JP5909466B2 - refrigerator - Google Patents

Description

  The present invention relates to a refrigerator.

  In Patent Document 1, a lithium ion secondary battery is built in a refrigerator, the lithium ion secondary battery is charged by power received from indoor wiring at night time, and the power discharged by the lithium ion secondary battery is discharged during daytime. We propose to supply power to the compressor. The refrigerator described in Patent Document 1 can contribute to leveling of power demand.

JP 2008-14501 A

  The lithium ion secondary battery built in the refrigerator described in Patent Document 1 includes a liquid electrolyte. Since the liquid electrolyte is volatile and flammable, the lithium ion secondary built in the refrigerator cannot be expected when the refrigerator is submerged or a fire occurs at the refrigerator installation location. Batteries have dangers such as ignition and explosion.

  The present invention is made to solve this problem. An object of the present invention is to provide a refrigerator that is highly safe and can contribute to leveling the demand for electric power.

  The present invention relates to a refrigerator. In the refrigeration cycle mechanism, a compressor compresses a refrigerant, a radiator releases heat from the refrigerant, and a cooler causes the refrigerant to absorb heat. The power receiving mechanism can be connected to the indoor wiring and receives power from the indoor wiring. The charging circuit charges the all solid-state polymer lithium secondary battery with the power received by the power receiving mechanism. The discharge circuit discharges the all solid-state polymer lithium secondary battery. The compressor consumes electric power discharged from the all solid-state polymer lithium secondary battery and compresses the refrigerant. The controller permits the charging circuit to charge in the first time zone, and permits the discharging circuit to discharge in the second time zone.

  The secondary battery does not contain an ignitable solvent. Even when the operation of the protective device cannot be expected, such as when the refrigerator is submerged or a fire occurs at the place where the refrigerator is installed, the secondary battery does not ignite. The safety of the refrigerator is increased.

  The compressor consumes the electric power received from the indoor wiring in the first time zone in the second time zone. It can contribute to the leveling of power demand.

  These and other objects, features, aspects and advantages of the invention will become more apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.

It is a schematic diagram of a refrigerator. It is a block diagram of the electric circuit etc. which are incorporated in a refrigerator. It is a flowchart which shows the algorithm of control by a control circuit. It is a flowchart which shows the algorithm of control by a control circuit. It is sectional drawing of a cell. It is a schematic diagram of the example of the matrix of a lithium ion conductive solid electrolyte. It is a schematic diagram of the example of the matrix of a lithium ion conductive solid electrolyte.

  The schematic diagram of FIG. 1 shows a refrigerator. The block diagram of FIG. 2 shows an electric circuit and the like built in the refrigerator.

  As shown in FIGS. 1 and 2, the refrigerator 100 includes a casing 102, a cord 104 with a plug, a secondary battery 106, an electric circuit 108, and a refrigeration cycle mechanism 110. The electric circuit 108 includes an AC / DC converter 114, a charging circuit 116, a discharging circuit 118, a temperature detection mechanism 120, a power failure detection mechanism 122, a state of charge (SOC) detection mechanism 124, and a control circuit 126. The refrigeration cycle mechanism 110 includes a refrigerant 128, a circulation path 130, a compressor 132, a radiator (condenser) 134, and a cooler (evaporator) 136. The refrigerator 100 may include a component other than these components. All or a part of the AC / DC converter 114, the charging circuit 116, the discharging circuit 118, the temperature detection mechanism 120, the power failure detection mechanism 122, the SOC detection mechanism 124, and the control circuit 126 may be integrated.

  A refrigerator compartment 138 is formed inside the housing 102. Chambers other than the refrigerator compartment 138 may be formed inside the housing 102. For example, the freezer compartment may be formed inside the housing 102. That is, the refrigerator 100 may be a freezer refrigerator.

  The cord 104 with a plug can be electrically and mechanically connected to an outlet for indoor wiring. The indoor wiring is a power supply path for commercial power. The plug-attached cord 104 receives power P from the indoor wiring. The cord with plug 104 supplies power P to the AC / DC converter 114. The cord with plug 104 may be replaced with another type of power receiving mechanism. For example, the cord with plug 104 may be replaced with a cord that is directly connected to the indoor wiring without going through the plug.

  The secondary battery 106 is an all solid-state polymer lithium secondary battery.

  The all solid-state polymer lithium secondary battery is a kind of lithium ion secondary battery. The all solid-state polymer lithium secondary battery includes a solid electrolyte, but does not include a liquid electrolyte and a gel electrolyte having volatility and flammability. For this reason, the all-solid-state polymer lithium secondary battery has a risk of ignition, explosion, etc. even in a situation where the operation of the protective device cannot be expected, such as when the refrigerator 100 is submerged or a fire occurs at the place where the refrigerator 100 is installed. Does not have sex. Thereby, the safety | security of the refrigerator 100 becomes high.

  A lithium ion secondary battery including a liquid electrolyte or a gel electrolyte includes a solvent having volatility and flammability, for example, an ethylene carbonate solvent. For this reason, the lithium ion secondary battery containing a liquid electrolyte or a gel electrolyte has dangers such as ignition and explosion in a situation where the operation of the protective device cannot be expected. In a medium-capacity or large-capacity lithium ion battery capable of discharging the electric power that drives the compressor 132, the risk of ignition, explosion, etc. becomes more prominent. For this reason, it is not realistic to incorporate the lithium ion secondary battery containing a liquid electrolyte or a gel electrolyte in the refrigerator 100 installed in the home. A nickel metal hydride battery, a nickel cadmium battery, and the like do not have dangers such as ignition and explosion, but do not have a sufficient cycle life and are not suitable for being built into the refrigerator 100 used for a long period of time.

  The secondary battery 106 is typically an assembled battery in which a plurality of cells are electrically connected.

  The AC / DC converter 114 converts the electric power P from alternating current to direct current, and separates the electric power P converted into direct current into electric power P1 and P2 and supplies power. The electric power P1 passes through the secondary battery 106. The power P2 does not pass through the secondary battery 106. The electric power P1 is supplied to the charging circuit 116. The electric power P2 is supplied to the compressor 132 via the control circuit 126. The AC / DC converter 114 may be replaced with another type of power feeding mechanism. For example, a power supply path having a branch may be provided outside the AC / DC converter 114, and the power P converted into direct current may be separately supplied to the powers P1 and P2 through the power supply path having the branch. When the power P is direct current and boosting or stepping down is necessary, the AC / DC converter 114 is replaced with a DC / DC converter. The DC / DC converter steps up or steps down the electric power P and separates the electric power P1 and P2 to supply power.

  The charging circuit 116 charges the secondary battery 106 with the supplied electric power P1. The charging circuit 116 charges the secondary battery 106 by a constant current constant voltage method. The charging circuit 116 may charge the secondary battery 106 by a method other than the constant current constant voltage method.

  The discharge circuit 118 discharges the secondary battery 106 and supplies power P3 discharged from the secondary battery 106 to the compressor 132 via the control circuit 126.

  The temperature detection mechanism 120 detects the temperature of the refrigerator compartment 138. The temperature detection mechanism 120 detects the temperature of the refrigerator compartment 138 by a temperature sensor installed in the refrigerator compartment 138, for example.

  The power failure detection mechanism 122 detects that the reception of the power P from the indoor wiring is stopped. The power failure detection mechanism 122 detects that the reception of the power P from the indoor wiring is stopped by monitoring the input voltage of the AC / DC converter 114, for example.

  The SOC detection mechanism 124 detects the SOC of the secondary battery 106. The SOC detection mechanism 124 detects the SOC of the secondary battery 106 from, for example, the voltage of the secondary battery 106, the time integration of the charge / discharge current, and the like.

  In the refrigeration cycle mechanism 110, the cooler 136 absorbs heat from the refrigerating chamber 138 to the refrigerant 128, and the radiator 134 releases heat from the refrigerant 128 to the outside. The refrigerant 128 circulates in the circulation path 130. The compressor 132, the radiator 134 and the cooler 136 are inserted into the circulation path 130. The compressor 132 consumes electric power P2 and P3 and compresses the refrigerant 128. The configuration of the refrigeration cycle mechanism 110 may be changed. For example, the circulation path 130 may be omitted, and the compressor 132, the radiator 134, and the cooler 136 may be directly connected.

  The control circuit 126 acquires the detection results of the temperature detection mechanism 120, the power failure detection mechanism 122, and the SOC detection mechanism 124, and controls the AC / DC converter 114, the charging circuit 116, and the discharging circuit 118. In the control circuit 126, functions such as a timer and system control are realized by causing the embedded computer to execute a control program. The control circuit 126 may be replaced with another type of controller having a similar function. For example, all or part of the functions of the control circuit 126 may be realized by hardware without a program. The hardware includes electronic circuits such as operational amplifiers, comparators, and logic circuits.

  The control circuit 126 basically allows the charging circuit 116 to charge during the night time period from 23:00 to 7 o'clock and permits the discharge circuit 118 to discharge during the daytime period from 7 o'clock to 23 o'clock. The compressor 132 consumes the electric power P received from the indoor wiring during the night time zone from 23:00 to 7 o'clock during the daytime zone from 7 o'clock to 23 o'clock. This can contribute to leveling of power demand.

  A time zone from 23:00 to 7:00 is a time zone in which a power charge for late-night power is applied. Depending on the system of power charges, social demands for leveling power demand, etc., the time zone for charging the charging circuit 116 may be changed to a time zone other than the time zone from 23:00 to 7 o'clock. The time zone in which the circuit 118 is allowed to discharge may be changed to a time zone other than the time zone from 7 o'clock to 23 o'clock.

  The secondary battery 106 is disposed along the radiator 134. Thereby, the temperature of the secondary battery 106 is increased by the heat released from the refrigerant 128. The all solid-state polymer lithium secondary battery has good charge / discharge performance when the temperature is high, as compared with a lithium ion secondary battery containing a liquid electrolyte or a gel electrolyte. For this reason, when the secondary battery 106 is installed along the radiator 134, the charge / discharge performance of the secondary battery 106 is improved. The all-solid-state polymer lithium secondary battery can be manufactured through a coating process and can be easily formed into a plate shape or a sheet shape. Therefore, even when the radiator 134 is plate-shaped, the secondary battery 106 is connected to the radiator 134. It is easy to arrange along. However, the arrangement of the secondary battery 106 may be changed.

  The compressor 132 is DC driven. A motor built in the compressor 132 and generating power for compressing the refrigerant 128 is a DC motor. This eliminates the need for DC-to-AC conversion when power P3 is supplied to the compressor 132, eliminates losses associated with DC-to-AC conversion, and compares the compressor 132 with AC drive. As a result, the loss of the power P3 is reduced. However, a DC / AC converter that converts the electric power P3 from direct current to alternating current may be provided, and the compressor 132 may be AC driven.

  The flowchart of FIG. 3 shows an algorithm for controlling the AC / DC converter, the charging circuit, and the discharging circuit by the control circuit.

  When the power failure detection mechanism 122 does not detect that the reception of the power P has stopped (NO in step S102) during the night time period from 23:00 to 7:00 (YES in step S101), the control circuit 126 The AC / DC converter 114 is allowed to supply power, the charging circuit 116 is allowed to charge, and the discharging circuit 118 is not allowed to discharge (step S105). In this case, the electric power P1 can be supplied to the charging circuit 116, and the secondary battery 106 can be charged with the electric power P1. The electric power P2 can be supplied to the compressor 132 via the control circuit 126, and the compressor 132 can consume the electric power P2 and compress the refrigerant 128.

  When the power failure detection mechanism 122 detects that the power P has stopped being received during the night time zone from 23:00 to 7:00 (YES in step S101), and the SOC detected by the SOC detection mechanism 124 is above the reference (YES in step S102, YES in step S103), control circuit 126 permits power supply to AC / DC converter 114, permits charging circuit 116 to charge, and permits discharging circuit 118 to discharge (step S104). . In this case, the electric power P3 can be supplied to the compressor 132 via the control circuit 126, and the compressor 132 can consume the electric power P3 and compress the refrigerant 128. Thereby, even when a power failure occurs, the operation of the refrigerator 100 is continued. In this case, power feeding by the AC / DC converter 114 and charging by the charging circuit 116 are permitted, but since the reception of the power P is stopped, the secondary battery 106 is actually charged by the power P1. In other words, the power P2 is not actually supplied to the compressor 132. Therefore, in this case, it is also permitted not to permit both or one of the power feeding by the AC / DC converter 114 and the charging by the charging circuit 116.

  If the power failure detection mechanism 122 detects that the power P has stopped being received during the night time zone from 23:00 to 7:00 (YES in step S101), and the SOC detected by the SOC detection mechanism 124 is not equal to or higher than the reference ( In step S102, YES in step S103, and in step S103, control circuit 126 permits power supply to AC / DC converter 114, permits charging circuit 116 to charge, and does not permit discharging circuit 118 to discharge (step S105). In this case, neither power P2 nor P3 is supplied to the compressor 132, and the compressor 132 does not compress the refrigerant 128. In this case, power feeding by the AC / DC converter 114 and charging by the charging circuit 116 are permitted, but since the reception of the power P from the indoor wiring is stopped, the charging of the secondary battery 106 by the power P1 is not performed. Actually, the power P2 is not actually supplied to the compressor 132. Therefore, in this case, it is also permitted not to permit both or one of the power feeding by the AC / DC converter 114 and the charging by the charging circuit 116.

  When the SOC detected by the SOC detection mechanism 124 is equal to or higher than the reference during the daytime period from 7:00 to 23:00 (NO in step S101), the control circuit 126 includes an AC / DC converter. 114 does not permit power feeding, does not permit charging to the charging circuit 116, and permits discharging to the discharging circuit 118 (step S107). In this case, the electric power P3 can be supplied to the compressor 132 via the control circuit 126, and the compressor 132 can consume the electric power P3 and compress the refrigerant 128.

  If the SOC detected by the SOC detection mechanism 124 is not equal to or higher than the reference (NO in step S106) during the daytime period from 7:00 to 23:00 (NO in step S101), the control circuit 126 causes the AC / DC converter 114 to Is allowed to supply power, the charging circuit 116 is allowed to be charged, and the discharging circuit 118 is not allowed to be discharged (step S108). In this case, electric power P2 can be supplied to the compressor 132 via the control circuit 126, and the compressor 132 can consume the electric power P2 and compress the refrigerant 128. Further, the electric power P1 can be supplied to the charging circuit 116 via the AC / DC converter 114, and the secondary battery 106 can be charged with the electric power P1. Thereby, the overdischarge of the secondary battery 106 is suppressed.

  The flowchart of FIG. 4 shows an algorithm for controlling the compressor by the control circuit.

  When electric power P2 or P3 can be supplied to the compressor 132, when the temperature detected by the temperature detection mechanism 120 is equal to or higher than the set temperature (YES in step S111), the compressor 132 is driven (step S112). ). When the temperature detected by temperature detection mechanism 120 is not equal to or higher than the reference temperature (NO in step S111), compressor 132 is not driven (step S113). By this ON-OFF control, the temperature of the refrigerator compartment 138 is adjusted to the vicinity of the set temperature. Control other than the ON-OFF control may be performed. For example, PID control or the like may be performed.

  The schematic diagram of FIG. 5 is a cross-sectional view of a cell of an all solid-state polymer lithium secondary battery.

  As shown in FIG. 5, the cell 140 includes a negative electrode current collector 142, a negative electrode active material layer 144, a solid electrolyte layer 146, a positive electrode active material layer 148, and a positive electrode current collector 150. The cell 140 may include components other than these components. For example, the cell 140 may include an exterior film. The negative electrode current collector 142, the negative electrode active material layer 144, the solid electrolyte layer 146, the positive electrode active material layer 148, and the positive electrode current collector 150 are stacked in this order. The solid electrolyte layer 146 is between the negative electrode active material layer 144 and the positive electrode active material layer 148. The negative electrode active material layer 144 and the positive electrode active material layer 148 are in contact with the negative electrode current collector 142 and the positive electrode current collector 150, respectively. The structure of the cell 140 may be changed.

  The negative electrode active material layer 144 includes a lithium ion conductive solid electrolyte, a negative electrode active material, and a conductive additive. The solid electrolyte layer 146 includes a lithium ion conductive solid electrolyte. The positive electrode active material layer 148 includes a lithium ion conductive solid electrolyte, a positive electrode active material, and a conductive additive. All or part of the negative electrode active material layer 144, the solid electrolyte layer 146, and the positive electrode active material layer 148 may contain other components. For example, all or part of the negative electrode active material layer 144, the solid electrolyte layer 146, and the positive electrode active material layer 148 may contain a binder such as polyvinylidene fluoride (PVdF). The lithium ion conductive solid electrolyte contained in the negative electrode active material layer 144, the lithium ion conductive solid electrolyte contained in the solid electrolyte layer 146, and the lithium ion conductive solid electrolyte contained in the positive electrode active material layer 148 are: , May be the same or different. The conductive assistant contained in the negative electrode active material layer 144 and the conductive assistant contained in the positive electrode active material layer 148 may be the same or different.

The negative electrode active material is a material capable of inserting / extracting lithium ions at a lower potential than the positive electrode active material. The negative electrode active material is carbon, graphite, a spinel compound such as Li ₄ Ti ₅ O ₁₂ , an alloy containing Si and Si, an alloy mainly containing Sn and Sn, and the like. The negative electrode active material may be a material other than these materials.

The positive electrode active material is a material capable of inserting / extracting lithium ions. The positive electrode active _material, LiCoO 2, LiNiO layered rock-salt compounds such as _2, spinel compounds such as LiMn ₂ O _4, a LiFePO _4, polyanionic compound such as LiMn _{x Fe 1-x} PO ₄ and the like. The positive electrode active material may be a material other than these materials.

  The conductive aid is a powder or fiber of a conductive substance. The conductive auxiliary agent is conductive carbon powder such as carbon black, conductive carbon fiber such as carbon nanofiber / carbon nanotube, and the like. The conductive auxiliary agent may be a substance other than these substances.

  The negative electrode current collector 142 is made of copper or an alloy containing copper as a main component. The material of the negative electrode current collector 142 may be changed.

  The positive electrode current collector 150 is made of aluminum or an alloy containing aluminum as a main component. The material of the positive electrode current collector 150 may be changed.

  The schematic diagram of FIG. 6 shows a first example of a matrix of lithium ion conductive solid electrolyte. FIG. 6 shows the microstructure of the matrix.

  The lithium ion conductive solid electrolyte is obtained by dissolving a lithium salt in the matrix 152.

  The matrix 152 has a microstructure in which a non-reactive polyalkylene glycol 160 is held in a co-crosslinked body 158 obtained by chemically crosslinking a hyperbranched polymer 154 and a crosslinkable ethylene oxide multi-component copolymer 156. The co-crosslinked body 158 has at least a crosslinking point 162 where the highly branched polymer 154 and the crosslinkable ethylene oxide multi-component copolymer 156 are chemically crosslinked, but may have a crosslinking point 164 where the highly branched polymers 154 are chemically crosslinked. In addition, the crosslinkable ethylene oxide multi-component copolymer 156 may have a cross-linking point 166 where the cross-linkable ethylene oxide copolymer 156 is chemically cross-linked. Non-reactive polyalkylene glycol 160 is retained primarily in the portion of hyperbranched polymer 154.

  The lithium ion conductive solid electrolyte comprises a hyperbranched polymer 154, a crosslinkable ethylene oxide multi-component copolymer 156, a non-reactive polyalkylene glycol 160 and a precursor mixture containing a lithium salt and a cross-linkable ethylene oxide multi-component copolymer. It can be obtained by cross-linking the polymer 156. The crosslinking reaction is preferably allowed to proceed by electron beam irradiation. The crosslinking reaction may be allowed to proceed by heating, light irradiation or the like.

  When the solid electrolyte contains the highly branched polymer 154 having a high molecular chain mobility and the non-reactive polyalkylene glycol 160 having a higher molecular chain mobility than the highly branched polymer 154, the lithium ion conductivity of the solid electrolyte is improved. The performance of the cell 140 at a low temperature is improved. According to the matrix 152, the molecular chain of the crosslinkable ethylene oxide multi-component copolymer 156 is sufficiently long, the mobility of the molecular chain of the hyperbranched polymer 154 is not easily lost, and the lithium ion conductivity of the solid electrolyte is unlikely to decrease.

  The highly branched polymer 154 and the polyalkylene glycol 160 also contribute to improving the tack property of the negative electrode active material layer 144, the solid electrolyte layer 146, and the positive electrode active material layer 148. Thereby, the adhesiveness of the negative electrode active material layer 144, the solid electrolyte layer 146, and the positive electrode active material layer 148 is improved, and the manufacture of the cell 140 is facilitated. The improvement in adhesion contributes to reducing the electrical resistance at the interface between layers and improving the charge / discharge performance of the cell 140.

  When the crosslinkable ethylene oxide multi-component copolymer 156 having high stretchability becomes a spacer, the stretchability of the matrix 152 is improved, the strength of the solid electrolyte is improved, and the strength of the cell 140 is improved.

  When the highly branched polymer 154 that is liquid or viscous at room temperature is crosslinked with the crosslinkable ethylene oxide multi-component copolymer 156, the highly branched polymer 154 is less likely to leak from the matrix 152, and the stability of the solid electrolyte is improved.

  By holding the non-reactive polyalkylene glycol 160 in the form of a waxy solid at room temperature at the portion of the hyperbranched polymer 154, the non-reactive polyalkylene glycol 160 is less likely to leak from the matrix 152, and the stability of the solid electrolyte is improved. To do.

  Hyperbranched polymer 154, crosslinkable ethylene oxide multi-component 156 and non-reactive polyalkylene glycol 160 contain multiple ether oxygens. Thereby, lithium ions can be solvated in ether oxygen and the lithium salt can be dissolved in the matrix 152.

  The weight of the hyperbranched polymer 154 in the total weight of the hyperbranched polymer 154 and the non-reactive polyalkylene glycol 160 is desirably 10 to 60% by weight, and more desirably 20 to 60% by weight. This is because when the content of the hyperbranched polymer 154 is less than these ranges, the tendency of the strength of the solid electrolyte to decrease is significant. Moreover, it is because the tendency for the lithium ion conductivity of a solid electrolyte to fall becomes remarkable when there is more content of the hyperbranched polymer 154 than these ranges.

  The weight of the crosslinkable ethylene oxide multi-polymer 156 with respect to 100 parts by weight of the total weight of the hyperbranched polymer 154 and the non-reactive polyalkylene glycol 160 is preferably 10 to 130 parts by weight, and more preferably 20 to 80 parts by weight. Part. This is because when the content of the crosslinkable ethylene oxide multi-component copolymer 156 is less than these ranges, the tendency of the strength of the solid electrolyte to decrease is significant. In addition, when the content of the crosslinkable ethylene oxide multi-component copolymer 156 is larger than these ranges, the tendency of the lithium ion conductivity of the solid electrolyte to decrease becomes remarkable.

  The molar ratio [Li] / [O] of the molar amount [Li] of lithium ions to the molar amount [O] of ether oxygen contained in the matrix 152 is preferably 1/5 to 1/25, more preferably 1 / 8 to 1/20, particularly preferably 1/10 to 1/13. This is because when the molar ratio [Li] / [O] is within this range, a solid electrolyte having good lithium ion conductivity can be obtained.

  The highly branched polymer 154 has a branched molecular chain including a polyalkylene oxide chain, and has a crosslinking group that reacts with the crosslinking group of the crosslinkable ethylene oxide multi-component copolymer 156. The polyalkylene oxide chain means a molecular chain in which alkylene groups and ether oxygens are alternately arranged. The polyalkylene oxide chain is typically a polyethylene oxide chain. The polyalkylene oxide chain may have a substituent.

  The average molecular weight of the hyperbranched polymer 154 is desirably 2000 to 15000.

  Since the highly branched polymer 154 has a crosslinking group that reacts with the crosslinking group of the crosslinkable ethylene oxide multi-component copolymer 156, a three-dimensional network co-crosslinked product 158 of the highly branched polymer 154 and the crosslinkable ethylene oxide multi-component copolymer 156 is obtained. Is formed.

  The crosslinking group is selected from a group having an unsaturated bond such as an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. Among these, an acryloyl group is desirably selected. This is because the acryloyl group has good reactivity and does not hinder the movement of lithium ions.

  The terminal groups of the highly branched polymer 154 are desirably cross-linked groups, but it is not necessary that all the terminal groups of the highly branched polymer 154 are cross-linked groups, and some of the terminal groups of the highly branched polymer 154 are acetyl groups or the like. It may be a group that is not a crosslinking group. However, the terminal group of the hyperbranched polymer 154 desirably does not include a hydroxyl group. This is because when a hydroxyl group is contained, lithium ions are captured by the hydroxyl group, and the lithium ion conductivity of the solid electrolyte tends to decrease.

  Hyperbranched polymer 154 has a chemical formula (1) in which two molecular chains whose terminal group is a hydroxyl group and containing a polyalkylene oxide chain and one molecular chain whose terminal group is A that reacts with a hydroxyl group extend from X. It is desirable that the polymer has a crosslinking group as a terminal group of the polymer obtained by reacting the hydroxyl group of the monomer shown with A. The polyalkylene oxide chain may have a substituent.

X in the chemical formula (1) is a trivalent group, Y ¹ and Y ² are alkylene groups, and m and n are integers of 0 or more. However, when X does not contain a polyalkylene oxide chain, at least one of m and n is an integer of 1 or more.

  A in chemical formula (1) is preferably an acidic group such as a carboxyl group, a sulfuric acid group, a sulfo group or a phosphoric acid group, a group obtained by alkylating these acidic groups, a group obtained by chlorinating these acidic groups, glycidyl A group obtained by alkyl esterifying an acidic group, and particularly preferably a group obtained by alkyl esterifying a carboxyl group. This is because when A is a group obtained by alkyl esterifying an acidic group, the hydroxyl group and A can be easily reacted by transesterification.

  The transesterification reaction is desirably performed in the presence of a catalyst such as an organotin compound such as tributyltin chloride / triethyltin chloride / dichlorobutyltin, an organotitanium compound such as isopropyl titanate, and the like, and is performed in a nitrogen stream. It is carried out at a temperature of 250 ° C. However, the transesterification reaction may be performed under other conditions.

  The introduction of the polyalkylene oxide chain is preferably carried out by adding the polyalkylene oxide chain to the hydroxyl group of the precursor in the presence of a base catalyst such as potassium carbonate. However, the polyalkylene oxide chain may be introduced by other methods.

X in the chemical formula (1) is preferably a group represented by the chemical formula (2) having three molecular chains including Z ¹ , Z ² and Z ³ extending from Q. Q in the chemical formula (2) is a methine group, an aromatic ring or an aliphatic ring, and Z ¹ , Z ² and Z ³ are an alkylene group or a polyalkylene oxide chain. An alkylene group or a polyalkylene oxide chain may have a substituent. All or part of Z ¹ , Z ² and Z ³ may be omitted.

  The hyperbranched polymer 154 is more preferably a polymer in which a terminal group of a polymer obtained by bonding a carbonyl group of a structural unit represented by the chemical formula (3) and a polyalkylene oxide chain is a crosslinking group. M and n in the chemical formula (3) are desirably 1 to 20. The polymer is synthesized by polymerizing an ethylene oxide adduct of 3,5-dihydroxybenzoic acid or a derivative thereof (for example, methyl 3,5-dihydroxybenzoate) and introducing a crosslinking group as a terminal group.

  The crosslinkable ethylene oxide multi-component copolymer 156 is a multi-component copolymer of two or more types of monomers including ethylene oxide and a glycidyl ether having a cross-linking group.

The crosslinkable ethylene oxide multi-component copolymer 156 is preferably a binary copolymer of ethylene oxide and a glycidyl ether having a cross-linking group. The binary copolymer is a binary copolymer in which structural units represented by chemical formulas (4) and (5) are irregularly arranged. R ^{1 in the} chemical formula (5) is a bridging group, desirably an alkenyl group, and more desirably an allyl group.

The crosslinkable ethylene oxide multi-component copolymer 156 may be a terpolymer of ethylene oxide, a glycidyl ether having a crosslinking group, and an alkylene oxide other than ethylene oxide. The ternary copolymer is a ternary copolymer in which the structural units represented by the chemical formula (6) are irregularly arranged in addition to the structural units represented by the chemical formulas (4) and (5). R ^{2 in the} chemical formula (6) is an alkyl group having 1 to 2 carbon atoms.

  When the crosslinkable ethylene oxide multi-component copolymer 156 is a binary copolymer, the proportion of the structural unit represented by the chemical formula (5) having a crosslinking group in the total of the structural units represented by the chemical formulas (4) and (5) Is preferably 20% or less, more preferably 0.2 to 10%, and particularly preferably 0.5 to 5%. When the crosslinkable ethylene oxide multi-component copolymer 156 is a ternary copolymer, the configuration shown in the chemical formula (5) having a cross-linking group in the total of the structural units shown in the chemical formulas (4), (5) and (6). The proportion of units is desirably 20% or less, more desirably 0.2 to 10%, and particularly desirably 0.5 to 5%. This is because when the proportion of the structural unit having a cross-linking group is larger than this range, the lithium ion conductivity tends to decrease. Moreover, it is because the tendency for the intensity | strength of a solid electrolyte to fall will become remarkable when the ratio of the structural unit which has a crosslinking group is less than this range.

  The weight average molecular weight of the crosslinkable ethylene oxide multi-component copolymer 156 is desirably 50,000 to 300,000. Thereby, the part which is easily expanded and contracted in the three-dimensional network structure of the co-crosslinked body 158 is formed, the elasticity of the solid electrolyte is improved, and the strength of the solid electrolyte is improved.

  Both ends of the molecular chain of the non-reactive polyalkylene glycol 160 are sealed with non-reactive end groups. “Non-reactive” means that it does not react with other elements of the matrix 152 and does not inhibit lithium ion migration. Thereby, it is suppressed that the non-reactive polyalkylene glycol 160 crosslinks and the mobility of the molecular chain of the non-reactive polyalkylene glycol 160 is reduced, and the non-reactive polyalkylene glycol 160 inhibits the conduction of lithium ions. It is suppressed.

  The non-reactive polyalkylene glycol 160 is a homopolymer of ethylene oxide, a homopolymer of propylene oxide, a binary copolymer of ethylene oxide and propylene oxide, and the like, and has a molecular chain including an oligoalkylene glycol chain.

  The terminal group is selected from an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group, an alkyl ester group, and the like.

  The non-reactive polyalkylene glycol 160 is desirably an oligomer represented by the chemical formula (7). N in the chemical formula (7) is desirably 4 to 45, and more desirably 5 to 25. The molecular weight of the non-reactive polyalkylene glycol 160 is desirably 200 to 2000, and more desirably 300 to 1000.

  FIG. 6 shows a state in which the linear non-reactive polyalkylene glycol 160 is held in the co-crosslinked body 158. Instead of the linear non-reactive polyalkylene glycol 160, an oligoalkylene glycol chain is used. Oligomer having a branched molecular chain containing may be held in the co-crosslinked body 158. Of course, all ends of the oligomer are sealed with non-reactive end groups.

The lithium salt is selected from LiPF ₆ , LiClO ₄ , LiBF ₄ , LiN (CF ₃ SO ₂ ) ₂ [LITFSI], LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiCF ₃ SO _{3 and the} like. Lithium salts other than these lithium salts may be dissolved in the matrix.

  The schematic diagram of FIG. 7 shows a second example of a lithium ion conductive solid electrolyte matrix.

  The matrix 166 has a microstructure in which a non-reactive polyalkylene glycol 174 is held in a co-crosslinked body 172 obtained by chemically crosslinking a highly branched polymer 168 and a crosslinkable ethylene oxide multi-component copolymer 170. Further, in the matrix 166, the non-crosslinkable ethylene oxide homopolymer 176 having no group that reacts with the crosslinking group of the hyperbranched polymer 168 is physically crosslinked to the co-crosslinked body 172. “Physical cross-linking” means that molecular chains are entangled without forming a chemical cross-linking by a chemical bond. The non-crosslinkable ethylene oxide homopolymer 176 further improves the strength of the solid electrolyte.

  The non-crosslinkable ethylene oxide homopolymer 176 is a homopolymer in which structural units represented by the chemical formula (8) are arranged.

  The weight average molecular weight of the non-crosslinkable ethylene oxide homopolymer 176 is desirably 50,000 to 300,000.

  Instead of the non-crosslinkable ethylene oxide homopolymer 176, or in addition to the non-crosslinkable ethylene oxide homopolymer 176, a non-crosslinkable ethylene oxide multi-polymer having no cross-linking group that reacts with the cross-linking group of the hyperbranched polymer 168 May be physically cross-linked to the co-crosslinked body 172.

  The non-crosslinkable ethylene oxide multi-component copolymer is a multi-component copolymer of two or more types of monomers including ethylene oxide and alkylene oxides other than ethylene oxide (for example, alkylene oxide having 3 to 4 carbon atoms).

The non-crosslinkable ethylene oxide multi-component copolymer is desirably a binary copolymer in which the structural unit represented by the chemical formula (9) is irregularly arranged in addition to the structural unit represented by the chemical formula (8). R ^{1 in the} chemical formula (9) is an alkyl group having 1 to 2 carbon atoms, preferably a methyl group.

  The weight average molecular weight of the non-crosslinkable ethylene oxide multi-component copolymer is desirably 50,000 to 300,000.

  Desirable contents of the highly branched polymer 168, the crosslinkable ethylene oxide multi-component copolymer 170, the non-reactive polyalkylene glycol 174, and the lithium salt are the same as in the case of the first example.

  The weight of the non-crosslinkable ethylene oxide homopolymer 176 or the non-crosslinkable ethylene oxide multipolymer relative to 100 parts by weight of the total weight of the hyperbranched polymer 168, the crosslinkable ethylene oxide multipolymer 170 and the nonreactive polyalkylene glycol 174 is The amount is preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight. This is because when the content of the non-crosslinkable ethylene oxide homopolymer or the non-crosslinkable ethylene oxide multi-component copolymer is less than these ranges, the effect of improving the strength of the solid electrolyte is less likely to appear. Moreover, when there is more content of a non-crosslinkable ethylene oxide homopolymer or a non-crosslinkable ethylene oxide multi-component copolymer than these ranges, the tendency for the lithium ion conductivity of a solid electrolyte to fall becomes remarkable.

  The lithium ion conductive solid electrolyte includes a highly branched polymer 168, a cross-linkable ethylene oxide multi-component copolymer 170, a non-reactive polyalkylene glycol 174, a non-cross-linkable ethylene oxide homopolymer 176 (non-cross-linkable ethylene oxide multi-component copolymer) and It can be obtained by crosslinking reaction of a highly branched polymer 168 of a precursor mixture containing a lithium salt and a crosslinkable ethylene oxide multi-component copolymer 170.

  The matrix of the lithium ion conductive solid electrolyte may be changed to other than the first example and the second example.

  While the invention has been shown and described in detail, the above description is illustrative in all aspects and not restrictive. Accordingly, it is understood that numerous modifications and variations can be devised without departing from the scope of the present invention.

DESCRIPTION OF SYMBOLS 100 Refrigerator 104 Cord with plug 106 Secondary battery 110 Refrigeration cycle mechanism 116 Charging circuit 118 Discharging circuit 126 Control circuit 128 Refrigerant 132 Compressor 134 Radiator 136 Cooler

Claims (5)

An all-solid-state polymer lithium secondary battery;
A power receiving mechanism that can be connected to indoor wiring and receives power from the indoor wiring;
A charging circuit that charges the all solid-state polymer lithium secondary battery with the power received by the power receiving mechanism;
A discharge circuit for discharging the all solid-state polymer lithium secondary battery;
A refrigerant, a compressor, a radiator, and a cooler, wherein the compressor consumes power discharged by the all solid-state polymer lithium secondary battery to compress the refrigerant, and the radiator absorbs heat from the refrigerant. A refrigeration cycle mechanism that releases and causes the cooler to absorb heat into the refrigerant;
A controller that permits charging to the charging circuit in a first time zone and permits discharging to the discharging circuit in a second time zone;
Equipped with a,
The all solid-state polymer lithium secondary battery is disposed along the radiator
refrigerator.   The all solid-state polymer lithium secondary battery is plate-shaped or sheet-shaped,
  The radiator is plate-shaped
The refrigerator according to claim 1.   An all-solid-state polymer lithium secondary battery;
  A power receiving mechanism that can be connected to indoor wiring and receives power from the indoor wiring;
  A charging circuit that charges the all solid-state polymer lithium secondary battery with the power received by the power receiving mechanism;
  A discharge circuit for discharging the all solid-state polymer lithium secondary battery;
  A refrigerant, a compressor, a radiator, and a cooler, wherein the compressor consumes power discharged by the all solid-state polymer lithium secondary battery to compress the refrigerant, and the radiator absorbs heat from the refrigerant. A refrigeration cycle mechanism that releases and causes the cooler to absorb heat into the refrigerant;
  A controller that permits charging to the charging circuit in a first time zone and permits discharging to the discharging circuit in a second time zone;
  A charge state detection mechanism for detecting a charge state of the all solid-state polymer lithium secondary battery;
With
  The controller is
  Allowing the discharging circuit to discharge when the charging state is above a reference in the second time zone, and allowing charging to the charging circuit when the charging state is not above the reference in the second time zone Do not allow discharge to the discharge circuit
refrigerator.   The compressor is DC driven
The refrigerator in any one of Claim 1 to 3.   Power failure detection mechanism for detecting that power reception from the indoor wiring is stopped
Further comprising
  The controller is
  Allowing the discharge circuit to discharge when the power failure detection mechanism detects that power reception has stopped in the first time period
The refrigerator in any one of Claim 1 to 4.

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