JP3570128B2 - Manufacturing method of non-aqueous electrolyte secondary battery - Google Patents

Manufacturing method of non-aqueous electrolyte secondary battery Download PDF

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JP3570128B2
JP3570128B2 JP32562696A JP32562696A JP3570128B2 JP 3570128 B2 JP3570128 B2 JP 3570128B2 JP 32562696 A JP32562696 A JP 32562696A JP 32562696 A JP32562696 A JP 32562696A JP 3570128 B2 JP3570128 B2 JP 3570128B2
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Prior art keywords
negative electrode
lithium
non
secondary battery
surface
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JPH10172540A (en
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寿和 安田
英司 遠藤
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ソニー株式会社
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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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a nonaqueous electrolyte secondary battery comprising a negative electrode made of a light metal and an alloy containing a light metal, a positive electrode capable of doping and undoping light metal ions, and a nonaqueous electrolyte, and in particular, The present invention relates to improvement of a negative electrode.
[0002]
[Prior art]
In recent years, with the miniaturization and weight reduction of various electronic devices such as VTRs and communication devices, the demand for secondary batteries with high energy density has increased as their power source, and light metals such as lithium, sodium, and aluminum have been used as negative electrode active materials. Batteries have been attracting attention as batteries having a high energy density.
[0003]
Primary batteries already using a light metal such as lithium as a negative electrode active material and using manganese dioxide (MnO 2 ), carbon fluoride ((CF) n ], thionyl chloride (SOCl 2 ), etc. as a positive electrode active material include calculators, It is often used as a backup battery for power supplies such as clocks and memories.
[0004]
On the other hand, a light metal such as lithium is used as a negative electrode active material, a metal chalcogenide or a metal oxide is used as a positive electrode active material, and a non-aqueous solvent such as propylene carbonate (PC) and 1,2-dimethoxyethane (DME) is used as an electrolyte. A secondary battery using a material obtained by dissolving an electrolyte salt such as LiClO 4 , LiBF 4 , and LiPF 6 has been widely studied.
[0005]
However, the above-mentioned secondary battery has not been put to practical use yet. This is because the above-described secondary battery has low charge / discharge efficiency and low cycle life (number of charge / discharge times). It is considered that this is largely due to the existence of a resistive film on the lithium surface and the lithium alloy surface which hinders the precipitation and dissolution reaction of lithium, and the deterioration of lithium due to the reaction between lithium and the electrolyte.
[0006]
That is, when the light metal that is the negative electrode active material is lithium, the negative electrode composed of lithium undergoes a lithium dissolution reaction during battery discharge and a lithium precipitation reaction during charge. However, on the surface of lithium, there is a resistive film that reacts with water and oxygen in the atmosphere to prevent the lithium precipitation / dissolution reaction before charging / discharging, and a part of it is already inactivated. ing. Further, it reacts with the electrolytic solution during lithium deposition, and the lithium surface is further inactivated. Therefore, as charge and discharge are repeated, lithium precipitation concentrates at a specific location on the negative electrode surface, forming needle-like dendrites, depositing in a spherical shape, and lithium detaching from the current collector. Occurs. In addition, battery characteristics deteriorate due to an increase in internal resistance due to inactivation / deterioration of the negative electrode active material. In addition, the grown dendritic metallic lithium penetrates through the separator or wraps around from the periphery of the separator to come into contact with the positive electrode, thereby causing a short circuit.
[0007]
Until now, in order to control the deterioration of the battery characteristics due to the denaturation of the negative electrode, attempts have been made to change the type of the solvent and to add an additive for preventing dendrite into the electrolyte.
[0008]
[Problems to be solved by the invention]
However, conventional electrolytes and additives have not been able to suppress the deterioration of lithium due to the reaction between lithium and the electrolyte, and have not solved the above-mentioned problems.
[0009]
Also, attempts have been made to suppress the reaction with an electrolytic solution by coating the surface of the negative electrode with a polymer compound having lithium ion conductivity. However, if the polymer compound film is formed directly on the negative electrode without removing the resistive film on the lithium surface, the electric resistance increases, and this electric resistance directly causes an increase in the internal resistance of the battery, resulting in a large decrease in battery characteristics. It is a factor that gives birth.
[0010]
The present invention has been proposed to solve the above-described problems, and suppresses the reaction between the electrolytic solution and the negative electrode active material, and the increase in the internal resistance of the battery, and the deposition and dissolution reaction of lithium. An object of the present invention is to provide a method for manufacturing a non-aqueous electrolyte secondary battery capable of improving reversibility and extending the life of a charge / discharge cycle.
[0011]
[Means for Solving the Problems]
The method for producing a non-aqueous electrolyte secondary battery according to the present invention includes a negative electrode made of any of lithium and an alloy containing lithium, a positive electrode capable of doping / dedoping lithium ions, and an electrolyte made of a lithium salt being non-aqueous. When manufacturing a non-aqueous electrolyte secondary battery comprising an electrolyte dissolved in a solvent, a carbon coating layer is formed by removing a resistance coating on the negative electrode surface by etching the negative electrode surface under an inert gas atmosphere. A carbon chemical layer is formed on the surface of the negative electrode by performing plasma chemical vapor deposition on the negative electrode in a gas phase capable of forming a film.
[0013]
In the surface treatment of the negative electrode, it is preferable that the negative electrode is etched by plasma and the carbon coating layer is formed by plasma chemical vapor deposition.
[0014]
For example, a resistive film having a high electric resistance value is formed on the surface of a negative electrode made of lithium or a lithium alloy by reacting with water or oxygen in the atmosphere. An etching process is performed on such a negative electrode to remove the resistive film. Then, a carbon coating layer having lithium ion conductivity is continuously formed on the negative electrode surface from which the resistance coating has been removed.
[0015]
As described above, when the resistive film is removed, even if a lithium ion conductive carbon film layer is subsequently formed, the electric resistance is suppressed to be lower than that when the film layer is directly formed without performing the etching process. Can be
[0016]
Here, the carbon coating layer having lithium ion conductivity functions as a so-called tunnel layer that allows lithium ions to pass between the negative electrode from which the resistance coating has been removed and the electrolytic solution. The carbon coating layer suppresses the reaction between the electrolytic solution and the negative electrode, suppresses an increase in the internal resistance of the battery, and improves the reversibility of the lithium deposition / dissolution reaction, thereby increasing the charge / discharge cycle. A longer life can be achieved.
[0017]
In addition, in this negative electrode, since the resistance film is removed, the electric resistance on the surface is kept low, so that good battery characteristics can be obtained.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the method for producing the nonaqueous electrolyte secondary battery according to the present invention will be described in detail. The method for manufacturing a nonaqueous electrolyte secondary battery according to the present invention relates to an improvement in a negative electrode made of a light metal and an alloy containing the light metal. That is, a non-aqueous electrolyte secondary comprising a negative electrode made of a light metal and an alloy containing a light metal, a positive electrode capable of doping and dedoping light metal ions, and an electrolyte obtained by dissolving an electrolyte made of a light metal salt in a non-aqueous solvent. In manufacturing a battery, first, the negative electrode surface is etched in an inert gas atmosphere to remove a resistive film on the negative electrode surface. Then, subsequently, a coating layer having light metal ion conductivity is formed on the negative electrode surface.
[0019]
Here, a method of manufacturing a nonaqueous electrolyte secondary battery using the present invention, for example, using lithium as a light metal and using lithium or a lithium alloy as a negative electrode will be described.
[0020]
First, a resistive film made of either lithium or a lithium alloy on the surface of a negative electrode is removed by etching in an inert gas atmosphere.
[0021]
The purpose of the etching treatment in an inert gas atmosphere is to remove a resistive film on the surface of the negative electrode that prevents the precipitation and dissolution reaction of lithium. When the resistive film is removed, even if a lithium ion conductive film layer is subsequently formed, the electric resistance can be suppressed to be lower than when a film layer is directly formed without performing an etching process.
[0022]
Note that the etching treatment is preferably performed in an inert gas atmosphere, preferably in plasma in a vacuum. It is important that the etching process is performed in a gas phase. If the etching process is performed in a liquid phase, lithium and a solvent come into contact with and react with each other from the side to be etched, and a new resistive film is generated.
[0023]
Further, in this manufacturing method, thereafter, a lithium ion conductive coating layer is continuously formed. This coating layer is continuously formed by vapor phase deposition in the same reactor where the etching treatment was performed. By forming a film continuously with the etching process, a film layer having lithium ion conductivity can be formed without forming a new resistance film on the surface of the negative electrode. Even if the etching process is performed in a gas phase, if it leaks into the atmosphere, it reacts with components such as water, nitrogen, and oxygen in the air to form a new resistance film, and thus needs to be continuously performed as described above. There is.
[0024]
Further, the vapor phase deposition of the film layer having lithium ion conductivity may be performed by a plasma chemical vapor deposition method (hereinafter, referred to as a plasma CVD method) in order to form a uniform thin film.
[0025]
The coating layer having the lithium ion conductivity, 10 -5 S / cm has the following electronic conductivity, inorganic compounds and a low resistance made of an organic or compounds having ion conductivity of more than 10 -5 S / cm A thin film may be used, and carbon or the like can be used. Specifically, it is preferable to introduce an ethylene gas or the like into the reactor and form a coating layer (carbon film) by a plasma CVD method.
[0026]
The film layer having lithium ion conductivity formed in this manner acts as a tunnel layer, which allows lithium ions to pass between the negative electrode from which the resistance film has been removed and the electrolytic solution. The coating layer suppresses the reaction between the electrolyte and the negative electrode, suppresses an increase in the internal resistance of the battery, and improves the reversibility of the lithium deposition / dissolution reaction. This prevents both electrodes from being short-circuited due to the generation of dendrites from the negative electrode, and extends the life of the charge / discharge cycle. In addition, in this negative electrode, since the resistance film is removed, the electric resistance on the surface is kept low, so that good battery characteristics can be obtained.
[0027]
As described above, a negative electrode obtained by the above-described production method and a positive electrode capable of doping / dedoping lithium are laminated via a separator, and a non-aqueous electrolyte obtained by dissolving an electrolyte composed of a lithium salt in a solvent is injected. Thereby, a non-aqueous electrolyte secondary battery can be obtained.
[0028]
In addition, as the positive electrode active material used for the positive electrode, a metal oxide, a metal sulfide, or a specific polymer can be used as the positive electrode active material, depending on the type of the intended battery. For example, lithium-free metal sulfides or metal oxides such as TiS 2 , MoS 2 , NbSe 2 , V 2 O 5 , or Li x MO 2 (where M represents one or more kinds of transition metals and usually 0 0.05 ≦ x ≦ 1.10.).
[0029]
In particular, the lithium composite oxide becomes a positive electrode active material excellent in energy density, and can be used with an appropriate negative electrode and an appropriate electrolyte to produce a battery that generates a high voltage. Specific examples of the lithium composite oxide Li x MO 2 include LiCoO 2 , LiNiO 2 , and Li x Ni y Co 1-y O 2 (where x and y vary depending on the charge / discharge state of the battery, and are generally 0 < x <1, 0.7 <y <1.02). As the transition metal M forming the lithium composite oxide, Co, Ni, Mn and the like are preferable. This lithium composite oxide is obtained by crushing and mixing lithium carbonate, nitrate, oxide or hydroxide and carbonate, nitrate, oxide or hydroxide such as cobalt, manganese or nickel according to a predetermined composition. Then, it can be obtained by firing in a temperature range of 600 to 1000 ° C. in an oxygen atmosphere.
[0030]
As the above-mentioned electrolytic solution, a solution obtained by dissolving a lithium salt as an electrolyte in a non-aqueous solvent is used. As the non-aqueous solvent, a mixed solvent of at least one selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and the like with a solvent selected from propylene carbonate or ethylene carbonate is preferably used. In this case, the mixing ratio of the solvent selected from propylene carbonate or ethylene carbonate is desirably 0.3 to 0.6 in terms of molar ratio from the viewpoint of the degree of dissociation of the electrolyte and the conductivity. As the lithium salt, conventionally known ones such as LiPF 6 , LiClO 4 , LiAsF 6 , and LiBF 4 can be used.
[0031]
Furthermore, although a non-aqueous electrolyte secondary battery using lithium or a lithium alloy for the negative electrode has been described above, the negative electrode active material is not limited to lithium and lithium alloys, and light metals such as sodium, magnesium, and calcium, An alloy containing them may be used, and the same effect as in the case of lithium can be obtained.
[0032]
Further, other configurations of the nonaqueous electrolyte secondary battery, for example, a separator, a battery can, and the like can be the same as a conventional nonaqueous electrolyte secondary battery, and are not particularly limited, and are wound. , A laminated type, or various shapes such as a cylindrical type, a square type, a coin type, and a button type.
[0033]
【Example】
Hereinafter, preferred embodiments of the present invention will be described based on experimental results.
[0034]
Example 1
First, as shown in FIG. 1, a lithium metal electrode 2 having a thickness of 1.0 mm and a diameter of 15 mm was closely adhered to a positive electrode can 1 in a dry air atmosphere having a dew point of −40 ° C. or lower by a conventional method. A lithium metal electrode 4 having a thickness of 1.0 mm and a diameter of 15 mm was adhered to 3.
[0035]
Then, a parallel plate electrode made of stainless steel was installed facing the inside of a reactor consisting of a glass bell jar and a stainless steel flange, and the above-mentioned lithium metal electrode 2 and lithium metal electrode 4 were installed on the cathode electrode. Next, with the argon gas flowing through the reactor at a flow rate of 10 ml / min, a DC power having an acceleration voltage of 0.7 kV and a current value of 7 mA was applied while maintaining the pressure in the reactor at 0.08 Torr by evacuation. And a plasma etching process for 5 minutes. As a result, the resistive films on the surfaces of the lithium metal electrodes 2 and 4 were removed.
[0036]
Next, after exhausting all of the argon gas in the reactor, while maintaining the pressure in the reaction vessel at 0.08 Torr by exhausting, while accelerating the flow of ethylene gas at a flow rate of 10 ml / min without leaking the system, acceleration was performed. A DC power of a voltage of 1.2 kV and a current value of 7 mA was applied, and gas phase deposition was performed for 1 minute by a plasma CVD method. Thus, a carbon film was formed on the surfaces of the lithium metal electrodes 2 and 4.
[0037]
After the resistive films on the surfaces of the lithium metal electrodes 2 and 4 were thus removed by etching, a carbon film having lithium ion conductivity was continuously formed on the surfaces of the lithium metal electrodes 2 and 4 by vapor deposition. .
[0038]
Then, as shown in FIG. 1, a positive electrode can 1 and a negative electrode can 3 having the above-mentioned surface-treated lithium metal electrodes 2 and 4 in close contact with each other are laminated with an electrically insulating separator 5 interposed therebetween. The solution 6 was injected, swaged with a gasket 7 and sealed. As the electrolyte, propylene carbonate and ethyl methyl carbonate were mixed at a ratio of 4: 6, and a mixed solvent of LiPF 6 at a ratio of 1 mol / l was used.
[0039]
Thus, a coin cell A for battery characteristic evaluation having a diameter of 20 mm and a height of 2.5 mm was obtained.
[0040]
Comparative Example 1
No carbon film was formed on the lithium metal electrode 2 and the lithium metal electrode 4. Then, the configuration was such that the lithium metal electrodes 2 and 4 were in direct contact with the electrolyte. Except for this, in the same manner as in Example 1, a coin cell B for battery characteristic evaluation having a diameter of 20 mm and a height of 2.5 mm was obtained.
[0041]
The handling of the lithium metal electrode was performed in a dry air atmosphere having a dew point of −40 ° C. or less by a conventional method. This is a standard sample for evaluating a lithium metal electrode.
[0042]
Evaluation of battery characteristics Regarding the coin cell A of Example 1 and the coin cell B of Comparative example 1 produced as described above, the lithium metal electrode 1 was tested at a current density of 0.25 mA / cm 2 with respect to the electrode area. Dissolution of lithium and deposition of lithium on the lithium metal electrode 3 were performed for 1 hour. Subsequently, the dissolution of the lithium metal electrode 3 and the deposition of the lithium metal electrode 1 were performed for 1 hour, and thereafter, the change with time of the cell impedance was measured. The result is shown in FIG. Further, a change with time in the cell impedance after 17 days had elapsed was measured. The result is shown in FIG.
[0043]
Note that the cell impedance is indicated by the diameter of the arc (z ′ 2 + z ″ 2 ) 0.5 in the graph in the figure. Further, here, for the evaluation of the negative electrode of the battery, a battery configuration using lithium for both the positive electrode and the negative electrode of the coin cells A and B was adopted. The deposition and dissolution of the lithium metal electrodes 2 and 4 of the coin cells A and B correspond to charging and discharging of the negative electrode in an actual battery.
[0044]
From the results of FIGS. 2 and 3, it can be seen that the change over time in the cell impedance of the coin cell A of Example 1 subjected to the plasma CVD treatment and the coin cell B of the comparative example 1 not subjected to the plasma CVD treatment tend to increase. I understand. However, the absolute value of the impedance in the coin cell A of Example 1 is smaller than that of the coin cell B of Comparative Example 1, and the increase in the impedance of the coin cell A of Example 1 is suppressed as compared with the coin cell B of Comparative Example 1. You can see that it is done. From the above results, it is understood that the cell impedance can be reduced by removing the resistive film on the surface of the lithium metal metal and continuously forming the carbon film.
[0045]
Similarly, for the coin cell A of Example 1 and the coin cell B of Comparative Example 1, at a current density of 0.25 mA / cm 2 with respect to the electrode area, the dissolution of lithium in the lithium metal electrode 1 and the lithium The precipitation was performed for 12 hours. Subsequently, dissolution of the lithium metal electrode 3 and deposition of the lithium metal electrode 1 were performed for 12 hours. Then, a pause time of 15 minutes was provided between the deposition and dissolution reactions, and the above deposition and dissolution cycle was repeated many times. Then, the change over time in the cell impedance was measured during the pause time. The result is shown in FIG.
[0046]
From the results of FIG. 4, it is understood that the cycle change of the cell impedance in the coin cell A of the example 1 subjected to the plasma CVD processing is smaller than that of the coin cell B of the comparative example 1 not subjected to the plasma CVD processing. From the above results, it is understood that the cycle change of the cell impedance can be reduced by removing the resistive film on the surface of the lithium metal electrode and continuously forming the carbon film.
[0047]
In this example, a mixture of propylene carbonate and ethyl methyl carbonate in which LiPF 6 was mixed at a ratio of 1 mol / l was used as the electrolytic solution. However, the material and composition are particularly limited. Instead, any conventionally known ones can be used, and it goes without saying that the same effect can be obtained. Further, in this example, the experiment was performed with the current density set to 0.25 mA / cm 2. However, it is not necessary to particularly limit the current density condition, and the same effect can be obtained by changing the current density. Needless to say.
[0048]
【The invention's effect】
As is clear from the above description, according to the present invention, by removing the resistive coating layer on the negative electrode surface and providing a carbon coating layer on the negative electrode surface, the reaction between the electrolytic solution and the negative electrode is suppressed, and the battery It is possible to suppress an increase in the internal resistance and improve the reversibility of the lithium precipitation / dissolution reaction. Therefore, according to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery having a long charge / discharge cycle life.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a coin cell manufactured in the present embodiment.
FIG. 2 is a characteristic diagram showing a change over time in cell impedance of a coin cell manufactured in this example.
FIG. 3 is a characteristic diagram showing a change over time of the cell impedance of the coin cell manufactured in this example.
FIG. 4 is a characteristic diagram showing a cycle change of the cell impedance of the coin cell manufactured in this example.
[Explanation of symbols]
1 positive electrode can, 2 lithium metal electrode, 3 negative electrode can, 4 lithium metal electrode, 5 separator, 6 electrolyte, 7 gasket

Claims (4)

  1. A non-aqueous electrolyte comprising a negative electrode made of either lithium or an alloy containing lithium , a positive electrode capable of doping / dedoping lithium ions, and an electrolyte obtained by dissolving an electrolyte made of a lithium salt in a non-aqueous solvent. When manufacturing secondary batteries,
    After removing the resistive film on the surface of the negative electrode by etching the surface of the negative electrode in an inert gas atmosphere , subjecting the negative electrode to plasma chemical vapor deposition in a gas phase capable of forming a carbon coating layer Forming the carbon coating layer on the surface of the negative electrode according to the method described above .
  2. 2. The method for producing a non-aqueous electrolyte secondary battery according to claim 1, wherein the carbon film layer is formed on the surface of the negative electrode in the gas phase composed of ethylene gas .
  3. 2. The method for manufacturing a nonaqueous electrolyte secondary battery according to claim 1, wherein the etching of the negative electrode is performed by plasma, and the formation of the carbon coating layer is performed by plasma enhanced chemical vapor deposition.
  4. 2. The method for producing a non-aqueous electrolyte secondary battery according to claim 1, wherein the etching of the negative electrode is performed by plasma, and the formation of the carbon coating layer is performed continuously by plasma enhanced chemical vapor deposition.
JP32562696A 1996-12-05 1996-12-05 Manufacturing method of non-aqueous electrolyte secondary battery Expired - Fee Related JP3570128B2 (en)

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US8062793B2 (en) 2004-11-26 2011-11-22 Panasonic Corporation Lithium primary battery and manufacturing method therefor
JP2006344808A (en) * 2005-06-09 2006-12-21 Nec Tokin Corp Electric double layer capacitor
JP5711615B2 (en) * 2010-06-14 2015-05-07 株式会社半導体エネルギー研究所 Method for manufacturing power storage device

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