US20020142222A1 - Nonaqueous electrolytic secondary battery and method of manufacturing the same - Google Patents

Nonaqueous electrolytic secondary battery and method of manufacturing the same Download PDF

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US20020142222A1
US20020142222A1 US10/107,208 US10720802A US2002142222A1 US 20020142222 A1 US20020142222 A1 US 20020142222A1 US 10720802 A US10720802 A US 10720802A US 2002142222 A1 US2002142222 A1 US 2002142222A1
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positive electrode
active material
electrode active
lithium
halogen
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Nobumichi Nishida
Shinya Miyazaki
Masatoshi Takahashi
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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Assigned to SANYO ELECTRIC CO., LTD. reassignment SANYO ELECTRIC CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIYAZAKI, SHINYA, NISHIDA, NOBUMICHI, TAKAHASHI, MASATOSHI
Publication of US20020142222A1 publication Critical patent/US20020142222A1/en
Priority to US11/429,259 priority Critical patent/US7799458B2/en
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H01M4/13915—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • 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
    • H01M4/582—Halogenides
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    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the present invention relates to a nonaqueous electrolytic secondary battery comprising a positive electrode active material capable of intercalating and deintercalating a lithium ion, a negative electrode active material capable of intercalating and deintercalating the lithium ion, and a nonaqueous electrolyte, and a method of manufacturing the nonaqueous electrolytic secondary battery.
  • a nonaqueous electrolytic secondary battery having an alloy or a carbon material capable of intercalating and deintercalating a lithium ion as a negative electrode active material and lithium containing transition metal oxide, for example, lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) or lithium manganese oxide (LiMn 2 O 4 ) as a positive electrode active material has been put into practical use to be a battery having a small size, a light weight and a high capacity and capable of carrying out a charge and discharge.
  • lithium cobalt oxide LiCoO 2
  • LiNiO 2 lithium nickel oxide
  • LiMn 2 O 4 lithium manganese oxide
  • lithium nickel oxide (LiNiO 2 ) in the lithium containing transition metal oxide to be used for the positive electrode active material of the nonaqueous electrolytic secondary battery has a feature of a high capacity and a drawback of a poor safety and a high overvoltage, it is inferior to the lithium cobalt oxide.
  • lithium manganese oxide (LiMn 2 O 4 ) has a rich source and is inexpensive, and has a drawback that an energy density is low and manganese itself is dissolved at a high temperature. Therefore, it is inferior to the lithium cobalt oxide.
  • the use of the lithium cobalt oxide (LiCoO 2 ) to be the lithium containing transition metal oxide has been a mainstream.
  • the lithium cobalt oxide is deteriorated by a charge and discharge.
  • the degree of the deterioration is correlated with the crystallinity of the lithium cobalt oxide and is remarkable with a low crystallinity of the lithium cobalt oxide.
  • the crystallinity of the lithium cobalt oxide is low, lithium is removed from the lithium cobalt oxide during charging so that an unstable state is set and oxygen is apt to be desorbed from the lithium cobalt oxide. For this reason, there is a problem in that the lithium cobalt oxide having a low crystallinity is not sufficient in respect of a thermal stability, resulting in a poor safety.
  • cobalt oxide to be the raw material of the lithium cobalt oxide or synthesis conditions such as a burning temperature are made proper to increase the crystallite size of the lithium cobalt oxide, thereby enhancing a crystallinity and improving a thermal stability.
  • a part of cobalt is substituted for a heterogeneous element such as V, Cr, Fe, Mn, Ni, Al or Ti.
  • lithium cobalt oxide having a large crystallite size is used as an active material or lithium cobalt oxide obtained by substituting a part of cobalt of the active material for a heterogeneous element such as V, Cr, Fe, Mn, Ni, Al or Ti is used as an active material, however, there is a problem in that the amount of gas generated in a battery is increased in a high temperature atmosphere (approximately 60° C. to 100° C.) so that a cycle property is deteriorated, and furthermore, a deterioration in a battery property is increased due to the preservation of a battery in a charging state.
  • a high temperature atmosphere approximately 60° C. to 100° C.
  • the invention has been made based on such a knowledge and has an object to provide a nonaqueous electrolytic secondary battery in which such a positive electrode active material as not to increase the pH value of a filtrate to suppress the generation of the gas in the battery, thereby enhancing the cycle property at a high temperature and suppressing a deterioration during charging preservation.
  • an nonaqueous electrolytic secondary battery uses, as a positive electrode active material, hexagonal system lithium containing cobalt composite oxide having a crystallite size in a (110) vector direction of 1000 ⁇ or more and having a halogen compound added thereto by burning at time of synthesis.
  • a value of 9.6 to 10.1 was obtained.
  • a pH value of 10 or more was obtained.
  • the particle surface of the lithium containing cobalt composite oxide is stabilized by the addition of the halogen at time of the synthesis so that the decomposed gas of an electrolyte is decreased, resulting in an enhancement in the high temperature cycle property.
  • a content of the halogen to a mass of the positive electrode active material is less than 0.001% by mass, the pH value of the filtrate having the positive electrode active material dispersed in the water is increased so that the high temperature cycle property is deteriorated.
  • the content of the halogen to the mass of the positive electrode active material is more than 5.0% by mass, the amount of the addition of the lithium containing cobalt composite oxide itself is decreased so that a capacity is reduced.
  • the content of the halogen to the mass of the positive electrode active material should be 0.001% by mass to 5.0% by mass.
  • the hexagonal system lithium containing cobalt composite oxide having a halogen compound added thereto by the burning at time of the synthesis should be lithium cobalt oxide to which the halogen compound is added.
  • lithium containing cobalt composite oxide having a part of cobalt substituted for a heterogeneous element such as V, Cr, Fe, Mn, Ni, Al or Ti
  • a filtrate having the lithium containing cobalt composite oxide dispersed in water has a pH value increased.
  • Such cobalt composite oxide has a heterogeneous element added thereto so that an ion conducting property can be enhanced to gain an excellent discharge property.
  • halogen when halogen is contained to be used as a positive electrode active material at time of the synthesis of lithium cobalt oxide having a part of cobalt substituted for at least one kind of heterogeneous element selected from V, Cr, Fe, Mn, Ni, Al and Ti and a molar ratio of the heterogeneous element to the cobalt of 0.0001 to 0.005, it is possible to obtain a nonaqueous electrolytic secondary battery in which a high temperature cycle property is enhanced without damaging an excellent discharge property.
  • Fluorine is desirable for the halogen to be contained at time of the synthesis of the lithium containing cobalt composite oxide.
  • the positive electrode active material preferably, there are provided the steps of mixing a first component having a lithium compound, a second component having a cobalt compound, and a third component having a halogen compound to obtain a 3-component mixture and burning the 3-component mixture to have a crystallite size in a (110) vector direction of 1000 ⁇ or more.
  • a lithium compound a cobalt compound substituted for at least one kind of heterogeneous element selected from V, Cr, Fe, Mn, Ni, Al and Ti, and a halogen compound to obtain a 3-component mixture and burning the 3-component mixture to have a crystallite size in a (110) vector direction of 1000 ⁇ or more.
  • a 4-compound mixture including a lithium compound, a cobalt compound, a compound such as oxide containing at least one kind of element selected from V, Cr, Fe, Mn, Ni, Al and Ti and a halogen compound in place of the 3-component mixture.
  • the invention provides a nonaqueous electrolytic secondary battery in which a thermal stability is excellent and a safety is high, and a cycle property is enhanced at a high temperature and a deterioration is suppressed during charging preservation, there is a feature in that a specific positive electrode active material is used.
  • a specific positive electrode active material is used for a negative electrode material, a separator material, a nonaqueous electrolytic material and a binder material, therefore, it is possible to use a well-known material.
  • FIG. 1 shows the results of measurement of pH value of positive electrode active material in this invention.
  • FIG. 2 shows the results of thermal analysis of charged positive electrode in this invention.
  • FIG. 3 shows the results of measurement of pH value of positive electrode active material from investigation of lithium cobalt oxide substituted for heterogeneous element in this invention.
  • FIG. 4 shows the results of thermal analysis of charged positive electrode from investigation of lithium cobalt oxide substituted for heterogeneous element in this invention.
  • lithium carbonate Li 2 CO 3
  • tricobalt tetraoxide Co 3 O 4
  • specific surface area 8.3 m 2 /g
  • lithium fluoride LiF
  • a mixture thus obtained was baked in the air (in this case, a burning temperature (for example, 980° C.) and a burning time (for example, 24 hours) were regulated such that a crystallite size in a (110) vector direction of a baked product thus obtained is 1000 ⁇ or more).
  • a burning temperature for example, 980° C.
  • a burning time for example, 24 hours
  • the baked product thus synthesized was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material a 1 according to an example 1 was obtained.
  • the positive electrode active material a 1 thus obtained was analyzed by ion chromatography so that a content of the fluorine to a mass of the positive electrode active material was 0.05% by mass.
  • the fluorine containing positive electrode active material a 1 thus obtained was measured by XRD (X-Ray Diffraction) and was found to be hexagonal system lithium cobalt oxide (LiCoO 2 ). By calculating a crystallite size using a Scheller expression, a crystallite size in the (110) vector direction was 1045 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 0.0007% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material b 1 according to an example 2 was obtained.
  • the fluorine containing positive electrode active material b 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1030 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 0.001% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material c 1 according to an example 3 was obtained.
  • the fluorine containing positive electrode active material c 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1050 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 5.0% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material d 1 according to an example 4 was obtained.
  • the fluorine containing positive electrode active material d 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1048 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 7.0% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material e 1 according to an example 5 was obtained.
  • the fluorine containing positive electrode active material e 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1053 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 0.01% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material f 1 according to an example 6 was obtained.
  • the fluorine containing positive electrode active material f 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1045 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 0.3% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material g 1 according to an example 7 was obtained.
  • the fluorine containing positive electrode active material g 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1050 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that lithium fluoride (LiF) was used as a starting material of a halogen source and was added to have a content of fluorine in 0.5% by mass with respect to a mass of a positive electrode active material.
  • a positive electrode active material h 1 according to an example 8 was obtained.
  • the fluorine containing positive electrode active material h 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1052 ⁇ .
  • a positive electrode active material was formed in the same manner as in the example 1 except that a halogen compound was not used. Thus, a positive electrode active material s 1 according to a comparative example 1 was obtained.
  • the positive electrode active material s 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 1042 ⁇ .
  • a fluorine containing positive electrode active material was formed in the same manner as in the example 1 except that tricobalt tetraoxide (Co 3 O 4 ) having a specific surface area of 0.9 m 2 /g was used for a starting material of a cobalt source.
  • a positive electrode active material t 1 according to a comparative example 2 was obtained.
  • the fluoride containing positive electrode active material t 1 thus obtained was hexagonal system lithium cobalt oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 700 ⁇ .
  • lithium carbonate (Li 2 CO 3 ) to be a starting material of a lithium source and tricobalt tetraoxide (Co 3 O 4 ) having a specific surface area of 0.9 m 2 /g to be a starting material of a cobalt source were prepared, and were then weighed and mixed such that a molar ratio (Li/Co) of a lithium (Li) component of the lithium carbonate (Li 2 CO 3 ) to a cobalt (Co) component of the tricobalt tetraoxide (Co 3 O 4 ) is 1.
  • a mixture thus obtained was baked in the same manner as in the example 1 and a baked product of LiCoO 2 was synthesized.
  • the baked product thus synthesized was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material u 1 according to a reference example 1 was obtained.
  • the positive electrode active material u 1 thus obtained was hexagonal system cobalt composite oxide (LiCoO 2 ) and a crystallite size in a (110) vector direction was 690 ⁇ .
  • each of the positive electrode active materials a 1 , b 1 , c 1 , d 1 , e 1 , f 1 , g 1 , h 1 , s 1 , t 1 and u 1 formed as described above was prepared in a weight of 2 g and was put in a 200 ml beaker filled with ion-exchange water of 150 ml. Thereafter, a stirring bar was put in the beaker and the beaker was sealed with a film, and stirring was then carried out for 30 minutes.
  • each solution thus stirred was sucked and filtered through a membrane filter (manufactured by PTFE and having a pore size of 0.1 ⁇ m) and a filtrate was then measured by a pH meter comprising an ISFET (Ion-Selective Field Effect Transistor: a field effect transistor comprising a gate electrode having a sensitivity for a certain kind of ion in an electrolyte). Consequently, results shown in the following FIG. 1 were obtained.
  • ISFET Ion-Selective Field Effect Transistor: a field effect transistor comprising a gate electrode having a sensitivity for a certain kind of ion in an electrolyte
  • the positive electrode active materials a 1 , b 1 , c 1 , d 1 , e 1 , f 1 , g 1 and h 1 having a crystallite size of 1000 ⁇ or more according to the examples with the positive electrode active material s 1 according to the comparative example 1, moreover, it is apparent that the positive electrode active materials a 1 , b 1 , c 1 , d 1 , e 1 , f 1 , g 1 and h 1 according to the examples have pH values more reduced This implies that the pH value is reduced when fluorine is added during the burning of the lithium cobalt oxide (LiCoO 2 ).
  • the positive electrode active materials a 1 , b 1 , c 1 , d 1 , e 1 , f 1 , g 1 , h 1 , s 1 , t 1 and u 1 formed as described above were used and 85 parts by mass of each positive electrode active material, 10 parts by mass of carbon powder to be a conducting agent and 5 parts by mass of polyfluorovinylidene (PVdF) powder to be a binder were mixed to prepare a positive electrode mixture. Then, the positive electrode mixture thus obtained was mixed with N-methyl pyrrolidone (NMP) to prepare a positive electrode slurry.
  • NMP N-methyl pyrrolidone
  • the positive electrode slurry was applied to both surfaces of a positive electrode collector having a thickness of 20 ⁇ m (an aluminum foil or an aluminum alloy foil) by a doctor blade method, thereby forming an active material layer on both surfaces of the positive electrode collector.
  • the active material layer was dried, and was then rolled to have a predetermined thickness (for example, 170 ⁇ m) by using a compression roll and was cut to have a predetermined dimension (for example, a width of 55 mm and a length of 500 mm).
  • a, b, c, d, e, f, g, h, s, t and u were fabricated, respectively.
  • the positive electrode active material a 1 was used to form the positive electrode a
  • the positive electrode active material b 1 was used to form the positive electrode b
  • the positive electrode active material c 1 was used to form the positive electrode c
  • the positive electrode active material d 1 was used to form the positive electrode d
  • the positive electrode active material e 1 was used to form the positive electrode e
  • the positive electrode active material f 1 was used to form the positive electrode f
  • the positive electrode active material g 1 was used to form the positive electrode g
  • the positive electrode active material h 1 was used to form the positive electrode h
  • the positive electrode active material s 1 was used to form the positive electrode s
  • the positive electrode active material t 1 was used to form the positive electrode t
  • the positive electrode active material u 1 was used to form the positive electrode u.
  • the active material layer was dried, and was then rolled to have a predetermined thickness (or example, 155 ⁇ m) by using a compression roll and was cut to have a predetermined dimension (for example, a width of 57 mm and a length of 550 mm). Thus, a negative electrode was fabricated.
  • the positive electrodes a, b, c, d, e, f, g, h, s, t and u fabricated as described above and the negative electrode fabricated as described above were used respectively to interpose a separator comprising a fine porous film formed of polypropylene, and they were then wound spirally to form a spiral electrode group. They were inserted into cylindrical casing respectively and a collecting tab extended from each collector was welded to each terminal, and a nonaqueous electrolyte having 1 mol/liter of LiPF 6 dissolved therein was injected into an equivolume mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • a positive electrode cover was attached to an opening of the armoring can to be sealed, thereby fabricating a nonaqueous electrolytic secondary battery having a typical capacity of 1500 mAh.
  • the positive electrode a was used to form a battery A
  • the positive electrode b was used to form a battery B
  • the positive electrode c was used to form a battery C
  • the positive electrode d was used to form a battery D
  • the positive electrode e was used to form a battery E
  • the positive electrode f was used to form a battery F
  • the positive electrode g was used to form a battery G
  • the positive electrode h was used to form a battery H.
  • the positive electrode s was used to form a battery S
  • the positive electrode t was used to form a battery T
  • the positive electrode u was used to form a battery U.
  • the batteries A to H and S to U were used to carry out a charge with a constant charge current of 1500 mA (l1It: It is a numerical value represented by a typical capacity (mA)/1 h (time)) at 60° C. until a battery voltage of 4.2 V could be obtained and to carry out the charge with a constant battery voltage of 4.2 V until a final current of 30 mA could be obtained. Thereafter, a charge and discharge was carried out once such that the discharge was performed to obtain a battery voltage of 2.75 V with a discharge current of 1500 mA (1It), thereby calculating a discharge capacity (an initial capacity) after one cycle since a deintercalating time. Consequently, results shown in the following FIG. 2 were obtained.
  • the batteries A to H and S to U were charged with a constant charge current of 1500 mA (1It) at 25° C. to obtain a battery voltage of 4.2 V and were then charged with a constant battery voltage of 4.2 V to obtain a final current of 30 mA. Thereafter, each battery was decomposed in a dry box to take out a positive electrode, and the positive electrode was washed with dimethyl carbonate and was vacuum dried so that a test piece was obtained. By putting the test pieces in a thermogravimetry (TG) apparatus to raise a temperature from a room temperature (approximately 25° C.) to 300° C.
  • TG thermogravimetry
  • the decrease in the mass was caused by the desorption of oxygen in the positive electrode active material from the positive electrode active material with the rise in the temperature.
  • the amount of the desorption of the oxygen (the amount of the decrease in the mass) is large, a thermal stability is low.
  • the positive electrode active material is used as an active material for a battery, a safety for a heat test in a charging state is deteriorated.
  • the batteries A, B, C, D, E, F, G, H and S using a positive electrode active material having a crystallite size in a (110) vector direction of 1000 ⁇ or more have smaller TG mass decreases than those of the batteries T and U using a positive electrode active material having a crystallite size in the (110) vector direction of approximately 700 ⁇ .
  • a positive electrode active material having a crystallite size in the (110) vector direction of 1000 ⁇ or more and having lithium fluoride added thereto should be used because a battery having an excellent high temperature capacity retention rate, a small TG mass decrease and a great thermal stability can be obtained.
  • the lithium fluoride should be added to the lithium cobalt oxide to have a content of the fluorine of 0.001 to 5.0% by mass and should be baked to have a crystallite size in a (110) vector direction of 1000 ⁇ or more.
  • an average discharge voltage and a high temperature cycle capacity retention rate can be more enhanced by adding the lithium fluoride to have a content of the fluorine of 0.01 to 0.3% by mass and burning them to have a crystallite size in the (110) vector direction of 1000 ⁇ or more.
  • lithium carbonate Li 2 CO 3
  • tricobalt tetraoxide CO 0.999 Ti 0.001
  • Ti tricobalt tetraoxide
  • Ti tricobalt tetraoxide
  • Ti tricobalt tetraoxide
  • Ti tricobalt tetraoxide
  • Ti tricobalt tetraoxide
  • Ti titanium
  • LiF lithium fluoride
  • the tricobalt tetraoxide (Co 0.999 Ti 0.001 ) 3 O 4 substituted for the titanium (Ti) was obtained by precipitating, as composite hydroxide, cobalt and titanium which are dissolved in an acid solution and calcining them at 300° C.
  • a mixture thus obtained was baked in the same manner as in the example 1 (also in this case, a burning temperature and a burning time were regulated such that a crystallite size in a (110) vector direction of a baked product thus obtained was 1000 ⁇ or more) and was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material i 1 according to an example 9 was obtained.
  • the positive electrode active material i 1 containing fluorine thus obtained was hexagonal system lithium cobalt oxide (LiCo 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1050 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium chloride (LiCl) was used as a starting material of a halogen source to have a content of chlorine of 0.05% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCo 0.999 Ti 0.001 O 2 ) containing chlorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material j 1 according to an example 10 was obtained.
  • the positive electrode active material j 1 containing chlorine thus obtained was hexagonal system lithium cobalt oxide (LiCo 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1047 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that tricobalt tetraoxide (CO 0.995 Ti 0.005 ) 3 O 4 substituted for titanium to have a content of titanium in a molar ratio of cobalt to titanium of 0.995:0.005 was used as a starting material of a cobalt source and lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.05% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.995 Ti 0.005 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • tricobalt tetraoxide (CO 0.995 Ti 0.005 ) 3 O 4 substituted for titanium to have a content of titanium in a molar ratio of cobalt to titanium of 0.995:0.005 was used as a starting material of a cobalt source and
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material k 1 according to an example 11 was obtained.
  • the positive electrode active material k 1 containing chlorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.995 Ti 0.005 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1032 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.0007% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material l 1 according to an example 12 was obtained.
  • the positive electrode active material l 1 containing chlorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1052 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.001% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material m 1 according to an example 13 was obtained.
  • the positive electrode active material m 1 containing chlorine thus obtained was lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing hexagonal system fluorine and having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 105 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 5.0% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material n 1 according to an example 14 was obtained.
  • the positive electrode active material n 1 containing fluorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1040 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 7.0% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material o 1 according to an example 15 was obtained.
  • the positive electrode active material o 1 containing fluorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1042 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.01% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material p 1 according to an example 16 was obtained.
  • the positive electrode active material p 1 containing chlorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1048 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.3% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material q 1 according to an example 17 was obtained.
  • the positive electrode active material q 1 containing fluorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1047 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that lithium fluoride (LiF) was used as a starting material of a halogen source to have a content of fluorine of 0.5% by mass, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) containing fluorine and having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material r 1 according to an example 18 was obtained.
  • the positive electrode active material r 1 containing fluorine thus obtained was hexagonal system lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1043 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that a halogen compound was not used, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material v 1 according to a comparative example 3 was obtained.
  • the positive electrode active material v 1 thus obtained was hexagonal system cobalt composite oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1030 ⁇ .
  • a mixture was obtained in the same manner as in the example 9 except that tricobalt tetraoxide (Co 0.995 Ti 0.005 ) 3 O 4 substituted for titanium to have a content of titanium in a molar ratio of cobalt to titanium of 0.995:0.005 was used as a starting material of a cobalt source and a halogen compound was not used, and was then baked in the same manner as in the example 9 to synthesize lithium cobalt oxide (LiCO 0.995 Ti 0.005 O 2 ) having a part of cobalt substituted for titanium.
  • the mixture was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material w 1 according to a comparative example 4 was obtained.
  • the positive electrode active material w 1 thus obtained was hexagonal system cobalt composite oxide (LiCO 0.995 Ti 0.005 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1010 ⁇ .
  • Lithium carbonate (Li 2 CO 3 ) to be a starting material of a lithium source, manganese dioxide (MnO 2 ) to be a starting material of a manganese source and chromium oxide (Cr 2 O 3 ) to be a chromium source were prepared respectively, and were then weighed and mixed such that a molar ratio of lithium, manganese and chromium was 1.04:1.86:0.1, and furthermore, lithium fluoride (LiF) was added and mixed with them to have a content of fluorine of 0.05% by mass.
  • LiF lithium fluoride
  • a mixture thus obtained was baked in the air for 20 hours at 800° C. to synthesize a baked product of Li 1.04 Mn 1.86 Cr 0.1 O 4 . Then, the baked product thus synthesized was ground to have an average particle size of 10 ⁇ m. Consequently, a positive electrode active material x 1 according to a comparative example 5 was obtained.
  • the positive electrode active material x 1 containing fluorine thus obtained was manganese composite oxide having a spinel structure.
  • a mixture was obtained in the same manner as in the example 9 except that a halogen compound was not used, and was then baked in the same manner as in the example 9 to synthesize a baked product of lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium. Subsequently, 5.0% by mass of lithium fluoride (LiF) was added to the baked product thus synthesized and was then heat treated for five hours at 350° C., and LiCO 0.999 Ti 0.001 O 2 was caused to contain fluorine and was ground to have an average particle size of 10 ⁇ m so that a positive electrode active material y 1 according to a comparative example 6 was obtained.
  • LiF lithium fluoride
  • the positive electrode active material y 1 containing fluorine thus obtained was hexagonal system cobalt composite oxide (LiCO 0.999 Ti 0.001 O 2 ) having a part of cobalt substituted for titanium and a crystallite size in a (110) vector direction was 1040 ⁇ .
  • a baked product of Li 1.04 Mn 1.86 Cr 0.1 O 4 was synthesized in the same manner as in the comparative example 5 except that lithium fluoride was not added at time of synthesis. Then, the baked product thus synthesized was ground to have an average particle size of 10 ⁇ m so that a positive active material z 1 according to a reference example 2 was obtained.
  • the positive electrode active material z 1 thus obtained was manganese composite oxide having a spinel structure.
  • the positive electrode active materials v 1 and w 1 according to the comparative examples 3 and 4 which have a part of cobalt substituted for Ti to be a heterogeneous element have pH values more increased than those of the positive electrode active material s 1 (see the FIG. 1) according to the comparative example 1. This implies that the pH value is increased if a part of cobalt of lithium cobalt oxide (LiCoO 2 ) is substituted for a heterogeneous element.
  • LiCoO 2 lithium cobalt oxide
  • the positive electrode active material x 1 according to the comparative example 5 which is obtained by adding lithium fluoride to spinel type lithium manganese oxide (Li 1.04 Mn 1.86 Cr 0.1 O 4 ) substituted for Cr to be a heterogeneous element has a pH value which is equal to the pH value of the positive electrode active material z 1 according to the reference example 2 having no fluorine added thereto and is not reduced even if the fluorine is added. Accordingly, it is supposed that the spinel type lithium manganese oxide and the lithium cobalt oxide have different effects of containing the fluorine.
  • a positive electrode i using the positive electrode active material i 1
  • a positive electrode j using the positive electrode active material j 1
  • a positive electrode k using a positive electrode active material k 1
  • a positive electrode l using a positive electrode active material l 1
  • a positive electrode m using a positive electrode active material m 1
  • a positive electrode n using a positive electrode active material n 1
  • a positive electrode o using a positive electrode active material o 1
  • a positive electrode p using a positive electrode active material p 1
  • a positive electrode q using a positive electrode active material q 1
  • a positive electrode r using a positive electrode active material r 1
  • a positive electrode v using the positive electrode active material v 1
  • a positive electrode w using the positive electrode active material w 1
  • a positive electrode x using the positive electrode active material x 1
  • a positive electrode y using the positive electrode active material y 1
  • a positive electrode z using the positive electrode active material z 1
  • nonaqueous electrolytic secondary batteries I using the positive electrode i
  • J using the positive electrode K (using the positive electrode k)
  • L using the positive electrode l
  • M using the positive electrode m
  • N using the positive electrode n
  • O using the positive electrode o
  • P using the positive electrode p
  • Q using the positive electrode q
  • R using the positive electrode r
  • V using the positive electrode v
  • W using the positive electrode w
  • X using the positive electrode x
  • Y using the positive electrode y
  • Z using the positive electrode z
  • the batteries I, J, K, L, M, N, O, P, Q and R using the positive electrode active material having a part of cobalt substituted for Ti to be a heterogeneous element have higher average discharge voltages than those of the batteries A, B, C, D, E, F, G and H (see the FIG. 2) using a positive electrode active material which is not substituted for a heterogeneous element.
  • the reason is that a part of cobalt is substituted for the heterogeneous element, resulting in an enhancement in the ion conducting property of the positive electrode active material.
  • the initial capacity and the high temperature capacity retention rate are more enhanced than those in the batteries L and O by using the positive electrode active material having lithium fluoride or lithium chloride added thereto such that the content of the fluorine is 0.001 to 5.0% by mass as in the batteries I, J, K, M, N, P, Q and R.
  • the lithium fluoride or the lithium chloride should be added to the lithium cobalt oxide having a part of cobalt substituted for a heterogeneous element such that the content of fluorine is 0.001 to 5.0% by mass and they should be baked to have a crystallite size in a (110) vector direction of 1000 ⁇ or more. Furthermore, it is more preferable that the lithium fluoride should be added to have a content of the fluorine of 0.01 to 0.3% by mass and they should be baked to have a crystallite size in the (110) vector direction of 1000 ⁇ or more, resulting in an enhancement in the average discharge voltage and the high temperature cycle capacity retention rate.
  • the lithium cobalt oxide (LiCO 0.999 Ti 0.001 O 2 ) including a part of cobalt substituted for a heterogeneous element should be caused to contain halogen irrespective of the type of halogen. Even if another halogen such as bromine (Br), iodine (I) or astatine (At) is used in addition to fluorine and chlorine, the same effects can be obtained.
  • halogen such as bromine (Br), iodine (I) or astatine (At)
  • the synthesis conditions are optimized and the halogen compound is added at time of the synthesis of the hexagonal system lithium containing cobalt oxide having a crystallite size in the (110) direction of 1000 ⁇ . Therefore, it is possible to obtain a nonaqueous electrolytic secondary battery having small deterioration in the high temperature cycle property and the capacity.
  • the heterogeneous element for substituting a part of the cobalt of the hexagonal system lithium containing cobalt oxide may be selected from vanadium (V), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni) and aluminum (Al).
  • the negative electrode active material moreover, it is also possible to use a carbon based material capable of intercalating and deintercalating a lithium ion, for example, carbon black, coke, glassy carbon, carbon fiber or their baked products in addition to natural graphite or to use metal oxide in which the electric potential of metal lithium, a lithium alloy such as a lithium—aluminum alloy, a lithium—lead alloy or a lithium—tin alloy, SnO 2 , SnO, TiO 2 or Nb 2 O 3 is lower than that of the positive electrode active material.
  • the mixed solvent furthermore, it is also possible to use an aprotic solvent having no capability to supply a hydrogen ion in addition to a mixture obtained by mixing diethyl carbonate (DEC) with the ethylene carbonate (EC) and to use an organic solvent such as propylene carbonate (PC), vinylene carbonate (VC) or butylene carbonate (BC), and a mixed solvent obtained by mixing them with a low boiling point solvent such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), 1,2-diethoxyethane (DEE), 1,2-dimethoxyethane (DME) or ethoxy methoxy ethane (EME).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • EMC 1,2-diethoxyethane
  • DME 1,2-dimethoxyethane
  • EME ethoxy methoxy ethane
  • LiBF 4 LiCF 3 SO 3 , LiAsF 6 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 and LiCF 3 (CF 2 ) 3 SO 3 in addition to LiPF 6 .
  • an electrolyte such as a polymer electrolyte, a gel-like electrolyte obtained by impregnating a nonaqueous electrolyte in polymer or a solid electrolyte without departing from the scope of the invention.
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KR20020077240A (ko) 2002-10-11
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DE60238014D1 (de) 2010-12-02
US20060204852A1 (en) 2006-09-14
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HK1050589A1 (en) 2003-06-27
CN1221048C (zh) 2005-09-28

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