JP2004006094A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

Info

Publication number
JP2004006094A
JP2004006094A JP2002159434A JP2002159434A JP2004006094A JP 2004006094 A JP2004006094 A JP 2004006094A JP 2002159434 A JP2002159434 A JP 2002159434A JP 2002159434 A JP2002159434 A JP 2002159434A JP 2004006094 A JP2004006094 A JP 2004006094A
Authority
JP
Japan
Prior art keywords
substituted
aluminum
gt
lt
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002159434A
Other languages
Japanese (ja)
Inventor
Yuichi Kumeuchi
Tatsuji Numata
沼田 達治
粂内 友一
Original Assignee
Nec Corp
日本電気株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nec Corp, 日本電気株式会社 filed Critical Nec Corp
Priority to JP2002159434A priority Critical patent/JP2004006094A/en
Publication of JP2004006094A publication Critical patent/JP2004006094A/en
Application status is Pending legal-status Critical

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/60Other road transportation technologies with climate change mitigation effect
    • Y02T10/70Energy storage for electromobility
    • Y02T10/7005Batteries
    • Y02T10/7011Lithium ion battery

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent nonaqueous electrolyte secondary battery having improved battery characteristics under an environment having high temperatures exceeding 50°C, especially DOD dependability of capacity preserving characteristics (capacity holding characteristics vary depending on discharge conditions). <P>SOLUTION: A positive electrode contains a component (a): an aluminum-substituted lithium manganate wherein a part of manganese in a lithium manganate having a spinel structure is substituted by lithium and aluminum, expressed by a composition formula Li<SB>1+x</SB>Mn<SB>2-x-y</SB>Al<SB>y</SB>O<SB>4+z</SB>(0.05≤x≤0.13, 0.03≤y≤0.1, -0.1≤z≤0.1), and a component (b): a cobalt-substituted lithium nickelate wherein part of nickel in a lithium nickelate having a layer structure is substituted by cobalt, or a cobalt/aluminum-substituted lithium nickelate. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a non-aqueous electrolyte secondary battery. More specifically, the present invention relates to a lithium ion secondary battery, and relates to a nonaqueous electrolyte secondary battery having improved capacity storage characteristics and charge / discharge cycle characteristics under a high temperature environment.
[0002]
[Prior art]
In a non-aqueous electrolyte secondary battery using graphite or amorphous carbon in which lithium ions can be inserted and desorbed from the negative electrode, if lithium cobaltate is used as the positive electrode active material, an electromotive force exceeding 4 V can be obtained. Research is being conducted. This lithium cobalt oxide is widely used as a positive electrode active material of today's lithium ion secondary batteries because it exhibits good properties in total performance such as potential flatness, capacity, discharge potential, and cycle characteristics. However, cobalt is an expensive material with low recoverable reserves. Lithium cobaltate has a layered rock salt structure (α-NaFeO). 2 Structure), an oxygen layer having a large electronegativity is adjacent to the oxygen layer due to the release of lithium during charging. Therefore, it is necessary to limit the amount of lithium extracted during actual use. If the amount of lithium extracted is too large, such as in an overcharged state, the structure changes due to electrostatic repulsion between the oxygen layers and heat is generated, and the safety of the battery is increased. Have serious problems, and alternative materials are required.
[0003]
Lithium nickelate having the same crystal structure as lithium cobaltate, lithium manganate having a spinel structure, and the like have been considered as a positive electrode active material for a 4V-class nonaqueous electrolyte secondary battery instead of lithium cobaltate. However, although lithium nickelate has a capacity higher than that of lithium cobaltate, its crystal structure is the same layered rock salt structure as that of lithium cobaltate. 4+ Due to the instability of the compound, the oxygen desorption temperature is lower than that of lithium cobalt oxide, and it is more difficult to ensure safety. Therefore, further improvement is required when used alone.
[0004]
On the other hand, spinel-type lithium manganate is made of inexpensive manganese, is a stable spinel-type crystal, and has high safety compared to lithium cobaltate because it contains almost no extra lithium used only during overcharge. It is a very promising material because of its properties. In addition to this, the large amount of recoverable reserves, low cost, and low environmental load make them very promising materials for electric vehicles and large-capacity batteries for stationary power sources.
[0005]
However, the spinel-type lithium manganate has a serious problem that the capacity is greatly deteriorated in charge / discharge cycles and storage at a high temperature exceeding 50 ° C. as compared with lithium cobaltate and lithium nickelate.
[0006]
Japanese Patent Publication No. 7-34368, Japanese Patent No. 2547137, Japanese Patent Application Laid-Open No. 8-162115, and Japanese Patent Application Laid-Open No. 11-240721 disclose the replacement of part of manganese with another element in order to improve the charge / discharge cycle characteristics. And JP-A-11-265717, JP-A-2000-156228, JP-A-2000-159522, and JP-A-2000-277110.
[0007]
Improvements in storage characteristics are also reported in JP-A-2000-294241, JP-A-2000-306577, JP-A-2001-180939, and the like. However, these documents describe that there is a certain effect on the improvement of the storage characteristics in a charged state, but there is no study on the improvement of the degradation mode peculiar to spinel-type lithium manganate. .
[0008]
That is, the spinel-type lithium manganate is charged up to 4.3 V on the basis of Li metal, deintercalates Li ions contributing to charge and discharge, and then discharges the depth of discharge (Depth of discharge, meaning how much discharge). (Hereinafter also referred to as "DOD"), when stored at a high temperature, the rate of capacity deterioration differs depending on the DOD, and the deterioration is particularly severe at DOD = 80%. This is known as a deterioration mode peculiar to spinel-type lithium manganate. This phenomenon is reported, for example, in the 41st Battery Symposium Abstracts p438. As a remedy, replacing a part of manganese with Cr in the collection of abstracts of the 68th Annual Meeting of the Institute of Electrical Chemistry, p236, and replacing a part of manganese with Cr in the 42nd Annual Meeting of the Battery Symposium, p180 and p182 It has been reported that the storage characteristics of batteries were improved by reducing the specific surface area of the negative electrode or by examining other elements than the positive electrode, such as changing additives and supporting electrolytes to the electrolytic solution. Not enough properties.
[0009]
In addition, various reports have been made on improvement of characteristics by mixing lithium nickelate. For example, Japanese Patent Application Laid-Open No. 11-54120 discloses that a mixed positive electrode of lithium nickelate in which a part of nickel of lithium nickelate is replaced with cobalt and aluminum and spinel-type lithium manganate is used to obtain high capacity and cycle characteristics. A technique for providing a lithium ion secondary battery excellent in the above is disclosed. Japanese Patent Application Laid-Open No. 10-112318 discloses that a mixed oxide of a lithium manganese composite oxide and a lithium nickel composite oxide is used to compensate for the irreversible capacity of the negative electrode active material in the first charge and discharge. There is disclosed a technology capable of increasing the capacity. Further, Japanese Patent Application Laid-Open No. 2002-3220 discloses a technique for improving cycle characteristics by mixing a spinel-type lithium manganese oxide in which a part of an Mn site is substituted with another element and a lithium nickel composite oxide. ing.
[0010]
Although there is a report that studies the use of the spinel-type lithium manganate and lithium nickelate mixed cathodes to increase capacity and improve cycle characteristics, it only improves the DOD dependency in high-temperature storage and can withstand practical use. A method for obtaining the characteristics of the above has not been known yet.
[0011]
Further, JP-A-2000-251892 and JP-A-2002-075361 disclose lithium manganate in which part of manganese is replaced by aluminum and lithium nickelate in which part of nickel is replaced by cobalt or cobalt and aluminum. Is described as being used in combination. However, there is no description of the problem of DOD dependence in high-temperature storage. Actually, examination was performed using lithium manganate and lithium nickelate having the compositions described therein, but there was no effect.
[0012]
Therefore, the problem of DOD dependence in high-temperature storage, which is a serious problem when using spinel-type lithium manganate, still exists, and the storage characteristics indispensable for practical use of electric vehicles and stationary power supply batteries are still present. It was not satisfactory.
[0013]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and has an excellent non-aqueous electrolyte secondary solution having improved DOD dependency in battery characteristics, particularly, capacity storage characteristics under a high temperature environment exceeding 50 ° C. It is intended to provide a battery.
[0014]
[Means for Solving the Problems]
According to the present invention, the positive electrode has a composition formula Li: wherein component (a): a part of manganese of lithium manganate having a spinel structure is replaced by lithium and aluminum. 1 + x Mn 2-xy Al y O 4 + z (0.05 ≦ x ≦ 0.13, 0.03 ≦ y ≦ 0.1, −0.1 ≦ z ≦ 0.1), and an aluminum-substituted lithium manganate;
Component (b): a part of nickel of lithium nickelate having a layered structure contains cobalt-substituted lithium nickelate substituted by cobalt or cobalt-aluminum-substituted lithium nickelate substituted by cobalt and aluminum. Non-aqueous electrolyte secondary battery.
[0015]
When such a positive electrode defined by the present invention is used, when DOD is changed and stored in a high-temperature environment exceeding 50 ° C., deterioration is peculiar to lithium manganate, in which DOD is 80% and the deterioration is greatest. The phenomenon can be improved.
[0016]
As described above, conventionally, as an improvement in capacity deterioration at high temperatures, many studies on the replacement of part of manganese in lithium manganate with another element have been reported. It was not improved and its capacity storage characteristics were not sufficient.
[0017]
Further, in the present invention, by mixing cobalt-substituted or cobalt-aluminum-substituted lithium nickelate, the DOD dependency and the capacity storage characteristics are further greatly improved, and the charge / discharge cycle characteristics under a high temperature environment are further improved. . Therefore, the secondary battery of the present invention is suitable as a large-capacity battery for an electric vehicle or a stationary power supply, which can be used for a long time and in a wide range from low to high temperatures.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
As described above, the positive electrode of the non-aqueous electrolyte secondary battery of the present invention contains the component (a) lithium-substituted aluminum manganate and the component (b) cobalt-substituted lithium nickelate or cobalt-aluminum-substituted lithium nickelate. Hereinafter, when the cobalt-substituted lithium nickelate and the cobalt-aluminum-substituted lithium nickelate are simultaneously referred to, they are also referred to as the substituted lithium nickelate of the component (b).
[0019]
The aluminum-substituted lithium manganate of the component (a) has a composition formula of Li in which part of manganese of lithium manganate having a spinel structure is substituted with lithium and aluminum. 1 + x Mn 2-xy Al y O 4 + z (0.05 ≦ x ≦ 0.13, 0.03 ≦ y ≦ 0.1, −0.1 ≦ z ≦ 0.1).
[0020]
Li and Al, which replace the manganese site (16d site), both have an effect of improving the high-temperature storage characteristics and the charge-discharge cycle characteristics, but various problems occur if they exceed this composition range. Even if the manganese site is replaced with only Li or only Al, the DOD dependency in high-temperature storage is not improved, and it is necessary to replace both with Li and Al.
[0021]
Here, any composition range is not necessary if both of Li and Al are substituted, and only the composition specified in this composition range shows a great effect. When the Li amount x is 0.05> x or the Al amount y is 0.03> y, the DOD dependency remains. When the amount x of Li is x> 0.13, the average valence of manganese is increased due to substitution with monovalent Li, resulting in a significant reduction in capacity, which is not practical. On the other hand, when the amount of Al y is y> 0.1, even if the amount of Li x is in the range of 0.05 ≦ x ≦ 0.13, Al is trivalent, so that the capacity decrease is small, but the Li metal counter electrode is When charging / discharging is performed in the range of 0.0V to 4.3V, a plateau appears around 3.3V. This plateau is caused by oxygen deficiency, and causes significant deterioration of charge / discharge cycle characteristics and storage characteristics. In addition, since a different phase appears, the Al amount y must be y ≦ 0.1. Therefore, as the aluminum-substituted lithium manganate, the composition formula Li 1 + x Mn 2-xy Al y O 4 + z (0.05 ≦ x ≦ 0.13, 0.03 ≦ y ≦ 0.1, −0.1 ≦ z ≦ 0.1).
[0022]
Further, finally, the composition of the aluminum-substituted lithium manganate is [Li] / [Mn] / [Al] = [1 + x] / [2-xy] / [y] (0.05 ≦ x ≦ 0.13, 0.03 ≦ y ≦ 0.1), some aluminum may be present as an aluminum oxide in the surface layer without replacing the manganese site of lithium manganate.
[0023]
When the component (b) is cobalt-substituted lithium nickelate, the composition formula LiNi 1-x Co x O 2 Those represented by (0.1 ≦ x ≦ 0.3) are preferable. When the Co substitution amount x of the cobalt-substituted lithium nickelate is x <0.1, many plateaus exhibiting a phase transition at the time of charging and discharging are observed, and the charge / discharge cycle characteristics are remarkably deteriorated. Also, ensuring safety in mechanical destructive tests such as nail penetration tests and crush tests at 4.2 V or 4.3 V, which is the normal upper limit voltage of lithium ion secondary batteries using graphite or amorphous carbon as a negative electrode. Becomes difficult. When x> 0.3, the specific capacity is greatly reduced.
[0024]
Furthermore, in order to improve the capacity storage characteristics, charge / discharge cycle characteristics, abnormal charge / discharge, mechanical and thermal safety, as component (b), cobalt aluminum in which part of nickel is replaced with aluminum in addition to cobalt. It is preferred to use substituted lithium nickelates. It is preferable that y ≦ 0.1 because this aluminum substitution deteriorates the initial charge / discharge efficiency. On the other hand, if the substitution amount is too small, the effect on safety is not seen, so that 0.02 ≦ y is required. That is, when the component (b) is cobalt-aluminum-substituted lithium nickelate, the composition formula LiNi 1-xy Co x Al y O 2 Cobalt / aluminum-substituted lithium nickelate represented by (0.1 ≦ x ≦ 0.3, 0.02 ≦ y ≦ 0.1) is preferable.
[0025]
The mixing ratio between the aluminum-substituted lithium manganate of the component (a) and the lithium nickel-substituted nickel of the component (b) is represented by the following weight ratio: [component (a)]: [component (b)] = (100-a): a When represented, it is preferable that 5 ≦ a ≦ 50. When the mixing ratio of the component (b) is 5% by weight or more, the DOD dependency in high-temperature storage is greatly improved. In particular, the improvement effect is larger when cobalt / aluminum-substituted lithium nickelate is used. As the mixing amount is increased, the effect of improvement is greater. However, when the mixing ratio of the component (b) exceeds the mixing ratio of the aluminum-substituted lithium manganate in the range of a> 50, cobalt / aluminum having excellent thermal stability is obtained. It is preferable that a ≦ 50 because substituted lithium nickelate may emit smoke in a mechanical destruction test.
[0026]
The particle shape of the aluminum-substituted lithium manganate of component (a) and the substituted lithium nickelate of component (b) is not particularly limited, and is not particularly limited, and the particle size is also positive electrode film thickness and positive electrode density. -It can be appropriately selected depending on the kind of binder and the like. However, if the specific surface area of the aluminum-substituted lithium manganate is too large, the amount of manganese eluted into the electrolytic solution increases, so that 3.0 m 2 / G or less, more preferably 1.0 m 2 / G or less. On the other hand, if the specific surface area is too small, it will affect the insertion / desorption of lithium ions when a large current is applied. 2 / G or more is preferred. The specific surface area of the substituted lithium nickelate of the component (b) is 0.3 m in order to suppress the elution of manganese from the lithium manganate. 2 / G or more is preferred. On the other hand, if the specific surface area is too large, problems such as generation of by-products due to the reaction with the electrolytic solution and reduction in thermal stability, and gelation of the slurry during electrode production occur. 2 / G or less, preferably 1 m 2 / G or less is preferred.
[0027]
Next, a method for manufacturing the positive electrode will be described.
[0028]
First, a method for synthesizing the aluminum-substituted lithium manganate of the component (a) will be described. As a starting material, Li as a Li source 2 CO 3 , LiOH, Li 2 O, Li 2 SO 4 And MnO as a Mn source. 2 , Mn 2 O 3 , Mn 3 O 4 , MnOOH, MnCO 3 , Mn (NO 3 ) 2 And the like as Al source 2 O 3 , Al (OH) 3 , Aluminum nitrate, Al acetate or the like can be used. Further, Mn-Al composite hydroxides, carbonates, and oxides in which Mn and Al are adjusted to a predetermined ratio in advance can also be used.
[0029]
Among the above, Li as a Li source 2 CO 3 However, as a Mn source, MnO 2 Or Mn 2 O 3 However, the source of Al is Al 2 O 3 Or Al (OH) 3 Is particularly preferred. Li of Li source 2 CO 3 Is preferably pulverized to improve the reactivity, and the average particle diameter is preferably 3 μm or less. The Al source was also pulverized to improve the reactivity. 2 O 3 And Al (OH) 3 It is preferred to use Since the Mn source preferably has a particle size of 5 to 20 μm from the viewpoints of ensuring uniformity of reaction, ease of slurry preparation, safety, etc. 2 Or Mn 2 O 3 Is preferably pulverized to a particle size of 5 to 20 μm, and classified if necessary.
[0030]
The above-mentioned Li source, Mn source and Al source are selected as starting materials, and the composition ratio Li 1 + x Mn 2-xy Al y O 4 + z The starting materials are weighed and mixed such that x and y in the range of 0.05 ≦ x ≦ 0.13 and 0.03 ≦ y ≦ 0.1. At this time, it is more preferable to mix the Mn source and the Al source at a predetermined Mn / Al ratio in advance and to mix the Li source with the baked Mn-Al composite oxide.
[0031]
The mixing is performed using a ball mill, a jet mill, a pin mill or the like, but is not particularly limited.
[0032]
The obtained mixed powder is fired in air or oxygen at a temperature range of 600 ° C to 950 ° C. From the viewpoint of uniform solid solution, high-temperature sintering is desirable. However, if oxygen deficiency occurs, a 4V foot is observed, which has adverse effects such as deterioration of cycle characteristics. Therefore, the sintering temperature is more preferably in the range of 700 ° C to 850 ° C. Next, the obtained aluminum-substituted lithium manganate may be classified and used as needed, and for example, it is preferable to remove fine particles having a particle size of 1 μm or less. In addition, a predetermined specific surface area can be obtained by appropriately selecting the particle size of the raw material, the sintering temperature, and the like, and performing classification as necessary.
[0033]
As for the aluminum-substituted lithium manganate in which aluminum oxide is present in the surface layer of the aluminum-substituted lithium manganate of the component (a), for example, lithium manganate is synthesized at a predetermined Li / Mn ratio in the first stage of synthesis. When a predetermined Al source is mixed with the synthesized lithium manganate and then calcined at a relatively low temperature, lithium manganate in which part of aluminum remains as aluminum oxide in the surface layer portion is obtained.
[0034]
Specifically, first, the above-mentioned Li source and Mn source are weighed and mixed at a predetermined composition ratio, and the obtained mixed powder is fired in air or oxygen in a temperature range of 600 ° C to 950 ° C. For the same reason, the temperature is more preferably from 700C to 850C. It is obtained by mixing the obtained lithium manganate with an Al source at a predetermined ratio and firing at 200 to 600 ° C, more preferably at 300 to 500 ° C. In addition, a predetermined specific surface area can be obtained by appropriately selecting the particle size of the raw material, the sintering temperature, and the like, and performing classification as necessary.
[0035]
Next, a method for synthesizing the substituted lithium nickelate of the component (b) will be described. As a starting material, Li as a Li source 2 CO 3 , LiOH, Li 2 O, Li 2 SO 4 As the Ni source and the Co source, hydroxides, carbonates, oxides, and the like of Ni or Co can be used. Further, a Ni—Co composite hydroxide, a composite carbonate, a composite oxide, or the like in which Ni and Co are adjusted to a predetermined composition ratio can also be used. Further, as the Al source, Al 2 O 3 , Al (OH) 3 , Aluminum nitrate, Al acetate or the like can be used. Ni-Co-Al composite hydroxides, composite carbonates and composite oxides in which Ni, Co and Al are adjusted to a predetermined composition ratio in advance can also be used.
[0036]
Among the above, Li as a Li source 2 CO 3 However, a composite hydroxide is used as the Ni—Co source, and Al is used as the Al source. 2 O 3 Or Al (OH) 3 Is preferred. More preferably, it is a Ni-Co-Al composite hydroxide.
[0037]
The above starting materials are appropriately selected, and as the cobalt-substituted lithium nickelate, the target composition is LiNi. 1-x Co x O 2 (0.1 ≦ x ≦ 0.3), the target composition of the cobalt / aluminum-substituted lithium nickelate is LiNi. 1-xy Co x Al y O 2 (0.1 ≦ x ≦ 0.3, 0.02 ≦ y ≦ 0.1) The composition is weighed and mixed at a composition ratio in the range.
[0038]
The obtained mixed powder is fired in air or oxygen at a temperature in the range of 600 ° C to 950 ° C. More preferably, it is in the range of 700C to 850C.
[0039]
In addition, a predetermined specific surface area can be obtained by appropriately selecting the particle size of the raw material, the sintering temperature, and the like, and performing classification as necessary.
[0040]
The thus obtained component (a) lithium-substituted lithium manganate and the component (b) substituted lithium nickelate are mechanically mixed in the aforementioned weight ratio. The method of mixing is not particularly limited.
[0041]
This mixture is mixed with a binder type and a conductivity imparting agent such as acetylene black or carbon to form an electrode. The binder may be a commonly used resin-based binder, and polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), or the like can be used. Al foil is preferable as the current collector metal foil.
[0042]
The negative electrode used in the present invention may be a Li metal or a Li alloy. Amorphous carbon materials are good. The negative electrode active material may be selected according to the purpose of use of the battery, such as capacity, energy density, rate characteristics, low-temperature discharge characteristics, pulse charge / discharge characteristics, and high-current charge / discharge characteristics.
[0043]
This negative electrode active material is mixed with a binder species to form an electrode. As the binder, generally used polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), or the like can be used, and a rubber-based binder can also be used. As the current collector metal foil, a Cu foil is preferable.
[0044]
The separator is not particularly limited, but a woven fabric, a glass fiber, a porous synthetic resin film, or the like can be used. For example, a polypropylene or polyethylene porous film is suitable in terms of a thin film, a large area, a film strength and a film resistance.
[0045]
As the solvent of the non-aqueous electrolyte, those commonly used may be used, and examples thereof include carbonates, chlorinated hydrocarbons, ethers, ketones, and nitriles. Preferably, at least one of ethylene carbonate (EC), propylene carbonate (PC), and γ-butyrolactone (GBL) is used as the high dielectric constant solvent, and diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate are used as the low viscosity solvent. (EMC), at least one kind selected from esters and the like, and a mixed solution thereof is used. EC + DEC, EC + EMC, PC + DMC, PC + EMC, PC + EC + DEC and the like are preferable. Further, a small amount of an additive may be added for the purpose of water consumption and improvement of oxidation resistance.
[0046]
As the supporting salt, LiBF 4 , LiPF 6 , LiClO 4 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) N, LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 3 C, Li (C 2 F 5 SO 2 ) 2 At least one kind is used from N and the like. 6 Are preferred. The concentration of the supporting salt is preferably 0.8 M to 1.5 M, and more preferably 0.9 M to 1.2 M.
[0047]
【Example】
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.
[0048]
[Li 1 + x Mn 2-xy Al y O 4 + z Synthesis of
Li 1 + x Mn 2-xy Al y O 4 + z In the synthesis of 2 CO 3 , Al (OH) 3 And electrolytic manganese dioxide. Prior to the mixing of the starting materials described above, Li having an improved reactivity and a target particle size is used. 1 + x Mn 2-xy Al y O 4 + z To obtain Li 2 CO 3 And Al (OH) 3 Was ground and the electrolytic manganese dioxide was classified. Li 1 + x Mn 2-xy Al y O 4 + z When used as a positive electrode active material of a battery, the average particle size of 5 to 30 μm is preferable in consideration of ensuring uniformity of charge / discharge reaction, ease of slurry preparation, safety, and the like. 1 + x Mn 2-xy Al y O 4 + z 5 to 30 μm, which is the same as the above.
[0049]
On the other hand, Li 2 CO 3 And Al (OH) 3 In order to ensure a uniform reaction, pulverization is desirably 5 μm or less. Therefore, pulverization was performed so that the respective average particle diameters became 1.5 μm and 0.85 μm.
[0050]
The starting materials thus pretreated were mixed at a predetermined ratio.
[0051]
This mixed powder was fired at 600 to 800 ° C. in an oxygen flow atmosphere. Then the obtained Li 1 + x Mn 2-xy Al y O 4 + z Among them, fine particles having a particle size of 1 μm or less were removed by an air classifier. At this time, the obtained Li 1 + x Mn 2-xy Al y O 4 + z 0.4-0.9m 2 / G, average particle size was 12 to 18 μm.
[0052]
As shown in Table 1, the Li content x and the Al content y were changed to obtain various compositions of Li. 1 + x Mn 2-xy Al y O 4 + z Are prepared and described as active materials 1-1 to 1-18.
[0053]
In addition, Li in which aluminum exists as an oxide in the surface layer portion 1 + x Mn 2-xy Al y O 4 + z Is synthesized using Li having an average particle size of 1.5 μm. 2 CO 3 And electrolytic manganese dioxide having an average particle size of 15 μm are first mixed in a molar ratio of [Li] / [Mn] = 1.12 / 1.88, and the mixed powder is fired at 800 ° C. in an oxygen flow atmosphere. Thus, lithium manganate was obtained. Next, Al (OH) having an average particle size of 0.85 μm 3 Was mixed at a ratio of 0.082 mol with respect to 1 mol of lithium manganate, and calcined at 400 ° C. in an oxygen flow atmosphere to obtain a mixture. This is referred to as active material 1-19.
[0054]
[Li 1.06 Mn 1.86 Mg 0.08 O 4 Synthesis of
Li 1.06 Mn 1.86 Mg 0.08 O 4 In the synthesis of 2 CO 3 Mg (OH) having an average particle size of 1.5 μm 2 And electrolytic manganese dioxide having an average particle size of 15 μm was used. These starting materials were mixed in a molar ratio of [Li] / [Mg] / [Mn] = 1.06 / 0.08 / 1.86. This mixed powder was fired at 800 ° C. in an oxygen flow atmosphere. Then the obtained Li 1.06 Mn 1.86 Mg 0.08 O 4 Among them, fine particles having a particle size of 1 μm or less were removed by an air classifier. At this time, the obtained Li 1.06 Mn 1.86 Mg 0.08 O 4 0.8m 2 / G, average particle size was 14 μm. This is referred to as active material 1-20.
[0055]
[LiNi 1-x Co x O 2 Synthesis of
LiNi 1-x Co x O 2 In the synthesis of 2 CO 3 And nickel were replaced with cobalt by 20% (Ni 0.8 Co 0.2 ) A hydroxide was used. These starting materials are used in a molar ratio of [Li] / [Ni 0.8 Co 0.2 ] = 1/1. The obtained mixed powder was fired at 750 ° C. in the air. The specific surface area at this time is 0.6 m 2 / G.
[0056]
[LiNi 1-xy Co x Al y O 2 Synthesis of
LiNi 1-xy Co x Al y O 2 In the synthesis of 2 CO 3 And nickel were replaced by 15% with cobalt and 5% with aluminum (Ni 0.8 Co 0.15 Al 0.05 ) A hydroxide was used. These starting materials are used in a molar ratio of [Li] / [Ni 0.8 Co 0.15 Al 0.05 ] = 1/1. The obtained mixed powder was fired at 750 ° C. in the air. The specific surface area at this time is 0.6 m 2 / G.
[0057]
[Evaluation using 2320 type coin cell]
<Manufacture of coin batteries 1-1 to 1-20 (all are comparative examples)>
A 2320 type coin cell was manufactured using each of the active materials 1-1 to 1-20 as a positive electrode active material.
[0058]
The positive electrode active material and the conductivity-imparting agent were dry-mixed, and uniformly dispersed in N-methyl-2-pyrrolidone (NMP) in which PVdF as a binder was dissolved to prepare a slurry. After applying the slurry on an aluminum metal foil having a thickness of 20 μm, NMP was evaporated to prepare a positive electrode sheet.
[0059]
The solid content ratio in the positive electrode was positive electrode active material: conductivity imparting agent: PVdF = 85: 10: 5 in weight percent. This positive electrode sheet was punched out to a diameter of 12 mm to form a positive electrode. As the negative electrode, metallic lithium having a diameter of 14 mmφ was used, and the positive electrode and the negative electrode were laminated via a 25 μm-thick polypropylene porous membrane separator to produce a 2320 type coin cell. 1 mol / L LiPF in electrolyte 6 Was used as a supporting salt, and ethylene carbonate (EC): diethyl carbonate (DEC) = 30: 70 (volume percent) was used as a solvent. Table 1 shows the compositions of the active materials used in the coin batteries 1-1 to 1-20.
[0060]
<Manufacture of coin batteries 2-3 and 2-5 (both comparative examples)>
As the positive electrode active material, LiNi was used in a weight percentage with respect to the active materials 1-3 and 1-5. 0.8 Co 0.2 O 2 Was used in a 20% mixture. The resulting mixture is referred to as active materials 2-3 and 2-5 with respect to lithium manganate active materials 1-3 and 1-5. Using this mixture, a 2320-type coin cell was produced in the same manner as in Comparative Example 1. Table 1 shows the compositions of the active materials used in the coin batteries 2-3 and 2-5.
[0061]
<Manufacture of coin batteries 2-14 to 2-19 (all examples)>
As a positive electrode active material, LiNi is used in a weight percentage with respect to the active materials 1-14 to 1-19. 0.8 Co 0.2 O 2 Was used in a 20% mixture. The resulting mixture is referred to as active materials 2-14 to 2-19 with respect to lithium manganate active materials 1-14 to 1-19. Using this mixture, a 2320-type coin cell was produced in the same manner as in Comparative Example 1. Table 1 shows the compositions of the active materials used in the coin batteries 2-14 to 2-19.
[0062]
<Production of Coin Battery 3-16 (Example)>
As the positive electrode active material, LiNi was used in a weight percentage relative to the active material 1-16. 0.8 Co 0.2 O 2 Was used in a 40% mixture. The obtained mixture is referred to as an active material 3-16 corresponding to the active material 1-16 of lithium manganate. Using this mixture, a 2320-type coin cell was produced in the same manner as in Comparative Example 1. Table 1 shows the composition of the active material used in the coin battery 3-16.
[0063]
<Production of Coin Battery 4-16 (Example)>
As the positive electrode active material, LiNi was used in a weight percentage relative to the active material 1-16. 0.8 Co 0.15 Al 0.05 O 2 Was used in a 20% mixture. The resulting mixture is referred to as an active material 4-16 corresponding to the lithium manganate active material 1-16. Using this mixture, a 2320-type coin cell was produced in the same manner as in Comparative Example 1. Table 1 shows the composition of the active material used in the coin battery 4-16.
[0064]
[Evaluation Test Example 1]
Using each of the manufactured coin batteries (type 2320 coin cell), discharge capacity and capacity storage characteristics were evaluated.
[0065]
First 0.1mA / cm 2 And then discharged to 3.0 V at the same current value to measure the discharge capacity.
[0066]
0.1mA / cm again 2 After the battery was charged to 4.3 V at a current value of, a battery was discharged to a DOD of 0, 20, 50, 80, and 100%, and was left in a thermostat at 60 ° C. for 2 weeks. After leaving, discharge once to 3.0 V, 0.1 mA / cm 2 And the discharge capacity up to 3.0 V after recharging to 4.3 V was measured. Table 1 shows the initial discharge capacity. In addition, the presence or absence of a 3.3 V plateau is shown for coin batteries 1-1 to 1-20 evaluated using lithium manganate alone.
[0067]
Table 2 shows the capacity retention ratio (= [discharge capacity after storage] / [initial discharge capacity]) indicating the ratio of the discharge capacity after storage to the initial discharge capacity of the battery stored at each DOD.
[0068]
The following was found from these results. DOD dependency was observed in the coin battery 1-1 in which the manganese site was not replaced with another element, and in the coin batteries 1-2 to 1-5 in which the manganese site was replaced with only one of Li and Al. . Also, the coin battery 1-6 and the coin battery 1-7 with the Li amount x = 0.04, the coin battery 1-8 and the coin battery 1-9 with the Al amount y = 0.02 still have the DOD dependency. there were. In the coin battery 1-10 and the coin battery 1-11 having the Li amount x = 0.14, although the DOD dependency is considerably improved, the initial discharge capacity is low and not practical. A 3.3 V plateau was observed in the coin batteries 1-12 and 1-13 having the Al amount y = 0.11, and DOD dependence was observed.
[0069]
In the coin batteries 1-14 to 1-19 satisfying the composition range of the component (a), the DOD dependency was improved. Thus, the Li amount x and the Al amount y 1 + x Mn 2-xy Al y O 4 + z (0.05 ≦ x ≦ 0.13, 0.03 ≦ y ≦ 0.1, −0.1 ≦ z ≦ 0.1), the aluminum-substituted lithium manganate is substituted under a high temperature environment of 60 ° C. It was shown that the storage rate was improved in any DOD area. However, it has not yet satisfied the characteristics required for large-capacity batteries for electric vehicles and stationary power sources, which can be used for a long time and in a wide range from low to high temperatures.
[0070]
In addition, in the coin battery 1-20 in which manganese sites, which are said to be effective in high-temperature cycle characteristics, were replaced with magnesium, DOD dependency was observed, and it was found that Li and Al substitution were effective.
[0071]
LiNi 0.8 Co 0.2 O 2 In the coin battery 2-3 and the coin battery 2-5 in which 20% is mixed, the DOD dependence is improved, but the DOD dependence is still observed, reflecting the characteristics of the base lithium manganate.
[0072]
On the other hand, in the coin batteries 2-14 to 2-19, no DOD dependency was observed, and it was found that the capacity retention rate was very high.
[0073]
Also, as in the coin battery 3-16, LiNi 0.8 Co 0.2 O 2 It was clarified that the improvement was further achieved by increasing the mixing amount of. Furthermore, comparing the coin batteries 2-16 and 4-16 with the same mixed amount, LiNi 0.8 Co 0.15 Al 0.05 O 2 It was found that there was an improvement effect when was used.
[0074]
[Table 1]
[0075]
[Table 2]
[0076]
[Evaluation using 18650 type cylindrical battery]
<Production of Cylindrical Battery 1-5 (Comparative Example)>
Graphite as a negative electrode active material is uniformly dispersed in N-methyl-2-pyrrolidone (NMP) in which PVdF as a binder is dissolved to prepare a slurry, and the slurry is applied on a 15-μm-thick copper foil. A negative electrode sheet was produced by evaporating NMP. The solid content ratio in the negative electrode was graphite: PVdF = 90: 10 in weight percent.
[0077]
This negative electrode sheet and a positive electrode sheet produced in the same manner as the coin battery 1-5 were wound in a cylindrical shape through a 25-μm-thick polyethylene porous membrane separator to produce an electrode element having a diameter of 18 mm and a height of 65 mm. An 18650 type cylindrical battery was produced. 1 mol / L LiPF in electrolyte 6 Was used as a supporting salt, and ethylene carbonate (EC): diethyl carbonate (DEC) = 30: 70 (volume percent) was used as a solvent.
[0078]
<Production of Cylindrical Battery 1-16 (Comparative Example)>
An 18650 type cylindrical battery was manufactured in the same manner as the cylindrical battery 1-5 except that the positive electrode sheet manufactured in the same manner as the coin battery 1-16 was used as the positive electrode.
[0079]
<Production of Cylindrical Battery 2-5 (Comparative Example)>
An 18650 type cylindrical battery was manufactured in the same manner as the cylindrical battery 1-5 except that a positive electrode sheet manufactured in the same manner as the coin battery 2-5 was used as the positive electrode.
[0080]
<Production of Cylindrical Battery 1-20 (Comparative Example)>
An 18650 type cylindrical battery was manufactured in the same manner as the cylindrical battery 1-5, except that a positive electrode sheet manufactured in the same manner as the coin battery 1-20 was used as the positive electrode.
[0081]
<Production of Cylindrical Battery 2-16 (Example)>
An 18650 type cylindrical battery was manufactured in the same manner as the cylindrical battery 1-5 except that the positive electrode sheet manufactured in the same manner as the coin battery 2-16 was used as the positive electrode.
[0082]
<Production of Cylindrical Battery 4-16 (Example)>
An 18650 type cylindrical battery was manufactured in the same manner as the cylindrical battery 1-5, except that a positive electrode sheet manufactured in the same manner as the coin battery 4-16 was used as the positive electrode.
[0083]
[Evaluation Test Example 2]
The charge / discharge cycle test was performed on the 18650 type battery produced in each of the production examples in a 50 ° C. environment. The charge / discharge cycle test is performed by repeating the operation of charging to 4.2 V at 500 mA, then performing constant-potential charging for 2 hours, and discharging to 3.0 V at 500 mA. The capacity retention rate after the test was calculated and is shown in Table 3.
[0084]
From these results, the cylindrical battery 1-16 using the aluminum-substituted lithium manganate in which the manganese site was replaced with lithium and aluminum as the positive electrode active material had better cycle characteristics than the cylindrical battery 1-5 in which only Li was replaced. Was found.
[0085]
On the other hand, it was found that the cylindrical battery 1-20 using the magnesium-substituted lithium manganate having no effect on the storage characteristics had the same effect on the charge-discharge cycle characteristics as the aluminum-substituted lithium manganate.
[0086]
In addition, LiNi is added to lithium manganate substituted with Li only. 0.8 Co 0.2 O 2 2-5 containing 20% of LiNi 0.8 Co 0.2 O 2 Cycle characteristics are improved as compared with the cylindrical battery 1-5 not mixed with 0.8 Co 0.2 O 2 The effect of mixing is seen. However, it has not yet satisfied the characteristics required for large-capacity batteries for electric vehicles and stationary power sources, which can be used for a long time and in a wide range from low to high temperatures.
[0087]
LiNi to aluminum substituted lithium manganate 0.8 Co 0.2 O 2 2-16 mixed with 20% of the same LiNi 0.8 Co 0.2 O 2 It can be seen that the capacity retention ratio is higher than that of the cylindrical battery 2-5 which is a mixed amount. LiNi 0.8 Co 0.2 O 2 The effect of mixing is large. That is, the improvement of the characteristics of the cylindrical battery 2-16 with respect to the cylindrical battery 1-16 is higher than the improvement of the characteristics of the cylindrical battery 2-5 with respect to the cylindrical battery 1-5. Although the reason for this is not clear, the base aluminum-substituted lithium manganese oxide suppresses manganese elution in the electrolytic solution, so that the amount of manganese deposited on the negative electrode is small and the deterioration of the electrolytic solution is suppressed. It is thought that it is.
[0088]
In addition, LiNi 0.8 Co 0.15 Al 0.05 O 2 It was found that the cylindrical battery 4-16 using No. 4 had a higher improvement effect.
[0089]
[Table 3]
[0090]
[Evaluation Test Example 3]
The substituted lithium nickelate having the composition shown in Table 4 was mixed with the active material 1-16 of the component (a) in a mixing amount shown in the table, and a 18650 type cylindrical battery was formed in the same procedure as the cylindrical battery 1-5. Produced.
[0091]
The prepared battery was charged to 4.2 V at 500 mA, and then was charged at a constant potential for 2 hours to prepare a charged battery. A nail penetration test was performed in which the battery was penetrated with a nail having a diameter of 3 mm. Table 4 shows the results.
[0092]
[Table 4]
[0093]
From this result, it can be seen that, even with cobalt / aluminum-substituted lithium nickelate having excellent thermal stability, if the mixing amount exceeds 50%, smoke is generated, and a problem occurs in thermal stability, and safety is increased. From the viewpoint, it is preferable that the mixing amount of lithium nickelate does not exceed 50% by weight.
[0094]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, even if it preserve | saves under high temperature environment of 60 degreeC, DOD dependence is small and the nonaqueous electrolyte secondary battery with which the capacity deterioration rate was improved can be provided. Further, the non-aqueous electrolyte secondary battery of the present invention has improved charge-discharge cycle characteristics under a high-temperature environment.

Claims (6)

  1. The positive electrode is
    Component (a): a part of the lithium manganate having a spinel structure manganese is substituted with lithium and aluminum, the composition formula Li 1 + x Mn 2-x -y Al y O 4 + z (0.05 ≦ x ≦ 0. 13, 0.03 ≦ y ≦ 0.1, −0.1 ≦ z ≦ 0.1), and an aluminum-substituted lithium manganate;
    Component (b): a part of nickel of lithium nickelate having a layered structure contains cobalt-substituted lithium nickelate substituted by cobalt or cobalt-aluminum-substituted lithium nickelate substituted by cobalt and aluminum. Non-aqueous electrolyte secondary battery.
  2. 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein an aluminum oxide is present on a surface layer of the aluminum-substituted lithium manganate. 3.
  3. 2. The nonaqueous electrolyte secondary battery according to claim 1, wherein the cobalt-substituted lithium nickelate has a composition formula of LiNi 1-x Co x O 2 (0.1 ≦ x ≦ 0.3). 3.
  4. Characterized in that said cobalt-aluminum-substituted lithium nickelate is a composition formula LiNi 1-x-y Co x Al y O 2 (0.1 ≦ x ≦ 0.3,0.02 ≦ y ≦ 0.1) The non-aqueous electrolyte secondary battery according to claim 1.
  5. When the weight ratio of the component (a) and the component (b) is represented by [component (a)]: [component (b)] = (100-a): a, 5 ≦ a ≦ 50. The non-aqueous electrolyte secondary battery according to claim 1.
  6. The nonaqueous electrolyte secondary battery according to claim 1, wherein the negative electrode is graphite or amorphous carbon.
JP2002159434A 2002-05-31 2002-05-31 Nonaqueous electrolyte secondary battery Pending JP2004006094A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002159434A JP2004006094A (en) 2002-05-31 2002-05-31 Nonaqueous electrolyte secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2002159434A JP2004006094A (en) 2002-05-31 2002-05-31 Nonaqueous electrolyte secondary battery

Publications (1)

Publication Number Publication Date
JP2004006094A true JP2004006094A (en) 2004-01-08

Family

ID=30429212

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002159434A Pending JP2004006094A (en) 2002-05-31 2002-05-31 Nonaqueous electrolyte secondary battery

Country Status (1)

Country Link
JP (1) JP2004006094A (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005243504A (en) * 2004-02-27 2005-09-08 Sanyo Electric Co Ltd Lithium secondary battery
JP2005339886A (en) * 2004-05-25 2005-12-08 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
WO2006071972A3 (en) * 2004-12-28 2007-10-18 Boston Power Inc Lithium-ion secondary battery
JP2008071625A (en) * 2006-09-14 2008-03-27 Nec Tokin Corp Positive electrode active material for secondary battery, positive electrode for secondary battery using it, and secondary battery
JP2008084743A (en) * 2006-09-28 2008-04-10 Nec Tokin Corp Positive electrode for secondary battery, and secondary battery using the same
US7656125B2 (en) 2005-07-14 2010-02-02 Boston-Power, Inc. Method and device for controlling a storage voltage of a battery pack
JP2010524817A (en) * 2007-04-16 2010-07-22 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Method for producing metal oxide with high lithium content
US7811707B2 (en) 2004-12-28 2010-10-12 Boston-Power, Inc. Lithium-ion secondary battery
US8003241B2 (en) 2006-06-23 2011-08-23 Boston-Power, Inc. Lithium battery with external positive thermal coefficient layer
US8138726B2 (en) 2006-06-28 2012-03-20 Boston-Power, Inc. Electronics with multiple charge rate
JP2013122927A (en) * 2013-01-29 2013-06-20 Nec Energy Devices Ltd Positive electrode for secondary battery, and lithium secondary battery including the same
US8483886B2 (en) 2009-09-01 2013-07-09 Boston-Power, Inc. Large scale battery systems and method of assembly
US8679670B2 (en) 2007-06-22 2014-03-25 Boston-Power, Inc. CID retention device for Li-ion cell
JP2014517453A (en) * 2011-05-23 2014-07-17 エルジー ケム. エルティーディ. High power lithium secondary battery with improved power density characteristics
US8828605B2 (en) 2004-12-28 2014-09-09 Boston-Power, Inc. Lithium-ion secondary battery
JP2014225359A (en) * 2013-05-15 2014-12-04 日産自動車株式会社 Positive electrode active material for lithium ion secondary battery
JP2015530721A (en) * 2013-08-29 2015-10-15 エルジー・ケム・リミテッド Lithium transition metal composite particles, production method thereof, and positive electrode active material including the same
US9166206B2 (en) 2008-04-24 2015-10-20 Boston-Power, Inc. Prismatic storage battery or cell with flexible recessed portion
US9184447B2 (en) 2011-05-23 2015-11-10 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high power density
US9263737B2 (en) 2011-05-23 2016-02-16 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high power density
US9385372B2 (en) 2011-05-23 2016-07-05 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high energy density
JP2016213205A (en) * 2011-07-13 2016-12-15 エルジー・ケム・リミテッド High-energy lithium secondary battery improved in energy density characteristic
US9601756B2 (en) 2011-05-23 2017-03-21 Lg Chem, Ltd. Lithium secondary battery of high energy density with improved energy property
US9985278B2 (en) 2011-05-23 2018-05-29 Lg Chem, Ltd. Lithium secondary battery of high energy density with improved energy property

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005243504A (en) * 2004-02-27 2005-09-08 Sanyo Electric Co Ltd Lithium secondary battery
JP2005339886A (en) * 2004-05-25 2005-12-08 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery
US7811707B2 (en) 2004-12-28 2010-10-12 Boston-Power, Inc. Lithium-ion secondary battery
WO2006071972A3 (en) * 2004-12-28 2007-10-18 Boston Power Inc Lithium-ion secondary battery
EP2325930A1 (en) * 2004-12-28 2011-05-25 Boston-Power, Inc. Lithium-ion secondary battery
JP2008525973A (en) * 2004-12-28 2008-07-17 ボストン−パワー,インコーポレイテッド Lithium ion secondary battery
JP2011091052A (en) * 2004-12-28 2011-05-06 Boston-Power Inc Lithium ion secondary battery
EP2178137A1 (en) 2004-12-28 2010-04-21 Boston-Power, Inc. Lithium-Ion secondary battery
US7811708B2 (en) 2004-12-28 2010-10-12 Boston-Power, Inc. Lithium-ion secondary battery
US8828605B2 (en) 2004-12-28 2014-09-09 Boston-Power, Inc. Lithium-ion secondary battery
US7656125B2 (en) 2005-07-14 2010-02-02 Boston-Power, Inc. Method and device for controlling a storage voltage of a battery pack
US8084998B2 (en) 2005-07-14 2011-12-27 Boston-Power, Inc. Method and device for controlling a storage voltage of a battery pack
US8003241B2 (en) 2006-06-23 2011-08-23 Boston-Power, Inc. Lithium battery with external positive thermal coefficient layer
US8138726B2 (en) 2006-06-28 2012-03-20 Boston-Power, Inc. Electronics with multiple charge rate
JP2008071625A (en) * 2006-09-14 2008-03-27 Nec Tokin Corp Positive electrode active material for secondary battery, positive electrode for secondary battery using it, and secondary battery
JP2008084743A (en) * 2006-09-28 2008-04-10 Nec Tokin Corp Positive electrode for secondary battery, and secondary battery using the same
JP2010524817A (en) * 2007-04-16 2010-07-22 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Method for producing metal oxide with high lithium content
KR101454501B1 (en) 2007-04-16 2014-10-23 바스프 에스이 Method for the production of lithium-rich metal oxides
US8679670B2 (en) 2007-06-22 2014-03-25 Boston-Power, Inc. CID retention device for Li-ion cell
US9166206B2 (en) 2008-04-24 2015-10-20 Boston-Power, Inc. Prismatic storage battery or cell with flexible recessed portion
US8483886B2 (en) 2009-09-01 2013-07-09 Boston-Power, Inc. Large scale battery systems and method of assembly
US9263737B2 (en) 2011-05-23 2016-02-16 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high power density
US9601756B2 (en) 2011-05-23 2017-03-21 Lg Chem, Ltd. Lithium secondary battery of high energy density with improved energy property
JP2017027947A (en) * 2011-05-23 2017-02-02 エルジー ケム. エルティーディ. High output lithium secondary battery with enhanced output density characteristics
US9385372B2 (en) 2011-05-23 2016-07-05 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high energy density
US9184447B2 (en) 2011-05-23 2015-11-10 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high power density
US9203081B2 (en) 2011-05-23 2015-12-01 Lg Chem, Ltd. Lithium secondary battery of high power property with improved high power density
JP2014517453A (en) * 2011-05-23 2014-07-17 エルジー ケム. エルティーディ. High power lithium secondary battery with improved power density characteristics
US9985278B2 (en) 2011-05-23 2018-05-29 Lg Chem, Ltd. Lithium secondary battery of high energy density with improved energy property
JP2016213205A (en) * 2011-07-13 2016-12-15 エルジー・ケム・リミテッド High-energy lithium secondary battery improved in energy density characteristic
US9525167B2 (en) 2011-07-13 2016-12-20 Lg Chem, Ltd. Lithium secondary battery of high energy with improved energy property
JP2013122927A (en) * 2013-01-29 2013-06-20 Nec Energy Devices Ltd Positive electrode for secondary battery, and lithium secondary battery including the same
JP2014225359A (en) * 2013-05-15 2014-12-04 日産自動車株式会社 Positive electrode active material for lithium ion secondary battery
JP2015530721A (en) * 2013-08-29 2015-10-15 エルジー・ケム・リミテッド Lithium transition metal composite particles, production method thereof, and positive electrode active material including the same
US9887420B2 (en) 2013-08-29 2018-02-06 Lg Chem, Ltd. Lithium transition metal composite particles, preparation method thereof, and cathode active material including the same

Similar Documents

Publication Publication Date Title
JP3890185B2 (en) Positive electrode active material and non-aqueous electrolyte secondary battery including the same
JP4742866B2 (en) Positive electrode active material for secondary battery, positive electrode for secondary battery, secondary battery, and method for producing positive electrode active material for secondary battery
JP5265187B2 (en) Lithium metal oxide material, synthesis method and use
US8173301B2 (en) Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery including the same
JP5153156B2 (en) Method for producing positive electrode for non-aqueous electrolyte secondary battery
US5783333A (en) Lithium nickel cobalt oxides for positive electrodes
US6682850B1 (en) Nonaqueous electrolyte solution secondary battery using lithium-manganese composite oxide for positive electrode
EP1487039B1 (en) Positive electrode active material, production method thereof and non-aqueous electrolyte secondary battery
TWI429132B (en) Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling
JP4080337B2 (en) Positive electrode active material and non-aqueous electrolyte secondary battery including the same
EP2006937A2 (en) Lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery, method for manufacturing the powder, spray dried product of the powder, firing precursor of the powder, and positive electrode for lithium rechargeable battery and lithium rechargeable battery using the powder
JP4644895B2 (en) Lithium secondary battery
JPWO2004105162A6 (en) Positive electrode active material for secondary battery, positive electrode for secondary battery, secondary battery, and method for producing positive electrode active material for secondary battery
KR100609789B1 (en) Non-Aqueous Electrolyte Secondary Battery
KR101970909B1 (en) Powder of lithium complex compound particles, method for producing the same, and nonaqueous electrolyte secondary cell
KR100946610B1 (en) Layered lithium nickel manganese cobalt composite oxide powder for material of positive electrode of lithium secondary battery, process for producing the same, positive electrode of lithium secondary battery therefrom, and lithium secondary battery
US7935270B2 (en) Cathode active material and lithium battery using the same
JP4595475B2 (en) Positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery using the same, and method for producing the same
JP2011034943A (en) Nonaqueous electrolyte secondary battery
JP2004207120A (en) Nonaqueous electrolyte secondary battery
JP5315591B2 (en) Positive electrode active material and battery
CN1220292C (en) Nonaqueous electrolyte secondary battery
JP4070585B2 (en) Lithium-containing composite oxide and non-aqueous secondary battery using the same
KR20100017344A (en) Lithium mixed metal oxide cathode compositions and lithium-ion electrochemical cells incorporating same
JP5095098B2 (en) Nonaqueous electrolyte secondary battery

Legal Events

Date Code Title Description
RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20041210

RD03 Notification of appointment of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7423

Effective date: 20041210

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20050422

RD04 Notification of resignation of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7424

Effective date: 20060127

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20071029

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20080409

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20080813