WO2015163279A1 - 蓄電デバイスの再生用電解液、その再生された蓄電デバイス及び蓄電デバイスの再生方法 - Google Patents
蓄電デバイスの再生用電解液、その再生された蓄電デバイス及び蓄電デバイスの再生方法 Download PDFInfo
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- WO2015163279A1 WO2015163279A1 PCT/JP2015/061974 JP2015061974W WO2015163279A1 WO 2015163279 A1 WO2015163279 A1 WO 2015163279A1 JP 2015061974 W JP2015061974 W JP 2015061974W WO 2015163279 A1 WO2015163279 A1 WO 2015163279A1
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- electrolyte
- storage device
- regeneration
- electrolyte solution
- discharge capacity
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrolyte for regenerating an electricity storage device, the regenerated electricity storage device, and a method for regenerating the electricity storage device.
- a secondary battery installed in an automobile also has a cost of replacing it with a new secondary battery if it does not have a battery life until the vehicle replacement time.
- the battery life is up to the time of vehicle replacement, if the used secondary battery is regenerated to the same as a new one and the secondary battery can be used for another purpose, from the viewpoint of the global environment. It is also very effective, and such research is being conducted.
- Patent Document 1 discloses a nonaqueous electrolyte secondary battery having a battery port stopper that can be opened and closed in a battery container, and the discharge capacity is lower than 90% of the initial discharge capacity. It is described that the discharge capacity is recovered by injecting an electrolytic solution into the battery from the liquid stopper.
- Patent Document 2 discloses a non-aqueous electrolyte secondary battery having a sub-accommodating chamber for containing a non-aqueous electrolyte for replenishment, and the electrolyte is applied to a battery whose discharge capacity is less than 70% of the initial discharge capacity. It is described that the discharge capacity after replenishment is restored by replenishing.
- Patent Document 3 describes that high-rate deterioration resistance is improved by supplying a high concentration electrolyte or supporting salt when the battery resistance exceeds a predetermined threshold.
- An object of the present invention is to provide an electrolytic solution for regenerating the power storage device, a regenerated power storage device, and a method for regenerating the power storage device.
- Patent Documents 1 and 2 As a result of examining the above prior art, the present inventors have found that when the same electrolytic solution composition as the initial electrolytic solution is used as the re-injection electrolytic solution as in Patent Documents 1 and 2, the battery performance after replenishment is as follows. Although it was possible to recover to some extent, the situation was not yet satisfactory. Note that Patent Document 3 has no specific description regarding the electrolyte composition.
- the inventors of the present invention have a composition different from that of the initial nonaqueous electrolytic solution as a regenerating electrolytic solution in an electricity storage device having means for adding an electrolytic solution. As a result, it was found that the battery performance after replenishment can be properly recovered (for example, it can be recovered more than conventional), and the present invention has been achieved.
- the present invention provides the following (1) to (7).
- the electrolytic solution for regenerating the electricity storage device having a higher electrolyte concentration and a lower viscosity.
- An electrolytic solution for regeneration of an electricity storage device that is added after the discharge capacity has decreased by 1% or more with respect to the initial discharge capacity, and the electrolyte concentration is 0.8M or more and 3.0M or less.
- a power storage device including a positive electrode, a negative electrode, a separator, and an electrolytic solution in which an electrolyte salt is dissolved in a solvent, wherein a container of the power storage device discharges gas generated in the power storage device and the electrolytic solution
- An electrical storage device comprising an openable and closable liquid spigot that can be added.
- An electricity storage device including an electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, a separator, and a solvent, and the container of the electricity storage device includes means capable of storing a regeneration electrolyte solution An electricity storage device characterized by that.
- a power storage device including an electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, a separator, and a solvent, wherein the container of the power storage device is an adapter and a gas discharge port in which a liquid injection pipe can be attached and detached
- An electricity storage device comprising:
- a method of regenerating an electricity storage device by adding a regeneration electrolyte to the electricity storage device, wherein the initial value contained in the electricity storage device when the discharge capacity is reduced by 1% or more with respect to the initial discharge capacity A method of regenerating an electricity storage device, comprising adding a regeneration electrolyte solution having a higher electrolyte concentration and lower viscosity than the electrolyte solution to the electricity storage device.
- a method for regenerating a power storage device comprising adding a regeneration electrolyte solution having a chain ester content of 80% by volume or more in a solvent to the power storage device.
- an electrolytic solution for regenerating an electricity storage device it is possible to provide an electrolytic solution for regenerating an electricity storage device, the regenerated electricity storage device, and a method for regenerating the electricity storage device.
- the present invention relates to an electrolytic solution for regenerating an electricity storage device, the regenerated electricity storage device, and a method for regenerating the electricity storage device.
- the regenerating electrolyte of the present invention is used after being assembled and sealed, and after charging and discharging at least once, preferably 2 times or more, more preferably 5 times or more, and most preferably 10 times or more.
- the electrolyte solution for regeneration is different in composition from the electrolyte solution initially injected at the time of battery production (initial electrolyte solution), so that it is used for re-injection performed in the battery assembly process known in the art. Different from electrolyte.
- the number of times of the addition is not particularly limited, and it is more preferable that the number of additions is performed a plurality of times during use of the electricity storage device.
- the regeneration electrolyte solution for a regeneration of 2 or more from which a composition differs with respect to one addition.
- the regeneration electrolyte is preferably added to a battery whose capacity has deteriorated due to charge / discharge cycles or charge storage, and more preferably after the discharge capacity has decreased by 1% or more with respect to the initial discharge capacity.
- 3% or more is more preferable, and 5% or more is particularly preferable.
- 25% or less is preferable, 20% or less is more preferable, and 15% or less is especially preferable. It is preferable to add the regeneration electrolyte solution within the above range because the effect of improving battery characteristics is enhanced.
- the electrolyte concentration and viscosity may be set as the electrolyte concentration and viscosity of the initial electrolyte solution as they are.
- the electricity storage device after charging and discharging a part of the initial electrolyte contained in the electricity storage device is sampled, and the sampled electrolyte is subjected to composition analysis using a known method, and the result of the composition analysis Based on the above, the electrolyte concentration and viscosity of the initial electrolyte solution can be obtained by preparing an electrolyte solution having the same composition and measuring the viscosity of the prepared electrolyte solution.
- the type of battery used in the present invention may be an aluminum laminate film type, a square battery, or a cylindrical battery, and is not particularly limited.
- Preferred examples of the means for adding the regeneration electrolyte solution of the present invention include the means shown in the following (A) to (C), but are not particularly limited.
- An electricity storage device having an openable / closable liquid stopper The electricity storage device is sealed after an electricity storage device container contains an electrolytic solution in which an electrolyte salt is dissolved in a power generation unit composed of a positive electrode, a negative electrode, and a separator. Make it.
- the electricity storage device container is provided with an openable / closable liquid stopper, and it is preferable to inject the regeneration electrolyte into the electricity storage device container from the liquid stopper when the regeneration electrolyte is added. Further, it is more preferable that the liquid port cap also functions as a gas discharge port of the electricity storage device container.
- the inside of the electricity storage device container is decompressed by depressurizing the inside of the electricity storage device container from the liquid plug so that the electrolyte for regeneration easily penetrates into the inside of the battery.
- “Liquid cap that can be opened and closed” means that the liquid spout provided on the electricity storage device container can be easily opened and closed whenever necessary using a simple tool such as a spanner or screwdriver. In this case, it means a liquid stopper that can be easily performed.
- FIG. 1 is an electrical storage device container
- 2 is an openable / closable liquid stopper
- 3 is a power generation unit
- 4 is an initial electrolyte.
- An electricity storage device including a sub-accommodating chamber for storing a regenerating electrolyte solution.
- a power storage device container is sealed after an electrolyte solution in which an electrolyte salt is dissolved in a power generation unit composed of a positive electrode, a negative electrode, and a separator.
- the electric storage device container is provided with a sub-accommodating chamber for accommodating a regenerating electrolyte solution, and the accommodating chamber and the sub-accommodating chamber communicate with each other through an opening, and when the regenerating electrolytic solution is added, It is preferable to inject the regenerating electrolyte from the sub-accommodating chamber through the opening into the accommodating chamber.
- the auxiliary storage chamber of the electricity storage device container is formed with a sub-opening that communicates the sub-storage chamber with the outside.
- a part of the plug is detachably fitted into the opening, and the other of the plug The part penetrates the sub-opening and is exposed to the outside of the container.
- the sub-accommodating chamber may be provided with an openable / closable liquid plug for injecting the regenerating electrolyte into the sub-accommodating chamber.
- the liquid port cap also functions as a gas discharge port of the electricity storage device container.
- the inside of the electricity storage device container is decompressed by depressurizing the inside of the electricity storage device container from the liquid plug so that the electrolyte for regeneration easily penetrates into the inside of the battery.
- “Liquid cap that can be opened and closed” means that the liquid cap provided on the battery container can be easily opened and closed whenever necessary using a simple tool such as a spanner or screwdriver. Also means a liquid stopper that can be easily performed. A cross section of the structural example is shown in FIG. In FIG.
- 5 is a power storage device container
- 6 is a sub-accommodating chamber
- 7 is an openable / closable liquid stopper
- 8 is a plug
- 9 is a sub-opening
- 10 is a regenerating electrolyte
- 11 is an opening.
- 12 is a power generation unit
- 13 is an initial electrolyte.
- An electricity storage device having an adapter capable of attaching and detaching a liquid injection pipe
- An electricity storage device container is sealed after containing an electrolytic solution in which an electrolyte salt is dissolved in a power generation unit composed of a positive electrode, a negative electrode, and a separator, and a solvent.
- the electricity storage device container is equipped with an adapter capable of attaching and detaching a liquid injection pipe, and when the regeneration electrolyte is added, the adapter and the liquid injection pipe are connected, and the regeneration electrolyte can be injected into the electricity storage device container.
- the injection pipe hoses such as a flexible hose are preferably used.
- the electricity storage device container is provided with a gas outlet. More preferably, the inside of the electricity storage device container is depressurized from the gas discharge port to remove the gas inside the electricity storage device container so that the electrolyte for regeneration easily penetrates into the battery.
- FIG. 3 A cross section of the structural example is shown in FIG. In FIG. 3, 14 is an electrical storage device container, 15 is an adapter, 16 is a gas outlet, 17 is a power generation unit, and 18 is an initial electrolyte.
- the decompression condition is preferably controlled so that the container does not deform, is preferably ⁇ 70 kPa or less, more preferably ⁇ 80 kPa or less, and particularly preferably ⁇ 90 kPa or less.
- the pressure can be measured with a general pressure gauge such as a Pirani gauge.
- a secondary battery or a capacitor is preferable.
- a lithium secondary battery and a nickel hydride battery are preferable, and a lithium secondary battery is more preferable.
- a capacitor a lithium ion capacitor and an electric double layer capacitor are preferable, and a lithium ion capacitor is more preferable.
- those using a non-aqueous electrolyte as the electrolyte for regeneration are more preferred, and those using lithium ions as the electrolyte are particularly preferred.
- the case of a lithium secondary battery will be described in detail below, but the regeneration electrolyte used in the present invention is not particularly limited. The effect that can be solved.
- Examples of the negative electrode active material for a lithium secondary battery include lithium metal, lithium alloy, and a carbon material capable of occluding and releasing lithium (easily graphitized carbon and a (002) plane spacing of 0.37 nm or more).
- Non-graphitizable carbon, graphite with (002) plane spacing of 0.34 nm or less, etc.] tin (single), tin compound, silicon (single), silicon compound, lithium titanate such as Li 4 Ti 5 O 12 A compound etc. can be used individually by 1 type or in combination of 2 or more types.
- the film grows significantly by repeated charge and discharge, so the battery characteristics can be recovered by adding a non-aqueous electrolyte for regeneration. Is preferable since it further increases.
- the lattice spacing ( 002 ) plane spacing (d 002 ) is preferably 0.340 nm (nanometer) or less, and more preferably in the range of 0.335 to 0.339 nm. The range of 0.335 to 0.336 nm is more preferable.
- the nonaqueous electrolytic solution for regeneration according to the present invention is a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent, and has a higher electrolyte concentration and lower viscosity than the initial nonaqueous electrolytic solution. This is a nonaqueous electrolytic solution for regeneration.
- the reason why the battery characteristics can be greatly improved by the non-aqueous electrolyte for regeneration of the present invention is not necessarily clear, but is considered as follows.
- the initial non-aqueous electrolyte is reduced and decomposed on the surface of the negative electrode by charge / discharge to grow a coating.
- the electrolyte newly decomposes at that portion and starts to generate gas.
- gas is generated in the battery and a gas passage is formed, liquid drainage starts to occur from that portion, which may cause performance deterioration such as cycle reduction.
- the decrease in the absolute amount of the electrolyte due to the consumption of the electrolyte accompanying the formation of the film further promotes the cycle reduction, which not only promotes the decomposition of the electrolytic solution, but also accompanies charging / discharging by repeated rapid charging / discharging. Electrolyte movement tends to be uneven.
- the non-aqueous electrolyte for regeneration according to the present invention has an electrolyte concentration higher than that of the initial non-aqueous electrolyte, and therefore effectively acts on the replenishment of consumed electrolyte.
- the nonaqueous electrolytic solution for regeneration has a lower viscosity than the initial nonaqueous electrolytic solution, it is considered that the regenerating nonaqueous electrolytic solution is quickly penetrated into the battery, and locally generated permeation unevenness is eliminated and the cycle characteristics are regenerated.
- Nonaqueous solvent Preferred examples of the non-aqueous solvent used in the non-aqueous electrolyte of the present invention (the initial non-aqueous electrolyte and the regenerating non-aqueous electrolyte) include cyclic carbonates, chain esters, lactones, and ethers. More preferably, the aqueous solvent includes both cyclic carbonates and chain esters.
- chain ester is used as a concept including chain carbonate and chain carboxylic acid ester.
- the cyclic carbonate is preferably at least one selected from ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and cyclic carbonate having a fluorine atom.
- cyclic carbonates having fluorine atoms include 4-fluoro-1,3-dioxolan-2-one (FEC) and trans or cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter, both One or more selected from “DFEC” in general are preferred.
- FEC 4-fluoro-1,3-dioxolan-2-one
- DFEC trans or cis-4,5-difluoro-1,3-dioxolan-2-one
- a symmetric chain carbonate such as dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, or dibutyl carbonate.
- Asymmetric chain carbonates such as methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, or ethyl propyl carbonate, methyl pivalate, ethyl pivalate, or propyl pivalate
- Pivalate ester or chain carboxylic acid ester such as methyl propionate, ethyl propionate, methyl acetate, or ethyl acetate is preferred.
- the content of the chain ester is preferably 70% by volume or more, more preferably 80% by volume or more, particularly 90% by volume or more, based on the total volume of the nonaqueous solvent. preferable. If the content is 70% by volume or more, the viscosity of the non-aqueous electrolyte can be reduced and the penetration into the electrode sheet is improved, so that the above range is preferable.
- the content of the chain ester in the initial nonaqueous electrolytic solution is not particularly limited, but is usually 70% by volume or less.
- the proportion of the volume occupied by dimethyl carbonate in the nonaqueous electrolytic solution for regeneration is preferably 51% by volume or more, more preferably 70% by volume or more, and particularly preferably 85% by volume or more based on the total volume of the nonaqueous solvent.
- the penetration into the electrode sheet is further improved, and the effect of improving the cycle characteristics at high temperatures is enhanced, which is preferable.
- the ratio of the volume which dimethyl carbonate occupies in the initial non-aqueous electrolyte is not particularly limited.
- a pivalic acid ester such as methyl pivalate or ethyl pivalate is included, and methyl pivalate is particularly preferable.
- the proportion of the volume occupied by the chain carboxylic acid ester in the nonaqueous electrolytic solution for regeneration is preferably 5% by volume or more, more preferably 7% by volume or more, and more preferably 10% by volume or more based on the total volume of the nonaqueous solvent. Particularly preferred. In the above case, the penetration into the electrode sheet is further improved, and the effect of improving the cycle characteristics at high temperatures is enhanced, which is preferable.
- the proportion of the volume occupied by the chain carboxylic acid ester in the initial non-aqueous electrolyte is not particularly limited.
- non-aqueous electrolyte in addition to the electrolyte salt and non-aqueous solvent, other additives are added to the non-aqueous electrolyte (initial non-aqueous electrolyte and regenerating non-aqueous electrolyte) in order to further improve the thermal stability of the negative electrode.
- additives are added to the non-aqueous electrolyte (initial non-aqueous electrolyte and regenerating non-aqueous electrolyte) in order to further improve the thermal stability of the negative electrode.
- the cyclic carbonate which has an unsaturated bond is mentioned suitably.
- cyclic carbonate having an unsaturated bond examples include the following compounds. Vinylene carbonate (VC), vinyl ethylene carbonate (VEC), 4-ethynyl-1,3-dioxolan-2-one (EEC), 2-propynyl 2-oxo-1,3-dioxolane-4-carboxylate, etc.
- the content of the cyclic carbonate having an unsaturated bond is preferably 5 to 30% by mass in the nonaqueous electrolytic solution. If it exceeds 5% by mass, the coating is sufficiently repaired, and the effect of improving the cycle characteristics at high temperatures is enhanced.
- the content is more preferably 5% by mass or more, more preferably 7% by mass or more in the non-aqueous electrolyte, and the upper limit thereof is more preferably 25% by mass or less, and further preferably 20% by mass or less.
- content of the cyclic carbonate which has an unsaturated bond in the initial non-aqueous electrolyte is not specifically limited.
- Electrolyte salt Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
- LiPF 6 , LiBF 4 , and LiAsF 6 are preferred, and LiPF 6 , LiBF 4 is more preferable.
- Li salt-3 LiSO 3 F, LiCF 3 SO 3 , CH 3 SO 4 Li, C 2 H 5 SO 4 Li, and C 3 H 7 SO 4 Li, lithium methanesulfonate pentafluorophosphate (LiPFMSP), and lithium methanesulfonate trifluoroborate (
- LiPFMSP lithium methanesulfonate pentafluorophosphate
- LiTFMSB lithium methanesulfonate trifluoroborate
- Li salt-4 One or two or more “P ⁇ O or Cl ⁇ O structure-containing lithium salts” selected from LiPO 2 F 2 , Li 2 PO 3 F, and LiClO 4 are preferred, and among them, LiPO 2 F 2 , Li 2 PO 3 F is preferred.
- Li salt-5 Bis [oxalate-O, O ′] lithium borate (LiBOB), difluoro [oxalate-O, O ′] lithium borate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), and tetrafluoro [
- LiBOB and LiPFO are more preferred. These 1 type or 2 or more types can be mixed and used.
- LiPF 6 LiPO 2 F 2 , Li 2 PO 3 F, LiBF 4 , LiSO 3 F, LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , CH 3 SO 4 Li, C 2 H 5 SO 4 Li, bis [oxalate-O, O ′] lithium borate (LiBOB), difluorobis [oxalate-O, O '] Lithium phosphate (LiPFO), tetrafluoro [oxalate-O, O'] lithium phosphate, lithium methanesulfonate pentafluorophosphate (LiPFMSP), and lithium methanesulfonate trifluoroborate (LiTFMSB)
- the concentration of the lithium salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, and further preferably 1.1 M or more with respect to the nonaqueous solvent.
- the upper limit is preferably 1.6 M or less, more preferably 1.5 M or less, and even more preferably 1.4 M or less.
- concentration of the lithium salt in the non-aqueous electrolyte for reproduction is higher than the initial non-aqueous electrolyte.
- the concentration of the lithium salt in the non-aqueous electrolyte is preferably equal to or higher than the initial concentration of the lithium salt in the non-aqueous electrolyte.
- the concentration of the lithium salt in the nonaqueous electrolytic solution for regeneration is usually preferably 0.8M or more, more preferably 0.9M or more, and further preferably 1.2M or more with respect to the nonaqueous solvent.
- the upper limit is preferably 3.0M or less, more preferably 2.5M or less, and further preferably 2.2M or less. If the concentration of the lithium salt is in the above range, the non-aqueous electrolyte can be sufficiently supplemented with Li ions, and the effect of improving the cycle characteristics at high temperatures is increased, which is preferable.
- LiPF 6 is included, and LiPO 2 F 2 , LiPO 2 F 2 , CH 3 SO 4 Li, C 2 H 5 SO 4 Li, lithium methanesulfonate pentafluorophosphate ( One or more selected from LiPFMSP) and lithium methanesulfonate trifluoroborate (LiTFMSB) are more preferable.
- LiPFMSP lithium methanesulfonate pentafluorophosphate
- LiTFMSB lithium methanesulfonate trifluoroborate
- LiPFMSP lithium methanesulfonate pentafluorophosphate
- LiTFMSB lithium methanesulfonate trifluoroborate
- LiPFMSP lithium methanesulfonate pentafluorophosphate
- LiTFMSB lithium methanesulfonate trifluoroborate
- a new low resistance film is formed by using a Li salt previously placed in the electrolyte for regeneration, or a new SEI film is formed by using an organic additive such as VC.
- an organic additive such as VC.
- the proportion of the lithium salt other than LiPF 6 in the non-aqueous solvent is preferably 0.001M or more, and the effect of improving the electrochemical properties is easily exhibited, and if it is 1.2M or less, the effect of improving the electrochemical properties is reduced.
- the concentration of the lithium salt other than LiPF 6 is in the above range, the effect of improving battery characteristics is increased, which is preferable.
- the nonaqueous electrolytic solution of the present invention can be obtained, for example, by mixing the nonaqueous solvent and adding the electrolyte salt and other additives to the nonaqueous solvent.
- the additive added to the non-aqueous solvent and the non-aqueous electrolyte to be used is one that is purified in advance and has as few impurities as possible within a range that does not significantly reduce the productivity.
- the electrolyte concentration for regeneration is 0.8M or more and 3.0M or less
- the regeneration electrolyte solution An electrolyte solution for regeneration having a chain ester content of 80% by volume or more in the solvent constituting the above may be employed.
- the regeneration electrolyte solution having such an electrolyte concentration and solvent composition has characteristics that the electrolyte concentration is not less than a predetermined value and has a low viscosity, and therefore, regardless of the composition and type of the initial nonaqueous electrolyte solution.
- the battery performance after replenishment can be recovered to a certain extent.
- the electrolyte concentration is preferably 0.9 M or more, more preferably 1.2 M or more, and the upper limit thereof is preferably 2.5 M or less, more preferably 2.2 M or less.
- 85 volume% or more is preferable, as for content of the chain ester in the solvent which comprises the electrolyte solution for reproduction
- what is necessary is just to make it the same as the above and the kind and content rate of the electrolyte salt to be used, a nonaqueous solvent, and another additive.
- Preparation of positive electrode sheet 94% by mass of LiNi 1/3 Co 1/3 Mn 1/3 O 2 and 3% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1-methyl-2-
- a positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in pyrrolidone. This positive electrode mixture paste was applied onto an aluminum foil (current collector), dried and pressurized, and cut into a predetermined size to produce a positive electrode sheet.
- Ethylene carbonate (EC) and methylethyl carbonate (MEC) and vinylene carbonate dimethyl carbonate (DMC) after the LiPF 6 in a solvent were mixed in a volume ratio of 30:30:40 was dissolved 1.2 mol / liter (VC)
- the initial non-aqueous electrolyte A was prepared by adding 2% by mass with respect to the total mass of the electrolyte. It was 2.78 (cSt) when the kinematic viscosity of the nonaqueous electrolyte A was measured under room temperature.
- Example 9 Comparative Examples 3, 4
- the positive electrode sheet obtained above, the separator made of a microporous polyethylene film, and the negative electrode sheet B obtained above were wound to produce a power generation unit composed of a flat wound body. And after accommodating this electric power generation part and the initial nonaqueous electrolyte A in the exterior body which consists of a bag-shaped aluminum laminated film, it sealed.
- Example 10 and Comparative Examples 5 and 6 A power generation unit was produced in the same manner as in Example 1. And after accommodating this electric power generation part and the initial nonaqueous electrolyte B in the exterior body which consists of a bag-shaped aluminum laminate film, it sealed.
- Comparative Examples 1, 3 and 5 the cumulative number of cycles until the discharge capacity falls below 80% of the initial discharge capacity from when the discharge capacity becomes 90% of the initial discharge capacity without adding the regeneration electrolyte is calculated. Examined. Moreover, what inject
- Example 11 Comparative Example 7 Similarly to Example 1, a power generation unit made of a laminate was produced.
- the power generation unit and the initial nonaqueous electrolytic solution A were housed in a battery container having an openable / closable liquid stopper as shown in FIG.
- Example 11 Comparative Example 7 was prepared by injecting a nonaqueous electrolytic solution (see Table 3) having the same composition as the initial nonaqueous electrolytic solution A as a regenerating nonaqueous electrolytic solution. The results are shown in Table 3.
- Example 12 Comparative Example 8 Similarly to Example 1, a power generation unit made of a laminate was produced. And after accommodating this electric power generation part in the battery container provided with the auxiliary
- Example 12 this battery was cycled again under the above conditions, and the cumulative number of cycles until the discharge capacity fell below 80% of the initial discharge capacity after the injection of the nonaqueous electrolyte for regeneration was examined.
- Comparative Example 8 was prepared by injecting a nonaqueous electrolyte solution (see Table 4) having the same composition as the initial nonaqueous electrolyte solution A as a nonaqueous electrolyte solution for regeneration. The results are shown in Table 4.
- Example 13 and Comparative Example 59 Similarly to Example 1, a power generation unit made of a laminate was produced. Then, the power generation unit and the initial nonaqueous electrolytic solution were housed in a battery container equipped with an adapter and a gas discharge port capable of attaching and detaching the injection pipe shown in FIG.
- Example 13 When the discharge capacity reaches 90% of the initial discharge capacity, the pressure is reduced until it reaches ⁇ 90 kPa from the gas discharge port, and after degassing, the injection pipe is connected to the adapter and then the initial A non-aqueous electrolyte for regeneration (see Table 5) corresponding to 10% by mass of the injected amount of the non-aqueous electrolyte A was injected, and the injection pipe was removed from the adapter.
- this battery was cycled again under the above conditions, and the cumulative number of cycles until the discharge capacity fell below 80% of the initial discharge capacity after the injection of the non-aqueous electrolyte for regeneration was examined.
- Comparative Example 9 was prepared by injecting a nonaqueous electrolyte solution (see Table 5) having the same composition as that of the initial nonaqueous electrolyte solution A as a nonaqueous electrolyte solution for regeneration. The results are shown in Table 5.
- a negative electrode mixture paste was prepared by adding 95% by mass of artificial graphite to a solution prepared by previously dissolving 5% by mass of polyvinylidene fluoride (binder) in 1-methyl-2-pyrrolidone. This negative electrode mixture paste was applied to one side of a copper foil (current collector), dried and pressurized, and cut into a predetermined size to produce a negative electrode sheet. And lithium metal foil was affixed on the surface of this negative electrode sheet.
- Example 14 and Comparative Example 10 The positive electrode sheet obtained above, the separator made of a microporous polyethylene film, and the negative electrode sheet obtained above were wound to produce a power generation unit composed of a flat wound body. And after accommodating this electric power generation part and the initial nonaqueous electrolyte A in the exterior body which consists of a bag-shaped aluminum laminated film, it sealed.
- Example 14 Comparative Example 10 was prepared by injecting a nonaqueous electrolyte solution (see Table 6) having the same composition as the initial nonaqueous electrolyte solution as a nonaqueous electrolyte solution for regeneration. The results are shown in Table 6.
- Example 1 and Comparative Examples 1 and 2 Comparison between Example 9 and Comparative Examples 3 and 4, Comparison between Example 10 and Comparative Examples 5 and 6, Comparison between Example 11 and Comparative Example 7, Example 12
- the cycle characteristics under high temperature are remarkably improved. It can also be seen that the cycle characteristics at high temperatures are further improved by adding a non-aqueous electrolyte containing a specific additive or lithium salt to Example 1 as in Examples 4 to 8. .
- the effect of the present invention is that when the regeneration nonaqueous electrolyte solution having a higher electrolyte concentration and lower viscosity than the initial nonaqueous electrolyte solution is added in the electricity storage device having means for adding the regeneration electrolyte solution. It turned out to be a peculiar effect.
- the regeneration electrolyte of the present invention is used, an electricity storage device having excellent electrochemical characteristics at high temperatures can be obtained. Especially when used as a non-aqueous electrolyte for regeneration of electricity storage devices mounted on hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc. Obtainable.
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Abstract
Description
また、特許文献2には、補充用非水電解液を収容するための副収容室を有する非水電解質二次電池が開示され、放電容量が初期放電容量の70%を下回った電池に電解液を補充することで補充後の放電容量が回復することが記載されている。
更に、特許文献3には、電池抵抗が所定の閾値を超えた場合に高濃度の電解液または支持塩を供給することによってハイレート劣化耐性が向上することが記載されている。
(1)放電容量が初期の放電容量に対して1%以上低下した際に、継ぎ足しする蓄電デバイスの再生用電解液であって、初期の電解液(電池作成時の最初に注液する電解液)よりも、電解質濃度が高く、かつ低粘度であることを特徴とする蓄電デバイスの再生用電解液。
本発明の再生用電解液は、電池を組み立てて封止した後、充放電を少なくとも1回以上、好ましくは2回以上、より好ましくは5回以上、最も好ましくは10回以上経た後に継ぎ足して使用する。また、該再生用電解液は電池作製時の最初に注液する電解液(初期の電解液)とは組成が違うため、従来知られている電池の組み立て工程で実施される再注液用の電解液とは異なる。前記継ぎ足しの回数は特に限定されず、蓄電デバイスの使用途中において複数回実施するのがより好ましい。また、一度の継ぎ足しに対し組成の異なる2種類以上の再生用電解液を使用してもよい。尚、再生用電解液の継ぎ足しは、充放電サイクルあるいは充電保存などにより容量劣化した電池に実施することが好ましく、放電容量が初期の放電容量に対して1%以上低下した後に実施するのがより好ましく、3%以上が更に好ましく、5%以上が特に好ましい。また、その上限としては、25%以下が好ましく、20%以下がより好ましく、15%以下が特に好ましい。上記の範囲内で再生用電解液の継ぎ足しを実施すると、電池特性の改善効果が高まるので好ましい。
本発明に使用される電池のタイプは、アルミラミネートフィルムタイプであっても、角型電池であっても、円筒電池であっても良く、特に限定されるものではない。
本発明の再生用電解液の継ぎ足し手段としては、例えば以下の(A)~(C)に示す手段等が好適に挙げられるが、特に制限はない。
蓄電デバイス容器に正極、負極、セパレータからなる発電部及び溶媒に電解質塩が溶解されている電解液を収容した後に封止して蓄電デバイスを作製する。蓄電デバイス容器は開閉可能な液口栓を設けたもので、再生用電解液の継ぎ足しの際に液口栓から、再生用電解液を蓄電デバイス容器に注入することが好ましい。
また、該液口栓は、蓄電デバイス容器のガス排出口としても機能させることがより好ましい。該液口栓から蓄電デバイス容器内部を減圧することで蓄電デバイス容器内部のガスを抜いて、再生用電解液が電池内部に浸透しやすくすることが更に好ましい。
「開閉可能な液口栓」とは、蓄電デバイス容器に備えられた液口栓が、必要な時にはいつでも、スパナやドライバー等の簡単な工具を用いて、容易に開くことができ、また、閉じる場合も同様に容易に行うことのできる液口栓を意味する。
構造例の断面を図1に示す。図1において、1は蓄電デバイス容器であり、2は開閉可能な液口栓、3は発電部、4は初期の電解液である。
蓄電デバイス容器に正極、負極、セパレータからなる発電部及び溶媒に電解質塩が溶解されている電解液を収容した後に封止して蓄電デバイスを作製する。蓄電デバイス容器は再生用電解液を収容する副収容室を設けたもので、該収容室と該副収容室が、開口部を介して連通しており、再生用電解液を継ぎ足す際に該開口部を通して該副収容室から再生用電解液を収容室に注入することが好ましい。蓄電デバイス容器の副収容室には外部と該副収容室を連通させる副開口部が形成されており、栓体の一部が開口部に着脱自在に嵌合され、かつ栓体の他の一部が副開口部を貫通して収容体の外側に露出している。尚、副収容室には副開口部の他に再生用電解液を副収容室に注入するための開閉可能な液口栓を設けてもよい。
また、該液口栓は、蓄電デバイス容器のガス排出口としても機能させることがより好ましい。該液口栓から蓄電デバイス容器内部を減圧することで蓄電デバイス容器内部のガスを抜いて、再生用電解液が電池内部に浸透しやすくすることが更に好ましい。「開閉可能な液口栓」とは、電池容器に備えられた液口栓が、必要な時にはいつでも、スパナやドライバー等の簡単な工具を用いて、容易に開くことができ、また、閉じる場合も同様に容易に行うことのできる液口栓を意味する。
構造例の断面を図2に示す。図2において、5は蓄電デバイス容器であり、6は副収容室、7は開閉可能な液口栓、8は栓体、9は副開口部、10は再生用電解液を示し、11は開口部、12は発電部、13は初期の電解液である。
蓄電デバイス容器に正極、負極、セパレータからなる発電部及び溶媒に電解質塩が溶解されている電解液を収容した後に封止して蓄電デバイスを作製する。蓄電デバイス容器は注液用配管の着脱が可能なアダプタを備え、再生用電解液の継ぎ足しの際に該アダプタと注液用配管を接続し、再生用電解液を蓄電デバイス容器に注入することが好ましい。該注液用配管としてはフレキシブルホース等のホース類が好適に使用される。該注液用配管とアダプタの接続方法としては、例えばワンタッチで着脱のできるカムアーム式ホースカプラ等のホースカプラをアダプタに嵌合させて使用することが好ましい。
また、蓄電デバイス容器にガス排出口が備えてあるとより好ましい。該ガス排出口から蓄電デバイス容器内部を減圧することで蓄電デバイス容器内部のガスを抜いて、再生用電解液が電池内部に浸透しやすくすることが更に好ましい。
構造例の断面を図3に示す。図3において、14は蓄電デバイス容器であり、15はアダプタ、16はガス排出口、17は発電部、18は初期の電解液である。
これらの中でも、人造黒鉛や天然黒鉛等の黒鉛型結晶構造を有する炭素材料を使用する場合、充放電の繰り返しによって被膜が顕著に成長するため、再生用非水電解液の継ぎ足しによる電池特性の回復が一段と高まるので好ましい。特に黒鉛型結晶構造を有する炭素材料としては、格子面(002)の面間隔(d002)が0.340nm(ナノメータ)以下であると好ましく、0.335~0.339nmの範囲であるとより好ましく、0.335~0.336nmの範囲であると更に好ましい。
本発明の再生用非水電解液は、非水溶媒に電解質塩が溶解されている非水電解液であって、初期の非水電解液よりも電解質濃度が高く、低粘度であることを特徴とする再生用非水電解液である。
電池を組み立てた後、初期の非水電解液は、充放電によって負極表面上で還元分解し被膜が成長していく。その際、電極上の被膜に欠損が生じると、その部分で電解液が新たに分解し、ガスを発生し始める。電池内にガスが発生し、ガスの通路が出来てしまうと、その部分が起点となって液枯れが起こり始めるため、サイクル低下などの性能低下の原因となると考えられる。また、被膜形成に伴う電解質の消費によって電解質の絶対量が減少することで更にサイクル低下は促進され、電解液の分解が促進されるだけでなく、急速な充放電の繰り返しによって、充放電に伴う電解質の移動が不均一になりやすい。
本願発明の再生用非水電解液は、初期の非水電解液よりも電解質濃度が高いため、消費された電解質の補充に対し有効に作用する。更に、再生用非水電解液は、初期の非水電解液よりも低粘度であるため電池内に速やかに浸透され、局所的に発生した浸透ムラが解消されサイクル特性が再生すると考えられる。また、再生用非水電解液に特定の添加剤を加えると更に好ましく、前記特定の添加剤が使用中に蓄積した被膜を剥ぎ取ったり、補修したりすることができ、電池性能を改善させることができるようになる。
本発明の非水電解液(初期の非水電解液及び再生用非水電解液)に使用される非水溶媒としては、環状カーボネート、鎖状エステル、ラクトン、又はエーテルが好適に挙げられ、非水溶媒としては、環状カーボネートと鎖状エステルの両方が含まれることがより好ましい。
なお、鎖状エステルなる用語は、鎖状カーボネート及び鎖状カルボン酸エステルを含む概念として用いる。
環状カーボネートとしては、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、1,2-ブチレンカーボネート、2,3-ブチレンカーボネート、及びフッ素原子を有する環状カーボネートから選ばれる一種以上が好ましい。
再生用非水電解液中にジメチルカーボネートが占める体積の割合は、非水溶媒の総体積に対して、51体積%以上が好ましく、70体積%以上がより好ましく、85体積%以上が特に好ましい。
上記の場合に一段と電極シートへの浸透が向上し、高温下でのサイクル特性の改善効果が高まるので好ましい。
なお、初期の非水電解液中における、ジメチルカーボネートが占める体積の割合は特に限定されない。
再生用非水電解液中に鎖状カルボン酸エステルが占める体積の割合は、非水溶媒の総体積に対して、5体積%以上が好ましく、7体積%以上がより好ましく、10体積%以上が特に好ましい。
上記の場合に一段と電極シートへの浸透が向上し、高温下でのサイクル特性の改善効果が高まるので好ましい。
なお、初期の非水電解液中における、鎖状カルボン酸エステルが占める体積の割合は特に限定されない。
ビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)、及び2-プロピニル 2-オキソ-1,3-ジオキソラン-4-カルボキシレート等から選ばれる1種以上の不飽和結合を有する環状カーボネート。中でもビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)から選ばれる一種以上が好ましい。
なお、初期の非水電解液中における、不飽和結合を有する環状カーボネートの含有量は特に限定されない。
本発明に使用される電解質塩としては、下記のリチウム塩が好適に挙げられる。
〔Li塩-1類〕
LiPF6、LiBF4、LiAsF6、LiSbF6、LiPF4(CF3)2、LiPF3(C2F5)3、LiPF3(CF3)3、LiPF3(iso-C3F7)3、及びLiPF5(iso-C3F7)から選ばれる一種又は二種以上の「ルイス酸とLiFの錯塩」が好適に上げられ、中でもLiPF6、LiBF4、LiAsF6が好ましく、LiPF6、LiBF4が更に好ましい。
〔Li塩-2類〕
LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2C2F5)2、(CF2)2(SO2)2NLi(環状)、(CF2)3(SO2)2NLi(環状)、及びLiC(SO2CF3)3から選ばれる一種又は二種以上の「イミド又はメチドリチウム塩」が好適に挙げられ、中でもLiN(SO2F)2、LiN(SO2CF3)2、又はLiN(SO2C2F5)2が好ましく、LiN(SO2F)2又はLiN(SO2CF3)2が更に好ましい。
〔Li塩-3類〕
LiSO3F、LiCF3SO3、CH3SO4Li、C2H5SO4Li、及びC3H7SO4Li、リチウム メタンスルホネート ペンタフルオロホスフェート(LiPFMSP)、及びリチウム メタンスルホネート トリフルオロボレート(LiTFMSB)から選ばれる一種又は二種以上の「S=O基を含有するリチウム塩」が好適に挙げられ、中でもリチウム メタンスルホネート ペンタフルオロホスフェート(LiPFMSP)、又はリチウム メタンスルホネート トリフルオロボレート(LiTFMSB)が好ましい。
〔Li塩-4類〕
LiPO2F2、Li2PO3F、及びLiClO4から選ばれる一種又は二種以上の「P=OもしくはCl=O構造含有リチウム塩」が好適に挙げられ、中でもLiPO2F2、Li2PO3Fが好ましい。
〔Li塩-5類〕
ビス[オキサレート-O,O’]ホウ酸リチウム(LiBOB)、ジフルオロ[オキサレート-O,O’]ホウ酸リチウム、ジフルオロビス[オキサレート-O,O’]リン酸リチウム(LiPFO)、及びテトラフルオロ[オキサレート-O,O’]リン酸リチウムから選ばれる一種又は二種以上の「オキサレート錯体をアニオンとするリチウム塩」が好適に挙げられ、中でもLiBOB、LiPFOが更に好ましい。
これらの一種又は二種以上を混合して使用することができる。
初期の非水電解液において、リチウム塩の濃度は、前記の非水溶媒に対して、通常0.3M以上が好ましく、0.7M以上がより好ましく、1.1M以上が更に好ましい。またその上限は、1.6M以下が好ましく、1.5M以下がより好ましく、1.4M以下が更に好ましい。
また、再生用非水電解液におけるリチウム塩の濃度は、初期の非水電解液よりも濃度が高いことが好ましい。再生用非水電解液を継ぎ足した後、非水電解液のリチウム塩の濃度は、初期の非水電解液のリチウム塩の濃度以上になることが好ましい。
再生用非水電解液におけるリチウム塩の濃度は、前記の非水溶媒に対して、通常0.8M以上が好ましく、0.9M以上がより好ましく、1.2M以上が更に好ましい。またその上限は、3.0M以下が好ましく、2.5M以下がより好ましく、2.2M以下が更に好ましい。リチウム塩の濃度が上記範囲であれば非水電解液へ十分にLiイオンを補充することができ、高温下でのサイクル特性の改善効果が高まるので好ましい。
本発明の非水電解液は、例えば、前記の非水溶媒を混合し、これに前記の電解質塩及びその他の添加剤を添加することにより得ることができる。
この際、用いる非水溶媒及び非水電解液に加える添加剤は、生産性を著しく低下させない範囲内で、予め精製して、不純物が極力少ないものを用いることが好ましい。
LiNi1/3Co1/3Mn1/3O2 94質量%、アセチレンブラック(導電剤)3質量%を混合し、予めポリフッ化ビニリデン(結着剤)3質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。この正極合剤ペーストをアルミニウム箔(集電体)上に塗布し、乾燥、加圧処理して所定の大きさに裁断し、正極シートを作製した。
格子面(002)の面間隔(d002)が0.337nmである黒鉛型結晶構造を有する人造黒鉛95質量%を、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、負極シートAを作製した。
格子面(002)の面間隔(d002)が0.335nmである天然黒鉛95質量%を、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、負極シートBを作製した。
エチレンカーボネート(EC)とメチルエチルカーボネート(MEC)とジメチルカーボネート(DMC)を容積比30:30:40で混合した溶媒にLiPF6を1.2モル/リットル溶解した後でビニレンカーボネート(VC)を電解液の総質量に対して2質量%となるように加えて初期の非水電解液Aを調整した。室温下で非水電解液Aの動粘度を測定したところ2.78(cSt)であった。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)とジメチルカーボネート(DMC)を容積比30:35:35で混合した溶媒にLiPF6を1.0モル/リットル溶解した後でビニレンカーボネート(VC)を電解液の総質量に対して2質量%となるように加えて初期の非水電解液Bを調整した。室温下で非水電解液Bの動粘度を測定したところ2.62(cSt)であった。
上記で得られた正極シート、微多孔性ポリエチレンフィルム製セパレータ、上記で得られた負極シートAを捲回し、扁平状の捲回体からなる発電部を作製した。そして、該発電部及び初期の非水電解液Aを袋状のアルミラミネートフィルムからなる外装体に収納した後、封止した。
上記で得られた正極シート、微多孔性ポリエチレンフィルム製セパレータ、上記で得られた負極シートBを捲回し、扁平状の捲回体からなる発電部を作製した。そして、該発電部及び初期の非水電解液Aを袋状のアルミラミネートフィルムからなる外装体に収納した後、封止した。
実施例1と同様に発電部を作製した。そして、該発電部及び初期の非水電解液Bを袋状のアルミラミネートフィルムからなる外装体に収納した後、封止した。
<初期特性>
上記の方法で作製した電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.2Vまで3時間充電し、1Cの定電流下終止電圧3Vまで放電して、初期の放電容量を測定した。
<高温サイクル特性>
上記の方法で作製した電池を用いて60℃の恒温槽中、3Cの定電流及び定電圧で、終止電圧4.2Vまで2時間充電し、次に3Cの定電流下、放電電圧3Vまで放電することを1サイクルとし、これを繰り返した。そして、放電容量が初期の放電容量の90%になった時点で、外装体の端部を切り取り、-90kPaに到達するまで開口部から減圧してガス抜きを実施した後、シリンジを用いて初期の非水電解液Aまたは非水電解液Bの注液量の10質量%に相当する再生用非水電解液(表1、表2参照)を注入し再度封止した。実施例1、9および10は、この電池を上記条件で再度サイクルし、再生用非水電解液の注入後から放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。比較例1、3および5は、放電容量が初期の放電容量の90%になった時点から再生用電解液の継ぎ足しなしで放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。また、再生用非水電解液として初期の非水電解液Aと同じ組成の非水電解液(表1参照)を注入したものを比較例2および4とし、初期の非水電解液Bと同じ組成の非水電解液(表2参照)を注入したものを比較例6とした。
実施例2は、減圧工程を省略する以外、実施例1と同じ方法で電池評価を行った。実施例3~8は、再生用非水電解液(表1参照)を変更すること以外、実施例1と同じ方法で電池評価を行った。結果を表1および表2に示す。
実施例1と同様に、積層体からなる発電部を作製した。そして、該発電部及び初期の非水電解液Aを図1に示す開閉可能な液口栓を具備する電池容器に収容した後に封止し、電池を作製した。
<初期特性>
上記の方法で作製した電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.2Vまで3時間充電し、1Cの定電流下終止電圧3Vまで放電して、初期の放電容量を測定した。
<高温サイクル特性>
上記の方法で作製した電池を用いて60℃の恒温槽中、3Cの定電流及び定電圧で、終止電圧4.2Vまで2時間充電し、次に3Cの定電流下、放電電圧3Vまで放電することを1サイクルとし、これを繰り返した。そして、放電容量が初期の放電容量の90%になった時点で、初期の非水電解液Aの注液量の10質量%に相当する再生用非水電解液を開閉可能な液口栓を開放し、-90kPaに到達するまで減圧してガス抜きを実施した後、再生用非水電解液(表3参照)を液口から注入し再度封止した。実施例11は、この電池を上記条件で再度サイクルし、再生用非水電解液の注入後から放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。再生用非水電解液として初期の非水電解液Aと同じ組成の非水電解液(表3参照)を注入したものを比較例7とした。結果を表3に示す。
実施例1と同様に、積層体からなる発電部を作製した。そして、該発電部を図2に示す再生用電解液を収納することができる副収容室を備える電池容器に収容した後に初期の非水電解液Aを開口部から注入し栓体で封止した。次に副収容室に設けた開閉可能な液口栓を開放し、液口から初期の非水電解液Aの注液量の10質量%に相当する再生用非水電解液を副収容室に注入した。
<初期特性>
上記の方法で作製した電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.2Vまで3時間充電し、1Cの定電流下終止電圧3Vまで放電して、初期の放電容量を測定した。
<高温サイクル特性>
上記の方法で作製した電池を用いて60℃の恒温槽中、3Cの定電流及び定電圧で、終止電圧4.2Vまで2時間充電し、次に3Cの定電流下、放電電圧3Vまで放電することを1サイクルとし、これを繰り返した。そして、放電容量が初期の放電容量の90%になった時点で、収容室と副収容室を連通する開口部を閉塞させていた栓体を外すことにより、開口部を介して副収容室から収容室に再生用非水電解液(表4参照)を注入した。そして、副収容室に設けた開閉可能な液口栓を開放し、-90kPaに到達するまで減圧してガス抜きを実施した後に再度封止した。実施例12は、この電池を上記条件で再度サイクルし、再生用非水電解液の注入後から放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。再生用非水電解液として初期の非水電解液Aと同じ組成の非水電解液(表4参照)を注入したものを比較例8とした。結果を表4に示す。
実施例1と同様に、積層体からなる発電部を作製した。そして、該発電部及び初期の非水電解液を図3に示す注液用配管の着脱が可能なアダプタ及びガス排出口を具備する電池容器に収容した後に封止し、電池を作製した。
<初期特性>
上記の方法で作製した電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.2Vまで3時間充電し、1Cの定電流下終止電圧3Vまで放電して、初期の放電容量を測定した。
<高温サイクル特性>
上記の方法で作製した電池を用いて60℃の恒温槽中、3Cの定電流及び定電圧で、終止電圧4.2Vまで2時間充電し、次に3Cの定電流下、放電電圧3Vまで放電することを1サイクルとし、これを繰り返した。そして、放電容量が初期の放電容量の90%になった時点で、ガス排出口から-90kPaに到達するまで減圧してガス抜きを実施した後、注液用配管をアダプタに接続してから初期の非水電解液Aの注液量の10質量%に相当する再生用非水電解液(表5参照)を注入し注液用配管をアダプタから外した。実施例13は、この電池を上記条件で再度サイクルし、再生用非水電解液の注入後から放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。再生用非水電解液として初期の非水電解液Aと同じ組成の非水電解液(表5参照)を注入したものを比較例9とした。結果を表5に示す。
〔正極シートの作製〕
活性炭粉末 85質量%、アセチレンブラック(導電剤)10質量%を混合し、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、正極合剤ペーストを調製した。この正極合剤ペーストをアルミニウム箔(集電体)上に塗布し、乾燥、加圧処理して所定の大きさに裁断し、正極シートを作製した。
〔負極シートの作製〕
人造黒鉛 95質量%を、予めポリフッ化ビニリデン(結着剤)5質量%を1-メチル-2-ピロリドンに溶解させておいた溶液に加えて混合し、負極合剤ペーストを調製した。この負極合剤ペーストを銅箔(集電体)上の片面に塗布し、乾燥、加圧処理して所定の大きさに裁断し、負極シートを作製した。そして、該負極シートの表面にリチウム金属箔を貼り付けた。
上記で得られた正極シート、微多孔性ポリエチレンフィルム製セパレータ、上記で得られた負極シートを捲回し、扁平状の捲回体からなる発電部を作製した。そして、該発電部及び初期の非水電解液Aを袋状のアルミラミネートフィルムからなる外装体に収納した後、封止した。
<初期特性>
上記の方法で作製した電池を用いて、25℃の恒温槽中、1Cの定電流及び定電圧で、終止電圧4.3Vまで3時間充電し、1Cの定電流下終止電圧3Vまで放電して、初期の放電容量を測定した。
<高温サイクル特性>
上記の方法で作製した電池を用いて60℃の恒温槽中、3Cの定電流及び定電圧で、終止電圧4.3Vまで2時間充電し、次に3Cの定電流下、放電電圧3Vまで放電することを1サイクルとし、これを繰り返した。そして、放電容量が初期の放電容量の90%になった時点で、外装体の端部を切り取り、-90kPaに到達するまで開口部から減圧してガス抜きを実施した後シリンジを用いて初期の非水電解液の注液量の10質量%に相当する再生用非水電解液(表6参照)を注入し再度封止した。実施例14は、この電池を上記条件で再度サイクルし、再生用非水電解液の注入後から放電容量が初期の放電容量の80%を下回るまでの積算サイクル数を調べた。再生用非水電解液として初期の非水電解液と同じ組成の非水電解液(表6参照)を注入したものを比較例10とした。結果を表6に示す。
2・・・液口栓
3・・・発電部
4・・・初期の非水電解液
5・・・蓄電デバイス容器
6・・・副収容室
7・・・液口栓
8・・・栓体
9・・・副開口部
10・・・再生用電解液
11・・・開口部
12・・・発電部
13・・・初期の電解液
14・・・蓄電デバイス容器
15・・・アダプタ
16・・・ガス排出口
17・・・発電部
18・・・初期の電解液
Claims (18)
- 放電容量が初期の放電容量に対して1%以上低下した後に継ぎ足す蓄電デバイスの再生用電解液であって、初期の電解液よりも、電解質濃度が高く、かつ低粘度であることを特徴とする蓄電デバイス用の再生用電解液。
- 放電容量が初期の放電容量に対して1%以上、25%以下低下した後に継ぎ足す蓄電デバイスの再生用電解液であることを特徴とする請求項1に記載の再生用電解液。
- 再生用電解液に含まれる電解質の濃度が0.8M以上、2.5M以下であることを特徴とする請求項1または2に記載の再生用電解液。
- 再生用電解液に含まれる電解質がLiPF6を含み、更にLiPO2F2、LiPO2F2、CH3SO4Li、C2H5SO4Li、リチウム メタンスルホネート ペンタフルオロホスフェート(LiPFMSP)、及びリチウム メタンスルホネート トリフルオロボレート(LiTFMSB)から選ばれる一種以上を含むことを特徴とする請求項1~3のいずれかに記載の再生用電解液。
- 再生用電解液に含まれる電解質がLiPO2F2、LiPO2F2、CH3SO4Li、C2H5SO4Li、リチウム メタンスルホネート ペンタフルオロホスフェート(LiPFMSP)、及びリチウム メタンスルホネート トリフルオロボレート(LiTFMSB)から選ばれる一種以上を0.001M以上、1.2M以下含むことを特徴とする請求項1~4のいずれかに記載の再生用電解液。
- 再生用電解液に鎖状エステルを含有し、再生用電解液を構成する溶媒中における、該鎖状エステルの含有量が80体積%以上であることを特徴とする請求項1~5のいずれかに記載の再生用電解液。
- 鎖状エステルが少なくともジメチルカーボネートを含むことを特徴とする請求項6に記載の再生用電解液。
- 再生用電解液が不飽和結合を有する環状カーボネートを5~30質量%含むことを特徴とする請求項1~7のいずれかに記載の再生用電解液。
- 不飽和結合を有する環状カーボネートがビニレンカーボネート(VC)、ビニルエチレンカーボネート(VEC)、及び4-エチニル-1,3-ジオキソラン-2-オン(EEC)から選ばれる1種以上である請求項8に記載の再生用電解液。
- 電解液がいずれも非水電解液である請求項1~9のいずれかに記載の再生用電解液。
- 放電容量が初期の放電容量に対して1%以上低下した後に継ぎ足す蓄電デバイスの再生用電解液であって、電解質の濃度が0.8M以上、3.0M以下であり、再生用電解液を構成する溶媒中における、鎖状エステルの含有量が80体積%以上である再生用電解液。
- 正極、負極、及び溶媒に電解質塩が溶解されている電解液を容器内に具備する蓄電デバイスであって、該蓄電デバイスが電解液を継ぎ足す手段を備えており、放電容量が初期の放電容量に対して1%以上低下した後に継ぎ足す電解液が、初期の電解液よりも、電解質濃度が高く、かつ低粘度であることを特徴とする蓄電デバイス。
- 蓄電デバイスが開閉可能な液口栓を有する容器を備えていることを特徴とする請求項12に記載の蓄電デバイス。
- 蓄電デバイスが再生用電解液を収容する副収容室を有する容器を備えていることを特徴とする請求項12に記載の蓄電デバイス。
- 蓄電デバイスが袋状のアルミラミネートフィルムを外装体とする容器を備えていることを特徴とする請求項12に記載の蓄電デバイス。
- 蓄電デバイス容器内の圧力が-70kPa以下に到達するまで減圧されていることを特徴とする請求項13~15のいずれかに記載の蓄電デバイス。
- 蓄電デバイスに、再生用電解液を継ぎ足すことで蓄電デバイスを再生させる方法であって、
放電容量が初期の放電容量に対して1%以上低下した際に、蓄電デバイスに含まれる初期の電解液よりも、電解質濃度が高く、かつ低粘度である再生用電解液を、前記蓄電デバイスに継ぎ足すことを特徴とする蓄電デバイスの再生方法。 - 蓄電デバイスに、再生用電解液を継ぎ足すことで蓄電デバイスを再生させる方法であって、
放電容量が初期の放電容量に対して1%以上低下した際に、電解質の濃度が0.8M以上、3.0M以下であり、溶媒中における、鎖状エステルの含有量が80体積%以上である再生用電解液を、前記蓄電デバイスに継ぎ足すことを特徴とする蓄電デバイスの再生方法。
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