JP2022093903A - Gel electrolyte for lithium secondary battery, lithium secondary battery, and method for manufacturing lithium secondary battery - Google Patents

Abstract

To provide a gel electrolyte for a lithium secondary battery, having both merits of a polymer-solid electrolyte and a high-concentration electrolytic solution.SOLUTION: A gel electrolyte for a lithium secondary battery contains a polymer compound including O atoms in a main chain, a lithium salt, a nonaqueous solvent having reduction stability, and a flame retardant having oxidation stability. In the gel electrolyte for a lithium secondary battery, the molar ratio (O/Li) between the molar concentration (O) of oxygen in repeating units of the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1-5, the ratio [C/(A+B)] of the mass (C) of the nonaqueous solvent to the total mass (A+B) of the polymer compound and the lithium salt is 20-40 in mass%, and the ratio [D/(A+B)] of the mass (D) of the flame retardant to the total mass (A+B) of the polymer compound and the lithium salt is 10-30 in mass%.SELECTED DRAWING: Figure 1

Description

The present invention relates to a gel electrolyte for a lithium secondary battery, a lithium secondary battery, and a method for manufacturing a lithium secondary battery.

In recent years, there has been an urgent need to reduce carbon dioxide emissions in order to protect the environment. In the automobile industry, expectations are rising for the reduction of carbon dioxide emissions through the introduction of electric vehicles (EVs) and hybrid electric vehicles (HEVs), and the development of secondary batteries for motor drive, which holds the key to their practical application, is enthusiastic. It is done. As the secondary battery, a laminated lithium ion secondary battery capable of achieving high energy density and high output density is attracting attention.

Currently, most of the lithium secondary batteries commercially available for small electronic and electrical equipment use a flammable organic solvent as an electrolytic solution. The organic solvent electrolytic solution has a risk of liquid leakage and associated ignition. The use of such a lithium secondary battery in a large-scale application such as an electric vehicle may increase the risk. Therefore, there is a need for safer electrolyte materials. As one of the solutions, a solid electrolyte that is nonflammable and has high thermal stability is attracting attention. The solid electrolyte is classified into a polymer type, a sulfide type, a LiSION type, a garnet type and the like. Sulfide-based, LiSICON-type and garnet-type solid electrolytes have high lithium ion conductivity at room temperature. However, the sulfide system is unstable in the atmosphere and easily emits toxic gas. LiSION type and Garnet type solid electrolytes have a contact problem with electrodes.

The study of polymer-solid electrolytes, which can conduct ions at high speed and selectively in the solid state, originated in the report of Wright et al. In 1973. Patent Document 1 discloses that polyethylene oxide (PEO- [CH ₂ CH ₂ O] _n- ) forms a complex with an alkali metal salt in a solid state and exhibits ionic conductivity at room temperature. Such Patent Document 1 suggests for the first time the possibility of an all-solid-state polymer battery using a polymer-solid electrolyte, and since then, research on a wide range of polymer electrolytes has been promoted to this day.

By the way, the following properties are required for the polymer-solid electrolyte. First, it has high ionic conductivity and low temperature dependence comparable to non-aqueous solvent electrolyte solutions. In order to obtain high ionic conductivity, it is necessary that the charge carrier degree (ionic degree) is high and the carrier moving speed in the solid is high. The carrier concentration is determined by the solubility of the salt (eg, lithium salt) in the polymer and the ease of ion dissociation. On the other hand, the movement of ions occurs in conjunction with the thermal motion of the amorphous part of the polymer complex. Therefore, in order to obtain high ion mobility, it is desirable that the polymer structure is easy to thermally move. Solvent-free, completely solid PEO-based polymers that have been studied so far have a problem that they have extremely low ionic conductivity at room temperature (~ ^10-8 S · cm ^-1 ) and can hardly operate at room temperature. .. Second, the polymer-solid electrolyte membrane is extremely difficult to manufacture and handle. The polymer-solid electrolyte membrane has a high viscosity, and it is almost difficult to inject liquid when manufacturing a power generation element in which a plurality of sheets are laminated. In addition, a method of applying a polymer-solid electrolyte to the surfaces of the positive electrode or the negative electrode facing each other in advance has also been proposed. However, the operation of laminating using a laminating machine on the current lithium ion secondary battery production line is difficult because the polymer-solid electrolyte has high viscosity. In addition, the polymer-solid electrolyte membrane contains a large amount of lithium salts and therefore has very high water absorption, so it must be handled in a dry room. This will require major changes to the current lithium-ion production line.

On the other hand, a gel-type polymer-electrolyte in which a flammable non-aqueous solvent is added as a plasticizer to the electrolyte to enhance ionic conductivity is known. By adding a plasticizer, the interaction between the chains of the polymer PEO or between the PEO and the lithium ion can be weakened, crystallization can be suppressed, and the segment movement of the PEO can be activated. For example, there is an example in which a non-aqueous solvent for carbonic acid esters such as ethylene carbonate, propylene carbonate, diethyl carbonate, and dimethyl carbonate is used as a plasticizer. Further, in Non-Patent Document 1, a plasticizer having a high dielectric constant is effective for promoting the dissociation of the lithium salt, and a non-aqueous solvent such as a propylene carbonate having a high dielectric constant is used as the plasticizer. It is disclosed that there is.

However, excessive addition may reduce the strength of the electrolyte membrane and increase the risk of liquid leakage and ignition.

Further, in recent years, a battery using a so-called gel electrolyte, in which the ionic conductivity is improved by using a gel in which a polymer film is swollen with an electrolyte solution, has attracted attention. For example, in Patent Document 2, as a plasticizer for a gel electrolyte used in a lithium ion battery, an electrolytic solution in which a lithium salt such as LiPF ₆ is dissolved in a carbonate ester-based non-aqueous solvent such as propylene carbonate is used. It is disclosed that a relatively high gel electrolyte can be obtained.

However, since the gel electrolyte uses a large amount of the electrolytic solution like the gel-type polymer electrolyte, there is a risk of ignition of the electrolytic solution due to liquid leakage to the outside of the battery. For this reason, improvements were still required in terms of safety.

Non-Patent Document 2 describes "high-speed reaction", "high decomposition resistance", "high lithium transport rate", etc., which are "concentrated liquids" containing lithium ions with a concentration four times higher than that of conventional electrolytes and are not found in existing electrolytes. High-concentration electrolytes with new functions are disclosed. Generally, the concentration of the organic electrolyte solution is selected to be around 1 mol / L, which maximizes the ionic conductivity. The intention is to dramatically change electrochemical stability by eliminating free solvent molecules.

However, since Non-Patent Reference 2 uses a high-concentration electrolytic solution having a very high viscosity, the fluidity is lowered, and it becomes difficult to apply the liquid injection method of the current lithium ion secondary battery production line, which makes it difficult to handle. Become.

US Pat. No. 4,303,748

Japanese Unexamined Patent Publication No. 11-102613

Z. Xue, D. He, X. Xie, Poly (ethylene oxide) －based electrolytes for lithium－ion batteries, J.Mater. Chem. A. 3 (2015) 19218–19253.

Y. Yamada, J. Wang, S. Ko, E. Watanabe, A. Yamada, Advances and issues in developing salt-concentrated battery electrolytes, Nat. Energy. (2019).

The present invention provides a gel electrolyte for a lithium secondary battery, which has the advantages of a polymer solid electrolyte and a high-concentration electrolytic solution, and a method for manufacturing a lithium secondary battery and a lithium secondary battery containing the same.

The present invention is a gel electrolyte for a lithium secondary battery containing a polymer compound containing an O atom in the main chain, a lithium salt, a non-aqueous solvent having reduction stability, and a flame retardant having oxidative stability. The molar ratio (O / Li) of the molar concentration (O) of oxygen in the repeating unit of the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1 to 5. The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%. The ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%.

According to the present invention, free non-aqueous solvent molecules present in the gel electrolyte disappear, and the polymer compound and the non-aqueous solvent having reduction stability have a special complex structure coordinated with lithium ions. Further, by blending a flame retardant having oxidative stability, it is possible to provide a gel electrolyte for a lithium secondary battery that has high electrochemical stability, does not leak, and does not burn.

Further, by incorporating the gel electrolyte, it is possible to provide a lithium secondary battery having high capacity, high performance and high safety characteristics, and a method for manufacturing the same.

FIG. 1 is a cross-sectional view showing an example of a coin-type lithium ion secondary battery according to an embodiment. FIG. 2 is a diagram showing a charge / discharge curve at 0.1 C in the coin-type lithium ion secondary batteries of Example 4 and Comparative Example 4.

Hereinafter, a method for manufacturing a gel electrolyte for a lithium secondary battery, a lithium secondary battery, and a lithium secondary battery according to an embodiment of the present invention will be described in detail.

<First Embodiment>
The gel electrolyte for a lithium secondary battery according to the first embodiment contains a polymer compound containing an O atom in the backbone, a lithium salt, a non-aqueous solvent having reduction stability, and a flame retardant having oxidation stability. The molar ratio (O / Li) of the molar concentration (O) of oxygen in the repeating unit of the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1 to 5. The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%. The ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%.

Examples of the polymer compound containing an O atom in the main chain include a polymer compound having an ethylene oxide structure. Specific examples of such polymer compounds include polyethylene oxide (PEO), polyethylene glycol dimethyl ester (PEGDME), polyethylene glycol (PEG), polyethylene carbonnet (PEC) and the like. .. The weight average molecular weight of the polymer compound is preferably 1,000 to 5,000,000.

The lithium salt is not particularly limited, but is, for example, LiClO ₄ , LiBOB, LiBF ₂ (C ₂ O ₄ ), LiBF ₄ , LiPF ₆ , LiAlCl ₄ , LiSbF ₆ , LiSCN, LiCF ₃ SO ₃ , LiAsF ₆ , LiB ₁₀ Cl ₁₀ . Lithium lower aliphatic carboxylate, LiCl, LiBr, LiI, lithium chloroboran, lithium tetraphenylborate, imide compound [(eg Li (FSO ₂ ) ₂ N, LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F) ₅ SO ₂ ) ₂ )] and the like can be used. These may be used alone or in combination of two or more.

The concentration of the lithium salt in the gel electrolyte can be selected as high as long as the precipitation of the lithium salt does not occur. The molar ratio of the molar concentration [O] of oxygen derived from the ether bond in the polymer compound to the molar concentration [Li] of the lithium ion of the lithium salt: [O] / [Li] is 1 to 5. If the molar ratio is less than 1, the lithium salt may not be completely dissolved and may partially precipitate. On the other hand, if the molar ratio exceeds 5, there is a risk that free non-aqueous solvent molecules (not coordinated with lithium ions) will increase.

The gel electrolyte of the embodiment preferably has appropriate fluidity in order to impregnate the separator of the lithium secondary battery described later. Therefore, the gel electrolyte of the embodiment contains a non-aqueous solvent in addition to the polymer compound and the lithium salt. The non-aqueous solvent preferably has a low viscosity and a low boiling point. This is because a certain amount of fluidity can be imparted by adding a minimum amount of non-aqueous solvent, and the lithium secondary battery can be easily volatilized by the heating step of the method for manufacturing a lithium secondary battery described later. The viscosity of the non-aqueous solvent at 25 ° C. is preferably 1 mPa · S or less, and more preferably 0.5 mPa · S or less. The boiling point is preferably 100 ° C. or lower. Further, a non-aqueous solvent having high reduction stability, particularly stable to lithium metal, is preferable. Examples of such a non-aqueous solvent having low viscosity, low boiling point and high reduction stability include tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,2-dimethoxyethane (DME) and dioxolane (DOL). Ethels are preferable. In addition to these, it is also possible to use a mixed solvent containing other non-aqueous solvents.

The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%. When the ratio is less than 20% by mass, when the separator of the lithium secondary battery is impregnated with the gel electrolyte of the embodiment, the interface resistance with the active material of the positive electrode adjacent to the separator is high, for example, at room temperature. The conductivity of lithium ions is reduced. If the ratio exceeds 40% by mass, not only the performance improvement of the lithium secondary battery is saturated, but also the possibility of leakage of the non-aqueous solvent when the secondary battery bursts increases.

The non-aqueous solvent having reduction stability may be easily oxidized by the cutoff voltage at the time of actual charge / discharge. For example, the ether-based non-aqueous solvent may be oxidized if it becomes 4 V (Li / Li ⁺ ) or more. Therefore, a flame retardant having oxidative stability is added to the present invention in the first embodiment. The purpose of adding the flame retardant is not only to make the gel electrolyte hard to burn, but also to suppress the oxidation of the gel electrolyte under high potential. The flame retardant contains at least one selected from, for example, phosphoric acid esters and sulfone compounds. Specific flame retardants are trimethyl phosphate (TMP), triethyl phosphate (TEP), 2,2,2-trifluoroethyl phosphate (TFP), triphenyl phosphate (TPP). ) And tritryl phosphate (TTP), tris (2,2,2-trifluoroethyl) phosphate (TFEP), sulfolane (SL) and the like.

The ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%. If this ratio is less than 10% by mass, the gel electrolyte cannot be sufficiently extinguished by the flame-retardant agent, and if the separator of the lithium secondary battery is impregnated with the gel electrolyte, the secondary battery may burn when ignited. There is. If the ratio exceeds 30% by mass, the battery performance may be adversely affected depending on the type of flame retardant added.

The boiling points of the non-aqueous solvent and the flame-retardant agent preferably satisfy the relationship of (a2-a1) ≧ 100 ° C., where the boiling point of the non-aqueous solvent is a1 and the boiling point of the flame-retardant agent is a2. That is, it is preferable that the boiling point of the non-aqueous solvent is 100 ° C. or higher lower than the boiling point of the flame retardant.

According to the first embodiment, the molar ratio (O / Li) of the molar concentration (O) of oxygen in the repeating unit of the polymer compound to the molar concentration (Li) of lithium ions in the lithium salt, and high. By specifying the ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the molecular compound and the lithium salt, the polymer compound not only coordinates with lithium ions, but also. Non-aqueous solvents can also form special complex structures coordinated to lithium ions. As a result, it is possible to obtain a gel electrolyte for a lithium secondary battery which has high reduction stability, lithium ion conductivity and good fluidity, does not require the formation of an electrolyte membrane, and is easy to handle.
Further, when blending the flame-retardant agent having oxidation stability, the gel is specified by specifying the ratio [D / (A + B)] of the flame-retardant agent mass (D) to the total mass (A + B) of the polymer compound and the lithium salt. Obtains a safe gel electrolyte for lithium secondary batteries with high retention of non-aqueous solvent, excellent liquid leakage property, high redox stability, refractory volatility and flame retardancy without impairing the original characteristics of the electrolyte. be able to.

Next, a second embodiment will be described.
<Second embodiment>
The lithium secondary battery according to the second embodiment includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. The gel electrolyte for a lithium secondary battery described in the first embodiment is impregnated into a positive electrode, a negative electrode and a separator.

The shape of the lithium ion secondary battery according to the second embodiment is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a square type, and a flat type.

Hereinafter, the structure of the lithium ion secondary battery according to the second embodiment will be described with reference to FIG. 1, using a coin-type lithium ion secondary battery as an example.
The coin-type lithium ion secondary battery 1 includes a positive electrode 2, a negative electrode 3, and a separator 4 arranged between the positive electrode 2 and the negative electrode 3. The positive electrode 2, the negative electrode 3, and the separator 4 are housed between the first external terminal 5 located on the lower side and the second external terminal 6 located on the upper side. The contact portion between the first external terminal 5 and the second external terminal 6 is insulated by a gasket 7.

The positive electrode 2 is composed of a positive electrode current collector 21 located on the inner surface of the first external terminal 5 and connected to the positive electrode current collector 21, and a positive electrode layer 22 provided on a surface of the positive electrode current collector 21 facing the separator 4. It is configured. The negative electrode 3 is composed of a negative electrode current collector 31 located on the inner surface of the second external terminal 6 and connected to the negative electrode current collector 31, and metallic lithium provided on the surface of the negative electrode current collector 31 facing the separator 4. It is composed of a negative electrode layer 32. The separator 4 is impregnated with the gel electrolyte. The second external terminal 6 is inserted into the first external terminal 5 with its lower end and both side surfaces wrapped in the gasket 7, and the open end of the lower first external terminal 5 is on the gasket 7 side. The second external terminal 6 is curved and crimped and fixed to the first external terminal 5, and the contact portions of the first external terminal 5 and the second external terminal 6 are insulated by the gasket 7.

The positive electrode, negative electrode and separator, which are power generation elements, will be described in detail below.
(1) Positive electrode As the positive electrode current collector constituting the positive electrode, for example, an aluminum foil or an aluminum alloy foil can be used.

The positive electrode layer constituting the positive electrode contains a positive electrode active material, a conductive material and a binder.
As the positive electrode active material, a known positive electrode active material for a lithium ion secondary battery can be used, for example, lithium cobalt oxide (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium nickel oxide (LiNiO ₂ ) and the like. Lithium-containing transition metal oxides containing one or more of the transition metals, transition metal sulfides, metal oxides, lithium iron oxide (LiFePO ₄ ), lithium iron pyrophosphate (Li ₂ FeP ₂ O ₇ ), and the like. Examples thereof include lithium-containing polyanionic compounds and sulfur-based compounds (Li _2S ) containing the above transition metals.

As the conductive material, for example, a carbon material, a conductive fiber such as a metal fiber, a metal powder such as copper, silver, nickel and aluminum, and an organic conductive material such as a polyphenylene derivative can be used. As the carbon material, graphite, soft carbon, hard carbon, carbon black, Ketjen black, acetylene black, graphite, activated carbon, carbon nanotube, carbon fiber, etc. can be used. .. Further, a mesoporous carbon obtained by firing a synthetic resin containing an aromatic ring, petroleum pitch, or the like can also be used.

As the binder, for example, a fluororesin such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), or ethylene tetrafluoroethylene (ETFE), or polyethylene or polypropylene can be preferably used.

(2) Negative electrode As the negative electrode current collector constituting the negative electrode, for example, a rod-shaped body, a plate-shaped body, a foil-shaped body, a mesh-like body or the like mainly composed of copper, nickel, aluminum, stainless steel or the like can be used. ..

The negative electrode layer constituting the negative electrode may contain only the negative electrode active material, or may contain a conductive material and a binder in addition to the negative electrode active material. For example, when the negative electrode active material is in the form of a foil, the negative electrode can be formed only by the negative electrode active material. On the other hand, when the negative electrode active material is in the form of powder, the negative electrode layer can be formed of the negative electrode active material, the conductive material and the binder. As a method for forming the negative electrode using the powdered negative electrode active material, a doctor-blade method, a molding method by a crimping press, or the like can be used.

The foil-shaped negative electrode layer can be formed from, for example, a lithium metal or an alloy containing a lithium element. Examples of the alloy having a lithium element include a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.

When the negative electrode active material is in the form of powder, a known negative electrode active material for a lithium ion secondary battery can be used. For example, carbonaceous materials such as natural graphite (graphite), highly oriented pyrolytic graphite (HOPG), and amorphous carbon can be mentioned. Examples of other negative electrode active materials include lithium oxides, sulfides and nitrides. Specific examples of the lithium oxide include lithium titanate (Li ₄ Ti ₅ O ₁₂ and the like) and the like. Examples of the lithium nitride include lithium cobalt nitride, lithium iron nitride, lithium manganese nitride and the like. These negative electrode active materials can be used alone or as a mixture of two or more kinds.

As the conductive material and the binder, the same ones as those of the above-mentioned positive electrode can be used.

(3) Separator The separator is a porous sheet or non-woven fabric made of a resin such as polyethylene (PE), polypropylene (PP), polyimide (PI), polyester, cellulose, polyamide, or glass fiber. A porous insulating material such as a non-woven fabric can be used.

In the second embodiment, the gel electrolyte for a lithium secondary battery described in the first embodiment is impregnated into the positive electrode, the negative electrode and the separator. When the negative electrode layer constituting the negative electrode contains a negative electrode active material, a conductive material and a binder, the gel electrolyte is impregnated in the negative electrode layer, but when the negative electrode is made of the foil-shaped negative electrode active material described above, the above. The gel electrolyte exists on the surface of the foil-shaped negative electrode active material, that is, at the interface between the foil-shaped negative electrode active material and the separator.

Although the electrolytic solution and the secondary battery of the present invention are suitable for use as a secondary battery, it does not exclude the use as a primary battery.

According to the second embodiment, the positive electrode has high lithium ion conductivity and good fluidity, and the gel electrolyte is impregnated into the positive electrode, the negative electrode, and the separator arranged between the positive electrode and the negative electrode. High energy and high output can be achieved because the resistance at the interface between the and the separator and between the negative electrode and the separator can be reduced, and the lithium ion conductivity of the positive electrode, the negative electrode and the separator can be improved. It is possible to realize a lithium secondary battery that has.

In addition, the gel electrolyte impregnated in the positive electrode, the negative electrode, and the separator arranged between the positive electrode and the negative electrode has high non-aqueous solvent retention, excellent liquid leakage, and high volatility and flame retardancy. Therefore, it is possible to realize a highly safe lithium secondary battery that is hard to burn.

Next, the method for manufacturing the lithium secondary battery according to the third embodiment will be described in detail.
<Third embodiment>
First, the main chain contains a polymer compound containing an O atom, a lithium salt, a non-aqueous solvent and a flame retardant, and the non-aqueous solvent is the sum of the polymer compound, the lithium salt, the non-aqueous solvent and the flame retardant. A gel electrolytic solution containing 70 to 80% by mass based on the amount is prepared.

Since the gel electrolyte has high fluidity by adjusting the blending amount of the non-aqueous solvent in the gel electrolyte to 70 to 80% by mass, the current manufacturing equipment for lithium secondary batteries using the non-aqueous electrolyte has been changed. It can be used without adding.

Next, a power generation element having a positive electrode, a negative electrode, and a separator arranged between the positive electrode and the negative electrode is manufactured. The positive electrode, the negative electrode and the separator have the structure described in the second embodiment.

Then, the gel electrolytic solution is injected into the power generation element. Usually, the power generation element is housed in an exterior material in which a cylindrical or square metal can or two shallow cans are insulated and fixed to each other with a gasket, and a gel electrolytic solution is injected into the exterior material.

Leave after injecting the gel electrolyte. By this step, the gel electrolytic solution diffuses into the positive electrode, the negative electrode and the separator.

Next, the power generation element is heated to volatilize a part of the non-aqueous solvent in the gel electrolyte. By this step, the positive electrode, the negative electrode and the separator of the power generation element are impregnated with the gel electrolyte described in the first embodiment. In this step, as described in the first embodiment, the boiling points of the non-aqueous solvent and the flame-retardant agent in the gel electrolyte are (a2-a1), where the boiling point of the non-aqueous solvent is a1 and the boiling point of the flame-retardant agent is a2. ) ≧ 100 ° C. is preferable. That is, it is preferable that the boiling point of the non-aqueous solvent is 100 ° C. or higher lower than the boiling point of the flame retardant. By satisfying such a relationship, it becomes possible to preferentially volatilize the non-aqueous solvent in the heating step without volatilizing the flame retardant.

According to the third embodiment described above, since the equipment can be used without changing the existing equipment for manufacturing a lithium secondary battery using a non-aqueous electrolyte solution, good electricity can be used inexpensively by a simple method. It is possible to produce lithium secondary batteries with high chemical performance and safety.

Hereinafter, the present invention will be described in detail with reference to examples.

(Example 1)
(1) Preparation of electrolyte solution 1 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 15 g of THF were mixed, and further LiN (SO ₂ CF ₃ ) ₂ 1.29 g was added. .. At this time, the molar ratio (Li / EO) of the molar concentration [EO] of ether oxygen in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 5. An electrolyte solution was prepared by adding 15 wt% sulfolane (SL) as a flame retardant to the obtained mixture of PEO, THF and a lithium salt.

(2) Preparation of positive electrode 84.4% by mass LiFePO ₄ 0.5 g, 5.0% by mass NASION type solid electrolyte (LICGCPW-01, manufactured by O'Hara) 0.03 g, 0.6% by mass multi-layer solvent After adding 0.13 g of Bonnanotube dispersion (solvent is N-methyl-2-pyrrolidone (NMP) manufactured by Canon) and 0.5 g of 10% by mass of polyvinylidene fluoride (PVDF) and mixing. An appropriate amount of NMP was further added to the mixture as a solvent to prepare a positive slurry. Subsequently, a positive electrode slurry was applied onto an aluminum foil having a thickness of 20 μm, which is a positive electrode current collector, and dried at 80 ° C. for 12 hours. Then, it was pressed at 5 MPa using a roll press and further punched to prepare a circular positive electrode having a diameter of 14 mm.

(3) Preparation of Negative Electrode A discoid lithium metal foil having a diameter of 15 mm and a thickness of 600 μm was used for the negative electrode.

(4) Applying gel electrolyte to the positive electrode layer and the separator layer An electrolyte solution prepared in advance was applied to the surfaces of the positive electrode and the separator under an atmosphere of a dew point of −50 ° C. or lower. That is, the positive electrode was placed on an external terminal, a separator was placed on the positive electrode, and 600 μL was directly applied to the surface using a pipette. The thickness of the separator layer was 10 to 25 μm. After that, it was placed on a hot plate and heated to the determined remaining amount of THF. The electrolyte solution changed from a smooth state before heating to a sticky gel electrolyte. The heating temperature and heating time are determined by the residual amount of THF. The heating temperature of this example was 50 ° C., and the heating time was 10 minutes. For the negative electrode, an electrolyte solution was directly applied to the surface using a pipette and heated in the same manner to form a gel electrolyte.

(5) Preparation of Battery A coin-type lithium ion secondary battery (2032 type) shown in FIG. 1 described above was assembled by laminating it with a negative electrode so as to face the positive electrode via a separator.

(Example 2)
(1) Preparation of electrolyte solution 1 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 15 g of tetrahydrofuran (THF) are mixed, and then LiN (SO ₂ CF ₃ ) ₂ 6.45 g. Was added. At this time, the molar ratio (Li / EO) of the molar concentration [EO] of ether oxygen in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 1. To the obtained mixture of PEO, THF and a lithium salt, 10 wt% TMP was added as a flame retardant to obtain an electrolyte solution.
Next, a coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate.

(Example 3)
The electrolyte solution was prepared by the same method as in Example 2, the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate in the same manner as in Example 2, and 15 wt% TMP was used as a flame retardant. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1.

(Example 4)
An electrolyte solution was prepared by the same method as in Example 2, the electrolyte solution was heated with a hot plate for 20 minutes in the same manner as in Example 2, and 15 wt% sulfolane was used as a flame retardant instead of TMP. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1.

(Example 5)
An electrolyte solution was prepared by the same method as in Example 2, the electrolyte solution was heated with a hot plate for 20 minutes in the same manner as in Example 2, and 25 wt% sulfolane was used as a flame retardant instead of TMP. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1.

(Example 6)
An electrolyte solution was prepared by the same method as in Example 2, the electrolyte solution was heated with a hot plate for 20 minutes in the same manner as in Example 2, and 10 wt% 2,2,2-trifluoroethylphos as a flame retardant was added. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that the fate (TFP) was used.

(Comparative Example 1)
A coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that no flame retardant was added.

(Comparative Example 2)
A coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that it was heated at 50 ° C. for 20 minutes by a hot plate without adding a flame retardant.

(Comparative Example 3)
A coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that 25 wt% sulfolane was used as a flame retardant and the hot plate was heated at a temperature of 100 ° C. for 20 minutes.

(Comparative Example 4)
A coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that 25 wt% sulfolane was used as a flame retardant and the battery was heated at a temperature of 100 ° C. for 40 minutes by a hot plate.

(Comparative Example 5)
An electrolyte solution was prepared by the same method as in Example 3 without adding a flame retardant, and the electrolyte solution was heated by a hot plate at a temperature of 50 ° C. for 20 minutes in the same manner as in Example 3, except that the same as in Example 1. A coin-type lithium-ion secondary battery was assembled by the same method.

(Comparative Example 6)
An electrolyte solution was prepared by the same method as in Example 3 without adding a flame retardant, and the electrolyte solution was heated by a hot plate at a temperature of 100 ° C. for 20 minutes in the same manner as in Example 3. A coin-type lithium-ion secondary battery was assembled by the same method.

(Comparative Example 7)
(1) Preparation of electrolyte solution 3 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 25 g of THF were mixed, and further LiN (SO ₂ CF ₃ ) ₂ 2.45 g was added. .. At this time, the molar ratio (Li / EO) of the molar concentration [EO] of ether oxygen in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 8. An electrolyte solution was prepared by adding 15 wt% trimethyl phosphate (TMP) as a flame retardant to the obtained mixture of PEO, THF and a lithium salt.
Next, a coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate.

(Comparative Example 8)
An electrolyte solution was prepared by the same method as in Comparative Example 7, the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate in the same manner as in Comparative Example 7, and 25 wt% TMP was used as a flame retardant. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1.

(Comparative Example 9)
An electrolyte solution was prepared by the same method as in Comparative Example 7, and the electrolyte solution was heated at 50 ° C. for 10 minutes by a hot plate in the same manner as in Comparative Example 7, and was further carried out except that 15 wt% TMP was used as a flame retardant. A coin-type lithium ion secondary battery was assembled by the same method as in Example 1.

(Comparative Example 10)
The same as in Example 1 except that the electrolyte solution was prepared by the same method as in Comparative Example 7 without adding a flame retardant, and the electrolyte solution was heated at 50 ° C. for 10 minutes by a hot plate in the same manner as in Comparative Example 7. A coin-type lithium-ion secondary battery was assembled by the method.

(Comparative Example 11)
79.4% by mass of positive electrode active material LiFePO ₄ , 10% by mass of NASION type solid electrolyte (LICGC PW-01, manufactured by O'Hara), and 0.6% by mass of conductive aid carbon nanotube. After adding 10% by mass of polyvinylidene fluoride (PVDF), which is a binder, and mixing them, N-methyl-2-pyrrolidone (NMP) was added as a solvent to the mixture to prepare a positive electrode slurry. did. Subsequently, a positive electrode slurry was applied onto an aluminum foil having a thickness of 20 μm, which is a positive electrode current collector, and dried at 80 ° C. for 12 hours. Then, after that, it was pressed at 5 MPa using a hand press and further punched to prepare a circular positive electrode having a diameter of 14 mm.
Next, the lithium foil was punched into a circle with a diameter of 15 mm to prepare a negative electrode. As the separator, a polypropylene polymer porous film was used. The non-aqueous electrolyte solution is 1.0 mol / L of LiPF ₆ in a mixed non-aqueous solvent (volume ratio, EC: DMC = 1: 1) of ethylene carbonate (EC) and dimethyl carbonate (DMC). Prepared by dissolving.

Using a positive electrode, a negative electrode, a separator, and a mixed non-aqueous solvent, they are incorporated and housed by a conventional method in an atmosphere with a dew point of -50 ° C or lower, and are coin-shaped lithium ion secondary as shown in FIG. The battery (2032 type) was assembled.

Next, the performance of the obtained coin-type lithium-ion secondary battery was evaluated.
"Ignition experiment"
The gel electrolytes prepared in Examples 1 to 6 and Comparative Examples 1 to 11 are ignited in air with a writer for 5 seconds or longer, and if combustion continues, it is "flammable", and if combustion does not continue, it is "flame retardant". And said. The results are shown in Table 1 below. In Table 1, the molar ratios of the gel electrolytes of Examples 1 to 7 and Comparative Examples 1 to 11 (molar concentration of oxygen in polyethylene oxide (O) and molar concentration of lithium ions in the lithium salt (LiFePO ₄ ) (Li). ), The molar ratio (O / Li), the organic solvent (THF), and the blending amount of the flame retardant are also described.

[Discharge rate characteristic test]
Using the coin-type lithium ion secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 11, charging and discharging were performed at room temperature according to the following charging and discharging conditions, and a discharge rate characteristic test was performed. Table 2 below shows the discharge capacity for each rate. In addition, "-" in Table 2 indicates that the discharge rate characteristic test could not be executed.

Charge / discharge conditions 0.1C discharge discharge test: 0.1C charge up to 4.0V, 0.1C discharge up to 2.5V.
0.5C discharge test: 0.5C charge up to 4.0V, 0.5C discharge up to 2.5V.
Discharge test of 1C discharge: 1C charge up to 4.0V, 1C discharge up to 2.5V.
Discharge test of 2C discharge: 2C charge up to 4.0V, 2C discharge up to 2.5V.

As is clear from Table 1, all of the gel electrolytes used in Comparative Examples 1, 2, 5, 6, 10 and 11 to which no flame retardant was added continued to burn due to ignition.
On the other hand, the gel electrolytes of Examples 1 to 6 having a molar ratio (O / Li) of 5 and 1 and a flame retardant added in an amount of 10 wt% or more showed flame retardancy.

On the other hand, in the gel electrolyte of Comparative Example 9 in which the molar ratio (O / Li) exceeds the range (1 to 5) of the present invention 8 and the amount of THF is 20 wt% or more, a flame retardant is added in an amount of 15 wt%. Also did not show flame retardancy.

As is clear from Table 2, the amount of the non-aqueous solvent (THF) is 20 wt% to 40 wt%, and the amount of the flame retardant is 10 wt% to 30 wt%. The secondary battery showed good discharge capacity at each late discharge. In particular, the coin-type lithium-ion secondary batteries of Examples 2 and 6 provided with the gel electrolyte containing a small amount of the flame-retardant agent are similar to the coin-type lithium-ion secondary batteries of Comparative Example 11 using the conventional liquid electrolyte. It was confirmed that it had the same discharge rate performance.

From the results in Table 2, the coin-type lithium-ion secondary batteries of Comparative Examples 1 and 5 provided with the gel electrolyte containing no flame retardant have excellent discharge characteristics, but have a safety problem of burning by ignition.

The coin-type lithium ion secondary batteries of Comparative Example 3, Comparative Example 4, and Comparative Example 6-8 provided with a gel electrolyte containing less than 20 wt% of THF have low fluidity of the gel electrolyte, so that lithium ions are conducted. It was confirmed that the rate was still low and the discharge capacity at 0.1 C also decreased.

When the molar ratio (O / Li) was 8, which exceeds the molar ratio range (1-5) of the present invention, it was found that even if the amount of THF was 20 wt% or more and the flame retardant was blended in 15 wt%, the mixture burned (1-5). See Comparative Example 9). Therefore, no electrochemical performance measurement was performed. When the amount of THF was reduced to 14 wt%, flame retardancy appeared, but it was confirmed that the discharge specific volume at 0.1 C decreased (see Comparative Examples 7 and 8).

The charge / discharge curves at 0.1 C were measured for the coin-type lithium ion secondary batteries of Example 4 and Comparative Example 4 provided with the gel electrolyte having a molar ratio (O / Li) of 1. The results are shown in FIG. Although the content of the solvent was close to that of both examples and showed flame retardancy (Example 4: 38 wt%, Comparative Example 3: 36 wt%), as is clear from FIG. 2, the blending amount of THF was 20 wt%. It can be seen that the lithium ion secondary battery of Example 4 provided with a gel electrolyte exceeding (THF: 23 wt%) has a large discharge capacity and a small polarization.

1 ... Lithium ion secondary battery, 2 ... Positive electrode, 3 ... Negative electrode, 4 ... Separator, 7 ... Gasket, 21 ... Positive electrode current collector, 22 ... Positive electrode layer, 31 ... Negative electrode current collector, 32 ... Negative electrode layer.

The present invention is a gel electrolyte for a lithium secondary battery containing a polymer compound containing an O atom in the main chain, a lithium salt, a non-aqueous solvent having reduction stability, and a flame retardant having oxidative stability. The molar ratio (O / Li) of the molar concentration (O) of oxygen derived from the ether bond in the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1 to 5. The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%. The ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%.

<First Embodiment>
The gel electrolyte for a lithium secondary battery according to the first embodiment contains a polymer compound containing an O atom in the backbone, a lithium salt, a non-aqueous solvent having reduction stability, and a flame retardant having oxidation stability. The molar ratio (O / Li) of the molar concentration (O) of oxygen derived from the ether bond in the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1 to 5. The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%. The ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%.

Examples of the polymer compound containing an O atom in the main chain include a polymer compound having an ethylene oxide structure. Specific examples of such polymer compounds include polyethylene oxide (PEO), polyethylene glycol dimethyl ester ( PEGDME ), polyethylene glycol (PEG), polyethylene carbonate (PEC) and the like. can. The weight average molecular weight of the polymer compound is preferably 1,000 to 5,000,000.

According to the first embodiment, the molar ratio (O / Li) of the molar concentration (O) of oxygen derived from the ether bond in the polymer compound and the molar concentration (Li) of the lithium ion in the lithium salt. ), And by specifying the ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt, the polymer compound coordinates with lithium ions. Not only that, a non-aqueous solvent can also form a special complex structure coordinated with lithium ions. As a result, it is possible to obtain a gel electrolyte for a lithium secondary battery which has high reduction stability, lithium ion conductivity and good fluidity, does not require the formation of an electrolyte membrane, and is easy to handle.
Further, when blending the flame-retardant agent having oxidation stability, the gel is specified by specifying the ratio [D / (A + B)] of the flame-retardant agent mass (D) to the total mass (A + B) of the polymer compound and the lithium salt. Obtains a safe gel electrolyte for lithium secondary batteries with high retention of non-aqueous solvent, excellent liquid leakage property, high redox stability, refractory volatility and flame retardancy without impairing the original characteristics of the electrolyte. be able to.

(Example 1)
(1) Preparation of electrolyte solution 1 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 15 g of THF were mixed, and Li N (SO ₂ CF ₃ ) ₂ 1.29 g was further added. .. At this time, the molar ratio (O / Li ) of the molar concentration [ O ] of oxygen derived from the ether bond in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 5. An electrolyte solution was prepared by adding 15 wt% sulfolane (SL) as a flame retardant to the obtained mixture of PEO, THF and a lithium salt.

(Example 2)
(1) Preparation of electrolyte solution 1 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 15 g of tetrahydrofuran (THF) are mixed, and then LiN (SO ₂ CF ₃ ) ₂ 6.45 g. Was added. At this time, the molar ratio (O / Li ) of the molar concentration [ O ] of oxygen derived from the ether bond in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 1. To the obtained mixture of PEO, THF and a lithium salt, 10 wt% TMP was added as a flame retardant to obtain an electrolyte solution.
Next, a coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate.

(Comparative Example 7)
(1) Preparation of electrolyte solution 3 g of polyethylene oxide (PEO: manufactured by Sigma-Aldrich) having a weight average molecular weight of 300,000 and 25 g of THF were mixed, and ₂ 2.45 g of Li N (SO ₂ CF ₃ ) was further added. .. At this time, the molar ratio (O / Li ) of the molar concentration [ O ] of oxygen derived from the ether bond in the polyethylene oxide and the molar concentration [Li] of the lithium ion in the lithium salt was set to 8. An electrolyte solution was prepared by adding 15 wt% trimethyl phosphate (TMP) as a flame retardant to the obtained mixture of PEO, THF and a lithium salt.
Next, a coin-type lithium ion secondary battery was assembled by the same method as in Example 1 except that the electrolyte solution was heated at 50 ° C. for 20 minutes by a hot plate.

Next, the performance of the obtained coin-type lithium-ion secondary battery was evaluated.
"Ignition experiment"
The gel electrolytes prepared in Examples 1 to 6 and Comparative Examples 1 to 11 are ignited in air with a writer for 5 seconds or longer, and if combustion continues, it is "flammable", and if combustion does not continue, it is "flame retardant". And said. The results are shown in Table 1 below. In Table 1, the molar ratios of the gel electrolytes of Examples 1 to 7 and Comparative Examples 1 to 11 (molar concentration (O) of oxygen derived from ether bond in polyethylene oxide and lithium salt ( LiN (SO ₂ CF ₃ )) are shown. ₂ ) The molar ratio (O / Li ) of the molar concentration (Li) of lithium ions in 2), the organic solvent (THF), and the blending amount of the flame retardant are also described.

Claims (5)

A gel electrolyte for lithium secondary batteries,
It contains a polymer compound containing an O atom in the main chain, a lithium salt, a non-aqueous solvent having reduction stability, and a flame retardant having oxidative stability.
The molar ratio (O / Li) of the molar concentration (O) of oxygen in the repeating unit of the polymer compound and the molar concentration (Li) of lithium ions in the lithium salt is 1 to 5.
The ratio [C / (A + B)] of the mass (C) of the non-aqueous solvent to the total mass (A + B) of the polymer compound and the lithium salt is 20 to 40 in terms of mass%.
A gel electrolyte for a lithium secondary battery in which the ratio [D / (A + B)] of the mass (D) of the flame retardant to the total mass (A + B) of the polymer compound and the lithium salt is 10 to 30 in terms of mass%. The gel electrolyte for a lithium secondary battery according to claim 1, wherein the flame retardant contains at least one selected from a phosphoric acid ester compound and a sulfone compound. A lithium secondary battery including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
The gel electrolyte for a lithium secondary battery according to claim 1 or 2, is a lithium secondary battery impregnated in the positive electrode, the negative electrode and the separator. The main chain contains a polymer compound containing an O atom, a lithium salt, a non-aqueous solvent and a flame retardant, and the non-aqueous solvent is relative to the total amount of the polymer compound, the lithium salt, the non-aqueous solvent and the flame retardant. In the process of preparing a gel electrolyte solution containing 70 to 80% by mass,
A process of manufacturing a power generation element having a positive electrode, a negative electrode, and a separator arranged between the positive electrode and the negative electrode, and
The step of injecting the gel electrolytic solution into the power generation element and
A step of diffusing the gel electrolytic solution into the positive electrode, the negative electrode and the separator by leaving the gel electrolytic solution after injection.
The lithium secondary according to claim 1 or 2, wherein the power generation element is heated to volatilize a part of the non-aqueous solvent in the gel electrolyte solution to the positive electrode, the negative electrode and the separator of the power generation element. A method for manufacturing a lithium secondary battery, which comprises a step of impregnating a gel electrolyte for a battery. The method for producing a lithium secondary battery according to claim 4, wherein the boiling point of the non-aqueous solvent is a1 and the boiling point of the flame retardant is a2.

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