JP2003168438A - Nonaqueous secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous secondary battery having a high capacity and a superior cycle property by suppressing volume changes of electrode(s) due to volume changes of an active material. <P>SOLUTION: On at least one side between the positive electrode and the negative electrode, spherical high polymer compound particles which are not dissolved in the nonaqueous electrolytic solution and which skid among active material particles smoothly are made to be impregnated. It is preferable that the spherical high polymer compound particles are composed of crystalline polymer compound containing fluorine, crystalline polyolefin or meshlike polymer compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-aqueous secondary battery,
Particularly, it relates to improvement of the electrode.

[0002]

2. Description of the Related Art In recent years, the performance of electronic devices such as mobile phones, notebook type personal computers, and camera-integrated video recorders has improved, and power consumption has increased. Furthermore, further downsizing, convenience of carrying, and long-time driving are strongly demanded for these electronic devices. In order to meet the demand for these electronic devices, it is an important issue to reduce the size and capacity of the secondary battery that is the power source. Recently, non-aqueous secondary batteries with high energy density such as lithium ion secondary batteries have been studied and researched to solve this problem.
It has been developed and the capacity is being increased.

In order to increase the capacity of a battery, in addition to the development of new active materials and electrolytes, efficient use of the internal volume of the battery,
Studies are underway to reduce the thickness of separators and to fill electrodes with high-density active materials. In the course of such studies, the volume of the active material increases with charge and discharge, especially in lithium-ion secondary batteries and other batteries that have electrodes containing a solid active material that reversibly absorbs and desorbs ions. The changing phenomenon is a major obstacle in developing a practical high capacity battery.

That is, when the volume of the active material changes due to charge / discharge, the volume of the electrode changes correspondingly. This causes a problem that the battery expands and cannot be stored in an allowable space in the device. Furthermore, when the electrodes contract, the pressing force of the electrode plate group decreases, and the ionic conductivity between the electrodes decreases. Further, the contact between the active material particles decreases as the active material expands and contracts repeatedly. Due to such a decrease in ionic conductivity and contact between active material particles, the internal resistance of the battery increases as the charging / discharging cycle progresses,
There is a problem that the charge / discharge capacity in the practical current region is reduced.

In order to avoid the above problems, an active material such as graphite, which has a relatively small volume change due to charge and discharge, has been conventionally used. However, even when such an active material is used, if the packing density of the active material is further increased, the adverse effect due to the volume change of the active material as described above cannot be avoided, and the desired charge / discharge performance is improved. You will not be able to get it. In addition, many new active materials having higher energy density than conventional active materials have a larger volume change due to charge and discharge than conventional active materials. From these facts, finding a means for reducing the above-mentioned problems due to the volume change of the active material has become an important issue in the future for providing a non-aqueous secondary battery having a high capacity and excellent cycle characteristics. .

In order to solve this problem, for example, Japanese Patent Laid-Open No. 20
As disclosed in Japanese Patent Application Laid-Open No. 01-196065, a proposal has been made to add an “elastic additive” to an electrode for performing a function of forming a space between active materials in an electrode and a function of adjusting a space according to a volume change of the active material. Has been done. This method attempts to absorb the expansion of the electrode by absorbing the expansion of the active material at the time of charging or discharging by the deformation of the voids provided between the active materials and the elastic additive material. Further, when the active material contracts, the elastic additive material is restored to its original shape and, at the same time, voids are formed again between the active materials to reduce the volume change of the electrode.

However, in reality, in addition to the decrease in the binding force of the binder for binding the active materials due to the repeated expansion and contraction of the active materials due to the charge / discharge cycle, the elasticity of the additive material causes Contact is reduced. Further, when the contact reduction between the active materials progresses, the phenomenon that the electrode collapses occurs. Therefore, it is not possible to effectively solve the problem that the discharge capacity decreases due to the progress of the charge / discharge cycle.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-aqueous secondary battery having a high capacity and excellent charge / discharge cycle characteristics by solving the problem caused by the volume change of the active material.

[0009]

A non-aqueous secondary battery of the present invention comprises a positive electrode, a negative electrode, and a non-aqueous electrolytic solution, and at least one of the positive electrode and the negative electrode is dissolved in the non-aqueous electrolytic solution. It is characterized by containing spherical polymer compound particles that do not exist and that allow smooth sliding between the active material particles in the electrode. The polymer compound particles are preferably composed of a crystalline polymer compound containing fluorine, a crystalline polyolefin, or a network polymer compound. At least one of the positive electrode and the negative electrode preferably further contains a resin that swells with the nonaqueous electrolytic solution.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the non-aqueous secondary battery of the present invention, at least one of the positive electrode and the negative electrode does not dissolve in the electrolytic solution, and has a spherical high surface so that the active material particles slide smoothly. Contains molecular compound particles. The polymer compound particles are
It is a spherical particle that does not have elasticity like the additive in the preceding example, but has hardness that does not deform due to the pressure applied by the expansion of the active material due to charge and discharge.
The spherical particles do not necessarily have to be true spherical, and it is preferable that the spherical particles have a small rolling friction and have a curved surface with no corners and a smooth surface. Further, the average particle size of the spherical particles is usually equal to or 1/10 or more, preferably 1/5 or more, of the average particle size of the active material particles. By adding such polymer compound particles to the electrode, it is possible to provide a non-aqueous secondary battery in which the characteristic deterioration due to the volume change of the active material is suppressed.

In the electrode of the present invention, since spherical polymer compound particles having a small rolling friction are interposed between the active material particles, the sliding friction resistance between the active material particles can be reduced. Therefore, when the active material particles expand,
The individual active material particles are easily slipped and repositioned in the direction of reducing the voids between the particles. As a result, at least a part of the expansion of the active material can be absorbed by the void in the electrode, and the expansion of the electrode can be effectively suppressed.

The effect of the spherical polymer compound particles in the present invention will be described in more detail with reference to FIG. FIG. 1A shows active material particles 1 and polymer compound particles 2 before expansion.
FIG. 1B shows the arrangement state of the active material particles 1 and the polymer compound particles 2 when the active material particles 1 are expanded. When the active material particles 1 expand and a force in the direction of expanding the electrode is generated, a pressure in the direction of preventing the expansion of the electrode is generated against the force. When this pressure is applied to the active material particles 1 that are about to expand, the active material particles 1 slide due to the above-described frictional resistance reducing action of the polymer compound particles 2 that intervene between the active material particles 1 so that the active material particles 1 are relatively separated from each other. Position relationship changes. At this time, as shown in FIG. 1B, each active material particle 1 moves in a direction in which the voids 3 formed between the active material particles 1 are minimized.

When the volume of the expanded active material particles 1 is contracted, and when the active material particles 1 are bound by a binder, the state of FIG. 1 (B) changes to the state of FIG. 1 (A). Changes reversibly. When the binding between the active material particles 1 is weak from the beginning, or when the binding force between the active material particles 1 decreases due to repeated expansion and contraction of the active material particles 1, the active material particles 1
The contraction changes the state of FIG. 1B to the state of FIG. As described above, when the expanded active material particles 1 contract, the state changes of FIG. 1 (B) to FIG. 1 (A) or FIG. 1 (B) to FIG. 1 (C) are shown. Also in the case of, the voids between the expanded active material particles 1 can be made small, which is effective for suppressing the volume change of the electrode. In the electrode, there may be conductive agent particles for ensuring electron conduction between the active material particles, but in order to briefly explain the action of the polymer compound particles,
This is omitted from FIG.

Generally, the surface of the active material particles is not always smooth, and the shape thereof is not necessarily spherical but may be rod-shaped or flat. Therefore, when the polymer compound particles are not present between the active material particles 1 as shown in FIG. 2, the active material particles expanded as shown in FIG. 1 due to the large frictional resistance between the active material particles 1. One cannot slip and move. Therefore, the relative positional relationship between the active material particles 1 does not change before and after the active material particles 1 in FIG. 2A expand and after the active material particles 1 in FIG. 2B expand. . As a result, the voids 3 between the expanded active material particles 1 are expanded in proportion to the expansion of the active material particles 1, and as a result, the electrodes are significantly expanded.

As the material of the polymer compound particles, it is necessary to select a material which does not dissolve in the electrolytic solution and which does not easily react with the electrolytic solution or the active material during battery storage or charging / discharging. Further, it is preferable that the material has hardness such that it is not deformed by the pressure applied by the expansion of the active material. Examples of preferable materials include crystalline polyolefin and crystalline polymer compounds containing fluorine.

In this case, the crystalline polyolefin and the crystalline polymer compound containing fluorine have a crystallinity of 40%.
Refers to the above. In general, the higher the crystallinity, the higher the hardness, the more difficult it is to dissolve in the solvent of the electrolytic solution, and the preferable properties as the material of the polymer compound particles in the present invention. Specifically, the material of the polymer compound particles for the positive electrode is crystalline polyethylene and crystalline polytetrafluoroethylene, and the material of the polymer compound particles for the negative electrode is crystalline polyethylene and crystalline polyvinylidene fluoride. preferable. Among these crystalline polymer compound materials, highly crystalline materials having a crystallinity of more than 50% are more preferable.

In order to include the polymer compound particles in the electrode, the polymer compound particles are kneaded with an electrode material such as active material particles to prepare an electrode mixture or electrode paste, and this is used to prepare an electrode. You can take the method. As a solvent for the electrode paste, it is desirable to use one that does not dissolve these polymer compound particles. As the combination of the material of the polymer compound particles and the solvent of the electrode paste, for example, water, toluene or xylene is used for crystalline polyvinylidene fluoride, N-methylpyrrolidone or water is used for crystalline polyethylene, and crystalline It is preferable to use N-methylpyrrolidone, toluene or xylene for polytetrafluoroethylene.

In addition to the above, as a preferable material for the spherical polymer compound particles, there is a polymer compound crosslinked in a network (hereinafter referred to as a network polymer compound). Since reticulated polymer compounds are generally difficult to dissolve in various solvents used for electrolytic solutions and electrode pastes, there are many choices of usable solvents, and they have relatively high hardness and are difficult to soften even when exposed to high temperatures. There are advantages such as.

The reticulated polymer compound used as the material for the spherical particles is a commonly used epoxy resin, urethane resin, phenol resin, melamine resin,
The main chain branched using a trifunctional precursor is polyester,
A polymer obtained by crosslinking and polymerizing a polymer having a side chain with a double bond such as methacrylic acid residue and curing, and a polymer having a double bond in the main chain such as butadiene residue with styrene etc. A cross-linked / cured material can be used.

The reason why the polymer compound as described above is used as the material of the spherical particles to be added to the electrode is that the polymer compound generally has a smaller specific gravity as compared with the inorganic compound and so on. It is possible to reduce the weight increase and to easily select a material having low reactivity with the electrolytic solution or the active material and low solubility in the electrolytic solution.

In the non-aqueous secondary battery of the present invention, at least one of the positive electrode and the negative electrode may contain, in addition to the active material particles and the spherical polymer compound particles, a resin that swells with an electrolytic solution. preferable. The presence of the resin swollen with the electrolytic solution in the electrode acts to fix each active material particle in the electrode. That is, by the active material particles repeatedly expanding and contracting, the active material particles try to move in a direction in which the distance between them expands, but the expansion action between the particles is prevented by the fixing action of the resin swollen by the electrolytic solution. . As a result, it is possible to prevent the deterioration of the electrode strength due to charge and discharge and the drop of the active material, and it is possible to further improve the charge and discharge cycle characteristics of the battery.

Since the resin swollen with the electrolytic solution has a weak binding force, even if the resin is present around the active material particles and the polymer compound particles in the electrode, there is almost no effect of binding these particles to each other. There is no. Therefore, when the volume of the active material particles changes, the action of the spherical polymer compound particles that facilitate the movement of the active material particles within the electrode is not hindered. Also,
The resin swollen with the electrolyte is soft, so the active material will
Even if the presence of interparticle voids changes due to contraction, the particles flow into the voids in accordance with the changes. Therefore, the electrode volume does not increase by including the resin swollen with the electrolytic solution in the electrode.

The resin that swells with the electrolytic solution may be selected depending on the type of solvent in the electrolytic solution. For example, in the case of using a carbonate-based solvent such as the electrolytic solution of many lithium ion secondary batteries, polyester, polyether,
Polyacrylonitrile, polymethacrylic acid ester, and copolymers containing these monomers can be used. Specific examples of the copolymer include ethylene glycol-propylene glycol copolymer, adipic acid-ethylene glycol copolymer, and methyl methacrylate-
Examples thereof include hydroxyethyl methacrylic acid-butadiene copolymer. In addition to these, a carboxymethyl cellulose compound or a resin in which a network polymer is formed by using a trifunctional monomer or a cross-linking agent in these resins can be used.

When a network polymer compound is included in the electrode as a resin that swells with the electrolyte solution, a mixture of the electrolyte solution and the precursor of the network polymer compound is impregnated into the dried electrode. A method in which the polymer compound is subsequently cured to form a polymer compound having a network structure can be adopted. As a curing method, a photopolymerization method, a thermal polymerization method, an electron beam polymerization method, or the like can be adopted. Among these methods, the thermal polymerization method is preferable because the required cost is relatively small and the effect is large.

Among the non-aqueous secondary batteries of the present invention, the non-aqueous electrolyte used in the lithium-ion secondary battery is a non-aqueous solvent in which a lithium salt is dissolved. The solvent is preferably one that is electrochemically stable within the operating potential of the battery and has a relatively high ionic conductivity when the lithium salt is dissolved. For example, a solvent selected from diethyl carbonate, ethylene carbonate, ethylmethyl carbonate, propylene carbonate, γ-butyrolactone and the like can be used alone or in combination. The counter ion of the lithium ion of the lithium salt contained in the electrolytic solution is preferably an anion that is electrochemically stable within the operating potential of the battery. Therefore, as the lithium salt, for example, LiBF ₄ , LiPF ₆ , Li (C
₂ F ₅ SO ₂ ) ₂ N and the like are preferably used alone or in combination.

As the positive electrode active material of the non-aqueous secondary battery of the present invention, lithium ions are reversibly released upon charging and discharging.
What can be occluded can be used. Specifically, L
i _x MO ₂ (0.1 ≦ x ≦ 1.1, M is Co, Ni, Mn
A lithium-containing composite oxide such as at least one selected from transition metals) is preferable. Further, other metal oxides capable of reversibly releasing and occluding lithium ions, such as iron-based oxides and vanadium-based oxides, can also be used.
Furthermore, metal sulfides such as titanium disulfide and molybdenum disulfide can also be used.

As the negative electrode active material, a material capable of reversibly occluding and releasing lithium ions by charging and discharging can be used. Specifically, tin dioxide, metallic tin, metallic aluminum, silicon oxide, silicon carbide, nickel silicide, copper silicide, iron silicide, cobalt silicide, manganese silicide, titanium silicide, magnesium silicide, graphite. , Non-graphitizable carbon, low temperature fired graphitizable carbon, and the like, and mixtures of these materials can be used.

The electrode of the non-aqueous secondary battery of the present invention contains graphite,
By adding a conductive agent such as carbon black or carbon fiber, the internal resistance of the battery can be reduced and the load characteristics can be improved. In the present invention, as the separator interposed between the positive electrode and the negative electrode, a porous polyolefin film and a polyolefin nonwoven fabric can be used alone or in combination. These separators are placed between the positive and negative electrodes in a state of being impregnated with the non-aqueous electrolytic solution or the gelled non-aqueous electrolytic solution. As the polyolefin, for example, polyethylene or polypropylene is preferable.

The constitution of the electrode plate group of the non-aqueous secondary battery of the present invention is such that three layers of positive electrode / separator / negative electrode are laminated, a plurality of these layers are laminated, and the above three layers are laminated and wound. Etc. can take various forms. These electrode plates can be housed in various battery containers such as a rectangular metal can, a cylindrical metal can, or a polyolefin resin-aluminum laminate film to form batteries of various forms. The material of the metal can is stainless steel,
It can be selected from various metals such as aluminum and aluminum alloys.

[0030]

EXAMPLES Next, the present invention will be described more specifically by way of examples.

Example 1 A positive electrode paste was a LiCoO ₂ powder having an average particle size of 15 μm as a positive electrode active material, acetylene black as a conductive agent, and 10% N of amorphous polyvinylidene fluoride as a binder. -Methylpyrrolidone solution was prepared by kneading. In addition, the compounding ratio of the positive electrode paste is, by weight ratio, active material: conductive agent: binder = 1.
It was set to 00: 3: 3. This positive electrode paste has a thickness of 20 μm
After being applied to one surface of the aluminum foil of No. 3, pre-dried at 65 ° C. for 15 minutes, and then vacuum-dried at 120 ° C. for 10 hours to produce a positive electrode.

To prepare the negative electrode paste, first, carboxymethyl cellulose as a thickener was added to nickel silicide powder having an average particle diameter of 15 μm as a negative electrode active material, and the mixture was kneaded with water. To this, acetylene black as a conductive agent and crystalline polyvinylidene fluoride beads as spherical polymer compound particles (crystallinity 59%, average particle diameter 4 μm) were added and kneaded, and further water as a binder was added. Dispersed styrene-butadiene rubber was added and kneaded to prepare a negative electrode paste. The compounding ratio of the negative electrode paste was active material: thickener: conductive agent: binder: spherical polymer compound particles = 100: 4: 12: 8: 10 by weight. This negative electrode paste was applied on one surface of a copper foil having a thickness of 15 μm, preliminarily dried at 65 ° C. for 15 minutes, and then vacuum dried at 180 ° C. for 10 hours to prepare a negative electrode.

The electrolytic solution was prepared by dissolving LiPF ₆ having a concentration of 1.25 mol / l in a solvent prepared by mixing ethylene carbonate and ethylmethyl carbonate at a volume ratio of 1: 3. By impregnating the negative electrode with a liquid obtained by mixing poly (ethylene oxide-propylene oxide) dimethacrylate, which is a polymer compound before cross-linking, an electrolytic solution, and lauroyl peroxide as a cross-linking agent, and heating at 80 ° C. to cross-link The resin swollen with the electrolytic solution was included in the negative electrode. The compounding ratio of the polymer compound before the crosslinking: the electrolytic solution: the crosslinking agent is 7:10 by weight.
It was set to 0: 0.7.

A 25 μm-thick porous polypropylene separator was sandwiched between the positive electrode prepared as described above and the negative electrode containing a resin swollen with an electrolytic solution to form an electrode plate group. The electrode group was housed in a battery case, and then an electrolytic solution was injected. Next, a sealing plate was attached to the opening of the battery case via a gasket, and then the battery case was bent and sealed to produce a coin-type battery.

Comparative Example 1 A coin type battery was manufactured in the same manner as in Example 1 except that spherical polymer compound particles were not mixed with the negative electrode.

Example 2 A coin-type battery was produced in the same manner as in Example 1 except that tin-titanium alloy powder (average particle diameter 15 μm) was used as the negative electrode active material instead of nickel silicide powder.

Example 3 A coin-type battery was manufactured in the same manner as in Example 1 except that silicon-titanium alloy powder (average particle size 15 μm) was used as the negative electrode active material instead of nickel silicide powder. .

Example 4 As spherical polymer compound particles, spherical particles of high-density polyethylene (average particle diameter 6 μm, crystallinity 60) were used instead of polyvinylidene fluoride beads.
%) Was used to prepare a coin-type battery in the same manner as in Example 1.

Example 5 As spherical polymer compound particles, styrene was used instead of polyvinylidene fluoride beads.
Spherical particles of a network polymer compound obtained by crosslinking a butadiene copolymer (butadiene 10%) with styrene (average particle size 1
A coin type battery was produced in the same manner as in Example 1 except that 0 μm) was used.

Comparative Example 2 Instead of polyvinylidene fluoride beads, spherical particles of poly (ethylene glycol) dimethyl ether (average molecular weight 2000) (average particle diameter 1)
A coin type battery was produced in the same manner as in Example 1 except that 5 μm) was used. A dissolution test was conducted on poly (ethylene glycol) dimethyl ether, and it was confirmed that this polymer compound was soluble in the electrolyte solution used.

With respect to the coin type batteries produced in each of the above Examples and Comparative Examples, after charging to 0.5V up to 4.2V, charging / discharging was repeated at a final voltage of 1.5V and discharging at 0.5mA. This charge / discharge cycle test was started after 3 days had passed since the coin-type battery was produced, and was carried out at an environmental temperature of 20 ° C. The discharge capacity after the first cycle and the 10th cycle of charging was measured for the five battery samples of each example and each comparative example. Table 1 shows the average value of the discharge capacities in each case.

[0042]

[Table 1]

As can be seen from Table 1, in all the batteries of Examples 1 to 5, the difference in discharge capacity between after charging in the first cycle and after charging in the tenth cycle was around 0.25 mAh. . On the other hand, in the batteries of Comparative Examples 1 and 2, the difference in discharge capacity was as large as about 1 mAh, which confirmed that the batteries of Examples 1 to 5 according to the present invention exhibited excellent cycle characteristics.

Next, in order to investigate the change in the volume of the electrode due to charging, the coin type batteries produced in each of the examples and each of the comparative examples were charged for the first cycle under the same conditions as in the above charge / discharge cycle test. The battery was disassembled and the thickness and area of the negative electrode were measured. The value obtained by subtracting the thickness of the copper foil from the measured thickness of the negative electrode was taken as the mixture thickness after charging, and the area of the electrode surface was taken as the mixture area after charging. This measurement was performed on five battery samples of each example and each comparative example. Table 2 shows the average values of the mixture thickness and the mixture area before and after charging in each case. The thickness of the mixture and the area of the mixture before charging are values measured for the negative electrode at the stage of forming the electrode plate group in the process of manufacturing the coin battery.

[0045]

[Table 2]

From Table 2, in the negative electrodes of Examples 1 to 5 containing the spherical polymer compound particles, the influence of the volume change of the active material on the electrode volume change was suppressed more than in the negative electrode of Comparative Example 1. I understand that. In addition, comparing Examples 1 to 3, it can be seen that the effect of suppressing the volume change of the electrode is obtained to the same degree regardless of the type of the negative electrode active material.
Further, comparing Examples 1, 4 and 5, it is understood that the effect of suppressing the volume change of the electrode is obtained to the same degree regardless of the type of the spherical polymer compound particles.

From Tables 1 and 2, the effect of suppressing the volume change of the electrode according to the present invention shown in Table 2 leads to the effect of improving the charge / discharge cycle characteristics of the battery shown in Table 1. I understand. In addition, in the case of Comparative Example 2 in which spherical polymer compound particles that are soluble in the electrolytic solution are added to the electrode,
Although the volume change of the electrode after the first cycle charging in Table 2 was relatively small, the discharge capacity after the 10th cycle charging in Table 1 was significantly deteriorated. From this,
It was confirmed that the spherical polymer compound particles in the present invention are preferably those which are not dissolved in the electrolytic solution.

[0048]

According to the present invention, it is possible to provide a high performance non-aqueous secondary battery in which the volume change of the electrode due to the volume change of the active material is suppressed and the discharge capacity deterioration due to the charge / discharge cycle is suppressed.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an arrangement state of active material particles when they are expanded and contracted in an electrode containing polymer compound particles according to the present invention.

FIG. 2 is a schematic cross-sectional view showing an arrangement state of active material particles at the time of expansion and contraction of the active material particles in the electrode containing no polymer compound particles according to the present invention.

[Explanation of symbols]

1 Active material particles 2 Polymer compound particles 3 Voids between active material particles

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuhiko Mito             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 5H029 AJ03 AJ05 AK03 AL11 AM03                       AM05 AM07 BJ03 DJ08 DJ16                       EJ12 EJ13 EJ14                 5H050 AA07 AA08 BA17 CA08 CB11                       DA12 EA23 EA24 EA28 FA17

Claims (5)

[Claims] 1. A positive electrode, a negative electrode, and a nonaqueous electrolyte solution are provided,
At least one of the positive electrode and the negative electrode contains spherical polymer compound particles that do not dissolve in the non-aqueous electrolyte and that facilitate sliding between the active material particles in the electrode. Non-aqueous secondary battery to be. 2. The non-aqueous secondary battery according to claim 1, wherein the polymer compound particles are composed of a crystalline polymer compound containing fluorine. 3. The non-aqueous secondary battery according to claim 1, wherein the polymer compound particles are made of crystalline polyolefin. 4. The non-aqueous secondary battery according to claim 1, wherein the polymer compound particles are composed of a network polymer compound. 5. The non-aqueous secondary battery according to claim 1, wherein at least one of the positive electrode and the negative electrode further contains a resin that swells with the non-aqueous electrolytic solution.