CN109786818B - Electrolyte composition and polymer electrolyte membrane and method for preparing same - Google Patents
Electrolyte composition and polymer electrolyte membrane and method for preparing same Download PDFInfo
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- CN109786818B CN109786818B CN201711132120.7A CN201711132120A CN109786818B CN 109786818 B CN109786818 B CN 109786818B CN 201711132120 A CN201711132120 A CN 201711132120A CN 109786818 B CN109786818 B CN 109786818B
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Abstract
本发明涉及全固态电池领域，具体涉及电解质组合物与聚合物电解质膜以及聚合物电解质及其制备方法和全固态电池及其制备方法。其中，该电解质组合物含有聚合物、锂盐、离子液体和交联剂，所述聚合物为由式(1)所示的结构单元、式(2)所示的结构单元组成的共聚物，本发明提供的电池正极和电解质层具有较高的剥离强度和合适的压实密度，从而使电池具有较好的比容量、循环寿命等； The invention relates to the field of all-solid-state batteries, in particular to an electrolyte composition, a polymer electrolyte membrane, a polymer electrolyte and a preparation method thereof, and an all-solid-state battery and a preparation method thereof. Wherein, the electrolyte composition contains a polymer, a lithium salt, an ionic liquid and a crosslinking agent, and the polymer is a copolymer composed of a structural unit represented by formula (1) and a structural unit represented by formula (2), The positive electrode and the electrolyte layer of the battery provided by the present invention have higher peel strength and suitable compaction density, so that the battery has better specific capacity, cycle life and the like;
Description
Technical Field
The invention relates to the field of all-solid-state batteries, in particular to an electrolyte composition, a polymer electrolyte membrane, a polymer electrolyte, a preparation method of the polymer electrolyte, an all-solid-state battery and a preparation method of the all-solid-state battery.
Background
At present, liquid electrolyte is mostly used as a conductive substance in lithium ion batteries on the market, but in the using process, the liquid electrolyte is volatile, flammable and explosive, so that a plurality of safety problems are caused; and lithium dendrites are easy to grow out, so that the application of the metal lithium as a negative electrode in a battery is limited. Therefore, Solid Polymer Electrolytes (SPE) have been proposed to replace liquid electrolytes. The solid polymer electrolyte membrane not only functions as ion conduction, but also prevents contact between the positive and negative electrodes. And because of its strong plasticity, can make into the film of different shapes according to different demands, the pliability is good, can bear the pressure of electrode in the charge-discharge process, and high temperature stability is good, has greatly improved the security of lithium cell.
CN105680091A discloses a high-performance all-solid-state lithium ion battery and a preparation method thereof, which is characterized by comprising the following steps: A. mixing 70-80% of a positive electrode material, 10-15% of a lithium super-ion conductor, 5-10% of conductive carbon and 1-5% of a high molecular polymer in an organic solvent in a vacuum manner to obtain a positive electrode mixed slurry, coating the positive electrode mixed slurry on an aluminum foil, airing, tabletting and preparing into a positive plate; B. stirring a mixed solution of molten metal lithium and hot silicone oil at the temperature of 200-250 ℃ at the rotating speed of 20000-30000 r/min to form a uniform emulsion, then cooling to room temperature, filtering, washing and naturally airing to obtain lithium powder with the particle size of 10-60 mu m; C. and C, mixing the lithium powder, the lithium super-ion conductor and the high molecular polymer prepared in the step B according to the weight ratio of 80-90%: 5-20%: stirring 1-5% of the mixture in an organic solvent in vacuum to obtain a negative electrode mixed slurry, coating the negative electrode mixed slurry on a copper foil, airing, tabletting and preparing a negative electrode plate; D. 70-90% of high molecular polymer and lithium super ion conductor: weighing high molecular polymers according to the mass ratio of 10-30%, adding the high molecular polymers into an organic solvent, adding a lithium super-ion conductor after complete dissolution, stirring, and volatilizing the solvent to form a semi-solid sol state to obtain a polymer electrolyte; E. and D, soaking the positive plate and the negative plate in the polymer electrolyte in the step D, lifting, laminating, and performing aluminum-plastic molding to obtain the slice all-solid-state lithium ion battery. The technical scheme has the following defects: 1. the preparation process of the negative pole piece is complex, and the lithium powder has high requirements on the environment and needs to be operated in an anhydrous and oxygen-free environment, so that the operations of mixing, filtering, coating, drying, tabletting and the like are difficult. 2. The negative electrode needs to mix the lithium powder with the super-ionic conductor and the polymer, and is difficult to mix uniformly, so that the uniformity of a pole piece is poor, and the consistency of the battery is poor. 3. The positive pole piece and the negative pole piece can be manufactured into a battery only by soaking in the polymer electrolyte, and after soaking, the gel-state polymer electrolyte is bonded with the pole pieces, so that the complexity of a lamination process and the difficulty of correct lamination are increased. 4. The ionic conductivity of the polymer electrolyte is low, and the difference from the commercial application requirement is large.
CN105098227A discloses an all-solid-state lithium ion battery and a method for manufacturing the same, wherein the all-solid-state lithium ion battery is composed of a positive electrode, a negative electrode, and a solid electrolyte membrane layer, and is characterized in that the positive electrode is composed of a positive electrode current collector, a positive electrode active material, an inorganic nano-filler, and a solid electrolyte, the doping amount of the inorganic nano-filler in the positive electrode is 5 wt% -15 wt%, and the doping amount of the solid electrolyte from the positive electrode active material/positive electrode current collector contact interface to the positive electrode/solid electrolyte membrane layer contact interface is reduced in a gradient manner from 50 to 10 wt%; the negative electrode is composed of a negative electrode current collector, a negative electrode active substance, an inorganic nano filler and a solid electrolyte, the doping amount of the inorganic nano filler in the negative electrode is 5-15 wt%, and the doping amount of the solid electrolyte from a negative electrode active substance/negative electrode current collector contact interface to a negative electrode/solid electrolyte membrane layer contact interface is reduced in a gradient manner from 50 wt% to 10 wt%; the solid electrolyte membrane layer is composed of a solid electrolyte and an inorganic nano filler, and the content of the inorganic nano filler in the solid electrolyte membrane layer is 10-20 wt.%. The preparation method adopts the ink-jet printing technology to prepare the all-solid-state lithium ion battery, different components are dissolved in a solvent to prepare slurry, the slurry is placed in different ink boxes, a computer program design is used, electrodes and electrolytes are printed in a longitudinal graded gradient mode, the longitudinal gradient of the electrolytes in electrode plates is changed, the gradient structure distribution of the electrolytes in the electrode plates can reduce the interface impedance of electrode active substances/electrolytes, the deep conduction of lithium ions is facilitated, and the capacity property of the active substances is exerted to the maximum extent; the all-solid-state lithium ion battery structure prepared by ink-jet printing has the advantages that the other parts except the current collector form an integral lamination structure, all components in the lamination structure are in close contact and regularly arranged, and the interface impedance is far lower than that of the all-solid-state lithium ion battery prepared by a mechanical lamination mode. The ink-jet printing mode is convenient and fast, and is suitable for large-scale production. The technical scheme has the following defects: 1. the anode material has larger particles, and the ink-jet printing method is easy to block a conveying pipe, a spray head and the like, thereby influencing the continuity of the manufacturing process. 2. The positive electrode particles are easy to settle, so that the prepared positive electrode film is not uniform, and the uniformity of the battery is influenced. 3. The conventional positive electrode slurry is viscous, so that ink-jet printing is difficult, and in order to adapt to an ink-jet process, the solid content of the slurry can be only reduced, and the battery capacity is sacrificed. 4. Physical vapor deposition equipment and manufacturing cost are high, the process is complex, high requirements on water and oxygen content are met, and the daily environment cannot meet the manufacturing requirements in the technology. 5. The ionic conductivity of the polymer electrolyte is low, and the difference from the commercial application requirement is large.
1937 Wirght et al[5]The ion conduction concept of the alkali metal salt-PEO composite system is presented. When a lithium salt is mixed with PEO, the positively charged lithium ions "dissolve" the lithium salt sufficiently in the polymer by interacting with ether oxygen functional groups in the polymer, and due to the presence of amorphous regions in the polymer, the lithium ions can be transported between polymer segments in the amorphous regions under the action of a power plant.
Aims to solve the problems of easy leakage and easy storage of liquid electrolyte in the existing lithium ion batteryIn the problems of potential safety hazard and low ionic conductivity of all-solid-state polymer electrolyte, the patent application of CN105489932A provides a method for preparing a polymer electrolyte film of a lithium ion battery by an ultraviolet crosslinking method. The solid electrolyte film is prepared by ultraviolet crosslinking monomer Methyl Methacrylate (MMA) and mixing polyurethane acrylate (PUA) and ionic liquid (DEYTFSI and Py13 TFSI), and the mechanical strength and the ionic conductivity of the electrolyte film are improved to a certain degree. The technical scheme has the following defects: firstly, mixing and stirring an initiator (dibenzoyl peroxide (BPO)) and a monomer MMA uniformly, and then, mixing and stirring a cross-linking agent (ethylene glycol Dimethacrylate (DEMA)), a polymer PUA and an ionic liquid (DEYTFSI or Py)13TFSI), heating and stirring uniformly, finally mixing the two liquids, adding solvent N, N-Dimethylformamide (DMF), stirring uniformly, then casting, and curing by ultraviolet irradiation to form a film. Secondly, because the ionic conductivity of the polymers PUA and PMMA used in the method is not high, the ionic conductivity of the polymer electrolyte membrane is improved mainly by adding the ionic liquid, and the ionic liquid has higher cost. And dibenzoyl peroxide as the initiator for ultraviolet crosslinking is extremely unstable in property, and has the risk of causing ignition and explosion when meeting light, high temperature and reducing agent, so the risk in the operation process is high.
Disclosure of Invention
An object of the present invention is to overcome the above problems of the prior art and to provide an electrolyte composition and a polymer electrolyte membrane as well as a polymer electrolyte and a method of preparing the same and an all-solid battery and a method of preparing the same.
In order to achieve the above object, a first aspect of the present invention provides an electrolyte composition, wherein the composition comprises a polymer, a lithium salt, an ionic liquid, and a crosslinking agent, the polymer is a copolymer composed of a structural unit represented by formula (1) and a structural unit represented by formula (2), the structural unit of the ionic liquid is a structural unit represented by any one of formula (3) to formula (7),
wherein R is1、R2Each is H or one of alkyl of C1-C4, and X is selected from Cl-、Br-、I-、Al2Cl7 -、Al3Cl10 -、Sb2F11 -、Fe2Cl7 -、Zn2Cl5 -、Zn3Cl7 -、CuCl2 -、SnCl2 -、NO3 -、PO4 3-、HSO4 -、SO4 -、CF3SO3 -、ROSO3 -、CF3CO2 -、C6H5SO3 -、PF6 -、SbF6 -、BF4 -、(CF3SO2)2N-、N(CN)2 -、(CF3SO2)3C-、BR4 -、RCB11H11 -And an anion of any of p-styrenesulfonate ions; the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (9): -O-C (O) -C (R') = CH2R' is H or C1-C4 alkyl.
In a second aspect, the present invention provides a polymer electrolyte membrane comprising the above-described electrolyte composition.
The third aspect of the present invention provides a method for preparing a polymer electrolyte, wherein the method comprises: an electrolyte slurry containing the electrolyte composition is provided and then dried to form a film.
The fourth aspect of the present invention provides a polymer electrolyte produced by the above-mentioned method for producing a polymer electrolyte.
The fifth aspect of the present invention provides an all-solid battery comprising a positive electrode, a negative electrode and a polymer electrolyte interposed between the positive electrode and the negative electrode, wherein the polymer electrolyte is the above-mentioned polymer electrolyte, the positive electrode comprises a positive electrode current collector and a positive electrode material layer attached to the surface, and the positive electrode material layer contains the above-mentioned electrolyte composition, a positive electrode active material, a positive electrode conductive agent and a binder.
The invention provides a preparation method of an all-solid-state battery, wherein a polymer electrolyte is arranged between a positive electrode and a negative electrode, the positive electrode and the negative electrode are welded with upper tabs, superposed and arranged in an aluminum-plastic film for sealing and pressing to obtain the all-solid-state battery; the preparation method of the positive electrode may include: providing an electrode slurry containing a positive electrode active material, a positive electrode conductive agent, a binder and the above electrolyte composition; and coating the electrode slurry and drying on an electrode current collector to form a positive electrode material layer.
The seventh aspect of the invention provides an all-solid battery produced by the above-described production method for an all-solid battery.
The battery anode and the polymer electrolyte layer provided by the invention have higher peel strength and proper compaction density, so that the battery has better specific capacity, cycle life and the like; the battery manufacturing process is greatly simplified, the manufacturing cost is reduced, the operability is improved, the continuous production can be realized, the production/manufacturing efficiency is improved, and the high-capacity battery can be prepared.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides an electrolyte composition, wherein the composition comprises a polymer, a lithium salt, an ionic liquid and a crosslinking agent, the polymer is a copolymer composed of a structural unit represented by formula (1) and a structural unit represented by formula (2), the structural unit of the ionic liquid is any one of structural units represented by formula (3) to formula (7),
wherein R is1、R2Each is H or one of alkyl of C1-C4, and X is selected from Cl-、Br-、I-、Al2Cl7 -、Al3Cl10 -、Sb2F11 -、Fe2Cl7 -、Zn2Cl5 -、Zn3Cl7 -、CuCl2 -、SnCl2 -、NO3 -、PO4 3-、HSO4 -、SO4 -、CF3SO3 -、ROSO3 -、CF3CO2 -、C6H5SO3 -、PF6 -、SbF6 -、BF4 -、(CF3SO2)2N-、N(CN)2 -、(CF3SO2)3C-、BR4 -、RCB11H11 -And an anion of any of p-styrenesulfonate ions; the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (9): -O-C (O) -C (R') = CH2R' is H or C1-C4 alkyl.
According to the invention, R1、R2Are each independentlyH. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably R1、R2Each is H, methyl or ethyl.
In the present invention, specific examples of the alkyl group having C1 to C4 may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group. Namely, R1、R2Each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably R1、R2Each is H, methyl or ethyl.
According to the present invention, the content of the polymer is 0.1 to 45 parts by weight, the content of the lithium salt is 0.1 to 20 parts by weight, the content of the ionic liquid is 0.1 to 45 parts by weight, and the content of the crosslinking agent is 0.1 to 20 parts by weight, corresponding to 100 parts by weight of the electrolyte composition.
Preferably, the polymer is contained in an amount of 1 to 40 parts by weight, the lithium salt is contained in an amount of 0.5 to 19 parts by weight, the ionic liquid is contained in an amount of 0.5 to 40 parts by weight, and the crosslinking agent is contained in an amount of 0.5 to 17 parts by weight, based on 100 parts by weight of the electrolyte composition.
According to the invention, the molar ratio of the structural unit of formula (1) to the structural unit of formula (2) in the polymer can vary within wide limits, preferably the molar ratio of the structural unit of formula (1) to the structural unit of formula (2) is 100: (1-100), preferably 100: (5-80), more preferably 100: (8-60), more preferably 100: (10-50). In a most preferred embodiment, the structural unit of the copolymer is composed of a structural unit represented by formula (1) and a structural unit represented by formula (2). The copolymer composed of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is preferably a linear random copolymer.
According to the invention, the weight average molecular weight of the polymer may vary within a wide range, preferably the weight average molecular weight of the copolymer is 500-500000 g/mol, preferably 800-300000 g/mol, more preferably 900-200000 g/mol, still more preferably 1000-100000 g/mol, such as 2000-90000 g/mol.
According to the invention, the cross-linking agent is one or more of acrylate cross-linking agents containing at least two acrylate groups, and the acrylate groups of the group shown in the formula (9) can be acrylate groups, methacrylate groups and the like. The crosslinking agent used in the present invention is a small molecule crosslinking agent, preferably, the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1-diacrylate, one or more of 3-butanediol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate, more preferably one or more of triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
According to the present invention, the electrolyte composition further includes an initiator in an amount of 2 to 15 parts by weight, corresponding to 100 parts by weight of the electrolyte composition, and the initiator is selected from one of 2-hydroxy-2-methylpropanone, ethyl (2,4, 6-trimethylbenzoyl) phosphonate, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, methyl o-benzoylbenzoate, and 4-chlorobenzophenone.
The amount of the photoinitiator may vary within wide limits, preferably 2 to 15 parts by weight, preferably 3 to 8 parts by weight, more preferably 3 to 6 parts by weight, based on 100 parts by weight of the electrolyte composition.
According to the invention, the lithium salt is LiClO4(lithium perchlorate) and LiPF6(lithium hexafluorophosphate),LiBF4(lithium tetrafluoroborate), LiBOB (lithium dioxalate borate), LiN (SO)2CF3)2Lithium bistrifluoro (methylsulfonate) imide), LiCF3SO3(lithium trifluoromethanesulfonate) and LiN (SO)2CF2CF3)2Of the polymer matrix and the content of the lithium salt in terms of Li in a molar ratio of 5 to 20: 1.
according to the present invention, the electrode current collector is not particularly limited, and an electrode current collector conventional in the art, for example, a copper foil, an aluminum foil, etc., may be used, and the thickness thereof may be, for example, 1 to 100 μm.
In a second aspect, the present invention also provides a polymer electrolyte membrane comprising the above-described electrolyte composition.
According to the present invention, the polymer electrolyte layer is preferably specially constructed, and the polymer electrolyte layer is a polymer electrolyte membrane attached to a positive electrode, and the polymer electrolyte membrane contains the above-described electrolyte composition. The electrolyte composition is as described above.
In a third aspect, the present invention also provides a preparation method of a polymer electrolyte, wherein the preparation method comprises: an electrolyte slurry containing the electrolyte composition is provided and then dried to form a film.
The preparation method according to the present invention, wherein the method comprises:
(1) providing an electrolyte slurry containing the electrolyte composition;
(2) the slurry is cast and molded to obtain a semi-dry film;
(3) and carrying out crosslinking curing on the semi-dry film.
According to the production method of the present invention, in the step (1), the solid content of the electrolyte slurry is 1 to 50%.
According to the preparation method of the present invention, in the step (1), an initiator is further included, corresponding to 100 parts by weight of the electrolyte composition, the content of the initiator is 2 to 15 parts by weight, and the initiator is selected from one or more of 2-hydroxy-2-methyl propyl ketone, ethyl (2,4, 6-trimethyl benzoyl) phosphonate, ethyl 4-dimethylamine benzoate, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether and methyl o-benzoylbenzoate and 4-chlorobenzophenone. The amount of the photoinitiator may vary within wide limits, preferably from 2 to 15 parts by weight, preferably from 3 to 8 parts by weight, more preferably from 3 to 6 parts by weight, relative to 100 parts by weight of the electrolyte composition.
According to the preparation method of the invention, the step (3) further comprises the step of irradiating ultraviolet light; in the present invention, crosslinking curing is performed under irradiation of ultraviolet light.
According to the preparation method of the invention, the lithium salt is selected from LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2In a molar ratio of the polymer aggregate to the lithium salt, calculated as Li, of from 5 to 20: 1.
according to the preparation method of the invention, the time for crosslinking and curing is 30s-15min, preferably 2-10 min.
In a fourth aspect, the invention also provides a polymer electrolyte prepared by the preparation method.
In a fifth aspect, the present invention further provides an all-solid battery, which includes a positive electrode, a negative electrode, and a polymer electrolyte interposed between the positive electrode and the negative electrode, wherein the polymer electrolyte is the polymer electrolyte membrane or the polymer electrolyte, the positive electrode includes a positive electrode current collector and a positive electrode material layer attached to a surface of the positive electrode current collector, and the positive electrode material layer includes the electrolyte composition, a positive electrode active material, a positive electrode conductive agent, and a binder.
The all-solid battery according to the present invention, wherein the electrolyte composition is contained in an amount of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the positive electrode conductive agent is 5-20 parts by weight, preferably 6-15 parts by weight, and the content of the binder is 1-20 parts by weight, preferably 2-15 parts by weight.
According to the present invention, the specific types of the positive electrode active materials are not particularly limited, and are all conventional raw materials, and may be selected as desired. For example, the positive active material includes, but is not limited to, lithium cobaltate (LiCoO)2) Lithium manganate (LiMn)2O4) Lithium manganate, ternary material (lithium transition metal oxide) and lithium iron phosphate (LiFePO)4) One or more of (a).
According to the present invention, the positive electrode material layer may further contain a lithium salt. Preferably, the lithium salt is contained in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of the positive electrode active material.
The specific types of the lithium salt, the conductive agent and the binder are not particularly limited, and are all conventional raw materials and can be selected according to requirements.
For example, the lithium salt is LiClO4(lithium perchlorate) and LiPF6(lithium hexafluorophosphate), LiBF4(lithium tetrafluoroborate), LiBOB (lithium dioxalate borate), LiN (SO)2CF3)2Lithium bistrifluoro (methylsulfonate) imide), LiCF3SO3(lithium trifluoromethanesulfonate) and LiN (SO)2CF2CF3)2Of the polymer matrix and the content of the lithium salt in terms of Li in a molar ratio of 5 to 20: 1.
for example, the conductive agent may be selected from one or more of superconducting carbon, conductive carbon black, conductive graphite, carbon nanotubes, graphene, and carbon nanofibers.
For example, the binder may be selected from one or more of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), and sodium carboxymethylcellulose (CMC).
In a sixth aspect, the invention also provides a preparation method of the all-solid-state battery, wherein the polymer electrolyte is placed between the positive electrode and the negative electrode, the positive electrode and the negative electrode are welded with upper tabs, then are superposed and are placed in an aluminum-plastic film for sealing and pressing to obtain the all-solid-state battery; the preparation method of the positive electrode may include: providing an electrode slurry containing a positive electrode active material, a positive electrode conductive agent, a binder and the above electrolyte composition; and coating the electrode slurry and drying on an electrode current collector to form a positive electrode material layer.
The preparation method according to the present invention, wherein the drying further comprises:
(1) providing an electrode slurry containing a positive electrode active material, a positive electrode conductive agent, a binder and the above electrolyte composition;
(2) and (2) coating the electrode slurry obtained in the step (1) on an electrode current collector, drying, and then performing crosslinking and curing on the electrode current collector under the irradiation of ultraviolet light to form a positive electrode material layer.
According to the preparation method, the concentration of the electrode slurry is 5-50%; the content of the electrolyte composition is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the positive electrode conductive agent is 5-20 parts by weight, preferably 6-15 parts by weight, and the content of the binder is 1-20 parts by weight, preferably 2-15 parts by weight.
According to the preparation method of the present invention, the electrode slurry further includes a dispersion solvent used, which may be, for example, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, chloroform, dichloromethane, and acetonitrile. The amount of the dispersion solvent may vary within a wide range, and preferably is 10 to 1000 parts by weight, preferably 20 to 800 parts by weight, more preferably 100 to 500 parts by weight, for example 200 to 400 parts by weight, relative to 100 parts by weight of the electrolyte composition.
According to the preparation method of the invention, in the preparation method of the polymer electrolyte, the electrode slurry is coated on the electrode current collector in the step (2), and is dried to form a semi-dry film on the current collector, and then is crosslinked and cured by ultraviolet irradiation, so that the positive electrode material layer can be formed on the current collector. The ultraviolet irradiation may be performed by any conventional ultraviolet irradiation method in the art, and the present invention is not particularly limited thereto. The time for crosslinking and curing is 30s-15min, preferably 2-10 min.
According to the preparation method of the present invention, by the above method, a transparent crosslinked polymer film (i.e., a positive electrode material layer) can be formed on the surface of the electrode current collector, and the method can further comprise drying the current collector with the positive electrode material layer attached thereto obtained in step (2) to remove residual solvent, moisture, and the like, for example, drying at 40 to 80 ℃ for 10 to 30 hours.
After the positive electrode material layer is formed, the same positive electrode material layer may be formed on the other surface of the positive electrode current collector in the same manner, thereby forming a battery positive electrode having the positive electrode material layer of the present invention on both surfaces.
According to the preparation method of the present invention, the negative electrode is a conventional negative electrode, and for example, may be a negative electrode current collector (copper foil, copper mesh, etc.) with metal lithium attached to the surface.
According to the production method of the present invention, preferably, the thickness of the positive electrode material layer is 10 to 100 μm (single-sided thickness).
According to the preparation method of the present invention, the electrode current collector is not particularly limited, and an electrode current collector conventional in the art, such as a copper foil, an aluminum foil, etc., may be used, and the thickness thereof may be, for example, 1 to 100 μm.
According to the production method of the present invention, in another preferred embodiment, the electrolyte layer is a polymer electrolyte membrane attached to a positive electrode, and the production method of the polymer electrolyte membrane is the production method described above.
Wherein the polymer containing the structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (3), the crosslinking agent, the structural unit of the ionic liquid, and the photoinitiator are as described above.
According to the preparation method of the present invention, the organic solvent used for the electrolyte slurry may be, for example, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, chloroform, dichloromethane, and acetonitrile. The amount of the organic solvent may vary within wide limits, preferably from 20 to 100 parts by weight, preferably from 30 to 80 parts by weight, relative to 100 parts by weight of the electrolyte composition.
The crosslinking and curing may further include drying the resulting cathode having the electrolyte layer attached thereto to remove residual solvent, moisture, and the like, for example, at 40 to 80 ℃ for 10 to 30 hours, as described above.
After the electrolyte layer is formed, the same electrolyte layer may be formed on the other surface of the positive electrode in the same manner, thereby forming a positive electrode having the electrolyte layer of the present invention on both surfaces. After the electrolyte layer is formed on both sides, hot pressing (for example, hot pressing at 50 to 70 ℃) may be performed to improve the bonding strength between the electrolyte layer and the battery positive electrode.
According to the production method of the present invention, the thickness of the electrolyte layer may be, for example, 10 to 200 μm (single-sided thickness).
The negative electrode of the above battery according to the preparation method of the present invention may also be a negative electrode conventional in the art, and may be, for example, a negative electrode current collector having metallic lithium and optionally a polymer matrix attached to the surface thereof. The negative electrode collector may be, for example, a copper foil, a copper mesh, or the like.
In a seventh aspect, the invention further provides an all-solid-state battery prepared by the preparation method.
The battery of the invention can obtain higher specific capacity, cycle life and the like by adopting the battery electrode, particularly matching with the electrolyte layer.
The present invention will be described in detail below by way of examples.
In the following examples:
copolymer 1# copolymer available from Aladdin Industrial Co., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1、R2Each H), wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 100: 15, weight average molecular weight 1500 g/mol.
Copolymer # 2 is a copolymer available from Aladdin Industrial CoWhich is a structural unit represented by the formula (1) and a structural unit (R) represented by the formula (2)1=H，R2Methyl group), wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 100: 20, weight average molecular weight 2000 g/mol.
Copolymer No. 3 is a copolymer available from Aladdin Industrial Co., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1=H，R2Ethyl group), wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is 100: 25, weight average molecular weight 3000 g/mol.
Copolymer No. 4 is a copolymer available from Aladdin Industrial Co., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1，R2Each being a methyl group), wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 100: 30, weight average molecular weight 4000 g/mol.
Copolymer No. 5 is a copolymer available from Aladdin Industrial Co. chemical Co., Ltd., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1，R2Each being a methyl group), wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 100: 35, weight average molecular weight 5000 g/mol.
Copolymer No. 6 is a copolymer available from Aladdin Industrial Co., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1Is H, R2Is H), wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 100: 40, weight average molecular weight 6000 g/mol.
Copolymer No. 7 is a copolymer available from Aladdin Industrial Co., which is a structural unit represented by formula (1) and a structural unit (R) represented by formula (2)1Is methyl (CH)3)，R2Is methyl (CH)3) Random co-polymerization ofA copolymer in which the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is 100: 45, weight average molecular weight 7000 g/mol.
Polyvinylidene fluoride: product commercially available from Aladdin Industrial Co. having a weight average molecular weight of 1.5X 105~5×105g/mol。
PEO: product commercially available from Aladdin Industrial Co. having a weight average molecular weight of 105~5×106 g/mol。
Example 1
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
Preparing a battery positive plate:
(1) 50 parts by weight of positive electrode material LiFePO412.5 parts by weight of copolymer 1#, 6.1 parts by weight of LiN (SO)2CF2CF3)2Dispersing 5.2 parts by weight of pentaerythritol tetraacrylate, 1.2 parts by weight of 2-hydroxy-2-methyl propyl ketone, 15 parts by weight of ionic liquid L1 (1-vinyl-2-ethyl imidazole), 5 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive graphite in 200 parts by weight of N-methyl pyrrolidone solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 5min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 50 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 31.2 parts by weight of copolymer 1#, 15.3 parts by weight of LiN (SO)2CF2CF3)213 parts by weight of pentaerythritol tetraacrylate, 3 parts by weight of 2-hydroxy-2-methylpropanone and 37.5 parts by weight of ionic liquid L1 were dispersed in 25 parts by weight of N-methylpyrrolidone solvent to obtain an electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 5min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 50 microns (single-side thickness).
Assembling the battery:
placing the positive electrode and the lithium-coated copper foil slice (negative electrode, the same below) attached with the electrolyte layer into a glove box containing high-purity Ar atmosphere, placing for 8 hours, then respectively slicing by a die cutting machine to obtain the positive electrode and the negative electrode, welding a tab of the cut positive electrode and the cut negative electrode by a spot welding machine, then laminating the positive electrode and the negative electrode, placing the stacked positive electrode and the stacked negative electrode in an aluminum plastic film, sealing the opening in a sealing machine, taking out the battery after preparation, and hot-pressing for 1 hour at 60 ℃; thus, battery C1 was produced.
Example 2
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
Preparing a battery positive plate:
(1) 60 parts by weight of LiCoO as a positive electrode material210 parts by weight of copolymer 2#, 4.88 parts by weight of LiN (SO)2CF2CF3)2Dispersing 4.16 parts by weight of pentaerythritol tetraacrylate, 0.96 part by weight of 4-ethyl dimethylaminobenzoate, 15 parts by weight of ionic liquid L1, 5 parts by weight of polyvinylidene fluoride and 4 parts by weight of conductive carbon black in 240 parts by weight of N, N-dimethylformamide solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 10min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive electrode plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 30 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 32.3 parts by weight of copolymer 2#, 15.7 parts by weight of LiN (SO)2CF2CF3)213.4 parts by weight of pentaerythritol tetrapropyleneDispersing alkenoic acid ester, 3.1 parts by weight of 4-dimethyl ethyl aminobenzoate and 35.5 parts by weight of ionic liquid L1 in 30 parts by weight of N, N-dimethylformamide solvent to obtain electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 10min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 30 mu m (single-side thickness).
Assembling the battery:
placing the positive electrode and the lithium-coated copper foil slice attached with the electrolyte layer into a glove box containing high-purity Ar atmosphere, placing for 8h, respectively slicing by using a die cutting machine to obtain a positive electrode and a negative electrode, welding tabs of the cut positive electrode and the cut negative electrode by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated positive electrode and the laminated negative electrode into an aluminum-plastic film, sealing in a sealing machine, taking out the battery after preparation, and hot-pressing for 1h at 60 ℃; thus, battery C2 was produced.
Example 3
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
Preparing a battery positive plate:
(1) 70 parts by weight of LiCoO as a positive electrode material27.5 parts by weight of copolymer 3#, 3.66 parts by weight of LiBOB, 3.12 parts by weight of pentaerythritol tetraacrylate, 0.72 part by weight of 2-hydroxy-2-methyl propyl ketone, 7 parts by weight of ionic liquid L1, 5 parts by weight of polyvinylidene fluoride and 3 parts by weight of conductive graphite are dispersed in 280 parts by weight of acetonitrile solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 6min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 20 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) dispersing 34 parts by weight of copolymer 3#, 16.7 parts by weight of LiBOB, 14.2 parts by weight of pentaerythritol tetraacrylate, 3.3 parts by weight of ethyl 4-dimethylaminobenzoate and 31.8 parts by weight of ionic liquid L1 in 30 parts by weight of acetonitrile solvent to obtain electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 6min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 20 mu m (single-side thickness).
Assembling the battery:
placing the positive electrode and the lithium-coated copper foil slice attached with the electrolyte layer into a glove box containing high-purity Ar atmosphere, placing for 8h, respectively slicing by using a die cutting machine to obtain a positive electrode and a negative electrode, welding tabs of the cut positive electrode and the cut negative electrode by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated positive electrode and the laminated negative electrode into an aluminum-plastic film, sealing in a sealing machine, taking out the battery after preparation, and hot-pressing for 1h at 60 ℃; thus, battery C3 was produced.
Example 4
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
The method of embodiment 1, except that:
when the battery positive plate is prepared, the component content is changed into: 80 wt% of positive electrode material LiFePO46.1 parts by weight of copolymer 1#, 3 parts by weight of LiN (SO)2CF2CF3)22.6 parts by weight of pentaerythritol tetraacrylate, 0.6 part by weight of 2-hydroxy-2-methyl propyl ketone, 3.7 parts by weight of ionic liquid L1, 5 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive graphite were dispersed in 320 parts by weight of N-methylpyrrolidone solvent.
Thus, battery C4 was produced.
Example 5
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
The method of embodiment 1, except that:
preparing a battery positive plate: positive electrode material LiFePO4In an amount of 80 parts by weight, copolymer No. 1 in an amount of 5 parts by weight, LiN (SO)2CF2CF3)2The amount of the compound is 2.44 parts by weight, the amount of pentaerythritol tetraacrylate is 2.08 parts by weight, the amount of 2-hydroxy-2-methylpropanone is 0.48 part by weight, and the amount of the ionic liquid L1 is 3 parts by weight.
Finally, cell C5 was obtained.
Example 6
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
The method of embodiment 1, except that:
preparing a battery positive plate: positive electrode material LiFePO4The amount of the modified acrylic acid copolymer was 50 parts by weight, the amount of copolymer No. 1 was 19.1 parts by weight, the amount of pentaerythritol tetraacrylate was 8 parts by weight, the amount of 2-hydroxy-2-methylpropiophenone was 1.8 parts by weight, and the amount of ionic liquid L1 was 23 parts by weight.
Finally, cell C6 was obtained.
Examples 7 to 9
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
According to the method described in example 1, except that in the preparation of the positive electrode sheet for a battery and the formation of the electrolyte layer, copolymers 4#, 5# and 6# were used instead of copolymer 1#, respectively, batteries C7, C8 and C9 were prepared, respectively.
Examples 10 to 12
This example is intended to illustrate the polymer electrolyte and the method for producing the same, and the all-solid-state battery and the method for producing the same according to the present invention.
According to the method described in example 1, except that, in preparing a positive electrode sheet for a battery and forming an electrolyte layer, example 10: replacing the ionic liquid L1 with the same amount of ionic liquid L2 (1-ethyl-4-vinylpiperidine) to prepare a battery C10;
example 11: the equivalent ionic liquid L3 (ethyl methacrylate quaternary ammonium salt) is adopted to replace the ionic liquid L1, so that the battery C11 is prepared;
example 12: the same amount of ionic liquid L4 (4-methyl styryl-3-butyl quaternary ammonium salt) was used in place of the ionic liquid L1, thereby producing a battery C12.
Comparative example 1
Preparing a battery positive plate:
(1) 50 parts by weight of positive electrode material LiFePO420 parts by weight of PEO, 6.1 parts by weight of LiN (SO)2CF2CF3)2Dispersing 20 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive graphite in 200 parts by weight of N-methylpyrrolidone solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 50 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 40 parts by weight of PEO and 10 parts by weight of LiN (SO)2CF2CF3)2Dispersing in 30 parts by weight of an N-methylpyrrolidone solvent to obtain an electrolyte slurry;
(2) the electrolyte slurry was applied to one surface of the positive electrode sheet of the above-mentioned battery, dried at 60 ℃ for 24 hours, and after drying, the same electrolyte layer was formed on the reverse surface of the positive electrode sheet of the battery by the same method, and hot-pressed at 60 ℃ to obtain a positive electrode having an electrolyte layer attached thereto, the electrolyte layer having a thickness of 50 μm (one-sided thickness).
Assembling the battery:
placing the positive electrode and the lithium-coated copper foil slice attached with the electrolyte layer into a glove box containing high-purity Ar atmosphere, placing for 8h, respectively slicing by using a die cutting machine to obtain a positive electrode and a negative electrode, welding tabs of the cut positive electrode and the cut negative electrode by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated positive electrode and the laminated negative electrode into an aluminum-plastic film, sealing in a sealing machine, taking out the battery after preparation, and hot-pressing for 1h at 60 ℃; thus, battery DC1 was produced.
Comparative example 2
According to the method described in example 1, except that copolymer 7# was used in place of copolymer 1# in the preparation of the positive electrode sheet for a battery and in the formation of the electrolyte layer, the corresponding positive electrode sheet for a battery and battery DC2 were obtained.
Test example 1
The peel strength and the compacted density of the electrode tabs of the batteries in the above examples, and the specific capacity of the resulting batteries were tested, and the results are shown in table 1, in which:
testing the peel strength of the electrode slice: the universal testing machine of WDW-0.5 of Shenzhen Junrui testing instrument Limited is adopted for testing, and the universal testing machine specifically comprises the following components: cutting the electrode sheet into a sample with a length and width of 60 × 20mm, adhering the back surface of the electrode sheet to a stainless steel plate A for testing by using an adhesive tape, adhering an adhesive tape with a width of 18mm to the back surface of the electrode sheet, exposing a part of the adhesive tape, adhering the adhesive tape to a stainless steel plate B, clamping the stainless steel plate A, B on a testing machine, and testing the peel strength at a speed of 30mm/min under the conditions of 25 ℃ and a relative humidity of less than 5% RH.
Electrode compaction density test: the universal testing machine of WDW-0.5 of Shenzhen Junrui testing instrument Limited is adopted for testing, and the universal testing machine specifically comprises the following components: respectively measuring the thickness of the electrode slice and the aluminum foil by using a digital display micrometer, recording the thickness as L (mum), cutting the electrode into a wafer with the diameter of 13mm, weighing the mass as m (mg); compacted density, noted ρ, ρ = m × 10-3/(3.14×(1.3/2)2×L×10-4)=7.54m/L g/cm3。
Specific capacity test: the method adopts a blue battery test system (CT2001C, blue electronic corporation of Wuhan city) to carry out charge and discharge test on the battery, and comprises the following specific processes: and (3) carrying out constant-current charge-discharge mode test on the lithium ion batteries by using a charge-discharge instrument at 60 ℃, wherein the charge cut-off voltage is 4.0V, the discharge cut-off voltage is 3.0V, and the charge-discharge multiplying power is 0.5C, and the first specific capacity and the circulating 20-time specific capacity of each lithium ion battery are obtained through test.
TABLE 1
As can be seen from the examples and comparative examples and the data in Table 1, the electrode sheet obtained by the invention has high glass strength and compaction density, is suitable for being used as an electrode sheet of a lithium battery, and the obtained battery also has high specific capacity and long cycle life.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (36)
1. An electrolyte composition, characterized in that the composition contains a polymer, a lithium salt, an ionic liquid and a cross-linking agent, wherein the polymer is a copolymer composed of a structural unit shown in a formula (1) and a structural unit shown in a formula (2), the structural unit of the ionic liquid is any one of structural units shown in a formula (3) and a formula (7),
wherein R is1、R2Each is H or C1-C4Wherein X is selected from Cl-、Br-、I-、Al2Cl7 -、Al3Cl10 -、Sb2F11 -、Fe2Cl7 -、Zn2Cl5 -、Zn3Cl7 -、CuCl2 -、SnCl2 -、NO3 -、PO4 3-、HSO4 -、SO4 -、CF3SO3 -、ROSO3 -、CF3CO2 -、C6H5SO3 -、PF6 -、SbF6 -、BF4 -、(CF3SO2)2N-、N(CN)2 -、(CF3SO2)3C-、BR4 -、RCB11H11 -And an anion of any of p-styrenesulfonate ions; the cross-linking agent is one or more of acrylate cross-linking agents containing at least two acrylate groups, wherein the acrylate groups are as follows: -O-C (O) -C (R') = CH2R' is H or C1-C4Alkyl group of (1).
2. The electrolyte composition of claim 1, wherein the polymer is present in an amount of 0.1 to 45 parts by weight, the lithium salt is present in an amount of 0.1 to 20 parts by weight, the ionic liquid is present in an amount of 0.1 to 45 parts by weight, and the crosslinking agent is present in an amount of 0.1 to 20 parts by weight, based on 100 parts by weight of the electrolyte composition.
3. The electrolyte composition of claim 2, wherein the polymer is present in an amount of 1 to 40 parts by weight, the lithium salt is present in an amount of 0.5 to 19 parts by weight, the ionic liquid is present in an amount of 0.5 to 40 parts by weight, and the crosslinking agent is present in an amount of 0.5 to 17 parts by weight, based on 100 parts by weight of the electrolyte composition.
4. The electrolyte composition according to claim 2, further comprising an initiator in an amount of 2 to 15 parts by weight based on 100 parts by weight of the electrolyte composition, the initiator being selected from one of 2-hydroxy-2-methylpropanone, ethyl (2,4, 6-trimethylbenzoyl) phosphonate, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenylketone, benzoin dimethyl ether, methyl o-benzoylbenzoate, and 4-chlorobenzophenone.
5. The electrolyte composition of claim 1, wherein R1、R2Each H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
6. The electrolyte composition of claim 5, wherein R1、R2Each is H, methyl or ethyl.
7. The electrolyte composition according to claim 1, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the copolymer is 100: (1-100).
8. The electrolyte composition according to claim 7, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the copolymer is 100: (5-80).
9. The electrolyte composition according to claim 8, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the copolymer is 100: (8-60).
10. The electrolyte composition according to claim 9, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the copolymer is 100: (10-50).
11. The electrolyte composition of any of claims 1-10, wherein the weight average molecular weight of the copolymer is 500-500000 g/mol.
12. The electrolyte composition of claim 11 wherein the weight average molecular weight of the copolymer is 800-300000 g/mol.
13. The electrolyte composition of claim 12, wherein the weight average molecular weight of the copolymer is 900-.
14. The electrolyte composition of claim 13 wherein the weight average molecular weight of the copolymer is 1000-.
15. The electrolyte composition of claim 1, wherein the crosslinker is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1-1 diacrylate, 3-butanediol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
16. The electrolyte composition of claim 15, wherein the cross-linking agent is one or more of triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
17. The electrolyte composition of claim 1, wherein the lithium salt is selected from LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2In a molar ratio of the polymer to the lithium salt, calculated as Li, of from 5 to 20: 1.
18. a polymer electrolyte membrane comprising the electrolyte composition of any one of claims 1 to 17.
19. A method for producing a polymer electrolyte, comprising: providing an electrolyte slurry comprising the electrolyte composition of any of claims 1 to 17 and then drying to form a film.
20. The method for preparing a polymer electrolyte according to claim 19, wherein the method comprises:
(1) providing an electrolyte slurry comprising the electrolyte composition of any one of claims 1-17;
(2) the slurry is cast and molded to obtain a semi-dry film;
(3) and carrying out crosslinking curing on the semi-dry film.
21. The method for preparing a polymer electrolyte according to claim 20, wherein the solid content of the electrolyte slurry is 1 to 50% in step (1).
22. The method for preparing a polymer electrolyte according to claim 21, further comprising an initiator in the step (1), the initiator being contained in an amount of 2 to 15 parts by weight based on 100 parts by weight of the electrolyte composition, the initiator being selected from one or more of 2-hydroxy-2-methylpropanone, ethyl (2,4, 6-trimethylbenzoyl) phosphonate, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenylketone, benzoin dimethyl ether and methyl o-benzoylbenzoate and 4-chlorobenzophenone.
23. The method for preparing a polymer electrolyte according to claim 20, wherein a step of irradiating ultraviolet light is further included in the step (3).
24. The method for preparing a polymer electrolyte according to claim 20, wherein the time for the cross-linking curing is 30s-15 min.
25. The method of claim 24, wherein the time for the cross-linking curing is 2-10 min.
26. A polymer electrolyte prepared by the method for preparing a polymer electrolyte according to any one of claims 20 to 25.
27. An all-solid battery comprising a positive electrode, a negative electrode and a polymer electrolyte interposed between the positive electrode and the negative electrode, wherein the polymer electrolyte is the polymer electrolyte membrane according to claim 18 or the polymer electrolyte according to claim 26, the positive electrode comprises a positive electrode current collector and a surface-attached positive electrode material layer containing the electrolyte composition according to any one of claims 1 to 17, a positive electrode active material, a positive electrode conductive agent and a binder.
28. The all-solid battery according to claim 27, wherein the electrolyte composition is contained in an amount of 5 to 100 parts by weight, the positive electrode conductive agent is contained in an amount of 5 to 20 parts by weight, and the binder is contained in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the positive electrode active material.
29. The all-solid battery according to claim 28, wherein the electrolyte composition is contained in an amount of 10 to 80 parts by weight, based on 100 parts by weight of the positive electrode active material; the content of the positive electrode conductive agent is 6-15 parts by weight, and the content of the binder is 2-15 parts by weight.
30. The all-solid battery according to claim 29, wherein the electrolyte composition is contained in an amount of 20 to 50 parts by weight, based on 100 parts by weight of the positive electrode active material.
31. A preparation method of an all-solid-state battery is characterized in that a polymer electrolyte is arranged between a positive electrode and a negative electrode, the positive electrode and the negative electrode are welded with lugs, then are superposed and are arranged in an aluminum-plastic film for sealing and pressing to obtain the all-solid-state battery; the preparation method of the positive electrode comprises the following steps: providing an electrode slurry comprising a positive electrode active material, a positive electrode conductive agent, a binder, and the electrolyte composition of any one of claims 1-17; and coating the electrode slurry on an electrode current collector and drying to form a positive electrode material layer.
32. The method of manufacturing an all-solid battery according to claim 31, wherein the drying further comprises:
(1) providing an electrode slurry comprising a positive electrode active material, a positive electrode conductive agent, a binder, and the electrolyte composition of any one of claims 1-17;
(2) and (2) coating the electrode slurry obtained in the step (1) on an electrode current collector, drying, and then performing crosslinking and curing on the electrode current collector under the irradiation of ultraviolet light to form a positive electrode material layer.
33. The method of manufacturing an all-solid battery according to claim 32, wherein the concentration of the electrode paste is 5-50%; the electrolyte composition comprises 5-100 parts by weight of an electrolyte composition, 5-20 parts by weight of a positive electrode conductive agent and 1-20 parts by weight of a binder, based on 100 parts by weight of a positive electrode active material.
34. The production method of an all-solid battery according to claim 33, wherein the content of the electrolyte composition is 10 to 80 parts by weight, the content of the positive electrode conductive agent is 6 to 15 parts by weight, and the content of the binder is 2 to 15 parts by weight, based on 100 parts by weight of the positive electrode active material.
35. The production method of an all-solid battery according to claim 34, wherein the content of the electrolyte composition is 20 to 50 parts by weight based on 100 parts by weight of the positive electrode active material.
36. An all-solid battery produced by the method for producing an all-solid battery according to any one of claims 31 to 35.
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| WO2000067340A1 (en) * | 1999-05-04 | 2000-11-09 | Moltech Corporation | Electroactive polymers of high sulfur content for use in electrochemical cells |
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