JP4954902B2 - Non-aqueous electrolyte secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte secondary battery such as a lithium secondary battery.

  In general, graphite is used as a negative electrode active material of a lithium secondary battery. However, with the recent increase in functionality of electronic devices, their power consumption has increased remarkably, and the need for large-capacity secondary batteries is increasing. It is difficult to meet. Therefore, development of a negative electrode active material made of a Si-based material, which is a material having a higher capacity than graphite, has been actively conducted. However, the negative electrode active material made of a Si-based material has a large degree of expansion / contraction due to charge / discharge, and thus is easily pulverized.

  By the way, it is known that the Si-based negative electrode active material decomposes the electrolyte solution on the surface of the battery when it is charged. By this decomposition, a film called SEI (solid electrolyte interface) is formed on the surface of the active material. The formation of SEI is an irreversible reaction, and once SEI is formed on the surface of the active material, it remains there. As described above, since the Si-based negative electrode active material is easily pulverized with charge / discharge, a new surface, that is, a surface on which SEI is likely to be formed is newly generated each time the charge / discharge is performed. SEI is formed on the new surface, and new SEI may be deposited on the already formed SEI. As a result, with the repetition of charge and discharge, the arrival of lithium ions to the active material surface is gradually hindered by SEI, and the electrode reaction may be inhibited. Also, the amount of electrolyte may decrease due to the formation of SEI. For these reasons, it is not easy to improve the cycle characteristics of the battery.

  From the viewpoint of preventing the decomposition of the electrolytic solution, it has been proposed to use 4-fluoro-ethylene carbonate as a non-aqueous solvent used in the electrolytic solution (see Patent Documents 1 and 2). In these patent documents, 4-fluoro-ethylene carbonate is used in combination with diethyl carbonate and dimethyl carbonate which are linear carbonates. However, in these documents, 4-fluoro-ethylene carbonate and linear carbonate are used so that the blending ratio of both is approximately 1: 1. As a result, the rate characteristics are likely to deteriorate.

US2006 / 0099515A1 US2006 / 0134524A1

The present invention relates to a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte solution in which a lithium salt is dissolved in a positive electrode, a negative electrode, and a non-aqueous solvent.
The negative electrode has an active material layer including a current collector and an active material containing Si formed on at least one surface thereof,
The non-aqueous solvent contains a compound represented by the following formula (1) and a compound represented by the following formula (2), and the ratio of the compound represented by the formula (1) in the non-aqueous solvent is 15 to 40 Ri vol% der, in which the proportion of the compound represented by formula (2) occupying the non-aqueous solvent to provide a non-aqueous electrolyte secondary battery, characterized 55-85 vol% der Rukoto.

It is a schematic diagram which shows the cross-sectional structure of one Embodiment of the negative electrode used for the nonaqueous electrolyte secondary battery of this invention. It is process drawing which shows the manufacturing method of the negative electrode shown in FIG.

  Hereinafter, the present invention will be described based on preferred embodiments thereof. The nonaqueous electrolyte secondary battery of the present invention (hereinafter also simply referred to as a secondary battery or a battery) has a positive electrode, a negative electrode, and a separator disposed between them as its basic constituent members. The space between the positive electrode and the negative electrode is filled with a non-aqueous electrolyte via a separator. The battery of the present invention may be in the form of a cylindrical shape, a square shape, a coin shape or the like provided with these basic components. However, it is not limited to these forms.

The positive electrode used in the battery of the present invention has, for example, a positive electrode active material layer formed on at least one surface of a current collector. The positive electrode active material layer contains an active material. As this active material, for example, a lithium transition metal composite oxide is used. LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiCo _0.5 Ni _0.5 O ₂ , LiNi _0.7 Co _0.2 Mn _0.1 O ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , Li (Li _x Mn _2x Co _1-3x ) O ₂ (where x is 0 <x <1/3) or the like is used. However, it is not limited to these. These positive electrode active materials can be used singly or in combination of two or more.

Among the various positive electrode active materials described above, materials containing Li and Co as constituent elements such as LiCoO ₂ have the property of contracting when lithium is occluded and expanding when released. On the other hand, those containing Ni as a constituent element such as LiNiO ₂ and those containing Mn as a constituent element such as LiMn ₂ O ₄ are expanded when lithium is occluded or the degree of contraction when lithium is occluded However, it has the property that it is smaller than the lithium transition metal complex oxide containing Li and Co as constituent elements.

  The positive electrode used in the present invention is prepared by suspending the positive electrode active material in a suitable solvent together with a conductive agent such as acetylene black and a binder such as polyvinylidene fluoride to produce a positive electrode mixture, which is an aluminum foil. It is obtained by applying and drying on at least one surface of a current collector such as roll rolling and pressing.

  When the positive electrode is produced by the above method, the lithium transition metal composite oxide preferably has an average primary particle diameter of 5 μm or more and 10 μm or less in view of the packing density and the reaction area. The polyvinylidene fluoride used as the binder preferably has a weight average molecular weight of 350,000 or more and 2,000,000 or less from the viewpoint of improving discharge characteristics in a low temperature environment.

  The negative electrode used in the battery of the present invention has, for example, a negative electrode active material layer formed on at least one surface of a current collector. The negative electrode active material layer contains an active material. The active material used in the present invention is a substance containing Si. The secondary battery of the present invention is characterized in that a substance containing Si is used as a negative electrode active material and this is combined with a nonaqueous solvent described later. Details thereof will be described later.

  The negative electrode active material containing Si is capable of occluding and releasing lithium ions. The negative electrode active material containing Si has a property of expanding when lithium is occluded and contracting when released. The degree of expansion and contraction is extremely large as compared with the carbon-based material that has been used as the negative electrode active material of the conventional lithium secondary battery. As an example of the negative electrode material containing Si, silicon alone, an alloy of silicon and metal, silicon oxide, silicon nitride, silicon boride and the like can be used. These materials can be used alone or in combination. Examples of the metal include one or more elements selected from the group consisting of Cu, Ni, Co, Cr, Fe, Ti, Pt, W, Mo, and Au. Among these metals, Cu, Ni, and Co are preferable, and Cu and Ni are preferably used from the viewpoint of excellent electronic conductivity and a low ability to form a lithium compound. A particularly preferable negative electrode active material containing Si is silicon alone or silicon oxide from the viewpoint of high lithium storage capacity.

  The negative electrode active material containing Si preferably contains lithium before the start of battery charging. As a result, lithium is accumulated as an irreversible capacity in the negative electrode active material before the start of charge / discharge. Therefore, since charging / discharging is started from the state in which lithium is occluded in the negative electrode active material, charging / discharging is performed reversibly almost 100%. Moreover, since Si-based materials have low electron conductivity, during discharge, lithium is constantly occluded in the negative electrode active material, so that the electron conductivity is improved and the negative electrode polarization is reduced. Get smaller. This makes it difficult for the voltage of the negative electrode to rapidly decrease at the end of discharge.

  The fact that the negative electrode active material containing Si contains lithium before the start of charging of the battery is advantageous in that overvoltage can be kept low during the lithium insertion reaction (during charging) on the surface of the negative electrode active material. It is. This is because, by suppressing the overvoltage to a low level, side reactions such as excessive SEI formation can be prevented.

In order to allow lithium to be contained in the negative electrode active material containing Si from the start of charging, for example, Si is contained by a known means before or after incorporating the negative electrode into the battery and before the start of charging. What is necessary is just to occlude lithium with respect to a negative electrode active material. As a means for occluding lithium, for example, the method described in WO2006 / 100794A1 and the method described in US5556721A according to the previous application of the present applicant can be used. In addition, the negative electrode and metallic lithium before occlusion of lithium are immersed in a non-aqueous solvent containing lithium salt through a mesh made of a conductive material, and the negative electrode and metallic lithium are electrochemically short-circuited to occlude lithium. Can be made. In this case, the occlusion amount can be controlled by the environmental temperature, the mesh size, the mesh material, the configuration of the nonaqueous solvent, and the immersion time. Whichever method is employed, the lithium storage amount is preferably set to 10 to 40%, more preferably 20 to 40%, and still more preferably 25 to 35% with respect to the initial charge theoretical capacity of the negative electrode active material. To do. In the present embodiment, when a material containing silicon is used as the negative electrode active material, theoretically, silicon occludes lithium to the state represented by the composition formula SiLi _4.4. Therefore, the occlusion amount of lithium is the initial charge of silicon. 100% of the theoretical capacity means that lithium is occluded by silicon to the state represented by the composition formula SiLi _4.4 .

  The negative electrode active material layer can be, for example, a continuous thin film layer made of the negative electrode active material. In this case, the negative electrode active material layer made of a thin film is formed on at least one surface of the current collector by various thin film forming means such as chemical vapor deposition, physical vapor deposition, and sputtering. The thin film may be etched to form a large number of voids extending in the thickness direction. In addition to the wet etching method using a sodium hydroxide aqueous solution or the like, a dry etching method using a dry gas or plasma can be employed for the etching. In addition to the form of the continuous thin film layer, the negative electrode active material layer may be a coating layer containing particles of the negative electrode active material, a sintered body layer containing particles of the negative electrode active material, or the like. Moreover, it may be a layer having a structure shown in FIG.

  As the separator in the secondary battery of the present invention, a synthetic resin nonwoven fabric, a polyolefin such as polyethylene or polypropylene, or a polytetrafluoroethylene porous film is preferably used. From the viewpoint of suppressing the heat generation of the electrode that occurs when the battery is overcharged, it is preferable to use a separator in which a thin film of a ferrocene derivative is formed on one side or both sides of a polyolefin microporous membrane. The separator preferably has a puncture strength of 0.2 N / μm thickness or more and 0.49 N / μm thickness or less, and a tensile strength in the winding axis direction of 40 MPa or more and 150 MPa or less. This is because even when a Si-based material that is a negative electrode active material that expands and contracts greatly with charge and discharge is used, damage to the separator can be suppressed, and occurrence of internal short circuits can be suppressed.

  The nonaqueous electrolytic solution is a solution in which a lithium salt as a supporting electrolyte is dissolved in a nonaqueous solvent. The secondary battery of the present invention has one of the characteristics in the type of the non-aqueous solvent. Specifically, the non-aqueous solvent contains the compounds represented by the above formulas (1) and (2). In the secondary battery of the present invention, as described above, the material containing Si is used as the negative electrode active material. The negative electrode active material containing Si has a property of decomposing a nonaqueous solvent during charging. ing. From the viewpoint of preventing this decomposition, in the present invention, a non-aqueous solvent containing each of the above compounds, that is, a fluorinated non-aqueous solvent is used.

  When a non-aqueous solvent used for a lithium secondary battery is generally fluorinated, the viscosity is higher than before fluorination due to the bulky steric hindrance of fluorine atoms. In addition, the introduction of fluorine with strong electronegativity increases the polarity and intermolecular interaction. A stronger intermolecular interaction leads to an increase in viscosity. A stronger polarity leads to an increase in dielectric constant. The increase in the viscosity causes an increase in the internal resistance of the battery due to the decrease in the conductivity, and acts in a negative direction such as a decrease in rate characteristics. On the other hand, an increase in the dielectric constant acts in the positive direction of increasing the conductivity. Comparing the negative effect resulting from the increase in the viscosity and the positive effect resulting from the increase in the dielectric constant, the negative effect resulting from the increase in the viscosity tends to be larger. Therefore, if an attempt is made to reduce the amount of the fluorinated nonaqueous solvent to prevent an increase in the viscosity, the conductivity of the entire nonaqueous mixed solvent is lowered, and the internal resistance of the battery is increased. This is because the compound itself represented by the formula (1) has a characteristic that the dielectric constant is higher than that of the compound represented by the formula (2). In consideration of these circumstances, in the present invention, the ratio of the compound represented by the formula (1) in the non-aqueous solvent is set to 15 to 40% by volume, which is a lower value than conventional, and preferably 20 to It is set to 40% by volume, more preferably 25 to 40% by volume, and still more preferably 25 to 35% by volume. As a result, it is possible to prevent decomposition of the non-aqueous solvent and thus improve cycle characteristics while suppressing an increase in the internal resistance of the battery and a decrease in charge / discharge rate characteristics. On the other hand, the proportion of the compound represented by the formula (2) in the non-aqueous solvent is set to 55 to 85% by volume, which is a higher rate than before, preferably 55 to 80% by volume, more preferably 55 to 75%. Volume% is set, more preferably 65 to 75 volume%. Since the compound represented by the formula (2) is a substance having a lower viscosity than the compound represented by the formula (1), the viscosity of the non-aqueous electrolyte as a whole can be increased by increasing its use ratio. The rate increase is suppressed. In this specification, “volume” means a volume at 25 ° C.

In the present embodiment, in addition to the compound represented by the formula (1) and the compound represented by the formula (2), another nonaqueous solvent conventionally used in nonaqueous electrolyte secondary batteries is further used. May be. For example, a compound in which R ¹ and R ² are both H in formula (1) may be used. The amount of other nonaqueous solvent that can be optionally used in combination is preferably 1 to 50%, particularly 10 to 30%, based on the total volume of the nonaqueous solvent.

As a result of the study by the present inventors, in the compound represented by formula (1), only ^one of R ¹ and R ² is F and the other is H, that is, represented by formula (1). It was found that when the compound to be obtained is a monofluorinated compound, its decomposition is further prevented and the cycle characteristics are further improved. For the same reason, it has been found that it is preferable that all of R ^{3 to} R ⁶ are H for the compound represented by the formula (2). In addition, by including F in the compound represented by the formula (1), stable SEI is formed on the surface of the negative electrode active material when the battery is charged. Since LiF and the like are formed in this SEI, a part of Li responsible for charge / discharge is consumed due to this. Therefore, it is advantageous that the negative electrode active material contains Li before the start of charging / discharging of the battery in that the Li becomes a supply source of consumed Li.

As for the compound represented by formula (2), the compound is a mixture of a compound in which R ^{3 to} R ⁶ are H and a compound in which at least one of R ^{3 to} R ⁶ is F in the formula It is also preferable. This is because by using such a mixture, the capacity retention rate is further improved as compared with the case where only the compound in which R ^{3 to} R ⁶ are H in the compound represented by the formula (2). In the case of using such a mixture, from this viewpoint, the ratio of the compound represented by formula (2) in which at least one of R ^{3 to} R ⁶ is F to the nonaqueous solvent is 10 to 40% by volume. Is preferable, and it is still more preferable that it is 15-30 volume%. On the other hand, the proportion of the compound represented by formula (2) in which R ^{3 to} R ⁶ are H in the non-aqueous solvent is preferably 35 to 65% by volume, and 45 to 55% by volume. Is more preferable.

In particular, when the above mixture is used in combination with a compound represented by the formula (1) in which only ^one of R ¹ and R ² is F and the other is H, the capacity retention ratio is increased. Further improvement is preferable.

In addition, when the compound represented by Formula (2) contains F, it is preferable that only any one of R < ³ > -R < ⁶ > is F. In particular, it is preferable that only one of R ³ and R ⁶ bonded to carbon located at the terminal in the molecular skeleton is F.

  In this embodiment, 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI) may be used in addition to the compound represented by formula (1) and the compound represented by formula (2). preferable. By using DMI together, the capacity maintenance rate of the battery can be improved. The amount of DMI used in the non-aqueous solvent is preferably 0.5 to 1% by volume from the viewpoint of improving the capacity retention rate of the battery while controlling the decomposition behavior of DMI in the battery.

  As described above, in the present invention, by using the compounds represented by the formulas (1) and (2) together as a nonaqueous solvent, the decomposition of the nonaqueous solvent on the surface of the substance containing Si used as the negative electrode active material Can be effectively prevented. By the way, as described above, the negative electrode active material containing Si is preferably in a state containing lithium before the charging of the battery is started. Since the overvoltage during lithium insertion into the active material can be kept low, the SEI formed on the surface of the negative electrode active material tends to be thin and dense. The formation of such a thin and dense SEI suppresses contact between a new active material surface and a non-aqueous solvent that occurs each time charging / discharging, and therefore, continuous decomposition of the non-aqueous solvent is difficult to occur. Therefore, when the negative electrode active material containing Si contains lithium before the start of charging of the battery, the compounds represented by the formulas (1) and (2) are used in combination as non-aqueous solvents. The effect becomes even more remarkable.

  As described above regarding the negative electrode active material containing Si, this active material has a property of expanding when lithium is occluded and contracting when released. On the other hand, as described above regarding the positive electrode active material, the lithium transition metal composite oxide containing Li and Co as constituent elements has a property of contracting when lithium is occluded and expanding when released. That is, the lithium transition metal composite oxide and the Si-containing negative electrode active material exhibit the opposite behavior in terms of volume change with respect to insertion and release of lithium. Therefore, when the battery of the present invention is charged, the negative electrode active material expands and the positive electrode active material contracts. Conversely, during discharge, the positive electrode active material expands and the negative electrode active material contracts. Thus, during charging, the volume of expansion of the negative electrode active material is absorbed by the volume of contraction of the positive electrode active material. Conversely, during discharge, the volume of expansion of the positive electrode active material is the volume of the negative electrode active material. Absorbed by the volume of contraction. As a result, in both cases of charging and discharging, it is possible to suppress the generation of stress due to the volume change of the entire battery, and effectively prevent the positive electrode, the negative electrode, the separator, and the like from being damaged. . As a result, the cycle characteristics of the battery are improved. Thus, in the present invention, by using a specific positive electrode active material, in addition to improving the cycle characteristics by preventing the decomposition of the nonaqueous solvent, the cycle by suppressing the generation of stress due to the volume change of the whole battery The characteristics are also improved.

  In particular, the weight ratio of Co in the positive electrode to Co in the negative electrode (Co / Si) is preferably set to 0.3 to 5.5, more preferably 0.4 to 2.5, and still more preferably 0.4 to 1. By doing so, it is possible to more effectively suppress the generation of stress due to the volume change of the entire battery. Specifically, by setting the weight ratio of Co / Si to 0.3 or more, a decrease in rate characteristics due to a decrease in the amount of Co is avoided, and a high energy density (or capacity) is also obtained for the negative electrode. Will be. Further, by setting the Co / Si weight ratio to 5.5 or less, the balance between the contraction of the positive electrode active material and the expansion of the negative electrode active material during charging becomes good, and the stress is sufficiently relaxed.

LiCoO ₂ is a typical lithium transition metal composite oxide containing Li and Co as constituent elements, but the composite oxide that can be used in the present invention is not limited to this. For example, the following formula (1) Can be widely used.
LiCo _x M _1-x O ₂ (1)
(In the formula, x represents a positive number less than 1, and M represents a metal element.)

  In the above formula, examples of the metal element represented by M include transition metal elements other than Co and typical metal elements other than Li. Examples of the transition metal element include Ni, Mn, Fe, V, Zr, Ti, Mo, W, and Nb. In particular, it is preferable to use Ni and / or Mn as the transition metal element. On the other hand, examples of typical metal elements include Mg, Al, and Ga. As described above, x in the composite oxide is a positive number less than 1, preferably 0.1 to 0.4, and more preferably 0.11 to 0.30.

  The amount of Co contained in the composite oxide is preferably 10 to 40% by weight, more preferably 10 to 30% by weight, based on the total amount of transition metal elements contained in the composite oxide. By setting the amount of Co in the composite oxide within this range, it is possible to make the degree of shrinkage when the composite oxide occludes lithium within an appropriate range.

Specific examples of the composite oxide include, for example, Li (Co _a Mn _b Ni _c ) O ₂ (wherein a + b + c = 1, 0 <a <1, 0 ≦ b <1, 0 ≦ c <1, provided that b and c cannot be 0 at the same time), Li (Co _a Fe _b ) O ₂ (where a + b = 1, 0 <a <1, 0 <b <1), Li (Co _a V _b ) O ₂ (Wherein, a + b = 1, 0 <a <1, 0 <b <1). These composite oxides may be used alone or in combination of two or more. Of these composite oxides, it is preferable to use a material having a large volume change due to insertion and extraction of lithium. The reason for this is that the material containing Si, which is the negative electrode active material used in combination with the composite oxide, is a material that has a large volume change due to insertion and extraction of lithium. This is because volume changes of the entire battery are easily offset. Examples of preferable materials from this viewpoint include LiMn _0.3 Co _0.4 Ni _0.3 O ₂ , LiMn _0.45 Co _0.10 Ni _0.45 O ₂ , and LiMn _1/3 Co _1/3 Ni _1/3 O ₂ . These materials are produced by a known method, for example, by baking lithium carbonate and a transition metal oxide in the atmosphere.

  From the viewpoint of further improving the cycle characteristics of the battery, it is preferable to use a negative electrode having the structure shown in FIG. The negative electrode 10 of the embodiment shown in the figure includes a current collector 11 and an active material layer 12 formed on at least one surface thereof. 1 shows a state in which the active material layer 12 is formed only on one side of the current collector 11 for convenience, the active material layer may be formed on both sides of the current collector. .

  In the active material layer 12, at least a part of the surface of the active material particles 12 a containing Si is covered with a metal material having a low lithium compound forming ability. The metal material 13 is a material different from the constituent material of the particles 12a. Gaps are formed between the particles 12a coated with the metal material. That is, the metal material covers the surface of the particle 12a in a state in which a gap is ensured so that the non-aqueous electrolyte containing lithium ions can reach the particle 12a. In FIG. 1, the metal material 13 is conveniently represented as a thick line surrounding the periphery of the particle 12a. Each particle is in direct contact with other particles or through the metal material 13. “Low lithium compound forming ability” means that lithium does not form an intermetallic compound or solid solution, or even if formed, lithium is in a very small amount or very unstable.

  The metal material 13 has conductivity, and examples thereof include copper, nickel, iron, cobalt, and alloys of these metals. In particular, the metal material 13 is preferably a highly ductile material in which even if the active material particles 12a expand and contract, the coating on the surface of the particles 12a is not easily broken. It is preferable to use copper as such a material.

  The metal material 13 is preferably present on the surface of the active material particles 12 a over the entire thickness direction of the active material layer 12. The active material particles 12 a are preferably present in the matrix of the metal material 13. Thus, even if the particles 12a are pulverized due to expansion and contraction due to charge / discharge, the particles are less likely to fall off. In addition, since the electronic conductivity of the entire active material layer 12 is ensured through the metal material 13, the electrically isolated active material particles 12 a are generated, and in particular, the electrically isolated active material is deep in the active material layer 12. Generation of the particles 12a of the substance is effectively prevented. The presence of the metal material 13 on the surface of the active material particles 12a over the entire thickness direction of the active material layer 12 can be confirmed by electron microscope mapping using the material 13 as a measurement target.

  The metal material 13 coats the surface of the particle 12a continuously or discontinuously. When the metal material 13 continuously covers the surfaces of the particles 12a, it is preferable to form fine voids in the coating of the metal material 13 that allow the non-aqueous electrolyte to flow. When the metal material 13 discontinuously coats the surface of the particle 12a, the non-aqueous electrolyte is supplied to the particle 12a through a portion of the surface of the particle 12a that is not covered with the metal material 13. In order to form the coating of the metal material 13 having such a structure, the metal material 13 may be deposited on the surfaces of the particles 12a by, for example, electrolytic plating in accordance with conditions described later.

  The average thickness of the metal material 13 covering the surface of the active material particles 12a is preferably 0.05 to 2 μm, more preferably 0.1 to 0.25 μm. That is, the metal material 13 covers the surface of the active material particles 12a with a minimum thickness. As a result, while the energy density is increased, the particles 12a are prevented from falling off due to expansion / contraction and pulverization due to charge / discharge. Here, the “average thickness” is a value calculated based on a portion of the surface of the active material particle 12 a that is actually covered with the metal material 13. Accordingly, the portion of the surface of the active material particle 12a that is not covered with the metal material 13 is not used as the basis for calculating the average value.

  The surface of the active material particle 12 a is coated with the metal material 13, whereby electron conductivity is imparted to the particle 12 a. As a result, it is possible to keep the overvoltage during charging low. As a result, the SEI formed on the surface of the active material particles 12a can be made thin and dense. As described above, the formation of such a thin and dense SEI suppresses contact between a new active material surface and a non-aqueous solvent that occurs every time charging / discharging, and therefore, continuous decomposition of the non-aqueous solvent is prevented. It is hard to happen. Therefore, when the surfaces of the active material particles 12a are coated with the metal material 13, the effects of the present invention are further improved by using the compounds represented by the formulas (1) and (2) together as the non-aqueous solvent. It will be remarkable.

  The voids formed between the particles 12a coated with the metal material 13 have a function as a flow path of the non-aqueous electrolyte containing lithium ions. Since the non-aqueous electrolyte smoothly flows in the thickness direction of the active material layer 12 due to the presence of the voids, cycle characteristics can be improved. Further, the voids formed between the particles 12a also have a function as a space for relieving stress caused by the volume change of the active material particles 12a due to charge and discharge. The increase in the volume of the active material particles 12a whose volume has been increased by charging is absorbed by the voids. As a result, pulverization of the particles 12a is difficult to occur, and significant deformation of the negative electrode 10 is effectively prevented.

  As described later, the active material layer 12 is preferably electrolyzed using a predetermined plating bath on a coating film obtained by applying a slurry containing particles 12a and a binder onto a current collector and drying the slurry. It forms by plating and depositing the metal material 13 between the particle | grains 12a.

  In order to form necessary and sufficient voids in the active material layer 12 in which the non-aqueous electrolyte can be circulated, it is preferable to sufficiently infiltrate the plating solution into the coating film. In addition to this, it is preferable to make conditions suitable for depositing the metal material 13 by electrolytic plating using the plating solution. The plating conditions include the composition of the plating bath, the pH of the plating bath, and the current density of electrolysis. Regarding the pH of the plating bath, it is preferable to adjust this to 7.1-11. By controlling the pH within this range, the dissolution of the active material particles 12a is suppressed, the surface of the particles 12a is cleaned, and plating on the particle surface is promoted. Is formed. The value of pH is measured at the temperature at the time of plating.

When using copper as the metal material 13 for plating, it is preferable to use a copper pyrophosphate bath. When nickel is used as the metal material, for example, an alkaline nickel bath is preferably used. In particular, it is preferable to use a copper pyrophosphate bath, even if the active material layer 12 is thick, because the voids can be easily formed over the entire thickness direction of the layer. Further, since the metal material 13 is deposited on the surface of the active material particles 12a and the metal material 13 is less likely to be deposited between the particles 12a, the voids between the particles 12a are also successfully formed. preferable. When using a copper pyrophosphate bath, the bath composition, electrolysis conditions and pH are preferably as follows.
Copper pyrophosphate trihydrate: 85-120 g / l
-Potassium pyrophosphate: 300-600 g / l
-Potassium nitrate: 15-65 g / l
-Bath temperature: 45-60 ° C
・ Current density: 1 to 7 A / dm ²
PH: Ammonia water and polyphosphoric acid are added to adjust the pH to 7.1 to 9.5.

In particular, when a copper pyrophosphate bath is used, it is preferable to use one having a P ratio defined by a ratio of P ₂ O ₇ weight to Cu weight (P ₂ O ₇ / Cu) of 5 to 12. . When the P ratio is less than 5, the metal material 13 covering the active material particles 12a tends to be thick, and it may be difficult to form desired voids between the particles 12a. Further, when a P ratio exceeding 12 is used, current efficiency is deteriorated, and gas generation is likely to occur, so that production stability may be lowered. When a copper pyrophosphate bath having a P ratio of 6.5 to 10.5 is used as a more preferable copper pyrophosphate bath, the size and number of voids formed between the active material particles 12a may be reduced. This is very advantageous for the flow of the water electrolyte.

When an alkaline nickel bath is used, the bath composition, electrolysis conditions and pH are preferably as follows.
Nickel sulfate: 100 to 250 g / l
Ammonium chloride: 15-30 g / l
・ Boric acid: 15-45 g / l
-Bath temperature: 45-60 ° C
・ Current density: 1 to 7 A / dm ²
-PH: 25% by weight ammonia water: Adjust to pH 8-11 within the range of 100-300 g / l.
When this alkaline nickel bath and the above-described copper pyrophosphate bath are compared, there is a tendency that moderate voids are formed in the active material layer 12 when the copper pyrophosphate bath is used, and the life of the negative electrode is increased. It is preferable because it is easy to achieve.

  The characteristics of the metal material 13 can be appropriately adjusted by adding various additives used in the electrolytic solution for producing copper foil such as protein, active sulfur compound, and cellulose to the above various plating baths.

  The ratio of the voids in the entire active material layer formed by the various methods described above, that is, the void ratio is preferably about 15 to 45% by volume, particularly about 20 to 40% by volume. By setting the porosity within this range, it is possible to form necessary and sufficient voids in the active material layer 12 that allow the nonaqueous electrolyte to flow. The void amount of the active material layer 12 is measured by a mercury intrusion method (JIS R 1655). The mercury intrusion method is a method for obtaining information on the physical shape of a solid by measuring the size and volume of pores in the solid. The principle of the mercury intrusion method is to apply a pressure to mercury to inject it into the pores of the object to be measured, and to measure the relationship between the pressure applied at that time and the volume of mercury that has been pushed in (intruded). In this case, mercury enters sequentially from the large voids present in the active material layer 12. In the present invention, the void amount measured at a pressure of 90 MPa is regarded as the entire void amount. The porosity (%) of the active material layer 12 is obtained by dividing the void amount per unit area measured by the above method by the apparent volume of the active material layer 12 per unit area and multiplying it by 100. .

  In the negative electrode of the present embodiment, the porosity calculated from the void amount of the active material layer 12 measured by the mercury intrusion method is within the above range, and in addition, the active mass measured by the mercury intrusion method at 10 MPa. The porosity calculated from the amount of voids in the material layer 12 is preferably 10 to 40%. Moreover, it is preferable that the porosity calculated from the void amount of the active material layer 12 measured by the mercury intrusion method at 1 MPa is 0.5 to 15%. Furthermore, it is preferable that the porosity calculated from the void amount of the active material layer 12 measured by the mercury intrusion method at 5 MPa is 1 to 35%. As described above, in the mercury intrusion measurement, mercury intrusion conditions are gradually increased. Under low pressure conditions, mercury is pressed into large gaps, and under high pressure conditions, mercury is pressed into small gaps. Therefore, the porosity measured at a pressure of 1 MPa is mainly derived from large voids. On the other hand, the porosity measured at a pressure of 10 MPa reflects the presence of small voids.

The porosity can also be controlled by appropriately selecting the particle size of the active material particles 12a. From this viewpoint, the particle 12a has a maximum particle size of preferably 30 μm or less, more preferably 10 μm or less. Moreover, when the particle diameter of the particle is expressed by a D ₅₀ value, it is preferably 0.1 to 8 μm, particularly preferably 0.3 to 4 μm. The particle size of the particles is measured by laser diffraction / scattering particle size distribution measurement and electron microscope observation (SEM observation).

  If the amount of the active material relative to the whole negative electrode is too small, it is difficult to sufficiently improve the energy density of the battery. Conversely, if the amount is too large, the strength decreases and the active material tends to fall off. Considering these, the thickness of the active material layer is 10 to 40 μm, preferably 15 to 30 μm, and more preferably 18 to 25 μm.

  In the negative electrode 10 of the present embodiment, a thin surface layer (not shown) may be formed on the surface of the active material layer 12. Further, the negative electrode 10 may not have such a surface layer. The thickness of the surface layer is 0.25 μm or less, preferably 0.1 μm or less. There is no restriction | limiting in the lower limit of the thickness of a surface layer. By forming the surface layer, the pulverized active material particles 12a can be further prevented from falling off. However, in the present embodiment, by setting the porosity of the active material layer 12 within the above-described range, it is possible to sufficiently prevent the pulverized active material particles 12a from dropping without using a surface layer. Is possible.

  When the negative electrode 10 has the thin surface layer or does not have the surface layer, a secondary battery is assembled using the negative electrode 10 to reduce the overvoltage when the battery is initially charged. Can do. This means that lithium can be prevented from being reduced on the surface of the negative electrode 10 when the secondary battery is charged. The reduction of lithium leads to the generation of dendrites that cause a short circuit between the two electrodes.

  When the negative electrode 10 has a surface layer, the surface layer covers the surface of the active material layer 12 continuously or discontinuously. When the surface layer continuously covers the surface of the active material layer 12, the surface layer has a large number of microscopic voids (not shown) that are open at the surface and communicate with the active material layer 12. It is preferable. The fine voids are preferably present in the surface layer so as to extend in the thickness direction of the surface layer. The fine voids allow the non-aqueous electrolyte to flow. The role of the fine voids is to supply a non-aqueous electrolyte into the active material layer 12. When the surface of the negative electrode 10 is viewed in plan by electron microscope observation, the fine voids are such that the ratio of the area covered with the metal material 13, that is, the coverage is 95% or less, particularly 80% or less, especially 60% or less. It is preferable that the size is large. When the coverage exceeds 95%, it is difficult for a non-aqueous electrolyte having a high viscosity to penetrate, and the range of selection of the non-aqueous electrolyte may be narrowed.

  The surface layer is made of a metal material having a low lithium compound forming ability. This metal material may be the same as or different from the metal material 13 present in the active material layer 12. The surface layer may have a structure of two or more layers made of two or more different metal materials. Considering the ease of manufacture of the negative electrode 10, the metal material 13 present in the active material layer 12 and the metal material constituting the surface layer are preferably the same type.

  Since the porosity in the active material layer 12 has a high value, the negative electrode 10 of this embodiment has high resistance to bending. Specifically, the MIT folding resistance measured according to JIS C 6471 is preferably 30 times or more, more preferably 50 times or more. High folding resistance is extremely advantageous since the negative electrode 10 is less likely to be folded when the negative electrode 10 is folded or wound and accommodated in a battery container. As the MIT folding endurance device, for example, a film folding endurance fatigue tester (product number 549) manufactured by Toyo Seiki Seisakusho is used, and measurement can be performed with a bending radius of 0.8 mm, a load of 0.5 kgf and a sample size of 15 × 150 mm. it can.

  As the current collector 11 in the negative electrode 10, the same one as conventionally used as the current collector of the negative electrode for the non-aqueous electrolyte secondary battery can be used. The current collector 11 is preferably made of a metal material having a low lithium compound forming ability as described above. Examples of such metal materials are as already described. In particular, it is preferably made of copper, nickel, stainless steel or the like. Also, it is possible to use a copper alloy foil represented by a Corson alloy foil. Further, as the current collector, a metal foil having a normal tensile strength (JIS C 2318) of preferably 500 MPa or more, for example, a copper film layer formed on at least one surface of the aforementioned Corson alloy foil can be used. Furthermore, it is preferable to use a current collector having a normal elongation (JIS C 2318) of 4% or more. This is because when the tensile strength is low, wrinkles are generated due to stress when the active material expands, and when the elongation is low, the current collector may crack. By using these current collectors, it is possible to further improve the folding resistance of the negative electrode 10 described above. The thickness of the current collector 11 is preferably 9 to 35 μm considering the balance between maintaining the strength of the negative electrode 10 and improving the energy density. In addition, when using copper foil as the electrical power collector 11, it is preferable to give the rust prevention process using organic compounds, such as a chromate process and a triazole type compound and an imidazole type compound.

  Next, the preferable manufacturing method of the negative electrode 10 of this embodiment is demonstrated, referring FIG. In this manufacturing method, a coating film is formed on the current collector 11 using a slurry containing particles of an active material and a binder, and then electrolytic plating is performed on the coating film.

  First, a current collector 11 is prepared as shown in FIG. Then, a slurry containing active material particles 12 a is applied onto the current collector 11 to form a coating film 15. The surface roughness of the coating film forming surface of the current collector 11 is preferably 0.5 to 4 μm at the maximum height of the contour curve. If the maximum height exceeds 4 μm, the formation accuracy of the coating film 15 is lowered and current concentration of the permeation plating tends to occur on the convex portions. When the maximum height is less than 0.5 μm, the adhesion of the active material layer 12 tends to be lowered. As the active material particles 12a, those having the above-described particle size distribution and average particle size are preferably used.

  The slurry contains a binder and a diluting solvent in addition to the active material particles. The slurry may contain a small amount of conductive carbon material particles such as acetylene black and graphite. In particular, when the active material particles 12a are made of a silicon-based material, the conductive carbon material is preferably contained in an amount of 1 to 3% by weight based on the weight of the active material particles 12a. When the content of the conductive carbon material is less than 1% by weight, the viscosity of the slurry is lowered and the sedimentation of the active material particles 12a is promoted, so that it is difficult to form a good coating film 15 and uniform voids. Become. On the other hand, if the content of the conductive carbon material exceeds 3% by weight, plating nuclei concentrate on the surface of the conductive carbon material, and it becomes difficult to form a good coating.

  As the binder, styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), polyethylene (PE), ethylene propylene diene monomer (EPDM), or the like is used. As a diluting solvent, N-methylpyrrolidone, cyclohexane or the like is used. The amount of the active material particles 12a in the slurry is preferably about 30 to 70% by weight. The amount of the binder is preferably about 0.4 to 4% by weight. A dilution solvent is added to these to form a slurry.

  The formed coating film 15 has a large number of minute spaces between the particles 12a. The current collector 11 on which the coating film 15 is formed is immersed in a plating bath containing a metal material having a low lithium compound forming ability. By immersion in the plating bath, the plating solution enters the minute space in the coating film 15 and reaches the interface between the coating film 15 and the current collector 11. Under this condition, electrolytic plating is performed to deposit plating metal species on the surfaces of the particles 12a (hereinafter, this plating is also referred to as permeation plating). The osmotic plating is performed by using the current collector 11 as a cathode, immersing a counter electrode as an anode in a plating bath, and connecting both electrodes to a power source.

  The deposition of the metal material by the osmotic plating is preferably progressed from one side of the coating film 15 to the other side. Specifically, as shown in FIGS. 2B to 2D, electrolytic plating is performed so that the deposition of the metal material 13 proceeds from the interface between the coating film 15 and the current collector 11 toward the surface of the coating film. I do. By precipitating the metal material 13 in this way, the surface of the active material particles 12a can be successfully coated with the metal material 13, and a void is successfully formed between the particles 12a coated with the metal material 13. be able to.

  As described above, the conditions of the infiltration plating for depositing the metal material 13 include the composition of the plating bath, the pH of the plating bath, the current density of electrolysis, and the like. Such conditions are as already described.

  As shown in FIGS. 2B to 2D, when plating is performed such that the deposition of the metal material 13 proceeds from the interface between the coating film 15 and the current collector 11 toward the surface of the coating film. In the forefront portion of the precipitation reaction, fine particles 13a made of plating nuclei of the metal material 13 are present in layers with a substantially constant thickness. As the deposition of the metal material 13 proceeds, adjacent microparticles 13a combine to form larger particles, and when the deposition proceeds further, the particles combine to continuously cover the surface of the active material particles 12a. It becomes like this.

  The permeation plating is terminated when the metal material 13 is deposited on the entire thickness direction of the coating film 15. By adjusting the end point of plating, a surface layer (not shown) can be formed on the upper surface of the active material layer 12. In this way, the target negative electrode is obtained as shown in FIG.

  It is also preferable to subject the negative electrode 10 to rust prevention after the osmotic plating. As the rust prevention treatment, for example, organic rust prevention using triazole compounds such as benzotriazole, carboxybenzotriazole, tolyltriazole, and imidazole, and inorganic rust prevention using cobalt, nickel, chromate and the like can be employed.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples.

[Example 1]
(1) Production of Negative Electrode A current collector made of an electrolytic copper foil having a thickness of 18 μm was acid washed at room temperature for 30 seconds. After the treatment, it was washed with pure water for 15 seconds. A slurry containing silicon particles was applied on both sides of the current collector to a thickness of 15 μm to form a coating film. The composition of the slurry was particles: styrene butadiene rubber (binder): acetylene black = 100: 1.7: 2 (weight ratio). The average particle diameter D ₅₀ of the particles was 2 μm. The average particle diameter D ₅₀ was measured using a Microtrac particle size distribution measuring device (No. 9320-X100) manufactured by Nikkiso Co., Ltd.

The current collector on which the coating film was formed was immersed in a copper pyrophosphate bath having the following bath composition, and copper was permeated to the coating film by electrolysis to form an active material layer. The electrolysis conditions were as follows. DSE was used for the anode. A DC power source was used as the power source.
Copper pyrophosphate trihydrate: 105 g / l
-Potassium pyrophosphate: 450 g / l
・ Potassium nitrate: 30 g / l
-P ratio: 7.7
・ Bath temperature: 50 ° C
・ Current density: 3 A / dm ²
-PH: Ammonia water and polyphosphoric acid were added to adjust to pH 8.2.

  The permeation plating was terminated when copper was deposited over the entire thickness direction of the coating film. In this way, a target negative electrode was obtained. SEM observation of the longitudinal section of the active material layer confirmed that the active material particles were covered with a copper film having an average thickness of 240 nm in the active material layer. Moreover, the porosity of the whole active material layer was 30%. Furthermore, the porosity under 10 MPa was 29%, and the porosity under 1 MPa was 4%. The obtained negative electrode was punched into a diameter of 14 mm.

(2) Production of positive electrode LiCoO ₂ was used as a positive electrode active material. This positive electrode active material was suspended in N-methylpyrrolidone as a solvent together with acetylene black (AB) and polyvinylidene fluoride (PVdF) to obtain a positive electrode mixture. The weight ratio of the blending was LiCoO ₂ : AB: PVdF = 88: 6: 6. This positive electrode mixture was applied to a current collector made of aluminum foil (thickness 20 μm) using an applicator, dried at 120 ° C., and then roll-pressed with a load of 0.2 ton / cm to obtain a positive electrode. The thickness of this positive electrode was about 70 μm. This positive electrode was punched into a size of 13 mm in diameter.

(3) Production of lithium secondary battery The positive electrode and the negative electrode thus obtained were opposed to each other with a separator made of a polyethylene porous film having a thickness of 20 μm interposed therebetween. As the nonaqueous solvent in the electrolytic solution, in the compound represented by the formula (1), R ¹ is F and R ² is H (hereinafter referred to as F-EC), and the compound represented by the formula (2) A compound in which all of R ^{3 to} R ⁶ are H (hereinafter referred to as DEC) and a compound represented by formula (2) in which only R ³ is F (hereinafter referred to as F-DEC) are referred to below. The mixed solvent mixed in the ratio shown in Table 1 was used. A solution obtained by adding 2% by volume of vinylene carbonate to a solution obtained by dissolving 1 mol / l LiPF ₆ in this mixed solvent was used as a non-aqueous electrolyte. This produced a 2032 type coin battery. The weight ratio of Co / Si in the obtained battery was as shown in Table 1 below.

[Examples 2 to 4 and Comparative Examples 1 and 2]
As a non-aqueous solvent in the non-aqueous electrolyte, a mixed solvent in which F-EC, DEC, and F-DEC were mixed at a ratio shown in Table 1 below, and the amount of the positive electrode active material and the amount of the negative electrode active material A lithium secondary battery was obtained in the same manner as in Example 1 except that the amount was changed to the value shown in the table.

Example 5
A nonaqueous electrolytic solution in which LiClO ₄ was dissolved at a concentration of 1 mol / l in a diethyl carbonate nonaqueous solvent was prepared. In the argon atmosphere at 25 ° C., the negative electrode obtained in Example 2-1 and the 600 μm-thick lithium foil were immersed in this nonaqueous electrolytic solution through a SUS mesh (100 mesh), and the negative electrode and the metallic lithium And were short-circuited electrochemically. Thus, lithium was occluded in the active material in the negative electrode. The amount of lithium occluded was 25% of the initial charge theoretical capacity of the negative electrode active material by setting the immersion time to 40 minutes. The exact amount of occlusion was confirmed by ICP emission analysis. The obtained negative electrode was washed with dimethyl carbonate for the purpose of removing the lithium salt, and the solvent was removed by vacuum drying. A lithium secondary battery was obtained in the same manner as in Example 1 using the negative electrode having the negative electrode active material occluded with lithium thus obtained.

[Evaluation]
About the lithium secondary battery obtained by the Example and the comparative example, the capacity | capacitance maintenance factor and rate characteristic of 100th cycle were evaluated with the following method. The results are shown in Table 1 below.

[Capacity maintenance rate at 100th cycle]
The discharge capacity at the 13th cycle and the discharge capacity at the 100th cycle were measured. The capacity retention rate at the 100th cycle was calculated by dividing the discharge capacity at the 100th cycle by the discharge capacity at the 13th cycle and multiplying by 100. The charging conditions were 0.5 C, 4.2 V, and constant current / constant voltage. The discharge condition was 0.5 C, 2.7 V, and a constant current. However, charge / discharge at the first cycle is 0.05C, charge / discharge at the second to fourth cycles is 0.1C, charge / discharge at the fifth to seventh cycles is 0.5C, and charge / discharge at the eighth to tenth cycles is 1C. It was.

[Rate characteristics]
In the measurement of the capacity retention rate described above, the discharge capacity at the 13th cycle was divided by the discharge capacity at the 1st cycle, and a value obtained by multiplying this by 100 was taken as the rate characteristic.

  As is apparent from the results shown in Table 1, the batteries of Examples 1 to 4 (product of the present invention) have rate characteristics comparable to or higher than those of Comparative Examples 1 and 2, and Comparative Examples 1 and 2 It can be seen that the capacity retention rate is higher than that of the battery. That is, it can be seen that the cycle characteristics are good. In particular, it can be seen that the battery of Example 5 using the negative electrode in which lithium is occluded in the negative electrode active material before charging the battery has extremely high capacity retention rate and rate characteristics.

  As described above, according to the present invention, it is possible to prevent decomposition of the non-aqueous solvent and deterioration of the cycle characteristics without reducing the charge / discharge rate characteristics.

Claims (8)

In a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte obtained by dissolving a lithium salt in a positive electrode and a negative electrode and a non-aqueous solvent,
The negative electrode has an active material layer including a current collector and an active material containing Si formed on at least one surface thereof,
The non-aqueous solvent contains a compound represented by the following formula (1) and a compound represented by the following formula (2), and the ratio of the compound represented by the formula (1) in the non-aqueous solvent is 15 to 40 Ri vol% der, nonaqueous electrolyte secondary batteries proportion of the compound represented by formula (2) occupying the non-aqueous solvent and wherein 55-85 vol% der Rukoto.

^2. The nonaqueous electrolyte secondary battery according to claim 1, wherein in the compound represented by the formula (1), only ^one of R ¹ and R ² is F and the other is H. 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein R ^{3 to} R ⁶ are H in the compound represented by the formula (2). The compound represented by the formula (2) is a mixture of a compound in which R ^{3 to} R ⁶ are H in the same formula and a compound in which at least one of R ^{3 to} R ⁶ is F in the same formula. A non-aqueous electrolyte secondary battery according to claim 1 in the range. The non-aqueous solvent according to claim 4, wherein a proportion of the compound represented by the formula (2) in which at least one of R ^{3 to} R ⁶ is F is 10 to 40% by volume in the non-aqueous solvent. Water electrolyte secondary battery.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the active material containing Si contains lithium before charging of the battery is started.   The negative electrode has a negative electrode active material layer, the negative electrode active material layer contains particles of an active material containing Si, and at least a part of the surface of the particles is coated with a metal material having a low lithium compound forming ability. The nonaqueous electrolyte secondary battery according to claim 1, wherein voids are formed between the particles coated with the metal material. The positive electrode has a positive electrode active material layer containing a lithium transition metal composite oxide containing Li and Co as constituent elements,
The non-aqueous electrolyte secondary battery according to claim 1, wherein a weight ratio (Co / Si) of Co in the positive electrode to Si in the negative electrode is in a range of 0.3 to 5.5.

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