KR20080095352A - Secondary battery with high capacity and longevity comprising silazane-based compound - Google Patents

Secondary battery with high capacity and longevity comprising silazane-based compound Download PDF

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KR20080095352A
KR20080095352A KR1020070039663A KR20070039663A KR20080095352A KR 20080095352 A KR20080095352 A KR 20080095352A KR 1020070039663 A KR1020070039663 A KR 1020070039663A KR 20070039663 A KR20070039663 A KR 20070039663A KR 20080095352 A KR20080095352 A KR 20080095352A
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electrolyte
battery
lt
silazane
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KR1020070039663A
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KR101521646B1 (en
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손미영
이상영
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주식회사 엘지화학
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes

Abstract

The present invention relates to a battery electrolyte comprising an electrolyte salt and an electrolyte solvent, wherein the electrolyte is a compound capable of reacting electrochemically in a cell to form a passivation layer, and containing one or more silane groups and nitrogen. It provides a battery electrolyte and a secondary battery having the electrolyte characterized in that it comprises a silazane-based compound.
In the present invention, by using a silazane-based compound capable of forming an inert film on the positive electrode in the normal operating voltage range of the battery, by minimizing side reactions between the positive electrode and the electrolyte, high capacity and lifespan performance is improved. A secondary battery can be provided.
SEI layer, lifetime performance, increased capacity, lithium secondary battery

Description

A high capacity and long life secondary battery containing a silazane-based compound {SECONDARY BATTERY WITH HIGH CAPACITY AND LONGEVITY COMPRISING SILAZANE-BASED COMPOUND}

1 is a Cyclic voltammogram performed using the electrolyte solutions of Example 1 and Comparative Example 1.

2A is a graph showing a relationship between an initial formation charge and a voltage performed by forming the batteries of Example 2 and Comparative Example 2. FIG.

FIG. 2B is a graph obtained by differentiating the charging amount according to the voltage increase in the graph of FIG. 2A.

3 is a TPD-GC-MS-TIC graph of the negative electrode obtained after the battery of Example 2 and Comparative Example 2 were fully charged, respectively.

Figure 4 is a graph comparing the capacity and efficiency of the battery over the cycle of the battery of Example 2 and Comparative Example 2.

5 is a graph measuring life characteristics after storing the batteries of Example 2 and Comparative Example 2 at 90 ° C. for 4 hours in a fully charged (4.2V) state.

The present invention uses an electrolyte additive capable of forming an effective passivation layer on the anode and the cathode by an electrochemical redox reaction, thereby minimizing side reactions between the positive electrode and the electrolyte, thereby improving overall performance. It relates to a battery.

In recent years, the importance of a battery is increasing as a power source for portable electronic devices such as mobile phones, video cameras, notebook personal computers, and the like. Accordingly, research and development of a battery having a light weight, high voltage, high capacity, and high power as a driving power source of a portable electronic device, particularly a lithium secondary battery using a non-aqueous electrolyte, is being actively conducted.

Lithium secondary batteries generally use a lithium-containing transition metal oxide as a positive electrode active material, and a TiO 2 and SnO 2 having a potential of less than 2 V, which can occlude and release carbon, a lithium metal or an alloy thereof, and other lithium as a negative electrode active material. Use a metal oxide such as Lithium secondary batteries can be divided into lithium ion battery (LiLB), lithium ion polymer battery (LiPB), and lithium polymer battery (LPB) according to the electrolyte used, that is, LiLB is a liquid electrolyte, and LiPB is a gel polymer electrolyte. LPB uses a solid polymer electrolyte.

The non-aqueous solvents used in the above-mentioned battery electrolytes are various, but high-boiling solvents such as ethylene carbonate (EC), propylene carbonate (PC), gamma butyrolactone (γ-butylolactone, hereinafter GBL), etc. in terms of improving safety. Preference is given to using cyclic carbonates. Particularly, when LiMn 2 O 4 is used as a cathode active material, HF, a strong acid, is generated due to side reaction between a small amount of water and lithium salt in a battery, and such HF attacks the anode to dissolve Mn (dissolution). Cause. As such, when manganese (Mn) is ionized into the electrolyte, it moves to the cathode and is reduced to grow on the surface of the cathode, resulting in a decrease in capacity and an increase in battery internal resistance. In the case of using other positive electrode materials, the above phenomenon is not as severe as manganese-based active materials, but the possibility of occurrence generally is very high.

On the other hand, in general, in order to increase the capacity of the battery to increase the amount of electrode active material loading, Li metal is precipitated as charging and discharging are repeated, thereby deteriorating battery performance such as capacity and lifespan. In addition, some additives added as an electrolyte component in order to improve capacity and lifespan characteristics may cause gas generation at charge or discharge or at high temperatures, thereby causing a problem of deformation of the battery shape and reduction of battery performance. Therefore, the role of H 2 O scavenger that can hold moisture is required, and in addition, it is necessary to increase the capacity by protecting the positive and negative electrodes and to use the battery for a long time.

The inventors have found that when a silazane-based compound containing silane and nitrogen is used as a constituent of an electrolyte, an effective film is formed on both the positive electrode and the negative electrode through an oxidation-reduction reaction in the normal charge / discharge voltage range of the battery. It has been found that additional reactions that lead to performance degradation can be suppressed.

Accordingly, an object of the present invention is to provide an electrolyte containing the silazane-based compound described above and a secondary battery having the electrolyte.

The present invention relates to a battery electrolyte comprising an electrolyte salt and an electrolyte solvent, wherein the electrolyte is a compound capable of reacting electrochemically in a cell to form a passivation layer, and containing one or more silane groups and nitrogen. It provides a battery electrolyte and a secondary battery having the electrolyte characterized in that it comprises a silazane-based compound.

In addition, the present invention provides an electrode and a secondary battery having a passivation layer formed by the electrical oxidation or reduction of the silazane-based compound in which at least one silane and nitrogen are introduced at the same time on a part or all of the surface of the electrode active material to provide.

Further, the present invention is a compound capable of reducing on the negative electrode of a secondary battery to form a solid electrolyte interface (SEI) film, an electrolyte additive for forming an SEI film, which is a silazane-based compound containing one or more silane groups and nitrogen. to provide.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is characterized by using a silazane-based compound capable of forming a passivation layer effective for both the positive electrode and the negative electrode by being oxidized and reduced in the operating operating voltage range of the battery as a battery electrolyte component. .

Due to the above characteristics, the secondary battery of the present invention can implement high capacity, high efficiency, excellent long life characteristics and high temperature characteristics. The reason for such an excellent effect is not clear, but can be estimated as follows.

1) The performance of the battery is highly dependent on the basic electrolyte composition and the solid electrode interface (SEI) formed by the reaction between the electrolyte and the electrode. In the conventional lithium secondary battery, a surface of a cathode active material, such as carbon particles, and an electrolyte react with each other to form a solid electrolyte interface (SEI) film during a first charging process. The formed SEI film is mainly used for initial charging of a battery. when CO 3 2 of decomposition products of the organic solvent containing the carbonyl group-formed by the carbon dioxide, such as reaction with lithium ions, which is saturated in electrolyte solution, such a lithium for SEI film formation is dissipated irreversibly. Such an SEI membrane may be a side reaction between an electrode active material and an electrolyte solvent; And not only prevent the collapse of the negative electrode material due to co-intercalation of the electrolyte solvent into the negative electrode material, but also faithfully perform a conventional lithium ion tunnel, thereby minimizing performance degradation of the battery. However, the SEI membrane formed by the conventional carbonate organic solvent is weak, porous and not dense so that lithium ions cannot be moved smoothly, thereby increasing the irreversible reaction due to the progress of charging and discharging by reducing the amount of reversible lithium, thereby increasing the capacity and life of the battery. Deterioration of properties is caused.

Thus, the present invention uses a silazane-based compound as an electrolyte solution component capable of being oxidized-reduced in the operating voltage range of the battery to form a rigid and dense inert film on both electrodes.

The silazane-based compound consumes and regenerates SEI, compared to a solid electrode interface (SEI) of fluorine or other inorganic components formed on a cathode active material due to a reaction between a conventional carbonate-based electrolyte and a cathode. By forming the SEI film of an organic component containing ether and N excellent in terms, it is possible to reduce the reactivity of the electrolyte and the electrode to improve the life characteristics of the battery (see FIGS. 3 and 4). In addition, during the initial charging of the battery, a solid and dense SEI film is formed on the surface of the negative electrode material prior to other components to increase initial charge and discharge efficiency, and the formed SEI film selectively absorbs and releases only lithium ions (Li + ). Since it is a low passivation layer with low chemical reactivity, it can exhibit high stability even in a long cycle.

2) In addition, the lithium secondary battery of the related art causes a sudden deterioration of the performance of the battery, especially in a high temperature environment, which not only causes a sudden collapse of the SEI film formed on the surface of the negative electrode, but also increases side reactions between the electrode and the electrolyte and due to electrolyte decomposition decomposition. It is also estimated that gas generation and increase in electrode thickness (resistance) occur rapidly.

In contrast, since the SEI membrane of the present invention contains ethers and N which are excellent in terms of consumption and regeneration of SEI, the SEI membrane is not only rapidly regenerated when collapsed by high temperature, but also continuously maintained to increase the reactivity between the electrode and the electrolyte due to high temperature. The occurrence of side reactions may be reduced to indicate improved high temperature characteristics of the battery (see FIG. 5).

One of the elements constituting the battery electrolyte according to the present invention is a silazane-based compound containing at least one silane group and nitrogen.

The silazane-based compound is not particularly limited as long as it can be oxidized-reduced in the normal operating voltage range of the cell to form an effective passivation layer on the positive electrode and the negative electrode. The silazane-based compound may be represented as in Chemical Formula 1, but is not limited thereto.

R 1 R 2 R 3 Si-NR 7 -SiR 4 R 5 R 6

Where

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently hydrogen or a C 1 to C 6 alkyl group or alkenyl group unsubstituted or substituted with a halogen atom.

The silazane-based compound of the present invention is preferably a disilazane-based compound in which two or more silane groups in itself are present and connected by nitrogen. One example is hexamethyldisilazane (HMDS).

Hexamethyldisilazane (HMDS) is reduced during initial charging to form a solid SEI film of organic components containing cyclic ethers and nitrogen (N) on the surface of the negative electrode to achieve the initial capacity and long life characteristics of the battery. In addition, it is oxidized in the operating voltage range of the battery to form a protective layer (protection layer) on the surface of the positive electrode to suppress side reactions between the highly reactive positive electrode and the electrolyte can improve the high temperature storage characteristics. In fact, the HMDS effectively covers the positive electrode film through an oxidation reaction near about 3.1 V and about 4 V relative to the lithium potential (Li / Li + ), thereby suppressing side reactions between the positive electrode and the electrolyte which may be performed, thereby improving capacity and lifespan. May contribute to the improvement of properties (see FIGS. 2A and 2B). Thus, since both electrodes which are an essential component in a battery can be protected simultaneously, the improvement effect of the overall performance of the battery mentioned above can be raised.

In addition, the silazane-based compound is one of organic desiccants, and reacts with water in an organic solvent to serve as a water scavenger, as shown in Scheme 1, to suppress side reactions caused by water.

(CH 3 ) 3 Si-NH-Si (CH 3 ) 3 + H 2 O → (CH 3 ) 3 Si-O-Si (CH 3 ) 3 + NH 3

As the above reaction proceeds, it is possible to suppress a reaction that decreases battery performance caused by halogen acid (HX, X = F, Cl, Br, I, etc.) generated by the reaction of moisture and lithium salt, and in particular, manganese as a cathode active material. In the case of using a series active material (eg, LiMn 2 O 4 ), dissolution of transition metal (eg, Mn) in the electrode active material may be suppressed.

The content of the silazane-based compound depends on the goal of improving the performance of the battery, such as initial efficiency, capacity, cycle life characteristics and high temperature storage characteristics, but is preferably in the range of 0.01 to 10 parts by weight per 100% by weight of the nonaqueous electrolyte. Do. If the amount is less than 0.01 parts by weight, the performance improvement effect of the desired battery is insignificant. If it exceeds 10 parts by weight, the performance may be deteriorated due to an increase in irreversible capacity.

Battery electrolytes to which the compound is to be added together include conventional electrolyte components known in the art, such as electrolyte salts and organic solvents.

Using the electrolyte salts is A + B - A salt of the structure, such as, A + is Li +, Na +, K + comprises an alkaline metal cation or an ion composed of a combination thereof, such as, and B - is PF 6 -, BF 4 -, Cl -, Br - , I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 - is a salt containing an anion ion or a combination thereof, such as. In particular, a lithium salt is preferable. Non-limiting examples thereof include LiClO 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 or mixtures thereof.

Organic solvents include conventional solvents known in the art, such as cyclic carbonates with or without halogen substituents; Linear carbonate system; Ester-based, nitrile-based, phosphate-based solvents or mixtures thereof can be used. Non-limiting examples of these include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, Diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethylcarbonate (EMC), gamma butyrolactone (GBL), fluoroethylene carbonate (FEC), methyl formate, ethyl formate, formic acid Propyl, methyl acetate, ethyl acetate, propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, ethyl propionate, butyl propionate or mixtures thereof.

The present invention provides an electrode in which a passivation layer formed by electrically oxidizing or reducing a silazane-based compound in which one or more silane groups and nitrogen are introduced at the same time is formed on a part or all of an electrode active material surface.

The electrode may be formed automatically on the surface of the electrode active material with the reversible lithium ions of the silazane-based compound in the electrolyte when the charge and discharge using the above-described electrolyte, or coating the compound on the surface of the electrode active material, or It may be used in combination with the material, or may be made by coating on the other electrode surface prepared. In this case, the passivation layer may be a solid electrolyte interface film formed on a part or all of the surface of the electrode active material by polymerization of the silazane-based compound by electrical reduction.

As described above, the secondary battery having the silazane-based compound or a chemical reaction product thereof having an electrode formed on part or all of the surface of the electrode active material not only stabilizes the carbon material, the transition metal and the transition metal oxide in the electrode, but also the electrolyte solution By effectively controlling the exothermic reaction generated by the direct reaction and delaying the structure collapse of the electrode active material, it is possible to prevent ignition and rupture due to the temperature rise inside the battery. In addition, the generation of halogen acids (eg, HF) by reaction with moisture present in the battery can be suppressed, thereby fundamentally improving the structural stability of the electrode active material.

Electrode according to the present invention can be prepared in the form of the electrode active material bound to the electrode current collector according to a conventional method known in the art, for example, an electrode slurry comprising a positive electrode active material or a negative electrode active material It is prepared by applying and drying on a current collector. In this case, a small amount of a conductive agent and / or a binder may be optionally added.

The positive electrode active material may be a conventional positive electrode active material that can be used for the positive electrode of a conventional secondary battery, non-limiting examples of lithium such as LiM x O y (M = Co, Ni, Mn, Co a Ni b Mn c ) Transition metal composite oxides (for example, lithium manganese composite oxides such as LiMn 2 O 4 , lithium nickel oxides such as LiNiO 2 , lithium cobalt oxides such as LiCoO 2 , and some of the manganese, nickel and cobalt oxides of these oxides And the like, or a vanadium oxide containing lithium) or a chalcogen compound (for example, manganese dioxide, titanium disulfide, molybdenum disulfide, and the like). Preferably LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li (Ni a Co b Mn c ) O 2 (0 <a <1, 0 <b <1, 0 <c <1, a + b + c = 1), LiNi 1 - Y Co Y O 2, LiCo 1 - Y Mn Y O 2, LiNi 1-Y Mn Y O 2 ( here, 0≤Y <1), Li ( Ni a Co b Mn c) O 4 (0 <a <2, 0 <b <2, 0 <c <2, a + b + c = 2), LiMn 2 - z Ni z O 4, LiMn 2 -z Co z O 4 ( Here, 0 <Z <2), LiNi 1 - X Co X M Y O 2 (where M = Al, Ti, Mg, Zr, 0 <X ≤ 1, 0 ≤ Y ≤ 0.2), LiNi X Co Y Mn 1 -X- Y O 2 (where 0 <X ≤ 0.5, 0 <Y ≤ 0.5) or LiM x M ' y Mn (2-xy) O 4 (M, M' = V, Cr, Fe , Co, Ni, Cu, 0 <X ≦ 1, 0 <Y ≦ 1), LiCoPO 4 , LiFePO 4, or mixtures thereof.

The negative electrode active material may be a conventional negative electrode active material that can be used in the negative electrode of the conventional secondary battery, non-limiting examples of lithium metal or lithium alloy, carbon material, petroleum coke, activated carbon (activated carbon) , TiO 2 , which can occlude and release graphite, group 13, 14 subunits, solid solutions and alloys, and other lithium capable of inserting and deinserting lithium, and having a potential for lithium of less than 2V; Metal oxides such as SnO 2 and Li 4 Ti 5 O 12 ;

Non-limiting examples of the positive electrode current collector is a foil made by aluminum, nickel or a combination thereof, and non-limiting examples of the negative electrode current collector by copper, gold, nickel or copper alloy or a combination thereof Foils produced.

Conventional binders may be used, and non-limiting examples thereof include polyvinylidene fluoride (PVDF) or styrene butadiene rubber (SBR).

The conductive agent can be used as long as the conductive material does not cause chemical change in the battery. For example, carbon black, such as acetylene black, Ketjen black, Farnes black, and thermal black; Natural graphite, artificial graphite, conductive single fiber, etc. can be used. Carbon black, graphite powder and carbon fiber are particularly preferable.

As the binder, any one of a thermoplastic resin and a thermosetting resin may be used, or a combination thereof may be used. Among these, polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) is preferable, and PVdF is particularly preferable.

As the dispersion medium, an organic dispersion medium such as an aqueous dispersion medium or N-methyl-2-pyrrolidone can be used.

The present invention is an anode; cathode; Electrolyte; And (d) a secondary battery comprising the separator, wherein the electrolyte is an electrolyte containing the above-mentioned electrolyte additive; The positive electrode, the negative electrode or the positive electrode provides a secondary battery characterized in that the passivation film containing the silazane-based compound or a reduction (oxidation) product thereof is an electrode formed on part or all of the surface.

The secondary battery is preferably a lithium secondary battery, and non-limiting examples of the lithium secondary battery include a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.

The secondary battery of the present invention is prepared by interposing a porous separator between a positive electrode and a negative electrode in a conventional manner known in the art, except for using an electrolyte solution to which the silazane-based compound is added, and then introducing the electrolyte solution. Can be. . In addition, the electrode into which the above-mentioned compound was introduce | transduced can be used individually, or it can also be mixed with the electrolyte solution to which the above-mentioned electrolyte additive was added.

It is preferable to use a porous separator as the separator, for example, a polypropylene-based, polyethylene-based, polyolefin-based porous separator, or a porous separator into which inorganic particles are introduced, but is not limited thereto.

The shape of the secondary battery manufactured by the above method is not limited, but may be cylindrical, square, pouch type or coin type using a can.

In addition, the present invention is a compound that can be reduced on the negative electrode of the secondary battery to form a solid electrolyte interface (SEI) film, the electrolyte additive for forming SEI film, characterized in that the silazane-based compound containing one or more silane groups and nitrogen to provide.

The SEI film-forming electrolyte additive is preferably a silazane-based compound of Formula 1, more preferably hexamethyldisilazane (HMDS).

Additionally, the present invention provides a composition comprising: (a) a first compound which is oxidized within the operating voltage range of the anode to form a protective film which increases the electrode resistance; And (b) a second compound oxidized above the operating voltage of the anode and having at least one action selected from the group consisting of heat generation, gas generation, and passivation film formation, the protective film formed by oxidation of the first compound. It is possible to provide a battery electrolyte which is characterized in that the self-oxidation potential of two compounds changes fluidly.

In this case, the second compound may increase its own oxidation potential by a protective film formed by oxidation of the first compound, and the electrolyte may prevent an overcharge voltage in the range of 4.2V to 5V due to the increase in the oxidation potential of the second compound. have. In other words, in the electrolyte containing HMDS as the first compound, the oxidation potential of the second compound (eg, CHB) due to HMDS is increased, thereby suppressing the reaction of CHB within the practical range of the actual battery, and so on. It can be selectively operated in non-ideal situations such as overcharging without affecting overall performance.

The first compound is hexamethyldisilazane (HMDS), and the like, and non-limiting examples of the second compound are toluene (TL), fluorotoluene (FT), and butylbenzene (T-butyl benzene: BB). ), Di-t-butyl benzene (DBB), amyl benzene (t-amyl benzene (AB), cyclohexyl benzene (CHB), biphenyl (BP), fluorobiphenyl : FBP), anisol compounds or mixtures thereof.

The invention is explained in more detail based on the following examples and experimental examples. However, Examples and Comparative Examples are for illustrating the present invention and are not limited only to the following Examples and Experimental Examples.

Example 1

1-1. Electrolyte manufacturing

It was prepared by mixing 0.5 parts by weight of hexamethyldisilazane (HMDS) in an electrolyte having a composition of EC: EMC = 1: 1 to 1M LiPF 6 concentration.

1-2. Battery manufacturing

As the negative electrode active material, MAG D / AGM was added in a composition of 97.5 wt%, conductive agent 1.5 wt%, and CMC 1.0 wt% to prepare a negative electrode mixture slurry, and then coated on a copper current collector to prepare a negative electrode.

A positive electrode mixture slurry was prepared by adding NMP (N-methyl-2-pyrrolidone) as a solvent in a composition of 96 wt% of Sn-doped LiCoO 2 , 2 wt% of a conductive agent, and 2 wt% of PVDF (binder) as a positive electrode active material. After that, a positive electrode was prepared by coating on an aluminum current collector.

After interposing a porous separator between the positive electrode and the negative electrode prepared as described above, the electrolyte prepared in 1-1 was added to prepare a full cell.

Example 2

The above procedure was carried out except that an electrolyte having a composition of EC: PC: DEC = 3: 2: 5 with an electrolyte of 1 M LiPF 6 and mixing 0.5 parts by weight of HMDS was used instead of an electrolyte having a composition of EC: EMC 1: 2. In the same manner as in Example 1, an electrolyte and a battery having the electrolyte were prepared.

Comparative Example 1

A lithium secondary battery was manufactured in the same manner as in Example 1, except that HMDS was not added to the electrolyte.

Comparative Example 2

A lithium secondary battery was manufactured in the same manner as in Example 2, except that HMDS was not added to the electrolyte.

Experimental Example 1. Cyclic voltammetry evaluation of the electrolyte

Cyclic voltammetry was performed using the electrolyte solution of Example 1, in which HMDS was used as an electrolyte component, and the electrolyte solution of Comparative Example 1, in which HMDS was not added. At this time, the working electrode was Pt, the auxiliary electrode was Pt, and the reference electrode was Li metal, and the voltage moving speed was 20mV / s.

As shown in FIG. 1, in the electrolyte solution of Example 1 in which the HMDS is present in the electrolyte solution, it was found that a large oxidation current flows around 4.0 V, very small at the anode potential of 3.15 V based on Li metal. This means that the oxidation reaction is caused by the HMDS contained in the electrolyte component. These oxidation reactions do not affect the overall performance and can be expected to act as a film or compound that can effectively protect the anode.

Experimental Example 2. Evaluation of Battery Performance

According to the present invention, various performance evaluations of a lithium secondary battery using a silazane-based compound as an electrolyte component were performed as follows.

2-1. Early formation  Formed at the cathode SEI layer  Difference

The lithium secondary battery of Example 2, in which HMDS was used as an electrolyte component, and the lithium secondary battery of Comparative Example 2, including an electrolyte solution without HMDS added, were formed as follows.

Each cell was subjected to a constant current for 50 minutes in a constant current (CC) method at a rate of 0.2C. 2A, which is a result of the charge capacity and the voltage increase, was obtained. FIG. 2B shows a differential graph of the charge capacity change for each voltage increase by changing the X and Y axes. In FIG. 2A, since it is difficult to estimate a difference in formation of the negative electrode SEI layer during charging, it is possible to check the change of the charging amount according to each voltage (that is, the change in the charging amount according to the change in voltage, which is different). This is illustrated in Fig. 2b.

As a result of the experiment, it was confirmed that the battery of Example 2 using HDMS significantly reduced the reaction peak between 3.0 and 3.2V compared to the battery of Comparative Example 2 without using the electrolyte additive (see FIGS. 2A and 2B). . This shows that when HMDS is present in the electrolyte, the cathode reacts with the electrolyte and the lithium salt to form a reduction product. That is, it can be seen that the SEI layer is formed differently that can influence the performance of the battery.

In addition, the electrodes of Comparative Example 2 and Example 2 were respectively decomposed in a fully charged state, and TPD-GC-MS of the negative electrode was carried out. As a result of the analysis through FIG. 3, in the cathode of Example 2 using HMDS, cyclic ethers were additionally detected at a temperature lower than 200 ° C. It is determined that the SEI layer is decomposed. At high temperatures (200–350 degrees C), certain structures other than cyclic ether compounds are unknown, but nitrogen-containing molecules were also observed. That is, when HMDS is added as an electrolyte component, the formation of SEI layer rapidly increases due to the reduction reaction, and as a composition, it is an organic substance produced by the reaction of nitrogen with the electrolyte or a salt component in which NH 4 + and various anions are combined. Precipitates on the surface of the battery and acts as a protective film.

2-2. Capacity Characterization

The batteries of Example 2 and Comparative Example 2 were subjected to a constant current up to 4.2V in a constant current-constant voltage (CC-CV) manner at a rate of 0.92C, and then controlled at a constant voltage at 4.2V. At the time of discharging, cut-off at 3.0V in a CC (constant current) method at a rate of 1.0C was repeated four times, and then discharged at a rate of 0.2C after charging in the same manner.

As a result, it was confirmed that the lithium secondary battery of Example 2, in which HMDS was added as an electrolyte component, had a capacity characteristic improved by about 2% over the comparative example (see Table 1). This is because the HMDS component participates in the consumption and regeneration of SEI, so that the SEI film containing the organic component lowers side reaction of the electrolyte and the electrode, thereby inhibiting Li precipitation on the surface of the cathode, thereby improving capacity characteristics.

Discharge Capacity (mAh) Example 2 (including HMDS) Comparative Example 2 (without HMDS) 1.0C discharge-1 time 887 874 1.0C discharge-2 times 894 885 1.0C discharge-3 times 890 880 1.0C discharge-4 times 887 874 0.2C discharge-1 time 918 899

2-3. Life characteristic evaluation

Example 2 and Comparative Example 2 was applied to a constant current up to 4.2V in a constant current-constant voltage (CC-CV) method at a rate of 0.92C and then controlled to a constant voltage at 4.2V. At the time of discharging, life characteristics were tested by cutting-off at 3.0V with CC (constant current) method at 1.0C.

As confirmed in the capacity confirmation experiment, the battery of Example 2 in which the HMDS was present not only was charged and discharged at a high initial capacity, but also maintained an advantage of the discharge capacity in a subsequent charge and discharge cycle (see FIG. 4). ). That is, since the life characteristics of the battery have a close relationship with the SEI layer of the negative electrode, it could be determined that the qualitative improvement of the SEI layer of the negative electrode was achieved due to the use of the HMDS additive.

Experimental Example 3. Evaluation of High Temperature Storage Characteristics of Battery

In accordance with the present invention, the high temperature storage characteristics of the lithium secondary battery in which the silazane-based compound was used as an electrolyte component were evaluated as follows.

A lithium secondary battery of Example 2 having a lithium secondary battery of Example 2, in which HMDS was used as an electrolyte component and an electrolyte solution without HMDS, was used as a constant current-constant voltage (CV-CV) method at a rate of 0.92C. After applying a constant current up to V, the current was controlled at a constant voltage at 4.2V. After measuring the initial capacity, the battery was stored at 90 ° C. for 4 hours in a fully charged state and then cycled 50 times to measure the high temperature storage characteristics of the battery.

As a result of the experiment, the battery of Example 2 showed higher initial discharge capacity as well as excellent high temperature life characteristics even after repeated charge and discharge cycles compared to the battery of Comparative Example 2 (see FIG. 5).

As a result, it was found that the secondary battery of the present invention containing the silazane-based compound has excellent high temperature storage characteristics as well as high efficiency, high capacity, and long life.

Experimental Example 4. Comparative evaluation of HF concentration of electrolyte

In order to evaluate the HF concentration increase amount in the electrolyte solution containing the electrolyte additive according to the present invention, the following experiment was performed.

Experiments were performed with an HF measuring instrument (device 785 DMP Titrino) of the electrolyte solution using the electrolyte solution of Example 1 in which HMDS was used as an electrolyte component and the electrolyte solution of Comparative Example 1 without HMDS addition. After the initial acidity (pH) of the electrolyte was measured, the amount of HF remaining per 1 g of the electrolyte was measured through 0.01 N NaOH titration.

As a result of the experiment, it was found that the electrolyte solution of Example 1 had an effect of reducing the initial acidity (pH) and the HF concentration compared to the electrolyte solution of Comparative Example 1 in which the electrolyte additive was not used (see Table 2). This confirms that HMDS acts as an H 2 O scavenger.

Example 1 Comparative Example 1 EC / EMC = 1/2, LiPF 6 1.0M EC / EMC = 1/2, LiPF 6 1.0M, HDMS 0.02 parts by weight Initial pH (pH) 5.18 4.4 Residual HF per weight of electrolyte (ppm / g) 17 ppm / g 42 ppm / g

In the present invention, by using the silazane-based compound as a component of the electrolyte solution, it is possible to implement an improvement in capacity and lifespan of the battery by suppressing an additional reaction that lowers battery performance by forming a stable film on the surface of the positive electrode.

Claims (11)

  1. In a battery electrolyte comprising an electrolyte salt and an electrolyte solvent, the electrolyte is a compound capable of reacting electrochemically in a cell to form a passivation layer, and containing silazane containing one or more silane groups and nitrogen. A battery electrolyte comprising a) series compound.
  2. The battery electrolyte according to claim 1, wherein the silazane-based compound has two or more silane groups in itself and they are connected by nitrogen.
  3. The battery electrolyte of claim 1, wherein the silazane-based compound is represented by the following Chemical Formula 1:
    [Formula 1]
    R 1 R 2 R 3 Si-NR 7 -SiR 4 R 5 R 6
    In formula, R <1> , R <2> , R <3> , R <4> , R <5> , R <6> , R <7> is a C1-C6 alkyl group or alkenyl group which is unsubstituted or substituted by hydrogen, a halogen atom, respectively independently.
  4. The battery electrolyte of claim 1, wherein the silazane-based compound may be oxidized or reduced by charge and discharge in an operating voltage region of a battery to form a passivation layer on the positive electrode, the negative electrode, or both.
  5. The battery electrolyte of claim 1, wherein a content of the silazane-based compound is in a range of 0.01 to 10 parts by weight based on 100 parts by weight of an electrolyte.
  6. An electrode in which a passivation layer formed by electrically oxidizing or reducing a silazane-based compound in which one or more silane groups and nitrogen are simultaneously introduced is formed on a part or all of an electrode active material surface.
  7. The electrode of claim 6, wherein the passivation membrane comprises ether and nitrogen.
  8. The electrode of claim 6, wherein the electrode is an anode, a cathode, or both.
  9. A secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the secondary battery comprises an electrolyte of any one of claims 1 to 5, an electrode of any one of claims 6 to 8, or both. Secondary battery.
  10. An electrolyte solution additive for forming an SEI film, wherein the compound is reduced on a negative electrode of a secondary battery to form a solid electrolyte interface (SEI) film, and is a silazane-based compound containing one or more silane groups and nitrogen.
  11. The additive of claim 10, wherein the silazane-based compound is represented by Formula 1 below:
    [Formula 1]
    R 1 R 2 R 3 Si-NR 7 -SiR 4 R 5 R 6
    In formula, R <1> , R <2> , R <3> , R <4> , R <5> , R <6> , R <7> is a C1-C6 alkyl group or alkenyl group which is unsubstituted or substituted by hydrogen, a halogen atom, respectively independently.
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Cited By (4)

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US20130273426A1 (en) * 2012-04-13 2013-10-17 Lg Chem, Ltd. Secondary battery having improved safety
CN103928708A (en) * 2013-01-16 2014-07-16 三星Sdi株式会社 Electrolyte And Lithium Secondary Battery Comprising The Same
KR101445600B1 (en) * 2012-04-13 2014-10-06 주식회사 엘지화학 Secondary Battery Having Improved Safety
US8877380B2 (en) 2010-09-13 2014-11-04 Samsung Sdi Co., Ltd. Positive active material, method of preparing the same, and lithium battery including the positive active material

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Publication number Priority date Publication date Assignee Title
EP1184927A4 (en) * 2000-02-10 2006-06-28 Mitsubishi Electric Corp Nonaqueous electrolyte cell manufacturing method and cell manufactured thereby
KR100417085B1 (en) * 2001-05-09 2004-02-05 주식회사 엘지화학 New electrolyte and lithium ion battery using the same
KR20060118962A (en) * 2005-05-18 2006-11-24 삼성에스디아이 주식회사 Electrode including si material layer and lithium battery employing the same
KR100914840B1 (en) * 2006-08-21 2009-09-02 주식회사 엘지화학 Non-aqueous Lithium Secondary Battery Containing Hydrophobic, Inactive Particle

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8877380B2 (en) 2010-09-13 2014-11-04 Samsung Sdi Co., Ltd. Positive active material, method of preparing the same, and lithium battery including the positive active material
US20130273426A1 (en) * 2012-04-13 2013-10-17 Lg Chem, Ltd. Secondary battery having improved safety
KR101445602B1 (en) * 2012-04-13 2014-10-06 주식회사 엘지화학 Secondary Battery Having Improved Safety
KR101445600B1 (en) * 2012-04-13 2014-10-06 주식회사 엘지화학 Secondary Battery Having Improved Safety
US9318777B2 (en) 2012-04-13 2016-04-19 Lg Chem, Ltd Secondary battery having improved safety
CN103928708A (en) * 2013-01-16 2014-07-16 三星Sdi株式会社 Electrolyte And Lithium Secondary Battery Comprising The Same

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