WO2023191269A1 - 가교 시간이 단축된 겔 폴리머 전해질 조성물, 이를 포함하는 이차전지 및 상기 이차전지의 제조방법 - Google Patents
가교 시간이 단축된 겔 폴리머 전해질 조성물, 이를 포함하는 이차전지 및 상기 이차전지의 제조방법 Download PDFInfo
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- WO2023191269A1 WO2023191269A1 PCT/KR2023/000476 KR2023000476W WO2023191269A1 WO 2023191269 A1 WO2023191269 A1 WO 2023191269A1 KR 2023000476 W KR2023000476 W KR 2023000476W WO 2023191269 A1 WO2023191269 A1 WO 2023191269A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polymer electrolyte
- gel polymer
- secondary battery
- formula
- composition
- Prior art date
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- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 a gel polymer electrolyte composition with a shortened crosslinking time, a secondary battery including the same, and a method for manufacturing the secondary battery.
- a secondary battery has a structure in which an electrode assembly is built into a battery case along with an electrolyte, and the electrode assembly is sufficiently impregnated and wetted with the electrolyte to demonstrate electrical performance.
- electrolyte may leak, which can cause battery cell failure and even fire.
- Gel polymer electrolytes are being studied as a method to prevent electrolyte leakage.
- the gel polymer electrolyte goes through a crosslinking process after injecting the electrolyte into the battery. It takes a lot of time to cross-link the electrolyte, which reduces process efficiency and increases manufacturing costs.
- the present invention was created to solve the above problems, and its purpose is to provide a gel polymer electrolyte composition that can significantly reduce the curing time compared to existing ones, and a secondary battery containing the same.
- the present invention provides a composition for a gel polymer electrolyte.
- the composition for a gel polymer electrolyte according to the present invention includes an oligomer represented by the following formula (1); Reactive additives containing phosphate-based compounds; polymerization initiator; non-aqueous solvent; and lithium salts.
- R is hydrogen or alkylene having 1 to 5 carbon atoms substituted with an alkyl group having 1 to 5 carbon atoms
- the m is an integer from 1 to 50.
- the gel polymer electrolyte composition has a curing time in the range of 10 to 50 minutes under heat treatment conditions of 55 to 80°C.
- the content of the oligomer is in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for gel polymer electrolyte.
- the reactive additive is represented by the following formula (2).
- R 1 , R 2 and R 3 are each independently hydrogen or alkylene having 1 to 3 carbon atoms.
- R 4 , R 5 and R 6 each independently include an acrylate group, a methacrylate group or a vinyl group. It is a unit.
- the reactive additive is represented by one or more of the following formulas (a) to (d).
- the content of the reactive additive is in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition for gel polymer electrolyte.
- the present invention provides a method of manufacturing a lithium secondary battery by applying the gel polymer electrolyte composition described above.
- the method of manufacturing a lithium secondary battery according to the present invention is performed according to claim 1 in a state in which an electrode assembly including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode is stored in a battery case. It includes the step of injecting the gel polymer electrolyte composition into the battery case.
- the method of manufacturing a lithium secondary battery further includes performing thermal crosslinking in the range of 10 to 50 minutes after injecting the gel polymer electrolyte composition into the battery case.
- the step of performing the thermal crosslinking is performed in the range of 55 to 80°C.
- the manufacturing method according to the present invention further includes a wetting step of waiting for 1 minute to 30 hours between the step of injecting the gel polymer electrolyte composition into the battery case and the step of performing thermal crosslinking.
- the manufacturing method according to the present invention further includes at least one of an activation step and a degas step after performing thermal crosslinking.
- a lithium secondary battery according to the present invention includes an electrode assembly including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode; a battery case for storing and sealing the electrode assembly; and a composition for a gel polymer electrolyte injected into a battery case in which the electrode assembly is housed.
- the composition for the gel polymer electrolyte is the same as described above.
- the lithium secondary battery is a pouch-type battery.
- the present invention can increase the efficiency of the manufacturing process for secondary batteries using a thermally cross-linked gel polymer electrolyte and improve the quality of manufactured products.
- Figure 1 is a schematic diagram showing a leakage evaluation process for a pouch-type secondary battery according to an embodiment of the present invention.
- the present invention provides a composition for a gel polymer electrolyte.
- the composition for a gel polymer electrolyte according to the present invention includes an oligomer; Reactive additives containing phosphate-based compounds; polymerization initiator; non-aqueous solvent; and lithium salts.
- the present invention significantly increases the gelation rate of the electrolyte by adding a reactive additive that promotes the crosslinking reaction of the oligomer.
- the oligomer may be a polypropylene carbonate (PPC) series oligomer.
- PPC polypropylene carbonate
- the oligomer is represented by Formula 1 below.
- R is hydrogen or alkylene having 1 to 5 carbon atoms substituted with an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 50.
- R is arylene having 1 to 3 carbon atoms, and more specifically, arylene having 2 carbon atoms substituted with a methyl group.
- the m is an integer of 1 to 10, an integer of 2 to 5, an integer of 2 to 3, or 2.
- the content of the oligomer is in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the total composition for gel polymer electrolyte. More specifically, the content of the oligomer ranges from 1 to 10 parts by weight, 2 to 8 parts by weight, or 3 to 5 parts by weight. The content of the oligomer is within a range that prevents electrolyte leakage when applied to a secondary battery and does not deteriorate the performance of the secondary battery.
- the curing temperature of the gel polymer electrolyte composition may vary depending on the type of polymerization initiator.
- the composition for gel polymer electrolyte undergoes a crosslinking reaction under heat treatment conditions of 55 to 80°C, 60 to 75°C, or 68 to 75°C, and in this case, the curing time is in the range of 10 to 50 minutes, 10 minutes to 40 minutes or 20 to 40 minutes.
- the composition for gel polymer electrolyte reduces the curing time by more than 25% compared to the prior art through the use of reactive additives.
- the reactive additive is represented by the following formula (2).
- R 1 , R 2 and R 3 are each independently hydrogen or alkylene having 1 to 3 carbon atoms,
- R 4 , R 5 and R 6 each independently include an acrylate group, a methacrylate group or a vinyl group. It is a unit.
- R 1 , R 2 and R 3 are each independently hydrogen or alkylene having 1 to 2 carbon atoms, and at least one of R 1 , R 2 and R 3 has 1 carbon atom.
- R 4 , R 5 and R 6 are each independently an acrylate group or a methacrylate group.
- R 1 , R 2 and R 3 are each independently an alkylene having 1 to 2 carbon atoms
- R 4 , R 5 and R 6 are each independently an acrylate group or It is a methacrylate group.
- R 1 and R 2 are alkylene having 1 to 2 carbon atoms
- R 3 is hydrogen
- R 4 and R 5 are each independently an acrylate group or methacrylate. It's amazing
- the reactive additive is represented by one or more of the following formulas (a) to (d).
- the content of the reactive additive is in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition for gel polymer electrolyte. Specifically, the content of the reactive additive ranges from 0.1 to 10 parts by weight, 0.01 to 5 parts by weight, 0.2 to 5 parts by weight, or 0.5 to 2 parts by weight. The content of these reactive additives is within a range that can sufficiently reduce the curing speed while minimizing the input amount.
- the present invention provides a method for manufacturing a lithium secondary battery using the gel polymer electrolyte described above.
- the method of manufacturing a lithium secondary battery according to the present invention is for a gel polymer electrolyte in a state in which an electrode assembly including a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode is stored in a battery case. It includes the step of injecting the composition into the battery case.
- a secondary battery is manufactured by injecting the previously described gel polymer electrolyte composition into a battery case containing an electrode assembly. Then, the gel polymer electrolyte composition undergoes a process of gelling through heat treatment.
- the present invention includes the step of performing heat crosslinking in the range of 10 to 50 minutes after injecting the gel polymer electrolyte composition into the battery case.
- the step of performing this thermal crosslinking is a process of curing the injected gel polymer electrolyte by inducing a crosslinking reaction.
- the curing time ranges from 10 minutes to 50 minutes, from 10 minutes to 40 minutes, or from 20 to 40 minutes.
- the present invention has the effect of reducing curing time by more than 25% compared to the conventional method.
- the heat treatment temperature may vary depending on the type of polymerization initiator added.
- the reactive additive represented by the formula 2 described above can be used.
- the step of performing the thermal crosslinking can be performed at a temperature range of 55 to 80°C, 60 to 75°C, or 68 to 75°C.
- the present invention includes a wetting step of waiting for 1 minute to 30 hours between the step of injecting the gel polymer electrolyte composition into the battery case and the step of performing thermal crosslinking.
- the present invention includes at least one of an activation step and a degas step after performing thermal crosslinking.
- a secondary battery according to the present invention includes an electrode assembly including a positive electrode, one negative electrode, and a separator disposed between the positive electrode and the negative electrode; a battery case for storing and sealing the electrode assembly; and a composition for a gel polymer electrolyte injected into a battery case in which the electrode assembly is housed.
- the composition for gel polymer electrolyte is as described above.
- the electrode assembly can be classified into a jelly-roll type, which is a rolled type, and a stack type, which is sequentially stacked.
- secondary batteries can be divided into cylindrical batteries and prismatic batteries in which the electrode assembly is embedded in a cylindrical or square metal can, and pouch-type batteries in which the electrode assembly is embedded in a pouch-type case of aluminum laminate sheet. You can.
- the secondary battery of the present invention may be a cylindrical, prismatic, or pouch-type secondary battery, and is preferably a pouch-type secondary battery.
- the case may be made of a laminate sheet including a metal layer and a resin layer.
- the laminate sheet may be an aluminum laminate sheet.
- the battery case of the laminated sheet may be comprised of a lower case consisting of a recessed storage portion and an outer portion extending from the storage portion, and an upper case joined to the lower case by heat fusion.
- the positive electrode one of the components of a secondary battery, has a structure in which a positive electrode active material layer is stacked on one or both sides of a positive electrode current collector.
- the positive electrode active material layer includes a positive electrode active material, a conductive material, and a binder polymer, and, if necessary, may further include a positive electrode additive commonly used in the art.
- the positive electrode active material may be a lithium-containing oxide and may be the same or different.
- a lithium-containing transition metal oxide may be used as the lithium-containing oxide.
- the lithium-containing transition metal oxide may be coated with a metal such as aluminum (Al) or a metal oxide. Additionally, in addition to the lithium-containing transition metal oxide, one or more of sulfide, selenide, and halide may be used.
- the positive electrode active material may be included in the range of 94.0 to 98.5% by weight in the positive electrode active material layer.
- the content of the positive electrode active material satisfies the above range, it is advantageous in terms of manufacturing a high-capacity battery and providing sufficient conductivity of the positive electrode or adhesion between electrode materials.
- the current collector used in the positive electrode is a highly conductive metal, to which the positive electrode active material slurry can easily adhere, and any metal that is non-reactive within the voltage range of the electrochemical device can be used.
- the positive electrode current collector include foil made of aluminum, nickel, or a combination thereof.
- the positive electrode active material layer further includes a conductive material.
- Carbon-based conductive materials are widely used as the conductive material, and include sphere-type or needle-type carbon-based conductive materials.
- the point-shaped carbon-based conductive material, mixed with a binder, can improve physical contact between active materials by filling pores, which are empty spaces between active material particles, thereby reducing interfacial resistance and improving adhesion between the lower positive electrode active material and the current collector.
- the conductive material may be included in the range of 0.5 to 5% by weight in the positive electrode active material layer. When the content of the conductive material satisfies the above range, it has the effect of providing sufficient conductivity to the positive electrode and lowering the interfacial resistance between the electrode current collector and the active material.
- the binder polymer may be any binder commonly used in the art without limitation.
- a water-insoluble polymer or a water-soluble polymer insoluble in organic solvents and soluble in water may be used.
- Insoluble polymers include polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polypropylene oxide (PPO), polyethylene oxide-propylene oxide copolymer (PEO-PPO), and polyvinylidene chloride (PVDC). It may be one or more selected from the group including tetrafluoroethylene (PTFE), polyimide (PI), polyetherimide (PEI), styrene butadiene rubber (SBR), polyacrylate, and derivatives thereof.
- PTFE tetrafluoroethylene
- PI polyimide
- PEI polyetherimide
- SBR styrene butadiene rubber
- Water-soluble polymers include a variety of cellulose derivatives such as carboxymethylcellulose (CMC), methylcellulose (MC), cellulose acetate phthalate (CAP), hydroxypropylmethylcellulose (HPMC), and hydroxypropylmethylcellulose phthalate (HPMCP). It may be one or more types selected from.
- CMC carboxymethylcellulose
- MC methylcellulose
- CAP cellulose acetate phthalate
- HPMC hydroxypropylmethylcellulose
- HPMC hydroxypropylmethylcellulose phthalate
- HPMC hydroxypropylmethylcellulose phthalate
- the binder polymer content is proportional to the content of the conductive material included in the upper and lower positive electrode active material layers. This is to provide adhesion to a conductive material whose particle size is relatively very small compared to the active material. As the content of the conductive material increases, more binder polymer is needed, and when the content of the conductive material decreases, less binder polymer can be used.
- the negative electrode has a structure in which a negative electrode active material layer is laminated on one or both sides of a negative electrode current collector.
- the negative electrode active material layer includes a negative electrode active material, a conductive material, and a binder polymer, and, if necessary, may further include a negative electrode additive commonly used in the art.
- the negative electrode active material may include carbon material, lithium metal, silicon, or tin.
- a carbon material is used as a negative electrode active material
- both low-crystalline carbon and high-crystalline carbon can be used.
- Representative low-crystalline carbons include soft carbon and hard carbon
- high-crystalline carbons include natural graphite, Kish graphite, pyrolytic carbon, and liquid crystal pitch carbon fiber.
- Representative examples include high-temperature calcined carbon such as mesophase pitch based carbon fiber, mesocarbon microbeads, liquid crystal pitches, and petroleum orcoal tarpitch derived cokes.
- Non-limiting examples of the current collector used in the negative electrode include foil made of copper, gold, nickel, or copper alloy, or a combination thereof. Additionally, the current collector may be used by laminating substrates made of the above materials.
- the cathode may include conductive materials and binders commonly used in the field.
- the separator can be any porous substrate used in lithium secondary batteries.
- a polyolefin-based porous membrane or non-woven fabric can be used, but is not particularly limited thereto.
- polystyrene-based porous membrane examples include polyethylene such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene, polyolefin-based polymers such as polypropylene, polybutylene, and polypentene, each singly or a mixture thereof.
- polyethylene such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene
- polyolefin-based polymers such as polypropylene, polybutylene, and polypentene, each singly or a mixture thereof.
- One membrane can be mentioned.
- the non-woven fabric includes, in addition to polyolefin-based non-woven fabric, for example, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, and polycarbonate. ), polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfide, polyethylenenaphthalene, etc., individually or Examples include nonwoven fabrics formed from polymers that are a mixture of these.
- the structure of the nonwoven fabric may be a sponbond nonwoven fabric composed of long fibers or a melt blown nonwoven fabric.
- the thickness of the porous substrate is not particularly limited, but may be 5 to 50 ⁇ m, and the pore size and pores present in the porous substrate are also not particularly limited, but may be 0.01 to 50 ⁇ m and 10 to 95%, respectively.
- a porous coating layer containing inorganic particles and a binder polymer may be further included on at least one side of the porous substrate.
- the electrolyte may include an organic solvent and an electrolyte salt, and the electrolyte salt is a lithium salt.
- the lithium salt may be those commonly used in non-aqueous electrolytes for lithium secondary batteries without limitation.
- cations include Li +
- anions include F - , Cl - , Br - , I - , NO 3- , N(CN) 2- , BF 4- , ClO 4- , AlO 4- , AlCl 4- , PF 6- , SbF 6- , AsF 6- , BF 2 C 2 O 4- , BC 4 O 8- , (CF 3 ) 2 PF 4- , (CF 3 ) 3 PF 3- , (CF 3 ) 4 PF 2- , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3- , C 4 F 9 SO 3- , CF 3 CF 2 SO 3- , (CF 3 SO 2 ) 2 N - , (FSO 2 )
- Organic solvents included in the above-mentioned electrolyte can be used without limitation those commonly used in electrolytes for secondary batteries, for example, ether, ester, amide, linear carbonate, cyclic carbonate, etc., individually or in a mixture of two or more types. You can use it. Among them, representative examples may include carbonate compounds that are cyclic carbonate, linear carbonate, or a mixture thereof.
- cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, There is any one selected from the group consisting of 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halogenates thereof, or a mixture of two or more thereof.
- halides include, but are not limited to, fluoroethylene carbonate (FEC).
- linear carbonate compound examples include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- EMC ethylmethyl carbonate
- methylpropyl carbonate methylpropyl carbonate
- ethylpropyl carbonate methylpropyl carbonate
- ethylpropyl carbonate methylpropyl carbonate
- ethylpropyl carbonate methylpropyl carbonate
- ethylene carbonate and propylene carbonate which are cyclic carbonates
- cyclic carbonates are high viscosity organic solvents and have a high dielectric constant, so they can better dissociate lithium salts in the electrolyte.
- These cyclic carbonates include dimethyl carbonate and diethyl carbonate.
- the ether among the organic solvents may be any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, and ethyl propyl ether, or a mixture of two or more of these. , but is not limited to this.
- esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ .
- the electrode assembly may be of a lamination/stack type in which unit cells are stacked with a separator interposed between them, or a stack/folding type in which unit cells are wound by a separation sheet.
- the electrode assembly is made by applying an electrode active material to the positive and negative electrode current collectors to form a composite layer, then using a notching device to manufacture the positive and negative electrodes with pin holes formed on the electrode tab and electrode plate, and then forming the positive and negative electrodes. It is manufactured by bonding to a separator that does not contain pinholes.
- the type of the separator is not limited, but may be an organic/inorganic composite porous SRS (Safety-Reinforcing Separators) separator.
- the SRS separator is manufactured using inorganic particles and a binder polymer as active layer components on a polyolefin-based separator substrate.
- the empty space (interstitial volume) between the inorganic particles that are active layer components as well as the pore structure contained in the separator substrate itself. ) has a uniform pore structure formed by.
- the use of such an organic/inorganic composite porous separator has the advantage of suppressing the increase in battery thickness due to swelling during the formation process compared to the case of using a conventional separator, and the binder polymer component If a gelatable polymer is used when impregnated with a liquid electrolyte, it can also be used as an electrolyte.
- the organic/inorganic composite porous separator can exhibit excellent adhesive properties by controlling the content of the inorganic particles and binder polymer, which are active layer components in the separator, and thus has the feature that the battery assembly process can be easily performed.
- LiPF6 was dissolved at a concentration of 1M as a lithium salt in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7, and additives were added to the total weight of the gel polymer electrolyte as shown in Table 1 below.
- a gel polymer electrolyte composition was prepared by adding each amount.
- the oligomer was added in an amount of 4% by weight, and the structural formula of the oligomer is in Chemical Formula 1, where R is alkylene having 2 carbon atoms substituted with a methyl group, and m is an integer in the range of 2 to 3.
- the reactive additive was added in an amount of 4% by weight, and the structural formula of the oligomer is as shown in the following chemical formula (a).
- FUJIFILM WAKO's azo initiator V-59 a thermal initiator, was used at a content of 1% by weight.
- LiNi0.5Mn1.5O4 with a particle size of 5 ⁇ m as the positive electrode active material, and mix it with polyvinylidene fluoride as a carbon-based conductive agent and binder and N-methyl pyrrolidone (NMP) at a weight ratio of 94:3:3.
- NMP N-methyl pyrrolidone
- a negative electrode active material in which artificial graphite and silicon oxide (SiO2) are mixed at a weight ratio of 9:1, and mix 97 parts by weight of the negative electrode active material and 3 parts by weight of styrene butadiene rubber (SBR) with water to form a slurry.
- SiO2 artificial graphite and silicon oxide
- SBR styrene butadiene rubber
- a separator made of 18 ⁇ m polypropylene was interposed between the obtained anode and cathode, inserted into a case, and then the prepared gel polymer electrolyte composition was injected. Then, a pouch-type lithium secondary battery was manufactured through a curing time of 30 minutes at 70°C.
- the reactive additive was added in an amount of 4% by weight, and a gel polymer electrolyte composition was prepared in the same manner as in Example 1, except that the structural formulas of the oligomers were the following formulas b to d, respectively.
- a lithium secondary battery was manufactured in the same manner as in Example 1 using the prepared gel polymer electrolyte composition.
- An electrolyte composition was prepared by dissolving LiPF6 as a lithium salt at a concentration of 1M in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7.
- EC ethylene carbonate
- EMC ethylmethyl carbonate
- LiNi0.5Mn1.5O4 with a particle size of 5 ⁇ m as the positive electrode active material, and mix it with polyvinylidene fluoride as a carbon-based conductive agent and binder and N-methyl pyrrolidone (NMP) at a weight ratio of 94:3:3.
- NMP N-methyl pyrrolidone
- a negative electrode active material in which artificial graphite and silicon oxide (SiO2) are mixed at a weight ratio of 9:1, and mix 97 parts by weight of the negative electrode active material and 3 parts by weight of styrene butadiene rubber (SBR) with water to form a slurry.
- SiO2 artificial graphite and silicon oxide
- SBR styrene butadiene rubber
- a separator made of 18 ⁇ m polypropylene was placed on the obtained positive and negative electrodes, inserted into a case, and the prepared electrolyte composition was injected to prepare a pouch-type lithium secondary battery.
- LiPF6 was dissolved at a concentration of 1M as a lithium salt in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7, and additives were added to the total weight of the gel polymer electrolyte as shown in Table 1 below.
- a gel polymer electrolyte composition was prepared by adding each amount.
- a lithium secondary battery was manufactured in the same manner as in Example 1, but the curing time was 30 minutes.
- LiPF6 was dissolved at a concentration of 1M as a lithium salt in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7, and additives were added to the total weight of the gel polymer electrolyte as shown in Table 1 below.
- a gel polymer electrolyte composition was prepared by adding each amount.
- a lithium secondary battery was manufactured in the same manner as in Example 1, but the curing time was 100 minutes.
- LiPF6 was dissolved at a concentration of 1M as a lithium salt in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7, and additives were added to the total weight of the gel polymer electrolyte as shown in Table 1 below.
- a gel polymer electrolyte composition was prepared by adding each amount.
- a lithium secondary battery was manufactured in the same manner as in Example 1 using the prepared gel polymer electrolyte composition, but the curing time was 300 minutes.
- LiPF6 was dissolved at a concentration of 1M as a lithium salt in a solvent mixed with ethylene carbonate (EC) and ethylmethyl carbonate (EMC) at a volume ratio of 3:7, and additives were added to the total weight of the gel polymer electrolyte as shown in Table 1 below.
- a gel polymer electrolyte composition was prepared by adding each amount.
- a lithium secondary battery was manufactured in the same manner as in Example 1, but the curing time was 30 minutes.
- Example 1 1M LiPF6 EC/EMC 3/7 4wt% 1wt% 1wt% formula a 30min
- Example 2 1M LiPF6 EC/EMC 3/7 4wt% 1wt% 1wt% formula b 30min
- Example 3 1M LiPF6 EC/EMC 3/7 4wt% 1wt% 1wt% formula c
- Example 4 1M LiPF6 EC/EMC 3/7 4wt% 1wt% 1wt% formula d
- Comparative Example 1 1M LiPF6 EC/EMC 3/7 - - - - - Comparative
- Example 2 1M LiPF6 EC/EMC 3/7 4wt% 1wt% - - 30min
- Comparative Example 3 1M LiPF6 EC/EMC 3/7 4wt% 1wt% - - 100min Comparative Example 4 1M LiPF6 EC/EMC 3/7 4wt% 1wt% - - 100min Comparative Example 4 1M
- Each secondary battery manufactured in Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated for electrolyte leakage.
- Each secondary battery is a 100 Ah class large cell.
- each pouch-type secondary battery 100 is a 100 Ah class large battery cell.
- the pouch-type secondary battery 100 has a structure in which the electrode assembly is stored in a pouch-type case. Based on the pouch-type case, a sealing area 120 was formed on the slope surrounding the electrode assembly storage area 110 through heat fusion, and the electrode terminals 130 are structured to extend on both sides.
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Abstract
Description
구분 | 전해질 | Oligomer 함량 | 중합개시제 함량 | 반응첨가제 함량 | 반응첨가제 종류 | 경화시간 |
실시예 1 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | 1 wt% | 화학식 a | 30 min |
실시예 2 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | 1 wt% | 화학식 b | 30 min |
실시예 3 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | 1 wt% | 화학식 c | 30 min |
실시예 4 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | 1 wt% | 화학식 d | 30 min |
비교예 1 | 1M LiPF6 EC/EMC 3/7 | - | - | - | - | - |
비교예 2 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | - | - | 30 min |
비교예 3 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | - | - | 100 min |
비교예 4 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | - | - | 300 min |
비교예 5 | 1M LiPF6 EC/EMC 3/7 | 4 wt% | 1 wt% | - | - | 100 min |
구분 | 전해질 누액 여부 |
실시예 1 | X |
실시예 2 | X |
실시예 3 | X |
실시예 4 | X |
비교예 1 | O |
비교예 2 | O |
비교예 3 | O |
비교예 4 | X |
비교예 5 | O |
Claims (13)
- 제 1 항에 있어서,상기 겔 폴리머 전해질용 조성물은, 55 내지 80℃ 열처리 조건에서 경화 시간이 10분 내지 50분 범위인 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,올리고머의 함량은, 겔 폴리머 전해질용 조성물 전체 100 중량부에 대하여, 0.1 내지 30 중량부 범위인 겔 폴리머 전해질용 조성물.
- 제 1 항에 있어서,반응첨가제의 함량은, 겔 폴리머 전해질용 조성물 전체 100 중량부에 대하여, 0.01 내지 10 중량부 범위인 겔 폴리머 전해질용 조성물.
- 양극, 음극, 및 상기 양극과 음극 사이에 배치되는 분리막을 포함하는 전극 조립체를 전지 케이스에 수납한 상태에서,청구항 1항에 따른 겔 폴리머 전해질용 조성물을 전지 케이스 내에 주액하는 단계를 포함하는 리튬 이차전지 제조방법.
- 제 7 항에 있어서,겔 폴리머 전해질용 조성물을 전지 케이스 내에 주액하는 단계 이후에,10 분 내지 50 분 범위에서 열가교를 수행하는 단계를 더 포함하는 리튬 이차전지 제조방법.
- 제 8 항에 있어서,열가교를 수행하는 단계는, 55 내지 80℃ 온도 범위에서 수행하는 리튬 이차전지 제조방법.
- 제 8 항에 있어서,겔 폴리머 전해질용 조성물을 전지 케이스 내에 주액하는 단계와 열가교를 수행하는 단계 사이에 1분 내지 30시간 동안 대기하는 웨팅 단계를 더 포함하는 이차전지 제조방법.
- 제 8 항에 있어서,열가교를 수행하는 단계 이후에, 활성화 단계 및 디가스 단계 중 어느 하나 이상을 더 포함하는 리튬 이차전지 제조방법.
- 양극, 음극, 및 상기 양극과 음극 사이에 배치되는 분리막을 포함하는 전극 조립체;상기 전극 조립체를 수납 및 실링하는 전지 케이스; 및전극 조립체가 수납된 전지 케이스 내에 주액된 청구항 1항에 따른 겔 폴리머 전해질용 조성물을 포함하는 리튬 이차전지.
- 제 12 항에 있어서,상기 리튬 이차전지는 파우치형 전지인 것을 특징으로 하는 리튬 이차전지.
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EP23781131.0A EP4310972A1 (en) | 2022-03-29 | 2023-01-11 | Gel polymer electrolyte composition having reduced crosslinking time, secondary battery comprising same, and method for manufacturing secondary battery |
JP2023563059A JP2024515949A (ja) | 2022-03-29 | 2023-01-11 | 架橋時間が短縮されたゲルポリマー電解質組成物、それを含む二次電池および上記二次電池の製造方法 |
CN202380011288.XA CN117203814A (zh) | 2022-03-29 | 2023-01-11 | 具有减少的交联时间的凝胶聚合物电解质组合物、包括该组合物的二次电池、以及用于制造二次电池的方法 |
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