crystalline intermetallic compound of 6 ° or more, or amorphous intermetallic compound having a broad scattering band having an apex from 20 ° to 40 ° in 2θ value by X-ray diffraction using CuKα rayThe present invention proposes a secondary battery characterized by using
  In the second aspect of the present invention, a crystalline intermetallic compound of at least one element selected from the element group of Ge, Si, Sn, and Zn and a metal or semimetal other than the above element group is mechanically processed by a ball mill. Low crystalline metal whose half-width of the strongest peak in the X-ray diffraction method using CuKα rays is 0.6 ° or more in terms of 2θ value by performing destruction or mechanical alloying from each pure element The manufacturing method of the secondary battery of this invention including the process of producing the negative electrode active material which consists of intermetallic compounds is proposed.
  In the third aspect of the present invention, a liquid roll is prepared by melting a crystalline intermetallic compound of at least one element selected from the element group of Ge, Si, Sn, and Zn and a metal or semimetal other than the element group. Including a step of producing a negative electrode active material made of an amorphous intermetallic compound having a broad scattering band having an apex from 20 ° to 40 ° with a 2θ value by an X-ray diffraction method using CuKα rays by a rapid cooling method. The manufacturing method of the secondary battery of this invention is proposed.
[0008]
  The secondary battery of the present invention has far better cycle characteristics than a secondary battery using a conventional alloy negative electrode, and has a capacity and energy density superior to those of a carbon negative electrode, and has the advantages of both of them. It is.
  The reason for this is that when the alloy negative electrode is repeatedly charged and discharged, the active material is microcrystallized and pulverized, but in the secondary battery of the present invention,Ge, Si, Sn, ZnIt is presumed that the microcrystallization and pulverization as described above are suppressed by the presence of other elements that are difficult to alloy with lithium around the element that is alloyed with lithium. Examples of elements that are difficult to alloy with lithium include B, Co, Cr, Cu, Fe, Mn, Mo, Ni, Ti, V, and W.
[0009]
  The intermetallic compound used in the present invention is low crystalline or amorphous.is there.Low crystallinity means that the half-width of the strongest peak is 0.6 ° or more in terms of 2θ value in the X-ray diffraction method using CuKα rays. The term “amorphous” as used herein refers to an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex from 20 ° to 40 ° as a 2θ value, and has a crystallinity peak. May be. By using an intermetallic compound having low crystallinity or amorphousness, the active material is hardly crystallized and / or finely powdered due to repeated charge / discharge, so that the cycle characteristics can be further improved.
[0010]
  Examples of basic components of the secondary battery of the present invention include a negative electrode and a positive electrode made of an active material capable of inserting and extracting lithium, and a lithium ion transfer medium.
  Although the intermetallic compound which is a negative electrode active material used for the secondary battery of this invention is illustrated concretely, especially limitation isNot.
[0011]
  As for containing Ge, As3GeLi5, CoFeGe, CoGeMn, FeGe2, Fe1.7Ge, FeGeMn, FeGeNi, GeLi5P3, GeMg2, GeMnNi, GeMo3, Β'-Ge2Mo, GeNb3, GeNi1.70, GeNi3, Ge3Pu, Ge3U, GeV3etcCan be mentioned.
  As containing Si, As3Li5Si, BeSiZr, CoSi2, Β-Cr3Si, Cu3Mg2Si, Fe3Si, Li5P3Si, Mg2Si, MoSi2, Nb3Si, NiSi2, Θ-Ni2Si, β-Ni3Si, ReSi2, Α-RuSi, SiTa2, Si2Th, Si2U, β-Si2U, Si3U, SiV3, Si2W, SiZr2Etc.
[0012]
  Examples of Sn-containing materials include AsSn, AuSn, and CaSn.3, CeSn3, CoCu2Sn, Co2MnSn, CoNiSn, CoSn2, Co3Sn2, CrCu2Sn, (Cr, Ni) Cu2Sn, Cu2FeSn, CuMgSn, Cu2MnSn, Cu4MnSn, (Cu, Ni)3Sn, Cu2NiSn, CuSn, FeSn2, IrSn, IrSn2, LaSn3, MgNi2Sn, Mg2Sn, MnNi2Sn, MnSn2, Mn2Sn, Mo3Sn, Nb3Sn, NdSn3, NiSn, Ni3Sn2, PdSn, Pd3Sn, Pd3Sn2, PrSn3, PtSn, PtSn2, Pt3Sn, PuSn3, RhSn, Rh3Sn2, RuSn2, SbSn, SnTi2, Sn3U, SnV3Etc.
[0013]
  Examples of Zn-containing materials include AgAsZn, β-AgZn, AsLiZn, AsNaZn, β-AuZn, CeZn, β'-CuZn, EuZn, LaZn, LiPZn, MgNiZn, and MgZn.2, PrZn, Pt3Zn, PuZn2, Th2Zn, TiZn2, TiZn3, Zn2Zr etc. are mentioned.
The composition of the intermetallic compound used in the secondary battery of the present invention is an ICP solution in which the intermetallic compound is subjected to fluorescent X-ray analysis while being powdered, or an aqueous solution in which the powder is dissolved with concentrated hydrochloric acid, hot concentrated sulfuric acid, concentrated nitric acid, aqua regia, etc. It can be identified by analysis or atomic absorption analysis. Further, other elements such as B and Co that are not included in the composition of the intermetallic compound, or other compounds may be contained as long as they are less than 10 wt%.
[0014]
  CrystallineIntermetallic compounds are powders or granular materials in which a predetermined amount of each pure element is weighed and mixed in an electric furnace, a high-frequency induction heating device, or an arc melting furnace in an inert gas atmosphere such as argon or nitrogen. It is obtained by heating to the following temperature and dissolving, followed by solidification. In addition, it can also be obtained from each oxide by using a reduction diffusion method. When it is desired to make it low crystalline or amorphous, the crystalline intermetallic compound produced as described above is melted by a high frequency induction heating device, a plasma jet device, an infrared intensive heating device, etc. Use the law. Examples of the ultra-quenching method include the gun method, Hammer-Anvil method, slap method, gas atomization method, water atomization method, disk atomization method, plasma spray method, centrifugal quenching method, ceramic processing (Gihodo Publishing 1987), pages 218-219, There are a single roll method, a twin roll method, a melt drag method, and the like. Especially in the liquid roll quenching method such as the single roll method and the twin roll method, 105-106K / sec, 10 for gas atomization method4-105A cooling rate of K / sec can be obtained, and the amorphous intermetallic compound of the present invention can be easily obtained. It is also possible to obtain a thin amorphous intermetallic compound by sputtering. Further, it is possible to produce a low crystalline or amorphous intermetallic compound by mechanically destroying a crystalline intermetallic compound with a ball mill or the like, or by mechanical alloying from each pure element.
[0015]
  The intermetallic compound having a form such as a plate-like ingot or spherical, flaky powder or ribbon obtained by the above method is made into a fine powder by using a known pulverization, classification and mixing method. Adjust the particle size distribution. The average particle size is preferably 1 μm or more and 50 μm or less.
  The electrode used for the secondary battery of the present invention is one in which an electrode mixture layer is formed on an electrode current collector. In such an electrode, an electrode mixture slurry obtained by dispersing an electrode mixture in which the intermetallic compound, a binder, and, if necessary, a conductive filler are mixed in a solvent is applied to an electrode current collector. Then get dry. If necessary, a roller press is performed.
[0016]
  Although it does not specifically limit as a collector used for the negative electrode of this invention, Metal foil or a net | network of about 10-100 micrometers thickness, such as Cu, Ni, stainless steel, etc. are used. Binders include polytetrafluoroethylene, polytrifluoroethylene, polyethylene, nitrile rubber, polybutadiene rubber, butyl rubber, polystyrene, styrene butadiene rubber, styrene butadiene latex, polysulfide rubber, nitrocellulose, acrylonitrile butadiene rubber, polyvinyl fluoride, Polyvinylidene fluoride and fluororubber are desirable, but are not particularly limited.
[0017]
  Further, when the electrical resistance of the active material is high, a conductive filler may be added to increase conductivity. As the conductive filler, a carbon material such as graphite or carbon black, or a metal powder such as Cu, Fe, or Ti is used.
  As the active material of the positive electrode combined with the negative electrode of the present invention, the chemical composition formula LixMyNzO2(M represents at least one selected from cobalt, nickel, manganese, and other transition metals, N represents at least one non-transition metal, and x, y, and z are each 0.05 <x <1.10. A lithium-containing metal oxide represented by 0.85 ≦ y ≦ 1.00 and 0 ≦ z <0.10) can be used. These have a high potential, a high voltage can be obtained as a battery, and the cycleability is good. As M, Co, Ni, Mn alone and a composite of Co / Ni, Mn / Cr, Mn / Fe are particularly preferable. N is not particularly limited as long as it is a non-transition metal, but Al, In, and Sn are preferable. Li(1 + x)Mn(2-x)O4It is also possible to use a lithium-containing metal oxide represented by (0 ≦ X ≦ 1)it can.
[0018]
  As the current collector of the positive electrode, a metal foil or net having a thickness of about 10 to 100 μm such as Al, Cu, Ni, stainless steel, etc. can be used. When using an active material having a potential, it is preferable to use a metal foil or net made of Al.
  Examples of the lithium ion medium used in the present invention include a solution in which a lithium salt is dissolved in an aprotic organic solvent, a solid in which a lithium salt is dispersed in a polymer matrix, or a lithium salt dissolved in an aprotic organic solvent. A mixture of a solution and a polymer matrix is used. The organic solvent preferably contains ethylene carbonate and linear carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate as essential components. In addition, ethers, ketones, lactones, nitriles, amines, amides, sulfone compounds, carbonates, esters and the like may be contained. Typical examples of these include propylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyllactone, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether , Sulfolane, methylsulfolane, acetonitrile, propionitrile and the like, but are not necessarily limited thereto. As the lithium salt, LiBF4, LiPF6LiClO4, LiAsF6, CF3SO3Li, CH3SO3Li, LiI, LiP, LiCl, LiBr, (CF3SO2)2NLi etc. are mention | raise | lifted. Examples of the polymer matrix include aliphatic polyethers such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyvinyl alcohol and polyvinyl butyral, aliphatic polythioethers such as polyethylene sulfide and polypropylene sulfide, polyethylene succinate, poly Aliphatic polyesters such as butylene adipate and polycaprolactone, polyethyleneimine, polyimide, polyvinylidene fluoride, and precursors thereof can be used.
[0019]
  Further, a separator for preventing a short circuit can be provided between the positive electrode and the negative electrode. As the separator, a single microporous film of polyolefin such as polyethylene or polypropylene, or a film obtained by bonding them together, or a non-woven fabric such as polyolefin, polyester, polyamide or cellulose, or a single film bonded to the microporous film. Can be used.
[0020]
  As other components of the secondary battery of the present invention, parts such as a terminal, an insulating plate, and a metal can may be used. Moreover, when using this invention as a battery can as shown in FIG. 1, stainless steel, nickel-plated steel, iron, aluminum, etc. are used as a material.
  The structure of the battery is not particularly limited, but is a paper-type battery, a laminated battery, or a cylinder shown in FIG. 1 in which the positive electrode, the negative electrode, and the separator are wound in a roll shape. And forms such as a square battery.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, the scope of the present invention is not limited to this.
[0022]
【Example】
    Comparative Examples 1-F to 1-N
  As a negative electrode active material, highly crystallineGeMg 2 ,GeNi3, Mg2Si, NiSi2, SiV3, Mg2Sn, Cu2NiSn, MgZn2, TiZn2(Hereafter, each active materialFNAn example using
[0023]
    Preparation of highly crystalline intermetallic compounds
  Active materialFNEach of the pure elements was weighed and mixed in a stoichiometric ratio, and the powder was heat-treated at each temperature shown in Table 1 for about 2 hours in an electric furnace in an argon atmosphere, and then slowly cooled and solidified. A shaped intermetallic compound was obtained. The coarse powder obtained by pulverizing the plate-like material with a hammer was powdered with a sample mill, and sieved with 400 mesh to obtain a fine powder having an average particle diameter of about 9 μm.
[0024]
    X-ray diffraction
  As a representative example, the measurement result of the X-ray diffraction using the CuKα ray is shown in FIG. Thus, it is a highly crystalline intermetallic compound, the peak with the strongest diffraction intensity exists in the vicinity of 24.2 °, and the half width of the peak is 0.16 °. The other active materials were confirmed to be highly crystalline as well.
[0025]
    Composition analysis
  Composition analysis of an aqueous solution in which the intermetallic compound was dissolved in aqua regia was conducted by ICP analysis, and it was confirmed that each active material had the above composition.
    Production of negative electrode
  42 wt% of intermetallic compound produced as described above, scaly graphite (KS6 manufactured by Lonza Co., Ltd.) 4 wt%, acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) 2 wt%, binder A polyvinylidene fluoride solution (Kureha KF Co., Ltd. Kureha KF Polymer # 9130 dissolved in N-methyl-2-pyrrolidone at a solid content of 13 wt%, hereinafter referred to as a PVdF solution) is 36 wt%, N-methyl- What added each 16 wt% 2-pyrrolidone (henceforth, NMP) was mixed and stirred with the three one motor, and the electrode mixture slurry was obtained. And after apply | coating this slurry on the 12-micrometer-thick copper foil which is a collector, and drying, roller press is performed at 150 degreeC, and the film thickness of about 30 micrometers consisting of a negative electrode collector and a negative mix layer is carried out. A negative electrode was obtained.
[0026]
    Fabrication of positive electrode
  LiCoO with an average particle size of 3 μm2To 100 parts by weight, 5 parts by weight of graphite as a conductive agent and 100 parts by weight of a dimethylformamide solution (5% by weight) in which polyvinylidene fluoride was dissolved as a binder were added, mixed and stirred to obtain a slurry. The slurry was coated on a 15 μm-thick Al foil as a current collector, dried, and press-molded to produce a positive electrode composed of the current collector and a positive electrode mixture layer.
[0027]
    Charge / discharge evaluation
  In order to see the performance of the negative electrode alone, cycle evaluation was performed while controlling the negative electrode potential as follows. Each of the positive electrode and the negative electrode obtained as described above was 2.00 cm.2And 2.05cm2Each electrode welded with a current collector was made to face each other through a polyethylene microporous membrane and sandwiched between a glass plate and a clip. Then, a lithium metal as a reference electrode was set so as to be near the negative electrode after being sandwiched between the mouth clip of the glass test cell so as not to short-circuit the positive and negative electrode current collectors. On the other hand, after the inside of this glass test cell was depressurized to sufficiently remove water, the electrolyte LiPF was mixed with ethylene carbonate and methyl ethyl carbonate in a 1: 2 solvent mixture at a volume ratio of 1 mol / liter.6Then, the electrolyte solution was dehydrated with molecular sieves and the electrolyte was dropped into the glass test cell from which water had been sufficiently removed, under extremely low humidity, and sufficiently impregnated.
[0028]
  The charge / discharge test of the test cell thus obtained is performed by controlling the potential of the negative electrode viewed from the reference electrode. Here, charging is a direction in which the negative electrode occludes lithium ions, and conversely, discharging is a direction in which lithium ions are released. The positive electrode active material is applied in an amount sufficient to cover the lithium ion occlusion amount of the negative electrode. Charge current density 1mA / cm210 mV, 24 hours constant voltage charge, discharge is 1 mA / cm current density2The 1.2V constant current cut-off discharge was performed. From this result and the mixture layer volume of the negative electrode used, the discharge amount per unit volume of the negative electrode mixture layer in the first cycle (hereinafter, discharge capacity) and 100 when the discharge capacity in the first cycle is 100% The discharge capacity retention rate at the cycle (hereinafter, capacity retention rate) was determined.
[0029]
    Comparative example1-Q~ 1-T
  As a metal negative electrode,Ge, Si, Sn, ZnAn example using is shown. As each metal or metalloid, a powder obtained by purchasing high-purity chemical research company powder and sieving with 400 mesh was used. Other than that,Comparative Examples 1-F to 1-NExperiments and evaluations were carried out in the same manner.
[0030]
    Comparative Example 1-U, V
  An example in which scaly graphite (CX3000 manufactured by Chuetsu Graphite Industries Co., Ltd., hereinafter referred to as graphite) and needle coke (manufactured by Kowa Oil Co., Ltd., hereinafter referred to as coke) is shown as the carbon negative electrode. Except for preparing a negative electrode from an electrode mixture slurry obtained by mixing and stirring each carbon material 47 wt%, PVdF solution 36 wt%, NMP 17 wt% added,Comparative Examples 1-F to 1-NExperiments and evaluations were carried out in the same manner.
[0031]
  The results are shown in Table 1.
[0032]
[Table 1]
[0033]
    Example 2-F ′, H ′, K ′, M ′
  As a negative electrode active material, low crystallineGeMg 2 ,Mg2Si, Mg2Sn, MgZn2(Less than,Each active material F ′, H ′, K ′, M ′An example using
[0034]
    Preparation of low crystalline intermetallic compounds
  In order to obtain a low crystalline intermetallic compound, a manufacturing method called mechanical alloying (MA method) was used. The MA method will be explained in detail.Active material F ′, H ′, K ′, M ′5 g of powder obtained by weighing and mixing each of the constituent elements according to the stoichiometric ratio together with 8 stainless steel balls with a diameter of 25 mm and an internal volume of 500 cm3Was placed in a stainless steel pot mill under an argon atmosphere, and a rotating ball mill was performed for 2 weeks. The powder obtained after ball milling was sieved with 400 mesh to obtain a fine powder having an average particle size of about 9 μm. As a representative example, the measurement result of the X-ray diffraction using CuKα rays for the active material F ′ is shown in FIG. Thus, it is a low crystalline intermetallic compound, and the peak with the strongest diffraction intensity exists in the vicinity of 24.1 °, and the half width of the peak is 0.66 °. The other active materials were confirmed to have low crystallinity as well. Subsequent experiments and evaluationsComparative Examples 1-F to 1-NWas done in the same way.
[0035]
    Example 3-G ′, I ′, J ′, L ′, N ′
  As a negative electrode active material, amorphousGeNi 3 ,NiSi2, SiV3, Cu2NiSn, TiZn2(Hereafter, eachActive material G ′, I ′, J ′, L ′, N ′An example using
    Preparation of amorphous intermetallic compounds
  In order to obtain an amorphous intermetallic compound, a high-frequency induction heating-single roll type ultra rapid cooling apparatus was used (hereinafter referred to as RS method). The high-frequency power source is a transistor inverter type, with an output of 3 KW and a frequency of 200 KHz. The single roll was made of copper and had a diameter of 200 mm and a width of 20 mm. The roll drive system was a magnetic coupling, and the operation was performed at a rotational speed of 3000 rpm.Comparative Examples 1-F to 1-N10 g of each highly crystalline intermetallic compound produced by the same production method as described above was rapidly solidified in the above-mentioned RS method under an argon atmosphere to obtain a ribbon-like substance. This is powdered with a sample mill, and further sieved with 400 mesh, and the average particle size is about 9 μm.Active material G ′, I ′, J ′, L ′, N ′Got. X-ray diffraction was measured using CuKα rays, and it was confirmed to be amorphous. Subsequent experiments and evaluationsComparative Examples 1-F to 1-NWas done in the same way. The results are shown in Table 1.
[0036]
  Examples 2 and 3Ge, Si, Sn, ZnIt is better to use a low crystalline or amorphous intermetallic compound containingComparative Example 1It can be seen that the capacity retention rate is higher than that using the highly crystalline intermetallic compound, and the cycle characteristics are excellent, which is more desirable.
[0037]
【The invention's effect】
  Ge, Si, Sn, ZnThe negative electrode using an intermetallic compound containing as an active material has a discharge capacity much higher than that of a carbon negative electrode, and has excellent cycle characteristics as compared with an alloy negative electrode. Further, by using a low crystalline or amorphous intermetallic compound as the negative electrode active material, better cycle characteristics can be obtained. Therefore, the secondary battery of the present invention has much higher capacity and higher energy density than the current secondary battery using a carbon negative electrode, and has better cycle characteristics than a secondary battery using an alloy negative electrode. is doing.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a non-aqueous electrolyte secondary battery of the present invention.
FIG. 2 Highly crystalline intermetallic compound GeMg2This is a result of X-ray diffraction.
FIG. 3 Low crystalline intermetallic compound GeMg2This is a result of X-ray diffraction.
[Explanation of symbols]
1 ... Negative electrode
2 ... Separator
3 ... Positive electrode
4 ... Positive terminal
5 ... Battery container (negative electrode terminal)

Claims (3)

  1. In a secondary battery having a positive electrode, a negative electrode, and a lithium ion transfer medium using an active material capable of occluding and releasing lithium , the chemical composition formula Li x M y N z O 2 (M is cobalt) Represents at least one selected from nickel, manganese, and other transition metals, N represents at least one non-transition metal, and x, y, and z are 0.05 <x <1.10, 0.85 ≦ As a negative electrode active material , a lithium-containing metal oxide represented by y ≦ 1.00, 0 ≦ z <0.10) or Li (1 + x) Mn (2-x) O 4 (0 ≦ X ≦ 1) is used . Ge, Si, Sn, an intermetallic compound of at least one element other than the above element group metal or metalloid selected from the element group of Zn (although plasma spraying or vacuum plasma spraying and Parusupura A low-crystalline metal whose half-width of the strongest peak in the X-ray diffraction method using CuKα ray is 0.6 ° or more in 2θ value. A secondary battery characterized by using an intermetallic compound or an amorphous intermetallic compound having a broad scattering band having an apex at 20 ° to 40 ° with a 2θ value by an X-ray diffraction method using CuKα rays .
  2. A ball-mill mechanically destroys a crystalline intermetallic compound of at least one element selected from the element group of Ge, Si, Sn, and Zn and a metal or metalloid other than the above element group, or each pure element A negative active material composed of a low crystalline intermetallic compound in which the half-width of the strongest peak in the X-ray diffraction method using CuKα rays is 0.6 ° or more is 2θ value by mechanical alloying from The manufacturing method of the secondary battery of Claim 1 including the process to produce.
  3. A CuKα ray is used by melting a crystalline intermetallic compound of at least one element selected from the element group of Ge, Si, Sn, and Zn and a metal or metalloid other than the above element group by a liquid roll quenching method. 2. A secondary battery according to claim 1, further comprising a step of producing a negative electrode active material made of an amorphous intermetallic compound having a broad scattering band having a peak at 20 [deg.] To 40 [deg.] In the 2 [theta] value by a conventional X-ray diffraction method. Manufacturing method.
JP2663797A 1997-02-10 1997-02-10 lithium secondary battery Expired - Fee Related JP3805053B2 (en)

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