JP6523629B2 - Nonaqueous electrolyte secondary battery and method of manufacturing nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery and method of manufacturing nonaqueous electrolyte secondary battery Download PDF

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JP6523629B2
JP6523629B2 JP2014160523A JP2014160523A JP6523629B2 JP 6523629 B2 JP6523629 B2 JP 6523629B2 JP 2014160523 A JP2014160523 A JP 2014160523A JP 2014160523 A JP2014160523 A JP 2014160523A JP 6523629 B2 JP6523629 B2 JP 6523629B2
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secondary battery
electrolyte secondary
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battery
lto
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JP2016038992A (en
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隆二 伊藤
隆二 伊藤
雄平 淵本
雄平 淵本
吉村 精司
精司 吉村
西口 信博
信博 西口
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Fdk株式会社
Fdk株式会社
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Description

  The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery using lithium titanate as a negative electrode active material.

As a non-aqueous electrolyte secondary battery using Li ion as a charge carrier, there is one using lithium titanate (Li 4 Ti 5 O 12 : hereinafter referred to as LTO) as a negative electrode active material. Although non-aqueous electrolyte secondary batteries using carbon for the negative electrode are widely used, LTO is excellent in cycle life and safety because the expansion of the crystal lattice is small against insertion and detachment of Li ions. It attracts attention as a negative electrode active material for realizing a non-aqueous electrolyte secondary battery. A coin-shaped non-aqueous electrolyte comprising a negative electrode using LTO as a negative electrode active material, a positive electrode containing a 4 V grade positive electrode active material (eg lithium cobaltate: LiCoO 2 ), and an electrolytic solution containing LiPF 6 as a solute. The following battery is put to practical use.

  In addition, as a manufacturing method of LTO, although there are wet and dry as it describes in the following patent documents 1 and 2, LTO is generated by solid phase diffusion reaction using a plurality of raw materials in any method. Therefore, in the production of LTO, the purity of the raw material itself is increased to reduce the impurities in LTO as much as possible.

International Publication No. 2012/147854 Unexamined-Japanese-Patent No. 2000-302547

  Among the substances contained as impurities in LTO, chlorine is ionized in the electrolytic solution to form chlorine ions. Chloride ions corrode the battery can and consequently increase the internal resistance of the non-aqueous electrolyte secondary battery. Therefore, in the conventional non-aqueous electrolyte secondary battery, the amount of chlorine contained in the LTO raw material is strictly defined. For example, in the invention described in Patent Document 2, the chlorine content of titanium oxide which is one of the raw materials of LTO is specified as 200 ppm or less, preferably 100 ppm or less. As described above, in the non-aqueous electrolyte secondary battery using LTO as the negative electrode active material, it is necessary to refine the raw material of the negative electrode active material to high purity, and the LTO is compared with the overall manufacturing cost of the non-aqueous electrolyte secondary battery. The percentage of manufacturing costs will be high. Then, the manufacturing cost of LTO is finally transferred to the price of the non-aqueous electrolyte secondary battery, and it becomes difficult to provide the non-aqueous electrolyte secondary battery inexpensively.

  Instead of strictly controlling the chlorine concentration in LTO, it is conceivable to use a material with a large pitting index (hereinafter also referred to as PI) and excellent corrosion resistance for the battery can, but a material with a large PI is expensive In the end, therefore, it is difficult to provide a non-aqueous electrolyte secondary battery inexpensively. Therefore, the present invention aims to provide a non-aqueous electrolyte secondary battery that can suppress the increase in internal resistance during storage due to the corrosion of a battery can while using LTO containing chlorine having a concentration higher than that of the conventional one at lower cost. And

The present invention for achieving the above object comprises a battery can made of stainless steel, a positive electrode containing a positive electrode active material capable of absorbing and desorbing Li ions, a negative electrode containing lithium titanate as a negative electrode active material, and 1. A non-aqueous electrolyte secondary battery comprising: an electrolyte containing a lithium salt containing fluorine as a solute;
Chlorine contained in the lithium titanate is at least 108 ppm and at most 500 ppm,
It is initially charged to 100% or more and 120% or less of the nominal capacity,
The non-aqueous electrolyte secondary battery is characterized in that.

The non-aqueous electrolyte secondary battery may also be made of stainless steel having a pitting index of 22 or more and 41 or less. A non-aqueous electrolyte secondary battery in which the positive electrode active material is 4V class can also be used. And the manufacturing method of the nonaqueous electrolyte secondary battery including the process of washing the lithium titanate contained in the negative electrode with pure water is also within the scope of the present invention.

  According to the non-aqueous electrolyte secondary battery of the present invention, the corrosion of the battery can and the associated increase in internal resistance due to chlorine in the battery can are reduced without using lithium titanate of high purity as the negative electrode active material. be able to. As a result, the manufacturing cost of lithium titanate can be reduced, and a non-aqueous electrolyte secondary battery can be provided at lower cost.

It is a figure showing the structure of the nonaqueous electrolyte secondary battery concerning the example of the present invention.

=== Process to think about the present invention ===
In the case of a non-aqueous electrolyte secondary battery (hereinafter, also referred to as a battery) containing LTO as a negative electrode active material, the present invention causes the battery after production to reach the user's hand when the concentration of chlorine contained as an impurity in LTO is high. It has been found that the corrosion progresses inside the battery can during the storage period up to the storage period, and as a result, there is a problem that the internal resistance increases. However, as described above, high purity LTO is expensive to produce. Then, when the method of removing chlorine from LTO with low purity was examined, it was found that the chlorine can be removed by washing the powdered LTO having a high concentration of chlorine with pure water. Furthermore, when we examined the phenomenon that internal resistance increased due to chlorine in LTO battery, the corrosion inside the battery can caused by chlorine is not only the chlorine concentration of LTO but also the charge amount to the battery after assembly It was found that they were related. Then, the present inventors have intensively studied based on the above findings and considered the present invention.

=== Examples ===
In order to evaluate the characteristics of the battery according to the example of the present invention, various non-aqueous electrolyte secondary batteries (hereinafter, also referred to as batteries) having different materials of battery cans and chlorine concentrations of lithium titanate were manufactured as samples. FIG. 1 shows the internal structure of the battery 1 manufactured as a sample and the size of each part. The illustrated battery is a coin-shaped lithium secondary battery which is flat at the top and bottom, and FIG. 1 shows a longitudinal cross section in which the thickness t direction is the top and bottom (longitudinal) direction. Also, the upper and lower directions are defined as shown in the figure. The battery 1 is called a 621 type, and its outer diameter is φ = 6 mm in diameter and t = 2.1 mm in thickness.

  The battery 1 is obtained by impregnating an electrolytic solution on an electrode body 10 in which a positive electrode 2 having a transition metal oxide containing Li as a positive electrode active material and a negative electrode 3 having LTO as a negative electrode active material facing each other via a separator 4. The electrode assembly 10 is housed in a battery can (hereinafter, also referred to as the positive electrode can 5), and the opening of the positive electrode can 5 is through a sealing gasket (hereinafter also referred to as the gasket 6) made of insulating resin. It is sealed with 8. The configuration and structure of the battery 1 will be more specifically described below.

The positive electrode 2 contains a lithium-containing transition metal complex oxide such as lithium cobaltate, lithium nickelate, spinel-type lithium manganate, lithium-containing cobalt-nickel-manganese complex oxide as a positive electrode active material. Here, lithium cobaltate (LiCoO 2 : hereinafter referred to as LCO) is used as a positive electrode active material. Specifically, it was obtained by mixing LCO, artificial graphite serving as a conductive agent, and a binder composed of a fluorine resin in a mass ratio of 90: 7: 3, respectively, drying the mixture and crushing it. The positive electrode mixture is placed in a molding jig with a diameter of 4.1 mm and pressed at a pressure of 600 kg · f to form a disc having a diameter φ p = 4.1 mm and a thickness t p = 0.9 mm. The positive electrode 2 is used.
With regard to the negative electrode 3, first, in order to obtain various LTOs having different chlorine concentrations according to the sample, powdered LTO (hereinafter, also referred to as raw material LTO) obtained from a material maker And LTO (hereinafter also referred to as chlorine-free LTO) removed to a chlorine concentration (.apprxeq.0 ppm) below the measurement limit. And the chlorine concentration of LTO was adjusted by changing the mixture ratio of raw material LTO and non-chlorinated LTO. Next, LTO with adjusted chlorine concentration, vapor grown carbon fiber (VGCF) as conductive agent, artificial graphite similarly as conductive agent, and fluorocarbon resin binder, weight ratio of 89: 5: 3: 3 respectively And the mixture was dried and crushed to obtain a negative electrode mixture. In the same manner as for the positive electrode 2, a negative electrode mixture is placed in a molding jig having a diameter of 4.1 mm and pressure-molded at a pressure of 600 Kg · f to form a disk with a diameter φ n = 4.1 mm and a thickness t n = 0.7 mm. Negative electrode 3 was obtained.

The electrolytic solution 20 contains, as a solvent, cyclic carbonate solvents such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) And lithium carbonate containing fluorine such as LIPF 6 , LiBF 4 , LiTFSI, and LiBETI as a solute. Still to notation LiTFSI and LiBETI in formula, the respective LiN (CF 3 SO 2) 2 and LiN (C 2 F 5 SO 2 ) 2. Here, in this example, LiPF 6 is dissolved as a solute at a concentration of 1 mol / L in a ternary solvent in which PC, EC and DMC are mixed at a mass ratio of, for example, 4: 3: 3. As an electrolyte.

  Next, the assembly procedure of the battery 1 will be described with reference to FIG. First, as the positive electrode can 5, types of well-known SUSs 316 (PI = 22) and SUS329J4L (PI = 41) having different PIs are prepared. Then, after laminating the positive electrode 2, the separator 4 formed by cutting a non-woven fabric made of polyphenylene sulfide into a circle, and the negative electrode 3 having different LTO chlorine concentration according to the sample, these are pressure-bonded to form the electrode body 10 After the constituent members (2 to 4) of the electrode assembly 10 are impregnated with the electrolytic solution, the electrode assembly 10 is accommodated in the positive electrode can 5 of the type according to the sample. At this time, the lower surface 21 of the positive electrode 2 and the inner bottom surface 51 of the positive electrode can 5 are electrically connected via the conductive paste 7 using a carbon-based conductive material.

  Next, the ring-shaped gasket 6 made of PFA is pressed into the positive electrode can 5. A groove 61 whose bottom is the bottom is formed concentrically in the ring-shaped gasket 6, and the peripheral portion 81 of the plate-like negative electrode terminal plate 8 which the lower part opens is inserted into the groove 61. Then, the outer periphery of the positive electrode can 5 is crimped inward, and the negative electrode terminal plate 8 is fitted to the inside of the positive electrode can 5 via the gasket 6. Thus, the battery 1 is completed. The negative electrode 3 and the negative electrode terminal plate 8 are electrically connected via the conductive paste 9 in the same manner as the positive electrode 2 and the positive electrode can 5.

=== Samples ===
As described above, various samples with different chlorine concentration of LTO contained in the negative electrode 3 and material of the positive electrode can 5 are stored for 50 days at room temperature by changing the amount of charge with respect to the nominal capacity. The change in internal resistance after storage testing for. The nominal capacity of the sample is defined as the capacity up to the final voltage of 2.0 V at the standard charge and discharge current of 0.025 mAh, as in the case of the commercially available 621 type lithium secondary battery. And while preparing individuals charged to 10%, 40%, 70%, and 120% of the nominal capacity for each sample, internal resistance immediately after charging for all individuals and internal after storage for 50 days at room temperature The resistance was measured and the increase in internal resistance was examined.

  The storage test results are shown in Tables 1 and 2 below.

Table 1 is a test result about the sample which used SUS316 as a material of cathode can 5, and Table 2 is a test result about a sample which used SUS329J4L. As shown in Tables 1 and 2, in the samples (D1 to D5, H1 to H5) in which the chlorine concentration is 1300 ppm, it can be said that the absolute change amount of the internal resistance is large and there is a problem in practical use. In samples (A1 to A5, B1 to B5, C1 to C5, E1 to E5, F1 to F5, and G1 to G5) whose chlorine concentration of LTO is 509 ppm or less, the increase in internal resistance is 8Ω if the charge amount is 40% or more It can be determined that it can be less than practical use. For all samples (A1 to A5, B1 to B5, C1 to C5, E1 to E5, F1 to F5, G1 to G5) where the chlorine concentration of LTO is 509 ppm or less if the charge amount is 70% or more and 120% or less The rise in internal resistance could be suppressed to less than 6 Ω. Certainly, even when the chlorine concentration is 1300 ppm, by setting the charge amount to 120% in sample D5, the increase in internal resistance can be made less than 8 Ω by setting the charge amount to 100% or more in samples H4 and H5. In sample H5 in which the positive electrode can 5 was made of SUS329J4L and the charge capacity was 120%, the increase in internal resistance could be made less than 6 Ω. However, since the range of the charge amount is defined to be equal to or more than the fully charged capacity, manufacturing conditions are limited. The charging time also increases and the productivity also decreases. If the chlorine concentration of LTO is 509 ppm or less, the charge amount can be selected in consideration of the expected use of the battery, storage period, and the like, in other words, in consideration of manufacturing cost and performance.

  As for the upper limit of the charge amount, the increase in internal resistance tends to be suppressed as the charge amount increases, but here the nominal capacity is a value considering overcharge, and for example, about 120% of the nominal capacity in constant voltage charge In consideration of the fact that the battery is charged up to 120%. As for the upper limit of the chlorine concentration, maintaining the upper limit of the chlorine concentration of LTO strictly at 509 ppm at the production site of the battery 1 rather increases the cost for quality control, so in the embodiment of the present invention It was defined as 500 ppm or less.

  As described above, in the battery 1 according to the embodiment of the present invention, even if low quality LTO having a high chlorine concentration and stainless steel having a relatively low PI of 22 ≦ PI ≦ 41 and PI are used for the positive electrode can 5, By defining the charge amount to 40% or more and 120% or less of the nominal capacity, it is possible to ensure a quality that can withstand practical use. If the charge amount is 70% or more and 120% or less, extremely excellent storage characteristics can be obtained. Then, it becomes possible to provide the LTO raw material less expensively by using highly purified low-PI stainless steel cathode can 5 without highly purifying the raw material of LTO.

By the way, regarding the mechanism that internal corrosion of the positive electrode can 2 can be prevented and the increase in internal resistance can be suppressed by storing in a proper charge state even if the chlorine concentration in LTO is 500 ppm, for example, electrolyte can be used by charging the battery 1 It can be considered that F (fluorine) liberated by the ionization of the LPF 6 which is the above generates a corrosion resistant film on the inner surface of the positive electrode can 5. And the charge amount which can suppress the corrosion reaction was 40 to 120%. With regard to the corrosion resistance effect, use of a 4V class positive electrode active material (such as LCO) is considered to be particularly effective because F in LiPF 6 is reliably released.

=== Other Examples etc. ===
Although a coin-shaped lithium secondary battery has been mentioned as a battery according to an embodiment of the present invention, a battery having a negative electrode including an LTO as a negative electrode active material in a positive electrode can is a battery having other shapes such as a cylindrical shape. May be

  In the battery according to the above-described embodiment, the usage mode is that after the assembly, the battery is charged at 40% or more and 120% or less of the nominal capacity, and the battery is stored in this charged state until the first use. It is assumed. That is, even if charge and discharge are performed in a quality inspection before shipment, the initial charge amount at the time the battery is shipped and first used for the user is maintained within the above numerical range. . Of course, in consideration of the characteristics of the battery of this embodiment, it is preferable that the user intentionally or by incorporating the battery into a dedicated electronic device to always use the battery at a charge amount of 40% or more and 120% or less.

  In the battery of the above embodiment, the chlorine concentration of LTO was adjusted by changing the mixing ratio of the raw material LTO and the non-chlorinated LTO, but even if the raw material LTO is washed with pure water until the desired chlorine concentration is achieved. Good. Of course, the chlorine concentration may be 500 ppm or less at the stage of the raw material LTO. In any case, the embodiment of the present invention effectively prevents corrosion inside the positive electrode can by adjusting the charge amount even if LTO containing much larger amount of chlorine than the conventional one is used for the negative electrode active material. It is possible to reduce the increase in internal resistance.

1 non-aqueous electrolyte secondary battery, 2 positive electrode, 3 negative electrode, 4 separator,
5 battery can (positive electrode can), 6 sealing gasket, 8 negative terminal plate

Claims (4)

  1. A battery can made of stainless steel, a positive electrode containing a positive electrode active material capable of absorbing and desorbing Li ions, a negative electrode containing lithium titanate as a negative electrode active material, and an electrolytic solution containing a lithium salt containing fluorine in the composition as a solute A non-aqueous electrolyte secondary battery comprising
    Chlorine contained in the lithium titanate is at least 108 ppm and at most 500 ppm,
    It is initially charged to 100% or more and 120% or less of the nominal capacity,
    Non-aqueous electrolyte secondary battery characterized in that.
  2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the battery can is made of stainless steel having a pitting index of 22 or more and 41 or less.
  3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material is 4V class.
  4. The method for producing a non-aqueous electrolyte secondary battery according to any one of claims 1 to 3 , comprising the step of washing the lithium titanate contained in the negative electrode with pure water. Method of manufacturing secondary battery
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Publication number Priority date Publication date Assignee Title
JPH0955203A (en) * 1995-08-15 1997-02-25 Fuji Photo Film Co Ltd Nonaqueous battery
JP4642960B2 (en) * 2000-01-26 2011-03-02 東邦チタニウム株式会社 Method of manufacturing a lithium titanate
JP2002008658A (en) * 2000-06-27 2002-01-11 Toyota Central Res & Dev Lab Inc Lithium titanium compound oxide for lithium secondary battery electrode active material, and its manufacturing method
JP3894778B2 (en) * 2000-11-20 2007-03-22 石原産業株式会社 Titanate and lithium battery prepared by using the same
US7811705B2 (en) * 2004-10-29 2010-10-12 Medtronic, Inc. Lithium-ion battery
JP4462022B2 (en) * 2004-12-02 2010-05-12 パナソニック株式会社 Flat type non-aqueous electrolyte battery
JP4997701B2 (en) * 2004-12-28 2012-08-08 大日本印刷株式会社 Method of manufacturing an electrode plate, and the electrode plate
JP2007294179A (en) * 2006-04-24 2007-11-08 Sony Corp Non-aqueous electrolyte secondary battery
HUE035407T2 (en) * 2008-11-04 2018-05-28 Huntsman P&A Finland Oy Process of preparing alkali metal titanates
JP2011113795A (en) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd Manufacturing method of lithium titanate for lithium secondary battery active material
JP2011111361A (en) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd Method for producing lithium titanate for lithium secondary battery active material
JP2011113796A (en) * 2009-11-26 2011-06-09 Nippon Chem Ind Co Ltd Active material for lithium secondary battery and lithium secondary battery using this
JP2011134690A (en) * 2009-12-25 2011-07-07 Air Products & Chemicals Inc Lithium ion secondary battery
JP5917049B2 (en) * 2011-08-26 2016-05-11 株式会社東芝 A nonaqueous electrolyte secondary battery and a manufacturing method thereof
JP2013058313A (en) * 2011-09-07 2013-03-28 Taiyo Yuden Co Ltd Production method of negative electrode material and lithium titanate compound for lithium secondary battery
JP2013211203A (en) * 2012-03-30 2013-10-10 Furukawa Battery Co Ltd:The Method of manufacturing negative electrode for nonaqueous electrolyte battery, and negative electrode for nonaqueous electrolyte battery, and manufacturing slurry

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