WO1995018467A1 - Materiau cathodique et son procede de production - Google Patents

Materiau cathodique et son procede de production Download PDF

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Publication number
WO1995018467A1
WO1995018467A1 PCT/JP1993/001929 JP9301929W WO9518467A1 WO 1995018467 A1 WO1995018467 A1 WO 1995018467A1 JP 9301929 W JP9301929 W JP 9301929W WO 9518467 A1 WO9518467 A1 WO 9518467A1
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Prior art keywords
carbon
negative electrode
carbon precursor
carbonaceous material
ray diffraction
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PCT/JP1993/001929
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English (en)
Japanese (ja)
Inventor
Hiroshi Imoto
Atsuo Omaru
Hideto Azuma
Yoshio Nishi
Yoshihisa Gonno
Masayuki Nagamine
Original Assignee
Sony Corporation
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Priority to JP08625593A priority Critical patent/JP3399015B2/ja
Priority claimed from JP08625593A external-priority patent/JP3399015B2/ja
Application filed by Sony Corporation filed Critical Sony Corporation
Priority to DE69324604T priority patent/DE69324604T2/de
Priority to EP94903101A priority patent/EP0687022B1/fr
Priority to US08/507,324 priority patent/US5643426A/en
Priority to CA002156424A priority patent/CA2156424C/fr
Priority to PCT/JP1993/001929 priority patent/WO1995018467A1/fr
Publication of WO1995018467A1 publication Critical patent/WO1995018467A1/fr
Priority to US08/812,734 priority patent/US5716732A/en

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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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 negative electrode material used for a non-aqueous electrolyte secondary battery and doped with and doped with lithium, and a method for producing the same.
  • Background Technology Electronic equipment Higher energy density of batteries is required with miniaturization, and various non-aqueous electrolyte batteries such as so-called lithium batteries have been proposed to meet such demands. .
  • batteries using lithium metal for the negative electrode have the following disadvantages especially when used as secondary batteries. That is,
  • a carbonaceous material for the negative electrode as a method for solving these problems.
  • a lithium-carbon interlayer compound can be easily formed electrochemically. For example, when charging is performed in a nonaqueous electrolyte using carbon as a negative electrode and a compound containing lithium as a positive electrode, lithium in the positive electrode is electrochemically doped between layers of the negative electrode carbon. Then, the carbon doped into lithium functions as a lithium electrode, and lithium in the negative electrode is dropped from the carbon layer with discharge and returns to the positive electrode.
  • the current capacity per unit weight of the negative electrode is determined by the amount of lithium doped in the carbonaceous material. Therefore, it is desirable that the doping amount of lithium is as large as possible as a carbonaceous material (theoretically, the ratio of one Li atom to six carbon atoms is the upper limit. ). From such a point of view, the above-mentioned carbonaceous material can provide a large amount of lithium doping compared to the conventional carbonaceous material, but is not sufficient.
  • An object of the present invention is to provide a negative electrode material having a large lithium doping amount and a sufficient current capacity, and a method for producing the same.
  • the negative electrode material of the present invention has been completed based on such findings, and is a non-graphitizable carbon material obtained by firing a carbon precursor.
  • the weight ratio P of the carbon having the integrated structure obtained from the (002) diffraction peak derived from the crystal lattice plane and the X-ray diffraction spectrum at a lower angle side from the diffraction peak derived from the (002) crystal lattice plane P It is characterized in that s is smaller than 0.59 or the stacking index SI is smaller than 0.76.
  • the X-ray diffraction spectrum is obtained from the diffraction peak derived from the (002) crystal lattice plane and the X-ray diffraction spectrum at a lower angle side than the diffraction peak derived from the (002) crystal lattice plane. It is an Toku ⁇ the average stacking number n ive of the laminate structure portion 2. less than 4 6.
  • a non-graphitizable carbon material obtained by calcining a carbon precursor, wherein the calcining temperature is T ° C, and the half-width at half maximum of a peak appearing around 140 cm- 1 in Raman spectrum is HW.
  • the method for producing a negative electrode material of the present invention comprises the steps of:
  • the carbon precursor is heat-treated at a temperature of 600 ° C. or more in an inert gas atmosphere having a flow rate of 0.1 ml / g or more per 1 g of the carbon precursor.
  • the present invention is characterized in that a carbon precursor which is to be calcined to become non-graphitizable carbon is heat-treated at a temperature of 600 ° C. or more in an atmosphere of a pressure of 5 OkPa or less.
  • the carbon precursor when heat-treated, it is characterized in that the carbon precursor is placed in a layered manner such that the contact area with the atmosphere becomes 10 cm 2 or more per kg.
  • the non-graphitizable carbon material whose number of layers n ave satisfies the predetermined conditions is such that when used as the negative electrode material of a lithium nonaqueous electrolyte battery, lithium is doped only between the carbon layers of the laminated structure.
  • Lithium doping amount has a lithium doping amount far exceeding 37 2 mA h / g. This is because the non-graphitizable carbon material in which the above parameter satisfies the predetermined conditions has many small voids as sites to be doped with lithium in addition to the carbon layer in the laminated structure. Conceivable.
  • Such a non-graphitizable carbon material is prepared by burning a carbon precursor that becomes non-graphitizable carbon by firing in an inert gas atmosphere at a flow rate of 0.1 m1 Zin or more per gram of the carbon precursor, or under pressure. It can be obtained by carbonization in an atmosphere where the volatile components generated during carbonization when heat-treated at a temperature of 600 ° C or more in an atmosphere of 50 kPa or less are removed outside the reaction system. . This is for the following reason.
  • the negative electrode material of the present invention is a non-graphitizable carbon material obtained by calcining a carbon precursor, and has a diffraction peak derived from a (002) crystal lattice plane in an X-ray diffraction spectrum.
  • FIG. 1 is a characteristic diagram showing a curve I c 0 rr ( ⁇ ) obtained by correcting the X-ray diffraction spectrum of a non-graphitizable carbon material.
  • FIG. 2 is a characteristic diagram showing a curve F ( ⁇ ) obtained by subtracting the minimum value Ia from the curve Icorr (0) and further raising sin ( ⁇ ).
  • Fig. 3 is a characteristic diagram showing a Pausson-son function curve obtained by Fourier-transforming the curve F ( ⁇ ).
  • Fig. 4 shows the curve obtained by smoothing the X-ray diffraction spectrum.
  • the non-graphitizable carbon material means a carbon material in which graphitization does not easily proceed even after a high-temperature heat treatment such as 300 ° C., but here, 260 ° C. D after heat treatment at ° C. . 2 means a carbon material with a value of 3.4 OA or more.
  • Such a non-graphitizable carbon material is composed of a laminated structure portion in which carbon atoms have a laminated structure and a non-laminated structure portion.
  • a non-graphitizable carbon material is used as the negative electrode material, lithium is doped between the carbon layers in the above-described laminated structure and also into minute voids in the disordered carbon layer in the non-laminated structure. It is thought that it is done. If the volume of the minute voids is too large, lithium cannot remain in the voids and does not contribute to lithium doping.However, the small voids have an appropriately small volume so that lithium can remain in them and lithium Contributes to doping. When there are many such microvoids, the theoretical lithium doping amount of 372 mAhZg, which was obtained on the assumption that lithium is doped only between the carbon layers, is far away. It is possible to obtain a lithium doping amount that exceeds the standard.
  • the parameter which reflects the ratio of the laminated structure proposed as the anode material in the present invention, Ps, and SKn are difficult graphite satisfying the above conditions.
  • the carbonized material is a non-graphitizable carbon material having a small ratio of the laminated structure portion, and has many microvoids in the non-laminated structure portion. Therefore, these many small voids effectively contribute to lithium doping, and a large amount of lithium doping can be obtained.
  • Isseki parameter that reflects the percentage of the laminated structure portion, Ps, SI, n eve, among the X-ray diffraction scan Bae spectrum of flame black ⁇ carbon material, derived from (00 2) crystal lattice plane Diffraction It can be obtained by subjecting data obtained from a spectrum at a lower angle side to the peak and a diffraction peak derived from the (002) crystal lattice plane to a predetermined procedure.
  • SI, P s, n.ve conforms to the method described in the above-mentioned literature, but is determined by a partially simplified method so that the method can be performed more easily.
  • Hara Correct by dividing by the square of the factor and the atomic scattering factor.
  • the child scattering factor is a function of s in, but I n t e r n a t i o n a 1 Tab l e s f or r X- r ay C ry s t a l 1 o g r ap hy, v o l .IV, p 7 1 (Th e Kyn o c h
  • FIG. 1 shows a curve I c 0 r r ⁇ ) obtained by correcting the X-ray diffraction spectrum.
  • I a the peak intensity of the peak derived from the (002) crystal lattice plane.
  • I a the peak intensity of the peak derived from the (002) crystal lattice plane.
  • 20 15. Smoothing processing is performed in advance for about 15 to 35 points in the range of ⁇ 38 °.
  • the SI value is obtained by substituting the thus obtained Im, Ia into the equation shown in Equation 3.
  • the weight ratio of the carbon atoms constituting the laminated structure consisting of ⁇ carbon layers among the carbon atoms having the laminated structure in the non-graphitizable carbon material can be calculated by using this ⁇ ( ⁇ ) as Desired.
  • Equation 5 the calculation of ⁇ ( ⁇ ) shown in Equation 5 is performed up to ⁇ , which is one less than ⁇ when the ⁇ ( ⁇ ) value becomes 0 or negative for the first time.
  • n ave is obtained by the equation shown in Equation 6 using the desired ( ⁇ ).
  • the (002) plane spacing do 02 of the crystal lattice plane is obtained as follows. That is, the diffraction peak derived from the (002) crystal lattice plane of the X-ray diffraction spectrum observed in (1) is subjected to a smoothing process of about 15 to 35 points.
  • Figure 4 shows the curve I (0) obtained by smoothing the X-ray diffraction spectrum. Then, as shown in Fig. 4, a baseline is drawn on the diffraction peak of this curve I (0), and the portion between the diffraction peak and the junction of the baseline and the portion surrounded by the diffraction peak is integrated. By substituting 20 into the Bragg equation, which divides the integrated intensity into two, d. . 2 is required.
  • Equation 7 n ave , SI and d 0 obtained as described above.
  • Ps of the carbon atom having a laminated structure in the carbon material is obtained from the equation shown in Equation 7. [Equation 7]
  • the transmission method it is not always necessary to determine by the method called the transmission method, but it is also possible to obtain the value by correcting with an appropriate absorption factor using the commonly used reflection method. it can.
  • the values corresponding to Im and Ia of the I ( ⁇ ) curve before correction it is possible to derive parameters that contain a large amount of error but are correlated with SI.
  • the non-graphitizable carbon material whose SI, n.ve and Ps satisfying the predetermined conditions thus obtained exhibits a high lithium doping amount.
  • the Raman spectrum is 1340 cm. -The half-width HW of the peak appearing near 1 is
  • a non-graphitizable carbon material satisfying the following conditions is also used as a negative electrode material. That is, when Raman spectrum is observed for the non-graphitizable carbon material, peaks are observed at around 1340 cm 1 and around 1580 cm ⁇ 1 . 1 580 cnt 1 near peak derived from graphite structure formed by strongly bound to each other carbon atoms, i.e. the multilayer structure portion of the above.
  • the peak near 1 340.cnT 1 is a phase that is inferior in symmetry to the graphite structure in which carbon atoms are weakly bonded to each other. Derived from The half width at half maximum HW of the peak near 1340 cnr 1 reflects the degree of variation in the bonding state between carbon atoms in the non-stacked structure portion.
  • the half-value half-width HW is larger than 13 8-0.06 ⁇ ⁇
  • the dispersion of carbon atoms in the non-laminated structure is moderately large, and the fine pores contributing to lithium doping are formed. Is presumed to have a large amount, and a large lithium doping amount can be obtained.
  • the term 1 3 4 0 c nr 1 near the peak of the half half-width and is half the value of the value called a normal half-width.
  • a base line is drawn on the peak waveform of the fitted Raman spectrum, and a straight line is drawn in parallel with the base line at a point 1 to 2 of the intensity from the peak top to the base line.
  • the points of intersection of this peak waveform and the straight line are points A and B, and the horizontal axis corresponding to points A and B is read.
  • the difference between the readings on the horizontal axis corresponding to points A and B is the half width, and the half value of the half width is the half width.
  • Such a non-graphitizable carbon material can be obtained by calcining a carbon precursor exemplified below.
  • examples of the precursor of the non-graphitizable carbon include those obtained by introducing an oxygen-containing functional group into petroleum pitch, and carbon materials that undergo solid-phase carbonization via a thermosetting resin. .
  • petroleum pitch is distilled from coal tar, ethylene bottom oil, tars obtained by high-temperature pyrolysis of crude oil, asphalt, etc. (vacuum distillation, atmospheric distillation, steam distillation), thermal polycondensation, extraction, chemical weight It is obtained by an operation such as condensation.
  • the HZC atomic ratio of the petroleum pitch needs to be 0.6 to 0.8 in order to obtain non-graphitizable carbon.
  • the specific means for introducing a functional group containing oxygen into these petroleum pitches is not limited.
  • a wet method using an aqueous solution of nitric acid, mixed acid, sulfuric acid, and hypochlorous acid, or an oxidizing gas (air, oxygen) A dry method, and a reaction with a solid reagent such as sulfur, ammonium nitrate, ammonium persulfate, and ferric chloride are used.
  • the oxygen content is not particularly limited, but is preferably 3% or more, more preferably 5% or more, as shown in JP-A-3-25053. This oxygen content affects the crystal structure of the finally produced carbonaceous material, and when the oxygen content is within this range, the plane spacing d of the (002) plane. . 2 for 3.7 OA or more, differential thermal analysis in air stream
  • the organic materials used as precursors include conjugated resins such as phenol resin, acryl resin, vinyl halide resin, polyimide resin, polyamide imide resin, boriamid resin, polyacetylene, poly (p-phenylene), etc. Resins, cellulose and derivatives thereof, and any organic polymer compounds can be used.
  • condensed polycyclic hydrocarbon compounds such as naphthalene, phenanthrene, anthracene, triphenylene, pyrene, perylene, pentaphane, and pentacene, and other derivatives (eg, carboxylic acids, carboxylic anhydrides, carboxylic acids Mide, etc.), various pitches mainly containing a mixture of the above-mentioned compounds, acenaphthylene, indole, isoindole, quinoline, isoquinoline, quinoxaline, phthalazine, phorbabul, acridine, phenazine, phenanthridine and the like.
  • Fused heterocyclic compounds and derivatives thereof can also be used.
  • furfuryl alcohol or furfura Furan resins comprising a homopolymer or a copolymer of polyester are also suitable.
  • Such an organic material may be subjected to an infusibilization treatment so as to undergo solid-phase carbonization.
  • an oxygen-containing group is introduced in the same manner as applied to the above-mentioned oil pitch, chlorine gas or sulfur gas. Or the presence of a catalyst that promotes the crosslinking reaction.
  • a carbonaceous material can be obtained by firing the above-exemplified carbon precursor, but in order to obtain a carbonaceous material with a large lithium doping amount, the firing atmosphere when firing the carbon precursor is important. .
  • the calcination of the carbon precursor is performed in an atmosphere of an inert gas at a flow rate of 0.1 ml / min or more per 1 g of the carbon precursor or in an atmosphere of a pressure of 5 OkPa or less. .
  • the firing of the carbon precursor is performed in an inert gas atmosphere with a flow rate of 0.1 mL or more per gram of the carbon precursor, volatile components are removed by the flow of the inert gas.
  • the carbon precursor is fired in a low-pressure atmosphere at a pressure of 50 kPa or less, diffusion and desorption of volatiles from the carbon precursor are promoted, and volatiles are efficiently removed.
  • the carbon precursor is fired in an atmosphere in which volatile components generated by the carbonization are removed from the outside of the reaction system, the carbonization proceeds smoothly, and a carbonaceous material with a large lithium doping amount is obtained. Will be done.
  • the inert gas refers to 900 ° C to 150 ° C. Does not react with carbonaceous materials at different carbonization temperatures It is a gas.
  • it is a gas containing nitrogen, argon, or a mixed gas thereof as a main component.
  • the flow rate of the atmosphere is defined by the flow rate per unit weight of the carbon precursor.
  • the flow rate per 1 g of carbon precursor is 0.1 ml or more, the anode capacity is improved.
  • the amount of the carbon precursor is preferably the entire amount in the furnace, and in the case of a continuous type carbonization furnace in which the carbonaceous material is taken out with time and taken out, preferably 800 ° C. or more. More preferably, it refers to the amount of the carbon precursor heated to a temperature of 700 ° C. or more.
  • the inert atmosphere flow rate is set to an amount that is in contact with the carbon precursor heated to preferably 800 ° C. or higher, more preferably 700 ° C. or higher, and discharged out of the carbonization furnace. Therefore, the purpose of the carbonization furnace is to replace the atmosphere in the system before the temperature of the carbon precursor is preferably raised to 800 ° C. or higher, more preferably to 700 ° C. or higher.
  • the flow of the inert atmosphere is not included in the present invention.
  • the contact area with the atmosphere per 1 kg of the carbon precursor is set to be 10 cm 2 or more in a rough surface shape, the carbon precursor becomes easy to contact with the inert gas, and the volatile component becomes more. It is efficiently removed and carbonization progresses more smoothly.
  • the contact area in the rough surface shape here does not include minute irregularities due to disorder of the material surface or minute specific surface area in the particles.
  • the contact area of the carbon precursor is determined, for example, by dividing the carbon precursor and placing it on multiple stages, or stirring (in this case, the specific surface area of the carbon precursor).
  • C) On the other hand, when the carbon precursor is fired in a low-pressure atmosphere at a pressure of 50 kPa or less, the pressure in the atmosphere increases when carbonization is reached. It is sufficient that the temperature be kept at 50 kPa or less at the time of the temperature or at one time during the heating process.
  • the exhaust in the carbonization furnace may be performed before the carbonization furnace or the carbon precursor is heated, during the heating process of the carbonization furnace or the carbon precursor, or during the holding time of the attained temperature.
  • the heating method of the carbonization furnace is not particularly limited, and may be any of induction heating, resistance heating, and the like.
  • the ultimate temperature and the rate of temperature rise during carbonization are not particularly limited.
  • temperature rise rate of 1 ° C or more in inert atmosphere
  • ultimate temperature of 900 to 150 ° C
  • Main firing at a temperature of 0 to 5 hours is sufficient.
  • the calcination operation may be omitted in some cases.
  • the carbonaceous material obtained in this manner is pulverized and classified to be used as a negative electrode material.
  • This pulverization may be performed before carbonization, after carbonization, after calcining, or in a misalignment.
  • the negative electrode made of the negative electrode material manufactured as described above is housed in the battery can together with the positive electrode and the electrolyte, and functions as the negative electrode of the battery.
  • the positive electrode has a negative electrode carbon in a steady state (for example, after repeating charge and discharge about 5 times). It is necessary to include Li equivalent to a charge / discharge capacity of 250 mAh or more per gram of the material, and preferably Li equivalent to a charge / discharge capacity of 300 mAh or more. It is more preferable to include Li corresponding to a charge / discharge capacity of 0 mAh or more. It is not always necessary to supply all of Li from the positive electrode material. In short, it is sufficient that Li has a charge / discharge capacity of 25 OmAh or more per gram of negative electrode carbonaceous material in the battery system. Also, the amount of Li is determined by measuring the discharge capacity of the battery.
  • the positive electrode material constituting the positive electrode for example, a composite metal oxide represented by the general formula L iM ⁇ 2 (where M represents at least one of Co and Ni) and an intercalation compound containing L i Is preferable, and in particular, good characteristics can be obtained by using L i C O 2 .
  • the non-aqueous electrolyte is prepared by appropriately combining an organic solvent and an electrolyte, and any of these organic solvents and electrolytes can be used as long as they are used for this type of battery.
  • L i C 10 As the electrolyte, L i C 10 4, L iAsF 6, L i PF 6 L i BF 4, L i B (C 6 H 5) 4, CH 3 S_ ⁇ 3 L i, CF 3 SO 3 L i, L iC1, LiBr, etc.
  • a carbonaceous material was manufactured as follows. Petroleum pitch (HZC atomic ratio 0.6 to 0.8) was oxidized to prepare a carbon precursor with an oxygen content of 15.4%. Next, the carbon precursor was carbonized at 500 ° C. for 5 hours in a nitrogen stream. Then, the beads obtained by carbonization were pulverized with a mill as a carbonization raw material, and about 10 g of the raw material was charged into a crucible. 10 g of the carbonized raw material charged into this crucible was placed in an electric furnace under a nitrogen flow of 101 Z, at a heating rate of 5 ° CZmin, an arrival temperature of 1100 ° C, and a holding time of 1 hour. After firing, a carbonaceous material was obtained. At this time, the layer thickness of the carbonization material in the crucible was about 30 mm, and the contact area with the nitrogen stream was ⁇ 7 cm 2 .
  • Petroleum pitch HZC atomic ratio 0.6 to 0.8
  • the Raman scattering spectrum and the X-ray diffraction spectrum of this carbonaceous material were measured. Then, the half-width at half maximum of a peak appearing at about 1340 cm- 1 in the Raman scattering spectrum is obtained, and the data obtained from the X-ray diffraction spectrum are subjected to data processing in a predetermined procedure, whereby the stacked structure is obtained.
  • the weight ratio P s of the carbon atoms to be taken, the stacking index SI, and the average number of stacked layers ⁇ ⁇ were determined.
  • the half width at half maximum of a peak appearing at about 1340 cm- 1 in the Raman scattering spectrum was determined as follows.
  • an Ar + laser with a wavelength of 54.5 nm and an irradiation power of 200 mW was irradiated to the carbonaceous material powder sample at an incident beam diameter of 1 mm ⁇ to collect scattered light from pseudo backscattering.
  • a Raman spectrum is measured by dispersing this condensed light using a spectroscope.
  • the beam diameter of the Ar + laser for obtaining scattered light is as large as lmm ⁇ , so the measured Raman scattering spectrum exists within the beam diameter. The scattering average of many carbon material particles is obtained. Therefore, the Raman spectrum is measured with high reproducibility and accuracy.
  • the spectrometer used was a U-1000 double monochromator manufactured by JOB IN-YVON.
  • the slit width is 400-800-800-400 ⁇ m.
  • the Raman scattering spectrum is measured four times in total in the same manner except that the irradiation position is shifted, and fitting processing is performed for each Raman scattering spectrum. Then, for each spectrum, the half width at half maximum of 1340 cm 1 was determined, the average value of the four half width data was calculated, and this value was used as the half width.
  • the X-ray diffraction spectrum was measured under the following conditions.
  • Sample filling method A sample of 0.5 mm thickness was inserted into a 5 mm x 18 mm opening formed in a 0.5 mm thick SUS plate. Filling
  • a negative electrode of a coin-type battery was prepared using the above carbonaceous material as a negative electrode material, and the negative electrode capacity of the carbonaceous material was measured.
  • the carbonaceous material was subjected to a pre-heat treatment in an argon atmosphere at a heating rate of about 30 / min, at a temperature of 600 ° C, and at a temperature holding time of 1 hour. (Note that this heat treatment was performed immediately before the preparation of the negative electrode mix described below.) Then, 10% by weight of polyvinylidene fluoride was added to the carbonaceous material, and dimethylformamide was mixed as a solvent. After drying, a negative electrode mix was prepared. The negative electrode mix (37 mg) thus prepared was kneaded with a nickel mesh as a current collector and formed into a pellet having a diameter of 15.5 mm to prepare a negative electrode.
  • the fabricated negative electrode was assembled in a coin-type battery with the following configuration, charged and discharged at 1 mA (current density 0.53 mA / cm 2 ), and the discharge capacity per gram of the negative carbonaceous material was measured. .
  • the configuration and charge / discharge conditions of the coin-type battery are shown below.
  • Coin cell battery dimensions diameter 20 mm, thickness 2.5 mm
  • Discharge Similar to charging, energizing for 1 hour and resting for 2 hours were repeated, and discharging was terminated when the battery voltage fell below 1.5 V in the energized state.
  • the negative electrode capacity of the carbonaceous material measured in this way is shown in Table 1 together with the above-mentioned HW, SI, Ps, n.v.
  • a carbonaceous material was produced in the same manner as in Example 1 except that the carbonization raw material was not fired under a nitrogen stream. The temperature reached during firing was 110,000, and the temperature was 130,000 ° C. Changed to C. Then, the obtained carbonaceous material, Raman spectra were measured X-ray diffraction scan Bae spectrum, determine the half value half width of a peak appearing in the vicinity of 1 340 c ⁇ 1 in the Raman scattering scan Bae spectrum, further X-ray diffraction scan ⁇ ⁇ By performing predetermined data processing on the data obtained from the vector, the weight ratio P s of carbon atoms having a laminated structure, the scanning index SI, and the average number of laminated layers n and ve in the laminated structure were obtained.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured.
  • Table 2 shows the measurement results of HW, Ps, SI, neve and negative electrode capacity.
  • the carbonaceous material produced in Example 1 had the HW, Ps, SI, n.ve under the predetermined conditions (HW> 138-0.06 ⁇ T, P s ⁇ 0. 59, SI ⁇ 0. 76, n. v. ⁇ 2. meets the 46), has a large negative electrode capacity and 378 mAh You.
  • HW, Ps, SI, n eve does not satisfy the predetermined condition, the negative electrode capacity is smaller than that of the carbonaceous material of Example 1 It has become something.
  • a carbonaceous material was produced in the same manner as in Example 1 except that the amount of the carbonized raw material charged into the crucible was set to 1 g.c. measures the X-ray diffraction scan Bae spectrum, determine the half value half width of a peak in the Raman scattering scan Bae spectrum appearing in the vicinity of 1340 c ⁇ 1, performs predetermined data processing on the addition data obtained from X-ray diffraction spectrum As a result, the weight ratio Ps of the carbon atoms having a laminated structure, the stacking index SI, and the average number of laminated layers ⁇ ⁇ , were determined.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured.
  • Table 3 shows the measurement results of HW, Ps, SI, n, ve, and negative electrode capacity.
  • the negative electrode capacity depends on the amount of the carbon precursor fired together with the flow rate of the inert gas flow when firing the carbon precursor.
  • the negative electrode capacity was found to increase as the inert gas flow rate per gram of carbon precursor increased.
  • a carbonaceous material was produced in the same manner as in Example 1, except that an alumina boat was used instead of the crucible and the carbonized material was placed on an alumina boat.
  • the layer thickness of the carbon raw material on an alumina boat is about 1 0 mm, the contact surface product of the nitrogen flow was ⁇ 300 cm 2.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured.
  • Table 4 shows the measurement results of P s, SI, n eve and negative electrode capacity.
  • the negative electrode capacity depends on the layer thickness of the carbon precursor when firing the carbon precursor, that is, the contact area.
  • the carbon precursor layer It was found that the smaller the thickness and the larger the contact area, the larger the negative electrode capacity. This is because the thinner the layer of the carbon precursor, the better the removal of volatile components.
  • the carbonized raw material When firing the carbonized raw material, about 1 Og of the carbonized raw material is charged into a crucible, and while maintaining the pressure in the electric furnace at about 20 kPa, the heating rate is 5 minutes and the ultimate temperature is 1100 ° C.
  • a carbonaceous material was manufactured in the same manner as in Example 1 except that the firing was performed under the conditions of 1 200 ° C, 1300 ° C, and a holding time of 1 hour at the ultimate temperature.
  • the obtained carbonaceous material was measured for Raman spectrum and X-ray diffraction spectrum, and the half-width at half maximum of 1340 cm 1 in the Raman scattering spectrum was determined.
  • the weight ratio P s of the carbon atoms forming the stacked structure, the stacking index SI, and the average number of stacked layers n eve of the stacked structure portion were obtained.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured.
  • Table 5 shows the measurement results of HW, Ps, SI, neve, and negative electrode capacity. [Table 5]
  • a carbonaceous material was manufactured in the same manner as in Example 4, except that the pressure in the electric furnace was set to 60 kPa when firing the carbonized raw material.
  • the obtained carbonaceous material, Raman spectra were measured X-ray diffraction scan Bae spectrum, determine the half value half width of a peak appearing in the vicinity of 1 340 cnt 1 in the Raman scattering scan Bae spectrum, further X-ray diffraction space
  • the weight ratio P s of the carbon atoms having a stacked structure, the stacking index SI, and the average number of stacked layers n eve of the stacked structure portion were obtained.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured. .
  • the HW, Ps, SI, neve and negative electrode capacity of the carbonaceous material of Comparative Example 2 were almost the same as those of Comparative Example 1, and the above parameters were The predetermined conditions were not satisfied, and the negative electrode capacity was small.
  • the carbonaceous material of Example 4 had HW, Ps, SI, n.ve satisfies the predetermined condition, and is much larger than that of the carbonaceous material of Comparative Example 2 and has a negative electrode capacity.
  • firing the carbon precursor in a low-pressure atmosphere is effective in obtaining a carbonaceous material with a large negative electrode capacity that satisfies the specified conditions for HW, Ps, SI, and n.ve. I understood.
  • a carbonaceous material was produced in the same manner as in Example 1, except that the carbonization raw material was fired as follows.
  • the obtained carbonaceous material was measured for Raman spectrum and X-ray diffraction spectrum, and the half-width at half maximum of 1340 cm 1 in the Raman scattering spectrum was determined.
  • the weight ratio P s of the carbon atoms forming the stacked structure, the stacking index SI, and the average number of stacked layers n eve of the stacked structure portion were obtained.
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured. .
  • This carbonaceous material, Raman spectra were measured X-ray diffraction scan Bae transfected Le obtains the half value half width of a peak appearing in the vicinity of 1 340 cnt 1 in the Raman scattering scan Bae spectrum, further from the X-ray diffraction scan Bae spectrum
  • the weight ratio of carbon atoms Ps, stacking index SI, and the average number of stacked layers n of the stacked structure part are obtained by subjecting the obtained data to predetermined data processing. asked for ve .
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the manufactured coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured. .
  • the HW, Ps, SI, nave and negative electrode capacity of the carbonaceous material were comparable to those of the carbonaceous material of Comparative Example 1. For this reason, when firing a carbon precursor in a low-pressure atmosphere to obtain a carbonaceous material, it is important that the pressure of the atmosphere be low at the ultimate temperature. I found it.
  • the carbonaceous material, Raman spectra were measured X-ray diffraction scan Bae spectrum, The peak of half half width appearing near 1340 cm one 1 in the Raman scattering scan Bae spectrum, further X-ray diffraction scan Bae transfected Le
  • the weight ratio Ps of the carbon atoms in the laminated structure, the stacking index SI, and the average number of laminated layers n and ve in the laminated structure were determined.
  • a coin-type battery was manufactured using the obtained carbonaceous material as a negative electrode material, and the manufactured coin-type battery was charged and discharged under an energizing condition of 1 mA, and the discharge capacity per 1 g of the negative electrode carbonaceous material was measured.
  • Table 6 shows the measurement results of HW, Ps, SI, n, ve, and negative electrode capacity.
  • a carbonaceous material was produced in the same manner as in Example 6, except that the firing of the furfuryl alcohol resin was performed in a closed electric furnace.
  • the obtained carbonaceous material, Raman spectra were measured X-ray diffraction scan Bae spectrum, 1 340 cm 'seeking half half width of the peak appearing in the vicinity of 1 in the Raman scattering scan Bae spectrum, further X-ray diffraction scan ⁇ ⁇ ⁇ Data obtained from the vector was subjected to a predetermined data processing to obtain the weight ratio P s of carbon atoms having a stacked structure, the scanning index SI, and the average number of stacked layers ⁇ ⁇ , .
  • a coin-type battery was prepared using the obtained carbonaceous material as a negative electrode material, and the prepared coin-type battery was charged and discharged under a current supply condition of 1 mA, and the discharge capacity per gram of the negative electrode carbonaceous material was measured.
  • Table 7 shows the measurement results of Ps, SI, n, ve, and the negative electrode capacity.
  • the carbonaceous material of Example 6 satisfies the predetermined conditions of HW, Ps, SI, and nv force, and is larger than the carbonaceous material of Comparative Example 4. It has a negative electrode capacity. On the contrary, In the carbonaceous material of Comparative Example 4, HW, Ps, SI, and nve did not satisfy predetermined conditions, and the negative electrode capacity was small.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Un matériau cathodique est constitué d'un matériau à base de carbone difficile à transformer en graphite et obtenu par combustion d'un précurseur de carbone. Le pourcentage en poids Ps de carbone dans ce matériau à base de carbone résistant à la transformation en graphite est inférieur à 0,59, ou son coefficient d'empilement SI est inférieur à 0,76. Ce carbone a une structure en sandwich déterminée par la crête de diffraction due au plan (002) du réseau cristallin et au fait que le spectre de diffraction aux rayons X d'un côté d'un angle est inférieur à la crête de diffraction dans le spectre de diffraction aux rayons X. L'indice Nave moyen du nombre de couches empilées est inférieur à 2,46. Alternativement, si la température de combustion est désignée par T °C, et si la moitié de la largeur d'une crête apparaissant près de 1,340 cm-1 dans le spectre Raman est désignée par HW, la condition suivante est remplie: HW > 138 0,06 T. Ce matériau à base de carbone est produit par traitement thermique d'un précurseur de carbone. Le précurseur de carbone est brûlé dans une atmosphère de gaz inerte en écoulement à une vitesse d'écoulement égale ou supérieure à 0,1 ml par minute par gramme de précurseur de carbone, à une température égale ou supérieure à 600 °C, ou dans une atmosphère sous une pression égale ou inférieure à 50 kPa à une température égale ou supérieure à 600 °C. Dans ce cas, le précurseur de carbone est disposé en une couche de sorte que la superficie de contact du précurseur avec l'atmosphère soit égale ou supérieure à 10 cm2.
PCT/JP1993/001929 1992-04-30 1993-12-28 Materiau cathodique et son procede de production WO1995018467A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP08625593A JP3399015B2 (ja) 1992-04-30 1993-04-13 負極材料及びその製造方法
DE69324604T DE69324604T2 (de) 1993-12-28 1993-12-28 Material für anode und verfahren zu deren herstellung
EP94903101A EP0687022B1 (fr) 1992-04-30 1993-12-28 Materiau anodique et son procede de production
US08/507,324 US5643426A (en) 1993-12-28 1993-12-28 Anode material and method of manufacturing the same
CA002156424A CA2156424C (fr) 1993-12-28 1993-12-28 Materiau pour anode et methode pour le produire
PCT/JP1993/001929 WO1995018467A1 (fr) 1992-04-30 1993-12-28 Materiau cathodique et son procede de production
US08/812,734 US5716732A (en) 1992-04-30 1997-03-06 Anode material and method of manufacturing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP13784692 1992-04-30
JP19210192 1992-07-20
JP08625593A JP3399015B2 (ja) 1992-04-30 1993-04-13 負極材料及びその製造方法
PCT/JP1993/001929 WO1995018467A1 (fr) 1992-04-30 1993-12-28 Materiau cathodique et son procede de production

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893176A (ja) * 1981-11-30 1983-06-02 Toray Ind Inc 二次電池
JPS60182670A (ja) * 1984-02-28 1985-09-18 Toray Ind Inc 充放電可能な電池
JPS61163562A (ja) * 1985-01-11 1986-07-24 Bridgestone Corp 二次電池
JPH0282466A (ja) * 1988-09-20 1990-03-23 Nippon Steel Corp 炭素繊維を両極に用いたリチウム二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5893176A (ja) * 1981-11-30 1983-06-02 Toray Ind Inc 二次電池
JPS60182670A (ja) * 1984-02-28 1985-09-18 Toray Ind Inc 充放電可能な電池
JPS61163562A (ja) * 1985-01-11 1986-07-24 Bridgestone Corp 二次電池
JPH0282466A (ja) * 1988-09-20 1990-03-23 Nippon Steel Corp 炭素繊維を両極に用いたリチウム二次電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP0687022A4 *
Synthetic Metals, 18 (1-3) (1987) (RAN), p. 537-542. *

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