TW201230470A - Secondary battery - Google Patents

Abstract

When a secondary battery is charged, the thickness of the second battery may increase due to gases such as CO and CH4 generated by resolution of a carbonate organic solvent during an SEI layer forming reaction. In addition, in a state of full charge, the SEI layer is gradually deteriorated over time at a high temperature and a side reaction in which an exposed negative electrode surface and electrolyte are reacted is developed. At this time, pressure in the secondary battery increases due to the gases. And then, the thickness of the second battery may increase and the second battery may be deformed. The electrolyte includes a material in which a relative permittivity at normal temperature is 20 or more and/or a dielectric loss tan δ at 60 DEG C is 10 or less at 1kHz, and further includes some organic solvents having a nitrile group, lithium bis(trifluoromethanesulfonyl)imide or sodium bis(trifluoromethane sulfonyl)imide, and fluorinated cyclic carbonate, thereby providing safe and high-performance secondary battery having a large potential window, a large temperature range, and resolution resistance even at high potential.

Description

201230470 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a secondary battery excellent in performance and safety. [Prior Art] A battery is a device that converts chemical energy of a chemical substance stored therein into electric energy by an electrochemical redox reaction. In recent years, it has been widely used in the world, such as portable electronic devices such as electronics, communications, and computers. In the future, large-scale batteries such as mobile vehicles and electric load averaging systems will be predicted. Practical, and increasingly become an important key device. Among them, lithium ion secondary batteries are particularly popular. This lithium ion secondary battery is mainly composed of the following materials: a positive electrode containing a lithium-containing transition metal composite oxide as an active material; and such as lithium metal and lithium. A negative electrode of an alloy, a metal oxide or a carbon capable of occluding/releasing lithium as an active material; a non-aqueous electrolyte and a separator; or a solid electrolyte, an example of which is a lithium ion secondary battery initially charged At the time, lithium ions emitted from the lithium metal composite oxide used as the positive electrode are moved to the graphite electrode used as the negative electrode, and inserted between the graphite electrodes. At this time, since the reactivity of lithium is high, a film layer of a thin film is formed on the surface of the graphite negative electrode. Such a layer is called a SEI (Solid Electrolyte Interface) layer. Once the above SEI layer is formed, it acts as an ion channel, allowing only lithium ions to pass. By protecting the 201230470 film with such an ion channel effect, it is possible to prevent disintegration of the graphite negative electrode structure caused by an electrolyte or the like. Once the SEI layer is formed, lithium ions do not again react with the graphite negative electrode or other substances, and the amount of lithium ions in the electrolyte is reversibly maintained to ensure stable charge and discharge. However, in the above-described reaction to form SEI, the decomposition of the carbonate-based organic solvent causes the generation of gases such as CO, co2, CH4, and C2H6, and causes the problem that the thickness of the battery expands during charging. Further, when a certain voltage (high voltage) is fully charged and stored at a high temperature, the SEI layer gradually disintegrates over time, and the side reaction of the exposed negative electrode surface and the surrounding electrolyte continues to occur. At this time, the internal pressure inside the battery rises due to the continuous generation of the gas, and as a result, the thickness of the battery increases. The same applies to the case where sodium is used as the positive electrode to replace lithium. Therefore, in the technical field, secondary batteries, particularly lithium ion secondary batteries or sodium ion secondary batteries, have been developed to suppress gas generation at high voltage or high temperature storage, and have no problem of internal pressure rise or volume expansion. The electrolyte with excellent high temperature performance has always been in demand. In addition, in general, most of the non-aqueous electrolyte solvents are those having a low withstand voltage. When the electrolytic solution obtained by using a solvent having a low withstand voltage is used in a secondary battery, the solvent is decomposed as the charge and discharge are repeated, and thus the problem that the internal pressure of the battery rises while the gas is generated may occur. As a result, there is a problem that the battery is deformed, the battery charging and discharging efficiency is lowered, the battery energy density is lowered, and the battery life is shortened. In order to solve such problems, an attempt has been made to add a small amount of a compound as an additive to an electrolyte solution of a lithium ion secondary battery to ensure battery performance -6-201230470. (Patent Document 1 and Patent Document 3) [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 8-22839 (Patent Document 2) [Patent Document 3] JP-A-2009-158240 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, even when the electrolytic solution using the method described in the above patent document is used, the operating voltage that can be used is increased, but when stored at a high temperature Battery performance and safety are still insufficient. Therefore, the present invention has been made to solve such problems, and it is an object of the present invention to provide a battery which is excellent in special performance and which is capable of preventing an increase in thickness, expansion, and deformation of the battery due to an increase in internal pressure, and which is excellent in safety. [Means for Solving the Problem] In order to solve the above problems, it was found that several organic solvents having a nitrile group and lithium bistrifluoromethanesulfonyl imide or sodium bistrifluoromethanesulfonate were found. A solvent of a quinoneimine and a fluorinated cyclic carbonate which can obtain a battery which is difficult to decompose even at a high positive potential, has a wide temperature range, a wide potential window, and is more safe. In other words, the electrolyte solution for a lithium ion battery of the present invention is an electrolyte solution for a lithium ion battery in which a lithium salt is dissolved in an organic solvent 201230470, and is an electrolyte solution for a lithium ion battery in which a lithium salt is dissolved in an organic solvent. The organic solvent contains a material having a dielectric constant of 20 or more at a normal temperature or a dielectric constant tanS of 10 or less at a temperature of 60 ° C, and contains lithium bistrifluoromethanesulfonyl quinone imine. (LiN(S02CF3)2) or sodium bistrifluoromethanesulfonylimine (NaN(S02CF3)2) and a nitrile-based material and a fluorinated cyclic carbonate. The lithium salt to be added to the electrolyte solution for a lithium ion battery of the present invention may be LiPF6, LiBF4, LiC104, LiSbF6, LiAsF6, LiCF3S03, LiN(S02CF3)2, LiN(S02C2F5)2, LiC(S02CF3)3,

One selected from the group consisting of LiN (S03CF3) 2, LiC4F9S03, LiA104, LiAlCl4, LiCl, Lil, LiBETI, and LiTFS, or a mixture of two or more. These lithium salts are dissolved in the nitrile-based organic solvent, the fluorinated cyclic carbonate solvent, the lithium bistrifluoromethanesulfonyl imide, or the sodium bistrifluoromethane used in the electrolytic solution for a lithium ion battery of the present invention. Sulfonyl imine, which has a sufficient potential window that does not decompose at high potential (high voltage). The concentration of the above lithium salt is preferably 0.01 mol/丨 or more, and is a concentration which is lower than the saturated state. When the concentration of the lithium salt is less than 0.1 mol/Ι, there is almost no dissociated lithium ion, so that the ion transporting force is insufficient and the performance is extremely lowered. Further, conversely, in the saturated state, precipitation of lithium occurs, and the constituent materials such as electrodes are deformed. The organic solvent in the above electrolyte solution preferably has a fluorinated cyclic carbonate content of less than 1% by weight based on the total organic solvent. As a result, S EI can be effectively formed on a carbon negative electrode which has been known in the past, and it is possible to ensure the resistance to reduction and to efficiently pass Li ions. Further, by using a material having a nitrile group of -8 to 201230470, the positive electrode acts in the same manner, so that the positive electrode is also provided in the form of SEI, and oxidation resistance can be imparted, and oxidation of the positive electrode material and the electrolytic solution can be suppressed. It can be used at high voltages. Further, the result of the removal reaction rate and the dissociation reaction rate are also improved. Further, it was found that the addition of bistrifluoromethanesulfonyl quinone imine can improve the low-temperature characteristics and high-temperature characteristics, and expand the operating temperature region. In the case of a sodium ion battery, the substitution of Li for Na is also true. [Effects of the Invention] The battery according to the present invention can be stably charged and discharged in a high operating voltage region (4.45 V or more). This battery is high-voltage, high-capacity, and exhibits excellent charge and discharge performance, life, and rate performance (output characteristics), and can be used without problems even at high voltage or high temperature storage. Further, it is possible to suppress the generation of the decomposition gas and obtain a battery having high safety, which is highly practical. [Embodiment] Hereinafter, preferred aspects of the invention are shown. First, the electrolytic solution according to the gist of the present invention contains a material having a dielectric constant of 20 or more at normal temperature or a dielectric loss of 10 or less at a temperature of 60 ° C, and having a dielectric constant of 10 or less at 1 kHz. Bis(trifluoromethanesulfonyl)imide (TFSI) and nitrile-based materials, and fluorinated cyclic carbonates, which can inhibit the increase of internal pressure of the battery or the battery tank due to gasification reaction at high temperature or high voltage charging Expansion, improve the stability of battery performance 'suppressed the size of -9-201230470, and get a battery with excellent safety. Further, the present invention relates to an electrolyte for a lithium ion secondary battery or a sodium ion secondary battery, or a lithium ion secondary battery or sodium ion containing the same, which has an extended temperature range of design specifications and further excellent life characteristics. Secondary battery. The embodiments are shown below to make the features of the present invention clearer, but the present invention is not limited by the embodiments. Regarding the positive electrode, it contains an active material capable of inserting or removing lithium ions or sodium ions. Examples of the active material include lithium nickel manganese oxide, lithium manganate, lithium nickelate, lithium nickel cobalt manganese oxide, lithium manganese phosphate, lithium iron manganate, lithium manganese titanate, and respective modified substances (aluminum or magnesium, etc.) The metal eutectic is used) or sodium is used instead of the composite oxide of lithium or the like. Among them, those containing manganese are preferred. The adhesive may be PVdF, PTFE, P (VdF/HFP), and the substrate may be a modified acrylonitrile rubber particle binder (BM-520B manufactured by Zeon Co., Ltd.), and may have a viscosity increasing effect. A combination of carboxymethyl cellulose (CMC), soluble modified acrylonitrile rubber (BM-720H, manufactured by Zeon Co., Ltd., Japan). The conductive agent may be used singly or in combination of acetylene black, Ketjen black, and various graphite iridium. Regarding the negative electrode, it contains an active material capable of inserting or removing lithium ions or sodium ions. As the active material, metal lithium, various natural graphite, lanthanide composite materials such as artificial graphite and ruthenium, ruthenium oxide materials, titanium alloy materials, and various alloy constituent materials can be used. As an adhesive, from the viewpoint of improving lithium ion acceptability, it is more preferable to use s BR and its modified substance in combination or to add a small amount of a fiber-based resin such as CMC, and the positive electrode is similarly an acrylic resin or PVdF. PTFE or P (VdF/HFP). -10- 201230470 Regarding the electrolytic solution, various lithium compounds such as a month can be used as the salt in addition to the above conditions. Further, as a solvent, bistrifluoromethanesulfonyl imide (TFSI), a fluorinated ring, and capable of reacting with ethyl carbonate (EC), dimethyl carbonate (DEC), and carbonic acid Ethyl ester (MEC), fluorinated carbon, trifluoromethylcyclohexane (TFMCH), bistrifluoromethane (TFSI), succinonitrile (SN), fluorinated phosphorus and nitrogen trimer, etc. For stability during charging, (VC), cyclohexylbenzene (CHB), propane sultone (PS), j (PRS), vinyl sulfite (ES), and the like can also be used. A solvent having a dielectric constant of 20 or more at normal temperature provides a sufficient polarity to dissociate the electrolyte salt and is provided in an aqueous solvent to dissociate the electrolyte salt. The dielectric loss tanS at 60 °C is 1 0 at 1 kHz to act over a wide range of temperatures. Furthermore, the thickness of the high-temperature battery is increased, and the life characteristics and safety are all. In many cases, the system has found that the liquid contains fine particles (preferably, the long axis is 2 μm or less).

Li2S-P2S5, Zr02_P2〇5, etc., can improve the low temperature characteristics. When phosphorus (P) is contained, holes are generated and the acceptor functions. Thereby, the active material (the surface of the positive frame forms a semiconductor intermediate suppressing positive electrode active material itself and the electrolyte in contact with it, the electric 3 LiPF6 and LiBF4 include at least a carbonate-containing and nitrile-based KDMC), and the carbonated ethyl ester (FEC) Enlarged bismuth iodide for use. Further, the carbonic acid-extended vinyl ester 3 propylene sulfate has a solvent which is sufficient for the electric storage device, and can be increased when it is placed. : The layer of I or the negative electrode is produced by the interface of L i 7 P 3 S 1 1 at the electrolysis). Therefore, the solution is oxidized due to high voltage -11 - 201230470. In addition, the addition of zinc (Zn) will enhance the receptor function. Further, it has been found that when copper (Cu) ions are exposed to a high potential, the carbon negative electrode acts as a receptor. Therefore, even when the cycle life is deteriorated and overdischarged, copper dendrites are less likely to be formed, and as a negative electrode. The receptor is consumed, which is related to safety and prolonged service life. Potential conversion at the nanometer level (to alleviate the energy of high potential), when the distance between the donor/acceptor is r, the probability of transition is observed as W = W〇e4/Rd (where Rd is the bulk of the precursor) Radius), so roughly, the degree of oxidation inhibition can be controlled by the size and amount of the substance P added. However, the balance between the consideration and the reaction rate, that is, the resistance or rate characteristics may be traded off, so the size and amount are determined according to the optimum amount of addition. The lithium salt or the sodium salt is preferably one which has a small lattice energy, a large degree of dissociation, an excellent ion conductivity, thermal stability and oxidation resistance. The separator is not particularly limited as long as it can be applied within the range of use of the lithium ion secondary battery, but generally, a microporous film of an olefin resin such as a single or composite polyethylene/polypropylene is used. A variety of aspects are also used. In addition, non-woven fabrics can be used, and the materials can be PPS, PP, modified PET, and the like. Although the thickness of the separator is not particularly limited, it is preferably designed to have a film thickness of a design capacity. That is, 6 to 30 μm 〇 Further, according to this system, it can be known that PC can be used as a solvent. Therefore, the electrolyte does not crystallize or freeze in the low temperature region, and the operating temperature range is expanded. This is because bis-trifluoromethanesulfonyl ruthenium imine (TFSI) -12- 201230470 and a nitrile-containing solvent and a fluorinated cyclic carbonate can be obtained in a graphite anode with unprecedented urgency. SEI layer. [Examples] The present invention is not limited by the examples shown below. In addition, the following battery is used to fill the electrolyte in a dry air environment, and after standing for a certain period of time, it is subjected to a preliminary charging step of about 20 minutes with a current equivalent to 0.1 C, and then sealed and made into a battery at 60°. The step of being placed in the C environment for one day after deterioration. (Snail safety) For a fully charged battery, the heat generation state and appearance when a 2.7 mm diameter nail was passed through the room at a speed of 5 mm/sec in a normal temperature environment was measured. (Example 1) In Example 1, 10% by weight of propylene carbonate (PC), fluorinated ethyl carbonate (?£(:) 10% by weight, dimethyl carbonate (DMC) 60% by weight, and dibutyl) were used. a mixed solvent of 15% by weight of nitrile (SN) and 5 wt% of lithium bistrifluoromethanesulfonyl sulfenimide (LiTFSI) as an organic solvent, in which lithium salt 1 ^??6 is dissolved to become IMol/L, as lithium The electrolyte for the ion battery. At this time, the PC shows that the dielectric constant at the normal temperature is 65, the dielectric loss tanS at 1 kHz is Oh, and the tanS of the FEC is 0.3. The DMC shows a specific dielectric constant of 2.8. Tan5 is 0.1. For the positive electrode, LiMnO 2 is used as the A1 foil. When the positive electrode is formed, -13-201230470 is used in an appropriate amount to mix acetylene black as a conductive agent and acrylic resin as an adhesive. The negative electrode is made of artificial graphite and Each of the semi-mixed natural graphite is formed into a copper foil. When a negative electrode is formed, a suitable amount of cellulose (cmc) of a styrene-butadiene rubber resin (SBR) and an adhesion-promoting material is used as an adhesive. A microporous membrane of pp (polypropylene) was used. (Example 2)

In Example 1, a phosphorus fluoride nitrogen trimer (Chemical Formula 1) was used instead of SN 〇 [Chemical 1] phosphonitrile fluoride triraer F f I/n, 丨 / P P \

Fchuan 1 F N \

P / \

F F (Example 3) The propylene carbonate (FPC) was used in place of FEC in Example 1. At this time, the dielectric loss tan 5 of the FPC was 0.05. (Example 4) In Example 1, a microparticle-like Zr〇2-P2〇5 mixture of 4 〇 nm to 5 μηη with respect to the electrolytic solution was added to the electrolytic solution to perform electrolysis for a lithium ion battery. liquid. -14-201230470 (Example 5) In the case of Example 4, LhPgSn was used in place of Zr〇2_p2〇5 mixture (Example 6). In Example 1, Li of the positive electrode was substituted with Na, and NaMn02 was used, with respect to LiTFSI. 'There was sodium bistrifluoromethanesulfonyl quinone imine (NaTFSI), which was used to obtain a sodium ion battery using 1M NaPF6 as a salt. (Example 7) In the same manner as in Example 6, in the same manner as in Example 6, NaTFSI was used instead of LiTFSI to obtain an electrolyte solution for a sodium ion battery using NaPF6 as a salt. At this time, the positive electrode was the same as that of Example 6. (Example 8) In Example 3, in the same manner as in Examples 6 and 7, NaTFSI was used instead of LiTFSI to obtain an electrolytic solution for a sodium ion battery using NaPF6 as a salt. At this time, the positive electrode was the same as that of the sixth embodiment. (Example 9) In Example 4, in the same manner as in Examples 6 to 8, 'NaTF s 1 was used instead of LiTFSI to obtain an electrolytic solution for a sodium ion battery using NaPF6 as a salt. At this time, the positive electrode was the same as that of the sixth embodiment. -15-201230470 (Example 10) In the same manner as in Examples 6 to 9, in the same manner as in Examples 6 to 9, an electrolytic solution for a sodium ion battery using NaPF6 as a salt was obtained by substituting NaTFSI for LiTFSI'. At this time, the positive electrode was the same as that of the sixth embodiment. (Example 1 1) In Example 1, the positive electrode was changed to LiMnP04 (in other words, the condition for increasing the positive electrode LMO in Example 1). (Example 12) In Example 1, the positive electrode was changed to LiNio.5Mm.5O4. (Example 13) In Example 1, the positive electrode was changed to LiFe〇.5Mn〇.5〇4. (Example 14) In Example 1, the positive electrode was changed to Lil.5Mn〇.7TiG.3〇2. (Example 15) In Example 1, the positive electrode was changed to Li2MnSi〇4. (Example 16) In Example 1, the positive electrode of L i M n 0 2 was fluorinated to be made into L i Μ η 0 2 F. -16-201230470 (Example 1 7) In the first embodiment, LiMnP04 positive electrode was subjected to fluorination treatment to obtain LiMnP04F. (Example 18) In Example 12, LiNiQ.5Mni.504 was subjected to a fluorination treatment to obtain LiNi〇.5Mni.5〇4F. (Example 19) In Example 13, fluorination treatment of LiFeo.5Mno.5O4 to obtain LiFe〇.5Mn〇5〇4F 〇 (Example 20) was carried out in Example 14, and 1^1. ().71'丨().3 02 fluorination treatment to make Li1.5Mno.7Tio.3O2F. (Example 21) In Example 15, Li2MnSi04 was subjected to a fluorination treatment to obtain Li2MnSi04F. (Example 22) In Example 6, NaMnP04 was used in place of NaMn02 of the positive electrode. -17 - 201230470 (Example 23) In Example 6, the positive electrode was set to N a N i 〇. 5 Μ η ! . 5 0 4. (Example 24) In the example 6, the positive electrode was set to NaFeo.5Mno.5O4. (Example 25) In Example 6, the positive electrode was set to Na1.5Mno.7Tio.3O2 (Example 26). In Example 6, the positive electrode was made Na2MnSi04. (Positive Electrode 27) In Example 6, the positive electrode was NaMn02F. (Example 28) According to Example 6, the positive electrode was made NaMnP04F. (Example 29) In Example 6, the positive electrode was designated as NaNiQ.5Mni.5 04F. (Example 30) In Example 6, the positive electrode was designated NaFeo.5Mno.5O4F. -18-201230470 (Example 3 1) In Example 6, the positive electrode was set to Nai.5Mn〇.7Ti〇.3〇2F ° (Example 32) In the example 6, the positive electrode was made Na2MnSi04F. (Example 33) In Example 1, 8 & 〇3 of a weight ratio of 〇.5% was added to the negative electrode. (Example 34) In Example 1, a-Ah〇3 in a weight ratio of 0.4% was added to the negative electrode. (Example 35) In Example 1, AIF3 in a weight ratio of 0.3% was added to the negative electrode. (Example 36) In Example 1, Si ° in a weight ratio of 0.5% was added to the negative electrode (Example 37). In Example 6, the same negative electrode as in Example 3 (Example 3 8) was used. In Example 6, the same negative electrode as in Example 34 was used. -19 - 201230470 (Example 39) In the same manner as in Example 6, the same negative electrode as in Example 35 was used. (Example 40) In the same manner as in Example 6, the same negative electrode as in Example 36 was used. (Example 4 1) In Example 2, the positive electrode was set to LiMnP04. (Example 42) In Example 2, the positive electrode was set to LiNiQ.5Mni.504. (Example 43) In Example 2, the positive electrode was set to LiFeQ.5MnQ 504. (Example 44) In Example 2, the positive electrode was designated as Lh.5Mno.7Tio.3O2. (Example 4 5) In Example 2, the positive electrode was made into Li2MnSi04. (Example 46) In Example 2, the positive electrode was set to LiMn02F. -20-201230470 (Example 47) In Example 2, the positive electrode was set to LiMnP04F. (Example 48) In Example 2, the positive electrode was set to LiNio.5Mm.5O4F. (Example 49) In Example 2, the positive electrode was designated as LiFeQ.5MnQ.504F. (Example 50) In Example 2, the positive electrode was set to Li1.5Mno.7Tio.3O2F. (Example 51) In Example 2, the positive electrode was made into Li2MnSi04F. (Example 52) In Example 3, the positive electrode was designated as LiMnP04. (Example 53) In Example 3, the positive electrode was set to LiNiQ.5Mn丨.504. (Example 54) In Example 3, the positive electrode was set to LiFeo.5Mno.5O4. -21 - 201230470 (Example 55) In the third embodiment, the positive electrode was set to LiK5Mno.7Tio.3O2. (Example 56) In Example 3, the positive electrode was made into Li2MnSi04. (Example 57) In Example 3, the positive electrode was set to LiMnO 2F. (Example 58) In Example 3, the positive electrode was set to LiMnP04F. (Example 59) In Example 3, the positive electrode was set to LiNio.5Mm.5O4F. (Example 60) In Example 3, the positive electrode was set to LiFeQ.5Mn().504F. (Example 61) In Example 3, the positive electrode was designated as LiuMno^Tio.sOzF. (Example 62) In Example 3, the positive electrode was made into Li2MnSi04F. -22-201230470 (Example 63) In Example 4, the positive electrode was set to LiMnP04. (Example 64) In Example 4, the positive electrode was set to LiNiQ.5Mni.504. (Example 65) In Example 4, the positive electrode was designated as LiFeo.5Mno.5O4. (Example 66) In the example 4, the positive electrode was set to Lh.5Mno.7Tio.3O2 (Example 67). In the example 4, the positive electrode was made into Li2MnSi04. (Example 68) In Example 4, the positive electrode was designated as LiMnO 2F. (Example 69) In Example 4, the positive electrode was designated as LiMnP04F. (Example 70) In Example 4, the positive electrode was set to LiNio.5Mm.5O4F. -23-201230470 (Example 71) In Example 4 |, the positive electrode was set to LiFeo.5Mno.5O4F. (Example 72) In Example 4, 1 the positive electrode was designated as LiK5Mno.7Tio.3O2F. (Example 73) In Example 4, the positive electrode was designated as Li2MnSi04F. (Example 74) In Example 5, the positive electrode was set to LiMnP04. (Example 75) In Example 5, the positive electrode was set to LiNiQ.5Mni.504. (Example 76) In Example 5, the positive electrode was designated as LiFeQ.5Mn().504. (Example 77) In Example 5, the positive electrode was designated as Lil 5MnQ.7TiQ.3 02. (Example 78) In Example 5, the positive electrode was made into Li2MnSi04. -24-201230470 (Example 79) In Example 5, the positive electrode was set to LiMn02F. (Example 80) In Example 5, the positive electrode was set to LiMnP04F. (Example 81) In Example 5, the positive electrode was set to LiNio.5MiM.5O4F. (Example 82) In Example 5, the positive electrode was set to LiFeo.5Mno.5O4F. (Example 83) In Example 5, the positive electrode was designated as LiK5Mno.7Tio.3O2F. (Example 84) In Example 5, the positive electrode was made into Li2MnSi04F. (Example 85) In Example 7, the positive electrode was made NaMnP04. (Example 86) In the example 7, the positive electrode was set to NaNiQ.5Mni.5 04. -25-201230470 (Example 87) In Example 7, the positive electrode was designated NaFeo.5Mno.5O4. (Example 88) It is based on Example 7; > The positive electrode was set to Na1.5Mno.7Tio.3O2. (Example 89) In Example 7, 'the positive electrode was made Na2MnSi04. (Example 90) In Example 7, the positive electrode was made NaMn02F. (Example 91) In Example 7, the positive electrode was NaMnP04F. (Example 92) In Example 7, (Example 93) The positive electrode was set to NaNio.5Mm.5O4F. In Example 7, the positive electrode was set to NaFeo.5Mno.5O4F. (Example 94) In Example 7, the positive electrode was designated as NauMnojTiuC^F. -26-201230470 (Example 95) In Example 7, the positive electrode was made Na2MnSi04F. (Example 96) In Example 8, the positive electrode was designated as NaMnP04. (Example 97) In Example 8, the positive electrode was set to NaNio.5Mm.5O4. (Example 98) In Example 8, the positive electrode was designated NaFeo.5Mno.5O4. (Example 99) In Example 8, the positive electrode was set to Na1.5Mno.7Tio.3O (Example 1). In Example 8, the positive electrode was made Na2MnSi04. (Example 101) In Example 8, the positive electrode was made NaMn02F. (Example 102) In Example 8, the positive electrode was designated as NaMnP04F. -27-201230470 (Example 103) In Example 8, the positive electrode was set to NaNiQ.5Mn1504F. (Example 104) In Example 8, the positive electrode was designated NaFeo.5Mno.5O4F. (Example 105) In Example 8 1 The positive electrode was set to Na1.5Mno.7Tio.3O2F. (Example 106) In Example 8, the positive electrode was made Na2MnSi04F. (Example 107) In Example 9, "the positive electrode was made NaMnP04. (Example 108) In the same manner as in Example 9, the positive electrode was designated NaNio.5Mn1.5O4. (Example 109) In Example 9, the positive electrode was designated NaFeo.5Mno.5O4. (Example Π 0) In Example 9, the positive electrode was set to Nar5Mno.7Tio.3O2. -28-201230470 (Example 1 1 1) In Example 9, the positive electrode was made Na2MnSi04. (Example 1 12) In Example 9, the positive electrode was set to NaMn〇2F. (Example 1 13) In Example 9, the positive electrode was designated as NaMnP04F. (Example 1 14) In Example 9, the positive electrode was designated NaNio.5Mn1.5O4F. (Example 1 15) In Example 9, the positive electrode was set to N a F e 〇. 5 Μ η 〇. 5 0 4 F. (Example 1 16) In Example 9, the positive electrode was set to Na1.5Mno.7Tio.3O2F (Example 1 17). In Example 9, the positive electrode was made Na2MnSi04F. (Example 1 18) In the example ίο, the positive electrode was set to NaMnP〇4. -29-201230470 (Example 1 19) In Example 1, 正极 , the positive electrode was set to NaNio.5Mn1.5O4. (Example 120) In the example 1 : 1 The positive electrode was set to NaFeo.5Mno.5O4. (Example 121) In Example 1, 正极, 1 The positive electrode was set to Na1.5Mno.7Tio.3O2. (Example 122) In Example 1, 正极, the positive electrode was made Na2MnSi04. (Example 123) In Example 1, 正极, the positive electrode was NaMn02F. (Example 124) In Example 1, 正极, the positive electrode was set to NaMnP04F. (Example 125) In Example 1, 正极, the positive electrode was set to NaNio.5Mm.5O4F. (Example 126) In Example 1, 正极, the positive electrode was designated NaFe().5Mn().504F. -30-201230470 (Example 1 2 7) In Example 10, the positive electrode was set to NaK5Mno.7Tio.3O2F ° (Example 128). In Example 10, the positive electrode was made Na2MnSi〇4F. (Example 1 2 9) In Example 2, BaTi〇3 ^ in a weight ratio of 〇.5% was added to the negative electrode (Example 1 3 0). In Example 2: a weight ratio 〇 was added to the negative electrode. 4% of α_Α丨2〇3 (Example 131) In Example 2, 8% by weight of 11.3% was added to the negative electrode. (Example 1 3 2) In Example 2: a weight ratio of 0.5% S i ° was added to the negative electrode (Example 133) In Example 3: a weight ratio of 〇.5% 2BaTi〇 was added to the negative electrode. 3. (Example 1 3 4) In Example 3: a weight ratio of 4.4% was added to the negative electrode α_Αΐ2〇3 -31 - 201230470 (Example 135) In Example 3, a weight ratio of 0.3 was added to the negative electrode. % of Alb. (Example 136) In Example 3, a weight ratio of 〇. 5 % s 1 ° was added to the negative electrode (Example 137) In Example 4, BaTi〇3 in a weight ratio of 0.5% was added to the negative electrode. (Example 138) In Example 4, α·Α12〇3 in a weight ratio of 0.4% was added to the negative electrode. (Example 1 39) In Example 4, A1F3 in a weight ratio of 0.3% was added to the negative electrode. (Example 1 40) In Example 4, Si was added in an amount of 〇.5% by weight to the negative electrode. (Example 1 4 1) In Example 5, BaTi〇3 was added to the negative electrode in a weight ratio of 5%. (Example 142) In Example 5, a weight ratio of 〇·4% 2α·Α12〇3 was added to the negative electrode. -32-201230470 (Example 143) In Example 5, 8% by weight of ^.3% was added to the negative electrode. (Example 144) In Example 5, Si ° by weight 〇·5% was added to the negative electrode (Example 145) In Example 1 1, BaTi〇3 was added to the negative electrode in a weight ratio of 〇.5%. . (Example 146) In Example 11, a weight ratio of Ο·4% 2α-Αΐ2〇 was added to the negative electrode (Example 147) In Example 1 1, A1F3 was added to the negative electrode in a weight ratio of 〇.3%. ° (Example 148) In Example 11, S 1 ° by weight 〇·5 % was added to the negative electrode (Example 149) In Example 12, BaTi having a weight ratio of 〇·5% was added to the negative electrode. 〇 3. (Example 150) In Example 12, α-Αΐ2〇-33-201230470 (Example 151) was added to the negative electrode in a weight ratio of 4.4%. In Example 12, a weight ratio was added to the negative electrode. . 3 % A 1F 3 . (Example 152) In Example 12, > weight ratio 〇. 5 % of S i was added to the negative electrode. (Example 153) In Example 13, 3, BaTi03 in a weight ratio of 0.5% was added to the negative electrode. (Example 154) In Example 13, a weight ratio of 〇. 4% a - A12 0 was added to the negative electrode (Example 1 5 5 ) In Example 13 , a weight ratio of 负极. 3 was added to the negative electrode. % of A 1F 3. (Example 156) In Example 13, a weight ratio of 〇. 5 % of S i was added to the negative electrode. (Example 157) In Example 14, 4% by weight of 〇.5% was added to the negative electrode. -34-201230470 (Example 158) In Example 14, a weight ratio of 〇.4% was added to the negative electrode (1-eight 120 (Example 159). In Example 14, the weight ratio was added to the negative electrode. 3%.3% of 八1?3. (Example 160) In Example 14, 4% by weight of Si was added to the negative electrode. (Example 161) In Example 15, weight was added to the negative electrode.实施例例1。 In Example 15, a weight ratio of 4. 4% a - A12 0 was added to the negative electrode (Example 163) In Example 15 8% by weight of 〇.3% was added to the negative electrode. (Example 164) In Example 15, a weight ratio of 〇. 5 % of S i was added to the negative electrode (Example 165) -35- 201230470 In Example 16, 65% by weight of BaTi03 was added to the negative electrode. (Example 166) In Example 16, 6 wt% of α-Α1203 (Example 167) was added to the negative electrode. In Example 16, a weight ratio of 3% to 3% of 3% was added to the negative electrode. (Example 168) In Example 16, a weight ratio of 〇. 5 % of S i was added to the negative electrode. 169) In Example 17, adding to the negative electrode Addition weight ratio 〇5°/83 83: 103. (Example 170) In Example 17, a weight ratio of 〇_4% of α-Α1203 was added to the negative electrode (Example 171). In the negative electrode, 8% by weight of 3% was added to the negative electrode. (Example 172) In Example 17, 7 wt% of Si was added to the negative electrode. -36 - 201230470 (Example 1 7 3) In Example 18, BaTiCh was added to the negative electrode at a weight ratio of 0.5 ° / (Example 174) In Example 18, a-Ah 〇 3 in a weight ratio of 0.4% was added to the negative electrode (Example 175) In Example 18, AIF3 was added to the negative electrode at a weight ratio of 〇·3 %. (Example 1 7 6) In Example 18, a weight ratio of 〇. 5 % of S i was added to the negative electrode. Example 1 77) In Example 19, BaTi03 was added to the negative electrode in a weight ratio of 5%. (Example 1 7 8) In Example 19, α-Α1203 was added to the negative electrode at a weight ratio of 0.4% ( Example 179) In Example 19, a weight ratio of 0.3% of A1F3 was added to the negative electrode » -37 - 201230470 (Example 180) In Example 19, Si was added in a weight ratio of 0.5% to the negative electrode. (Example 181) In Example 20, > 'BaTi03 was added to the negative electrode at a weight ratio of 0.5%. (Example 182) In Example 20, a weight ratio of 〇. 4% a - A12 0 was added to the negative electrode (Example 1 83) In Example 20, a weight ratio of 负极. 3 % was added to the negative electrode. A1 F 3. (Example 184) In Example 20, Si was added in an amount of 0.5% by weight to the negative electrode. (Example 185) In Example 2, a weight ratio of 〇.5% to 7^03 was added to the negative electrode. (Example 1 86) In Example 21, α-Α120 was added to the negative electrode in a weight ratio of 0.4%: (Example 187) -38 - 201230470 In Example 2, a weight ratio of 0.3% was added to the negative electrode. AIF3. (Example 188) In Example 2, a weight ratio of 0.5% by weight was added to the negative electrode (Example 189). In Example 2 2, BaTi〇3 in a weight ratio of 〇.5% was added to the negative electrode. (Example 190) In Example 22, a-Ah 重量 at a weight ratio of 0.4% was added to the negative electrode.

(Example 191) In Example 2 2, A1F3 ° in a weight ratio of 〇.3% was added to the negative electrode (Example 192) In Example 22, Si was added in a weight ratio of 0.5% to the negative electrode. (Example 1 9 3 ) In Example 2 3, BaTi〇3 in a weight ratio of 〇% was added to the negative electrode. (Example 194) In Example 23, a-AhO-39-201230470 was added to the negative electrode at a weight ratio of 0.4% (Example 195). In Example 23, a weight ratio of 负极.3 was added to the negative electrode. °/. AIF3. (Example 1 9 6) In Example 23, Si in a weight ratio of 〇 5% was added to the negative electrode. (Example 197) In Example 24, a weight ratio of 〇.5 ° / was added to the negative electrode. BaTi〇3. (Example 198) In Example 24, a-Ah 〇 3 in a weight ratio of 0.4% was added to the negative electrode (Example 199) In Example 24, a weight ratio of 0.3 ° / was added to the negative electrode. AIF3. (Example 200) In Example 24, Si ° in a weight ratio of 0.5% was added to the negative electrode (Example 201) In Example 25, BaTi〇3 in a weight ratio of 0.5% was added to the negative electrode. (Example 202) -40- 201230470

In Example 25, a weight ratio of OKia-AhO (Example 2 03) was added to the negative electrode. In Example 25, a weight ratio of 0.3 ° / was added to the negative electrode. A1F3 ° (Example 204) In Example 25, Si was added in a weight ratio of 0.5% to the negative electrode. (Example 2 0 5) In Example 26, 83^03 of a weight ratio of 5%.5% was added to the negative electrode. (Example 2 0 6) In Example 26, a-Ah 重量 at a weight ratio of 0.4% was added to the negative electrode (Example 2 0 7). In Example 26, the weight ratio 〇.3 was added to the negative electrode. % of eight ^3. (Example 2 0 8) In Example 26, Si in a weight ratio of 0.5% was added to the negative electrode (Example 209) In Example 27, BaTi〇3 in a weight ratio of 0.5% was added to the negative electrode. -41 - 201230470 (Example 2 1 0) In Example 27, α·Αΐ2〇 having a weight ratio of 〇·4% was added to the negative electrode (Example 21 1) In Example 27, it was added to the negative electrode. The weight ratio is 33°/. A1F3. (Example 212) In Example 27, Si ° was added in a weight ratio of 0.5% to the negative electrode (Example 2 1 3 ). In Example 28, BaTi〇 was added to the negative electrode in a weight ratio of 〇.5%. 3. (Example 2 1 4) In Example 28, 'α-Αΐ2〇 was added to the negative electrode at a weight ratio of °·4°/❶: (Example 215) In Example 28, the weight ratio was added to the negative electrode. 3%.3%2A1F3. (Example 216) In Example 28, S1 in a weight ratio of 0 _5% was added to the negative electrode. -42-201230470 (Example 217) In Example 29, BaTi〇3 was added to the negative electrode in a weight ratio of 〇.5%. (Example 2 1 8) In Example 29, α_Αΐ2〇 was added to the negative electrode in a weight ratio of 44% (Example 219). In Example 29, a weight ratio of 〇.3% was added to the negative electrode. A1F3. (Example 2 2 0) In Example 29, a weight ratio of 0.5% Si ° was added to the negative electrode (Example 2 2 1). In Example 30, a weight ratio of 〇.5% was added to the negative electrode. BaTi〇3. (Example 222) In Example 30, a weight ratio of 〇.4% of a_Al2〇 was added to the negative electrode (Example 223) In Example 30, a weight ratio of 〇.3°/ was added to the negative electrode. People 1?3. (Example 224) -43 - 201230470 In Example 30: a weight ratio 〇 5% of S i was added to the negative electrode. (Example 225) In Example 31, BaTi03 in a weight ratio of 0.5% was added to the negative electrode. (Example 226) In Example 31, a - A12 0 of a weight ratio of 〇·4% was added to the negative electrode (Example 227) In Example 31, a weight ratio of 〇.3% was added to the negative electrode. People 1?3. (Example 228) In Example 31, a weight ratio of 〇. 5 % of S i was added to the negative electrode. (Example 229) In Example 32, 831^03 of a weight ratio of 〇.5% was added to the negative electrode. (Example 2 3 0) In Example 32, α-Α120 was added to the negative electrode at a weight ratio of 0.4% (Example 231). In Example 32, a weight ratio of 〇.3% was added to the negative electrode. 1?3. -44-201230470 (Example 2 3 2) In Example 32, S1° by weight 〇.5% was added to the negative electrode (Example 2 3 3 ) In Example 70, weight was added to the negative electrode. 〇25%BaTi〇3 ° (Example 2 3 4) In Example 70, α_Αΐ2〇3 (Example 2 3 5 ) was added to the negative electrode in a weight ratio of 4.4°/c. In 0, AIF3 in a weight ratio of 0.3% was added to the negative electrode. (Example 2 3 6) In Example 70, Si ° in a weight ratio of 0.5% was added to the negative electrode (Example 23 7) In Example 114, BaTiCh in a weight ratio of 0.5% was added to the negative electrode (Example) 23) In Example 114, a weight ratio of 0.4 °/ was added to the negative electrode. α-Α12〇3 -45- 201230470 (Example 2 3 9) In Example 14, A1F3 was added to the negative electrode at a weight ratio of 0.3%. (Example 2 40) In Example 114, Si was added in an amount of 0.5% by weight to the negative electrode. (Example 2 4 1) In Example 23, the separator was a non-woven fabric (mixture of PP and cellulose) to replace the PP film. At this time, the aperture is 40 nm~. However, the aperture is not limited by it. (Example 2 4 2) In Example 2 37, the separator was a non-woven fabric (mixture of PP and cellulose) to replace the PP film. In this case, a pore diameter of 4 〇 nm to ΐμπι was used. However, the aperture is not limited by it. Further, it is known that the same effect can be obtained by using Α1Ρ〇4 instead of AIF3. As long as the Al-containing or Ρ'F-containing substance of the present invention is added to the negative electrode or the electrolyte solution, the effect can be obtained, which is particularly effective. The representative examples are shown in the examples. (Comparative Example 1) [In the content of Example 1] Electrolyte using EC/DMC (3/7 by weight) -46 - 201230470 Here, if there is no TFSI, SN, or MFEC, when using PC It will be gasified and cannot be used as a battery on the safety surface or the life surface. Further, the electrolyte solution is crystallized due to the inability to use the PC, and low temperature characteristics are not obtained. (Comparative Example 2) [The contents of Example 6 were carried out in the same manner as in Comparative Example 1. (Comparative Example 3) In Comparative Example 1, it was attempted to add V C (carbonated ethylene carbonate) 作为 as a film which was generally easy to produce 8 to have a film and was stable in performance. 5% by weight. However, it can be seen that performance as in the embodiment cannot be obtained. This can be considered as an increase in the SEI layer caused by VC, which increases the resistance' or becomes an uneven SEI layer, which is fragile at the design specification potential. A table summarizing the conditions of the above respective embodiments is shown in Figs. 1 to 6 . Further, a table summarizing the conditions of the above comparative examples is shown in Fig. 7. A table showing the battery performance of each of the above embodiments is shown in Figs. 8 to 15. Further, a table showing the battery performance of each of the above comparative examples is shown in Fig. i. Further, the battery of the present invention can be operated at -40 ° C, but there is no composition of the present invention, for example, at -40 ° C. Can't work. [Industrial Applicability] The secondary battery of the present invention has excellent performance and has a power supply for high safety -47-201230470. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a table summarizing the conditions in the first to the eleventh embodiment of the present invention. 2 is a table summarizing the conditions in the first embodiment to the fifth embodiment of the present invention. FIG. 3 is a table summarizing the conditions in the fifth embodiment to the first embodiment of the present invention. FIG. 4 is an embodiment of the present invention. A table summarizing the conditions is summarized from 丨〇1 to Example 150. Fig. 5 is a table summarizing the conditions in the embodiment 151 to the embodiment 200 of the present invention. Fig. 6 is a table summarizing the conditions in the embodiment 20 1 to the embodiment 242 of the present invention. Fig. 7 is a table summarizing the conditions in Comparative Example 1 to Comparative Example 3. Fig. 8 is a table showing the performance of the battery in the first to third embodiments of the present invention. Fig. 9 is a table showing the performance of the battery in the embodiment 31 to 60 of the present invention. Fig. 1 is a table showing the performance of a battery in Examples 61 to 90 of the present invention. Fig. 11 is a table showing the performance of a battery in an embodiment 191 to an embodiment 120 of the present invention. Figure 1 2 is a table showing the battery performance -48-201230470 in the embodiment 1 21 to the embodiment 150. Figure 13 is a table showing the performance of a battery in Embodiments 151 to 180 of the present invention. Figure 14 is a table showing the performance of batteries in Examples 181 to 210 of the present invention. Figure 15 is a table showing the performance of a battery in Examples 211 to 242 of the present invention. Fig. 16 is a table showing the performance of the battery in Comparative Example 1 to Comparative Example 3. -49-

Claims (1)

201230470 VII. Scope of application: 1. A secondary battery consisting of a positive electrode composed of a composite lithium oxide or a composite sodium oxide, a negative electrode composed of a material capable of retaining lithium or sodium, a P鬲-off film, and a non-aqueous solvent. The ion secondary battery comprising the electrolyte solution is characterized in that: the electrolyte solution contains a material having a dielectric constant of 20 or more or 60 ° C at a normal temperature and a dielectric loss tanS of 10 or less at 1 kHz, and contains Material and fluorine with lithium bistrifluoromethanesulfonyl quinone imine (LiN(S〇2CF3)2) or sodium bistrifluoromethyl fluorene imine (NaN(S〇2CF3)2) and nitrile group Cyclic carbonate. 2. The secondary battery of claim 1, wherein the material having a nitrile group is succinonitrile. 3. The secondary battery of claim 1, wherein the material having a nitrile group is a fluorinated phosphorus-nitrogen trimer. 4. The secondary battery of claim 1, wherein the fluorinated cyclic carbonate is ethyl fluorocarbonate. 5. The secondary battery of claim 1, wherein the fluorinated cyclic carbonate is propylene carbonate. 6. The secondary battery of claim 1, wherein the positive electrode contains at least manganese. The secondary battery of claim 6, wherein the positive electrode containing manganese contains at least lithium citrate (LiMn2〇4) or sodium manganate (NaMn2〇4). 8. The secondary battery of claim 6, wherein the positive electrode containing manganese contains at least a material having an olivine skeleton. -50- 201230470 9. The secondary battery of claim 8, wherein the manganese-containing positive electrode having the olivine skeleton contains at least lithium manganese phosphate (LiMnP〇4) or sodium manganese phosphate (NaMnP04). The secondary battery of claim 6, wherein the positive electrode containing manganese contains at least lithium nickel manganese oxide (LiNixMny〇4) or sodium nickel manganate (NaNixMny〇4). 11. The secondary battery of claim 6, wherein the positive electrode containing manganese comprises at least lithium iron manganate (LiFexMny04) or sodium iron manganate (NaFexMny〇4) 〇12. A secondary battery, wherein the positive electrode containing manganese contains at least lithium manganese titanate (LixMnyTi(1-y)02) or sodium manganese titanate (NaxMnyTi (b)2). 13. The secondary battery of claim 6, wherein the positive electrode containing the above comprises at least lithium cinnamate (Li2MnSi04) or sodium manganese silicate (Na2MnSi〇4). A secondary battery comprising a part or all of a positive electrode of a positive electrode as set forth in claims 7 to 13 of the patent application. 1 5 . The secondary battery of claim 1, wherein the operating voltage of the single cell is an area containing 4.45 V or more. 16. A secondary battery according to item 1 of the patent application, which is obtained by adding a particulate solid material containing phosphorus element to an electrolytic solution. 17. The secondary battery of claim 1, wherein the secondary material comprises a ceramic material other than the carbon material. 1 8 · The secondary battery of claim 17 of the patent application, wherein the ceramic-51 - 201230470 porcelain material contains at least barium titanate. 19. The secondary battery of claim 17 or 18, wherein the ceramic material comprises at least alumina. 20. The secondary battery of claim 17 or 18 or 19, wherein said ceramic material contains at least lithium fluoride. 21. The secondary battery of claim 17 or 18 or 19 or 20, wherein the ceramic material comprises at least a material containing a lanthanum element. -52-