JP4101927B2 - Non-aqueous electrolyte secondary battery - Google Patents

Non-aqueous electrolyte secondary battery Download PDF

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Publication number
JP4101927B2
JP4101927B2 JP11559498A JP11559498A JP4101927B2 JP 4101927 B2 JP4101927 B2 JP 4101927B2 JP 11559498 A JP11559498 A JP 11559498A JP 11559498 A JP11559498 A JP 11559498A JP 4101927 B2 JP4101927 B2 JP 4101927B2
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Prior art keywords
aqueous electrolyte
non
secondary battery
sn
electrolyte secondary
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JP11559498A
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JPH1145712A (en
Inventor
清作 熊井
誠 能代
良紀 藤江
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Agcセイミケミカル株式会社
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Priority to JP9-138869 priority
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-aqueous electrolyte secondary battery using a negative electrode active material that is excellent in charge / discharge characteristics such as a discharge potential, a discharge capacity, and a charge / discharge cycle life and has high safety.
[0002]
[Prior art]
Typical negative electrode active materials for non-aqueous electrolyte secondary batteries are lithium metals and lithium alloys that have been studied from the beginning of commercialization of lithium secondary batteries, but lithium metal grows in a dendritic shape during charge and discharge. There was a risk of internal short circuit or fire.
[0003]
On the other hand, in order to improve safety, a baked carbonaceous material capable of inserting and extracting lithium has been put into practical use. However, since such a carbonaceous material itself has electrical conductivity, there is a risk that dendritic lithium metal is deposited on the carbonaceous material when overcharged or rapidly charged. As measures at present, a device for a charger and a system for preventing overcharge have been introduced. However, the charge / discharge capacity inherently possessed by the carbonaceous material has been limited. Further, since the carbonaceous material has a low density, there is a drawback that the capacity per unit volume is small.
[0004]
On the other hand, many studies have been made on a negative electrode active material for putting a non-aqueous electrolyte secondary battery having high safety into consideration and high discharge potential and high discharge capacity into practical use. Recently, Sn oxides and composite oxides containing Sn have been proposed as negative electrode materials (JP-A-6-338325, JP-A-7-122274, JP-A-7-288123, JP-A-8-138653, JP-A-8- 203527). However, even when these oxides and composite oxide-based materials are used as the negative electrode active material, the cycle characteristics are not sufficient, the charge / discharge cycle characteristics are further improved, the discharge potential is higher, and the discharge capacity is higher. A negative electrode active material for obtaining a non-aqueous electrolyte secondary battery is desired.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a non-aqueous electrolyte secondary battery having high safety, high discharge potential, high discharge capacity, and excellent cycle characteristics by examining negative electrode active materials. .
[0006]
[Means for Solving the Problems]
The present invention provides a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte containing a lithium salt, wherein the active material of the negative electrode is a composite oxide represented by the following formula 1 , and F , Al, Cu, Ni, Mn , Co, Fe, Bi, Sb, Cr, Ti, Zr, 20 atomic% or less of at least one selected from the group consisting of In and Ga relative to Sn (where 0 atomic% A non-aqueous electrolyte secondary battery characterized by comprising the total amount of
SnZn h P i O j ... Formula 1
( However, in Formula 1, 0.01 ≦ h ≦ 1.0, 0.1 ≦ i ≦ 2.0, 2.0 ≦ j ≦ 5.0.)
[0007]
As a result of intensive studies on the negative electrode active material of the non-aqueous electrolyte secondary battery, the present inventors have found that adding Zn to the composite oxide of Sn and P of the negative electrode active material makes it possible to cycle the secondary battery. It has been found that there is a remarkable effect in improving the characteristics and improving the performance.
[0008]
The reason is not clear, but the amount of lithium that can be occluded and released in the composite oxide of Sn and P is 8 equivalents, whereas by adding Zn to this composite oxide, the amount of lithium that can be occluded and released can be reduced. It is considered that the amount increases to about 10 equivalents, and as a result, the capacity of the secondary battery increases and the performance increases. Further, it is considered that by adding Zn, the structure of the composite oxide of Sn and P is stabilized in a state where lithium is occluded, and as a result, cycle characteristics are improved. In this specification, “A equivalent amount of lithium is occluded in the composite oxide of Sn and P” means that the number of lithium atoms occluded with respect to the Sn1 atom in the composite oxide is A. For example, in SnZn h P i O j, it means Li A SnZn h P i O j .
[0009]
The composite oxide containing Sn, Zn, and P used in the present invention is amorphous in order to exhibit high performance and high durability when used as a negative electrode active material for a non-aqueous electrolyte secondary battery. It is preferable. The term “amorphous” as used herein may have a small amount of crystallinity in X-ray diffraction using CuKα rays, but as a whole, it is broad in the entire range of 20 to 70 degrees in terms of 2θ values. A substance that gives a scattering band.
[0010]
Further, the composite oxide containing Sn, Zn, and P in the present invention may have a crystalline peak in the range of 2θ value of 5 to 30 degrees, but the peak intensity is 20 in terms of 2θ value. The intensity is preferably not more than three times the intensity of the peak of the peak of the broad scattering band in the region of ˜40 degrees.
[0011]
In the synthesis of the composite oxide containing Sn, Zn, and P in the present invention, it is preferable to use Sn, Zn, and P oxides as the main raw materials. The raw material oxide includes a compound that becomes an oxide by a chemical treatment, a heat treatment, or the like, for example, a salt such as a hydroxide, carbonate, or nitrate.
[0012]
As the Sn compound as a raw material, SnO, SnO 2 , Sn hydroxide, and Sn compound that becomes an oxide by thermal decomposition can be basically used. For example, Sn carbonate, nitrate, organic salt, halogen salt Specific examples thereof include tin carbonate and tin oxalate. The Sn valence of the Sn compound used as a raw material is preferably divalent from the viewpoint of amorphization of the obtained composite oxide and the stability of the structure, and SnO is particularly preferable.
[0013]
In the present invention, Zn promotes amorphization. As the Zn compound as a raw material, oxides, hydroxides, and compounds that become zinc oxide by thermal decomposition can be basically used, and examples thereof include zinc carbonate and zinc oxalate. Of these, zinc oxide is particularly preferable. Examples of the P compound as a raw material include phosphorus pentoxide, phosphorus pentachloride, and orthophosphoric acid.
[0014]
In the present invention, in order to make the composite oxide containing Sn, Zn, and P amorphous, the composition ratio of Zn, P to Sn is important and needs to be expressed by Formula 1.
SnZn h P i O j ... Formula 1
However, in Formula 1, 0.01 ≦ h ≦ 1.0, 0.1 ≦ i ≦ 2.0, and 2.0 ≦ j ≦ 5.0. In order to advance the amorphization, it is more preferable that 0.02 ≦ h ≦ 0.2, 0.25 ≦ i ≦ 1.5, and 2.0 ≦ j ≦ 4.0 in Formula 1.
[0015]
The negative electrode active material in the present invention, Sn, Zn, P, O only contains, and composite oxides represented by Formula 1 above, further, F, Al, Cu, Ni , Mn, Co, Fe, Bi, Sb, Cr, Ti, Zr, 20 atomic% of at least one selected from the group consisting of in and Ga relative to S n or less, preferably in a total amount of 10 atomic% or less. In the present invention, the inclusion of these components is essential and contributes to the amorphization of the composite oxide, and is excluded when the content is 0 atomic%.
[0016]
As raw materials for Al, Cu, Ni, Mn, Co, Fe, Bi, Sb, Cr, Ti, Zr, In and Ga, in addition to metal oxides, chemical treatments such as carbonates, halogen salts and organic salts, heat treatments Any compound that can be converted to an oxide can be used. In the case of F, it is preferable to use tin fluoride.
[0017]
The composite oxide containing Sn, Zn, and P used in the present invention is preferably obtained by mixing raw materials, drying, and then melting and firing. About mixing of the raw materials, it can be dispersed in water and wet-mixed, or when all the raw materials are solid, they may be mixed as they are by a jet mill or a rotary stirrer. When wet mixing is performed, drying is performed by heat treatment under normal pressure or reduced pressure. Further, drying and firing can be sequentially performed using a melting furnace.
[0018]
As the melting and firing conditions, the firing temperature is preferably 800 to 1500 ° C. The firing atmosphere may be an air atmosphere or an inert atmosphere such as nitrogen or argon, but an inert atmosphere is preferable because Sn is easily maintained in a divalent state. The melted and fired product is flake-formed or poured onto a water-cooled roller and rapidly cooled to form a flaky amorphous complex oxide. This is pulverized by using a pulverizer such as a ball mill until the average particle diameter is about several tens μm to several μm, and further classified and used. Moreover, it is preferable that the pulverized product has a uniform shape, more preferably a spherical shape, it can be applied uniformly on the current collector, and the battery performance is stable.
[0019]
The positive electrode active material used in the non-aqueous electrolyte secondary battery of the present invention is preferably a lithium-containing metal oxide, and Li x CoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li y Co a Ni 1− a O 2 (where 0.7 ≦ x ≦ 1.2, 0.7 ≦ y ≦ 1.2, 0.1 ≦ a ≦ 0.9) and the like.
[0020]
The positive electrode and the negative electrode used in the non-aqueous electrolyte secondary battery of the present invention can be prepared by coating a positive electrode mixture or a negative electrode mixture on a current collector, or molding it into a pellet. At this time, various carbon materials conventionally used for the composite oxide containing Sn, Zn, and P of the present invention, such as coke, fired resin, graphite, graphitized mesocarbon microbeads, etc. Part can be included. Further, the positive electrode mixture or the negative electrode mixture includes a conductive agent, a binder, a dispersant, a filler, an ionic conductive agent, a pressure enhancer, and various additives, in addition to the positive electrode active material or the negative electrode active material, respectively. Can do.
[0021]
The negative electrode active material used in the present invention can occlude Li in advance before assembling as a battery. Specifically, it can be occluded by chemically and electrochemically reacting with lithium metal, lithium alloy (Li-Al, etc.), and lithium compound (n-butyllithium, etc.). A method of kneading or pressure bonding metal lithium in the presence of an electrolytic solution used in a battery is preferable. The occlusion amount can be occluded up to about 1 to 12 equivalents with respect to Sn in the negative electrode material, but preferably 1 to 6 equivalents.
[0022]
Graphite, acetylene black, carbon black or the like can be used as a conductive agent for the positive electrode and negative electrode that can be used in the present invention. As binders for positive and negative electrodes that can be used in the present invention, polytetrafluoroethylene (hereinafter referred to as PTFE), polyvinylidene fluoride, propylene-tetrafluoroethylene copolymer, propylene-tetrafluoroethylene-vinylidene fluoride copolymer Etc. can be used.
[0023]
In the present invention, aluminum, nickel, titanium or the like can be used as the positive electrode current collector, and copper, nickel, gold or the like can be used as the negative electrode current collector. As the separator interposed between the positive electrode and the negative electrode, a polyolefin-based material can be preferably used, and specifically, a porous film of polypropylene or polyethylene can be preferably used.
[0024]
In the non-aqueous electrolyte in the present invention, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane and the like can be used as a solvent. As the electrolyte, LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 CO 2 or the like can be used.
[0025]
【Example】
Examples of the present invention and comparative examples are given below, but the present invention is not limited to the examples. In each of the following examples, since Li metal is used as the active material of the opposing electrode, the negative electrode active material in the present invention was used as the positive electrode active material because of the potential relationship. The relative evaluation of the performance of the active material with respect to the charge / discharge characteristics was evaluated for its discharge capacity and cycle characteristics.
[0026]
[Example 1 ( comparative example)]
Put 310.6 g of SnO, 15.2 g of ZnO and 300 g of pure water in a 1 liter glass three-necked flask equipped with a stirrer, and add 283.0 g of normal phosphoric acid over 1 hour while stirring at room temperature. It was dripped. The obtained slurry was dried at 120 ° C. to obtain a raw material mixture. This raw material mixture is placed in a quartz crucible, melted and fired at 1000 to 1100 ° C. for 1 hour in an argon atmosphere, and the molten liquid is allowed to flow on a water-cooled rotary roller, whereby a flaky amorphous compound is obtained. Obtained. The composition of this compound was SnP 1.06 Zn 0.08 O 3.8 . This was coarsely pulverized with a ball mill and then pulverized with a jet mill to obtain a fine powder having an average particle diameter of 5 μm.
[0027]
The fine powder, acetylene black, and PTFE were mixed at a weight ratio of 80/16/4. This mixture was formed into a sheet by a roller press, heat-treated at 200 ° C. under reduced pressure, and a sheet (thickness 0.2 mm) was punched out to a diameter of 12.7 mm to obtain an electrode.
[0028]
The obtained electrode was used as a positive electrode, a lithium foil was used as a negative electrode, and a solution in which 1 mol / l LiPF 6 was dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (1/1 by weight) was used as an electrolytic solution. Then, a sealed pressure type two-electrode cell (based on the method described in J. Electrochem. Soc., 136, 3169 (1989)) was assembled, and a charge / discharge test was performed. The discharge cut voltage was 0.02V, and the charge voltage was 2.5V. Table 1 shows the discharge capacity after 2 cycles, 20 cycles, and 100 cycles. In addition, FIG. 1 shows the charge / discharge characteristics and the cycle characteristics according to the charge / discharge potential curves of the second and 20th cycles.
[0029]
[Examples 2 to 5 (Examples)]
In the same manner as in Example 1, the following amorphous compound was obtained. The mixing ratio of the raw materials is an atomic ratio. In Example 2 , Sn: P: Zn: Ni = 100: 106: 8: 2, and in Example 3 , Sn: P: Zn: Co = 100: 106: 8: 2, In Example 4 , Sn: P: Zn: In = 100: 106: 8: 2, and in Example 5 , the mixture was mixed so that Sn: P: Zn: F = 100: 106: 8: 2, and Ni, Co, In, NiO, Co 3 O 4 , In 2 O 3 and SnF 2 were used as raw materials for F, respectively. For Examples 2 to 5, the cycle characteristics were measured in the same manner as in Example 1 and are shown in Table 1.
[0030]
Example 2: SnP 1.06 Zn 0.08 Ni 0.02 O 4.0 ,
Example 3: SnP 1.06 Zn 0.08 Co 0.02 O 4.0 ,
Example 4: SnP 1.06 Zn 0.08 In 0.02 O 4.0
Example 5: SnP 1.06 Zn 0.08 F 0.02 O 3.8 .
[0031]
[Examples 6 to 9 (comparative examples)]
In the same manner as in Example 1, the following amorphous compound was obtained. The mixing ratio of the raw materials is atomic ratio, Sn: P = 100: 106 in Example 6, Sn: P: B = 10: 6: 4 in Example 7, Sn: P = 10: 3 in Example 8, Example 9 was mixed so that Sn: B = 10: 3, and B 2 O 3 was used as a raw material of B. For Examples 6 to 9, the cycle characteristics were measured in the same manner as in Example 1 and are shown in Table 1.
[0032]
Example 6: SnP 1.06 O 3.2
Example 7: SnP 0.6 B 0.4 O 3.1
Example 8: SnP 0.3 O m
Example 9: SnB 0.3 O n .
However, in Example 8, 1.75 ≦ m ≦ 2.05, and in Example 9, 1.45 ≦ n ≦ 1.75.
[0033]
When used as a positive electrode active material, the composite oxide containing Sn, Zn, and P in the present invention has a large discharge capacity and a high capacity retention rate after the charge / discharge cycle test. Therefore, even when these composite oxides are used as the negative electrode active material, a secondary battery having a large discharge capacity and excellent charge / discharge cycle characteristics can be obtained.
[0034]
[Table 1]
[0035]
【The invention's effect】
According to the present invention, a non-aqueous electrolyte secondary battery having a large discharge capacity and good cycle characteristics can be provided.
[Brief description of the drawings]
FIG. 1 is a graph of charge / discharge characteristics of the second and 20th cycles in Example 1. FIG.

Claims (2)

  1. In a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte containing a lithium salt, the active material of the negative electrode is a composite oxide represented by the following formula 1 , and F, Al, Cu Ni, Mn, Co, Fe, Bi, Sb, Cr, Ti, Zr, In and Ga, at least one selected from the group consisting of 20 atomic% or less (excluding 0 atomic%) with respect to Sn A non-aqueous electrolyte secondary battery comprising a total amount .
    SnZn h P i O j ... Formula 1
    ( However, in Formula 1, 0.01 ≦ h ≦ 1.0, 0.1 ≦ i ≦ 2.0, 2.0 ≦ j ≦ 5.0.)
  2.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the composite oxide is amorphous.
JP11559498A 1997-05-28 1998-04-24 Non-aqueous electrolyte secondary battery Expired - Fee Related JP4101927B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP13886997 1997-05-28
JP9-138869 1997-05-28
JP11559498A JP4101927B2 (en) 1997-05-28 1998-04-24 Non-aqueous electrolyte secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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JP4101927B2 true JP4101927B2 (en) 2008-06-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008078150A (en) * 1997-05-28 2008-04-03 Agc Seimi Chemical Co Ltd Nonaqueous electrolyte secondary battery

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3620703B2 (en) * 1998-09-18 2005-02-16 キヤノン株式会社 Negative electrode material for secondary battery, electrode structure, secondary battery, and production method thereof
JP3714205B2 (en) * 2001-07-10 2005-11-09 ソニー株式会社 Non-aqueous electrolyte secondary battery
JP5924237B2 (en) * 2012-11-08 2016-05-25 ソニー株式会社 Active material for lithium ion secondary battery, electrode for lithium ion secondary battery, lithium ion secondary battery, battery pack, electric vehicle, power storage system, electric tool and electronic device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008078150A (en) * 1997-05-28 2008-04-03 Agc Seimi Chemical Co Ltd Nonaqueous electrolyte secondary battery

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