CN114335525A - Solid electrode and preparation method and application thereof - Google Patents
Solid electrode and preparation method and application thereof Download PDFInfo
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- CN114335525A CN114335525A CN202011038219.2A CN202011038219A CN114335525A CN 114335525 A CN114335525 A CN 114335525A CN 202011038219 A CN202011038219 A CN 202011038219A CN 114335525 A CN114335525 A CN 114335525A
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- 239000007787 solid Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 147
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 108
- 239000002608 ionic liquid Substances 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000011149 active material Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 31
- 239000002482 conductive additive Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 46
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims description 25
- 159000000002 lithium salts Chemical class 0.000 claims description 25
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011888 foil Substances 0.000 claims description 22
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
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- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 6
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
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- 150000001412 amines Chemical class 0.000 claims description 5
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910021156 KS 6 Inorganic materials 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims 1
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- 230000002349 favourable effect Effects 0.000 abstract description 3
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- 125000004386 diacrylate group Chemical group 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- PQOPTKHODJNNPC-UHFFFAOYSA-N 1-butyl-3-ethenylimidazol-1-ium Chemical group CCCCN1C=C[N+](C=C)=C1 PQOPTKHODJNNPC-UHFFFAOYSA-N 0.000 description 1
- HHAHKYZCOOBXMS-UHFFFAOYSA-N 1-butyl-3-ethyl-2h-imidazole Chemical compound CCCCN1CN(CC)C=C1 HHAHKYZCOOBXMS-UHFFFAOYSA-N 0.000 description 1
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- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a solid electrode and a preparation method and application thereof. The solid electrode includes: the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles, and the polyion liquid-based solid electrolyte is a copolymer electrolyte obtained by in-situ polymerization reaction of an ionic liquid monomer with at least one reactive active group and a polymer monomer with at least one reactive active group. The solid electrode does not contain ionic liquid plasticizer, so that various problems caused by the plasticizer are greatly reduced, the structure of the solid electrode is favorable for reducing the interface impedance among active particles in the solid electrode and improving the ion conduction among the particles, and the all-solid-state battery containing the solid electrode can obtain higher specific capacity, lower internal resistance and better rate performance at 25 ℃.
Description
Technical Field
The invention relates to a solid electrode and a preparation method thereof, in particular to a solid electrode with effective ion transmission built inside and a preparation method thereof, and application thereof in a solid battery, belonging to the technical field of solid electrodes.
Background
The solid-state battery is a battery using a solid electrode and a solid electrolyte, has the advantages of incombustibility, no corrosion, no volatilization, no leakage and the like, and has higher safety compared with a commercial lithium battery using an organic electrolyte. In addition, the solid-state battery can realize lighter weight, smaller volume, better flexibility, higher energy density and the like, becomes an ideal object of a power battery of a next-generation new energy automobile, and provides more choices for military battery products.
In a solid-state battery, the solid-state electrolyte cannot diffuse as freely as a liquid-state electrolyte, on the one hand, there is difficulty in sufficient contact at the solid-electrode/solid-state-electrolyte interface, making it very difficult for ions to conduct at the solid-electrode/solid-state-electrolyte interface; on the other hand, the loose and porous electrode structure causes that the movement of ions among active material particles in the electrode becomes very difficult, higher contact resistance is formed among the interfaces easily, the internal resistance of the all-solid-state lithium ion battery is increased sharply and the battery cycle performance is poor, and the solid electrode with the porous structure is not suitable for a solid battery system.
At present, many documents and patents exist for improving interfacial ion conduction by adding a plasticizer in response to the problem of the solid electrode/solid electrolyte interface. For example, in the document Polymer 2019, 178, 121614, a mixed solution containing an ionic liquid monomer a, an ionic liquid B plasticizer, a lithium salt and an initiator is coated on the surface of a ternary material (NMC) cathode, a Lithium Titanate (LTO) anode and a glass fiber membrane respectively, and under the heating condition, the ionic liquid a undergoes radical polymerization, so that a plasticized polyion liquid electrolyte layer containing the ionic liquid B is formed in situ on the surfaces of the electrode and the membrane. However, the solid electrolyte layer is only coated on the surface of the electrode, the interface between the electrode/solid electrolyte and the surface of the electrode can be improved, the problem of ion transmission in the pole piece still exists, and the prepared NMC/LTO solid battery can only work at 50 ℃ and at a lower current density (0.05C). In addition, when graphite is used for the negative electrode, the ionic liquid plasticizer is also easily co-intercalated between graphite layers, resulting in failure of the graphite negative electrode.
There are also some documents trying to improve the ion conduction problem inside the solid electrode, such as Energy environ. sci, 2019, 12, 938 report that solid electrolyte layer of lithium iron phosphate (LFP) improves the solid/solid interface contact problem, they add solid electrolyte components including ethylene oxide (PEO), polyvinylidene fluoride (PVDF), aluminum oxide (Al) when preparing LFP electrode2O3) The lithium salt, the LFP and the conductive carbon black are mixed, coated and dried together, and finally the LFP cathode containing the solid electrolyte is prepared, and then a layer of solid electrolyte is coated on the surface of the LFP cathode, so that the prepared solid electrolyte layer supported by the lithium iron phosphate (LFP) greatly improves the contact problem between the inside of the LFP cathode and the interface of the LFP electrode/the solid electrolyte, and improves the transmission of ions in the inside of the solid electrode and at the interface. However, since the solid electrolyte material used is composed of a regular structure, a polymer having a high molecular weight and an inert inorganic filler, and its ion conductivity is not good, the capacity of the battery at 30 ℃ does not exert so much, and particularly, the capacity at a high rate of 0.5C is less than 30mAhg-1。
Disclosure of Invention
The invention mainly aims to provide a solid electrode with effective ion transmission built inside and a preparation method thereof, so as to overcome the defects in the prior art.
Another object of the invention is also the use of said solid electrode for the preparation of a solid-state battery.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
an embodiment of the present invention provides a solid electrode, including: the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles, and the polyion liquid-based solid electrolyte is a copolymer electrolyte obtained by in-situ polymerization reaction of an ionic liquid monomer with at least one reactive active group and a polymer monomer with at least one reactive active group.
In some embodiments, the solid electrode contains 70 to 95 wt% of active material particles, 3 to 10 wt% of conductive additive, and 1 to 10 wt% of polyion liquid-based solid electrolyte.
In some embodiments, the ionic liquid monomer is a cationic ionic liquid and/or an anionic ionic liquid, and preferably includes any one or a combination of two or more of imidazole ionic liquids, pyrrole ionic liquids, pyridine ionic liquids, piperidine ionic liquids, and the like, but is not limited thereto.
In some embodiments, the polymer monomer includes any one or a combination of two or more of an acrylate monomer having at least one reactive group, an acrylonitrile monomer, an ethylene oxide monomer, and the like, but is not limited thereto.
Further, the reactive group includes any one or a combination of two or more of vinyl, allyl, epoxypropyl, amine, hydroxyl, and the like, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the solid electrode, which comprises the following steps:
providing a uniformly mixed reaction system containing active material particles, a conductive additive, a solid electrolyte precursor solution, a binder and a dispersant, wherein the solid electrolyte precursor solution comprises a mixture of an ionic liquid monomer having at least one reactive active group, a polymer monomer having at least one reactive active group, an initiator and a lithium salt;
applying the uniformly mixed reaction system on a current collector, and carrying out heating or illumination treatment to enable ionic liquid monomers and polymer monomers in the uniformly mixed reaction system to carry out in-situ polymerization reaction on the surfaces of the active material particles, so as to coat the surfaces of the active material particles to form polyion liquid-based solid electrolyte; and the number of the first and second groups,
and removing the dispersing agent to ensure that the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles to obtain the solid electrode.
The embodiment of the invention also provides the application of the solid electrode in the preparation of a lithium battery.
Correspondingly, the embodiment of the invention also provides a solid-state lithium battery which comprises the solid electrode.
Compared with the prior art, the invention has the beneficial effects that:
(1) the solid electrode provided by the invention does not contain an ionic liquid plasticizer, so that various problems caused by the ionic liquid plasticizer are greatly reduced;
(2) according to the preparation method of the solid electrode, the polymerizable active monomer is added in the slurry mixing process, so that the polymerizable active monomer is favorably and uniformly dispersed on the surfaces of active material particles, the active material particles and the conductive additive in the prepared solid electrode are uniformly and compactly coated with a layer of nonflammable high-temperature-resistant polyion liquid solid electrolyte, and thus a solid electrode structure with the porosity of 0-20% is obtained, and the structure is favorable for reducing the interface impedance among the active particles in the solid electrode and improving the ion conduction among the particles, so that the problem of ion transmission among the active particles in the solid electrode is effectively solved;
(3) the polyion liquid-based solid electrolyte in the solid electrode is generated by in-situ polymerization of a precursor, and by adopting the in-situ polymerization method, the molecular weight of the polymer can be regulated and controlled within a proper range (10000-200000) by adjusting the addition proportion and the polymerization time of an initiator, so that the polymer with high ionic conductivity can be obtained;
(4) the polyion liquid-based solid electrolyte in the solid electrode is generated by copolymerizing an ionic liquid monomer and another polymer monomer containing a flexible chain segment, and the copolymerization of the two monomers has a self-plasticizing effect, so that the chain segment movement can be effectively enhanced, and the ion transfer capacity can be improved. Therefore, the all-solid-state battery containing the solid electrode can obtain higher specific capacity, lower internal resistance and better rate performance at 25 ℃.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view showing an internal structure of a solid electrode according to an exemplary embodiment of the present invention;
fig. 2 is a schematic view of the internal structure of the solid-state electrode in comparative example 1 of the present invention.
Detailed Description
The present inventors have made long-term studies and extensive practices to solve the problem of ion transport in the interior of a solid electrode and at the interface of the solid electrode/solid electrolyte, and have proposed a technical solution of the present invention, which is to provide an in-situ polymerization method capable of constructing a relatively high ion transport channel in the interior of a solid electrode, wherein two monomers having a relatively high ion conductivity, i.e., an ionic liquid monomer (also referred to as monomer a), a polymer monomer (also referred to as monomer B), a lithium salt and other solid electrolyte components, are added during the electrode slurry mixing process, and are uniformly mixed with an active material, a conductive additive and a binder, and after being coated on a current collector, the two monomers are polymerized in situ on the surface of active particles to form a coating layer, and after drying, a solid cathode and a solid anode in which the active material particles are uniformly coated with the conductive additive and the solid electrolyte can be finally prepared, effectively solves the problem of ion transmission among active particles in the solid electrode.
The technical solution, its implementation and principles, etc. will be further explained as follows.
An aspect of an embodiment of the present invention provides a solid electrode including: the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles, and the polyion liquid-based solid electrolyte is a copolymer electrolyte obtained by in-situ polymerization reaction of an ionic liquid monomer with at least one reactive active group and a polymer monomer with at least one reactive active group.
In some preferred embodiments, the solid electrode comprises an active positive electrode or negative electrode material, a conductive additive, a polyionic liquid-based solid electrolyte, and a current collector, wherein active material particles in the solid electrode are uniformly and densely coated with the conductive additive and the polyionic liquid-based solid electrolyte.
In some preferred embodiments, the porosity of the solid electrode is 3 to 20%, preferably 5 to 15%.
In some preferred embodiments, the mass content of the active material particles in the solid electrode is 70 to 95 wt%, the content of the conductive additive is 3 to 10 wt%, and the content of the polyion liquid-based solid electrolyte is 1 to 10 wt%.
Furthermore, the solid electrode also comprises a binder, and the content of the binder in the solid electrode is 0-10 wt%.
In some preferred embodiments, the solid-state electrolyte is a non-flammable, high temperature resistant polyionic liquid-based solid-state electrolyte that is a copolymer electrolyte containing an ionic liquid monomer (also referred to as monomer a) that is cationic or anionic and another polymer monomer containing a soft segment (also referred to as monomer B).
Furthermore, the content of an ionic liquid polymer formed by an ionic liquid monomer in the polyionic liquid-based solid electrolyte is 50-95 wt%, the content of a polymer formed by a polymer monomer B is 0-40 wt%, and the content of lithium salt is 5-40 wt%.
Further, the number average molecular weight of the polyion liquid-based solid electrolyte is 10000-200000, preferably 10000-100000.
In some preferred embodiments, the ionic liquid monomer is a cationic ionic liquid and/or an anionic ionic liquid, and preferably includes any one or a combination of two or more of imidazole ionic liquids, pyrrole ionic liquids, pyridine ionic liquids, piperidine ionic liquids, and the like, but is not limited thereto.
Further, the ionic liquid monomer is preferably 1-vinyl-3-butylimidazolium bistrifluoromethanesulfonylimide salt, but is not limited thereto.
Further, the ionic liquid monomer contains one or more reactive groups, and the reactive groups can be, but are not limited to, vinyl, allyl, epoxypropyl, amine, hydroxyl and the like.
In some preferred embodiments, the polymer monomer B is a polymer monomer comprising a soft segment.
Further, the polymer monomer includes any one or a combination of two or more of an acrylate monomer having at least one reactive group, an acrylonitrile monomer, an ethylene oxide monomer, and the like, but is not limited thereto.
Further, the reactive group may be, but is not limited to, vinyl, allyl, epoxypropyl, amine, hydroxyl, and the like.
Further, the polymer monomer B is preferably polyethylene glycol diacrylate, but is not limited thereto.
Further, the lithium salt includes any one or a combination of two or more of lithium bistrifluoromethanesulfonylimide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluorosulfonylimide, lithium difluorooxalatoborate, and the like, but is not limited thereto.
In some preferred embodiments, the active material particles may include positive electrode active material particles or negative electrode active material particles.
Further, the positive electrode active material particles may be not only lithium iron phosphate but also any one or a combination of two or more of positive electrode materials such as lithium manganate, lithium cobaltate, ternary materials, and the like, but are not limited thereto.
Further, the negative electrode active material particles may be any one of or a combination of two or more of negative electrode materials such as graphite, hard carbon, soft carbon, lithium titanate, silicon/carbon material, silicon/silicon oxide material, and the like, but are not limited thereto.
Further, the conductive additive includes any one or a combination of two or more of conductive carbon black, SUPER-P, KS-6, carbon nanotube, graphene, carbon fiber VGCF, and the like, but is not limited thereto.
Further, the binder includes any one or a combination of two or more of polyvinylidene fluoride (PVDF), polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyethylene imine, polyimide, and the like, but is not limited thereto.
Further, the current collector may be a foil, or may be a porous conductive material having a three-dimensional structure, but is not limited thereto.
The solid electrode provided by the invention does not contain an ionic liquid plasticizer, so that various problems caused by the ionic liquid plasticizer are greatly reduced; the polyion liquid-based solid electrolyte in the solid electrode is generated by in-situ polymerization of a precursor, and by adopting the in-situ polymerization method, the molecular weight of the polymer can be regulated and controlled within a proper range (10000-200000) by adjusting the addition proportion and the polymerization time of an initiator, so that the polymer with high ionic conductivity can be obtained; the polyion liquid-based solid electrolyte in the solid electrode is generated by copolymerizing an ionic liquid monomer and another polymer monomer containing a flexible chain segment, and the copolymerization of the two monomers has a self-plasticizing effect, so that the chain segment movement can be effectively enhanced, and the ion transfer capacity can be improved.
Another aspect of an embodiment of the present invention provides a method for preparing the aforementioned solid electrode, including:
providing a uniformly mixed reaction system containing active material particles, a conductive additive, a solid electrolyte precursor solution, a binder and a dispersant, wherein the solid electrolyte precursor solution comprises a mixture of an ionic liquid monomer having at least one reactive active group, a polymer monomer having at least one reactive active group, an initiator and a lithium salt;
applying the uniformly mixed reaction system on a current collector, and carrying out heating or illumination treatment to enable ionic liquid monomers and polymer monomers in the uniformly mixed reaction system to carry out in-situ polymerization reaction on the surfaces of the active material particles, so as to coat the surfaces of the active material particles to form polyion liquid-based solid electrolyte; and the number of the first and second groups,
and removing the dispersing agent to ensure that the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles to obtain the solid electrode.
In some preferred embodiments, the polymerization mechanism may be free radical polymerization, wherein the double bonds in the ionic liquid monomer a and the polymer monomer B are opened by an initiator, and multiple addition reactions are performed to sequentially connect the monomer units in series to form a high molecular polymer, and the polymerization mechanism may be cationic polymerization, anionic polymerization, gel factor-initiated polymerization, thermal chemical crosslinking polymerization without an initiator, gamma ray-initiated polymerization without an initiator, or the like.
In some preferred embodiments, the mass ratio of the active material particles, the conductive additive, the binder and the solid electrolyte precursor solution is 70-95: 3-10: 0-10: 1-10.
In some preferred embodiments, the content of the ionic liquid monomer, the content of the polymer monomer and the content of the lithium salt in the solid electrolyte precursor solution are respectively 50-95 wt%, 0-40 wt% and 5-40 wt%.
Further, the mass ratio of the initiator to the combination of the ionic liquid monomer and the polymer monomer is 0.5-5: 100, that is, the amount of the initiator is 0.5-5% of the total mass of the ionic liquid monomer A and the polymer monomer B.
In some preferred embodiments, the initiator may include a thermal initiator, a photoinitiator, and the like.
Further, the thermal initiator includes any one or a combination of two or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dialkyl peroxide, potassium persulfate, cumene hydroperoxide, t-butyl hydroperoxide, and the like, but is not limited thereto.
Further, the photoinitiator includes any one or a combination of two or more of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like, but is not limited thereto.
Further, the dispersant includes a solvent such as N-methylpyrrolidone, water, N-dimethylformamide, etc., preferably N-methylpyrrolidone (NMP), but is not limited thereto.
In some preferred embodiments, the method of preparation comprises: and applying the uniformly mixed reaction system on a current collector, wherein the coating thickness is 10-1000 mu m, and then heating or performing illumination treatment.
In some preferred embodiments, the temperature of the heating treatment is 50-80 ℃ and the time is 4-24 h.
Further, the illumination treatment time is 1-60 min.
In some more specific embodiments, the solid electrode is prepared by the following steps:
1) adding active material particles, a conductive additive and solid electrolyte precursor components including an ionic liquid monomer A, a polymer monomer B, an initiator, lithium salt and the like into a dispersing agent, and uniformly dispersing the mixture by high-speed mixing to obtain electrode slurry;
2) coating the electrode slurry on a current collector, heating for 4-24 h at 50-80 ℃ or irradiating for 1-60 min by UV (ultraviolet) light to promote the in-situ polymerization reaction of the two monomers on the surfaces of active material particles;
3) drying to remove the dispersant solvent, and obtaining the solid anode or solid cathode with active material particles uniformly wrapped by the conductive additive and the solid electrolyte.
According to the preparation method of the solid electrode, the polymerizable active monomer is added in the slurry mixing process, so that the polymerizable active monomer is favorably and uniformly dispersed on the surfaces of active material particles, the active material particles and the conductive additive in the prepared solid electrode are uniformly and compactly coated with a layer of nonflammable high-temperature-resistant polyion liquid solid electrolyte, and thus a solid electrode structure with the porosity of 0-20% is obtained, and the structure is favorable for reducing the interface impedance among the active particles in the solid electrode, improving the ion conduction among the particles, and effectively solving the problem of ion transmission among the active particles in the solid electrode.
Another aspect of an embodiment of the present invention provides a use of the aforementioned solid electrode for the preparation of a lithium battery.
Further, the lithium battery may be a solid state lithium battery.
Accordingly, another aspect of the embodiments of the present invention also provides a solid-state lithium battery including the foregoing solid electrode.
The electrochemical performance of the solid electrode is evaluated by using a solid electrode solid electrolyte membrane Li battery, 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt, polyethylene glycol diacrylate and bistrifluoromethanesulfonylimide lithium are uniformly mixed according to the mass ratio of 5: 2: 3, then a thermal initiator-azobisisobutyronitrile (1% of the total mass of the monomer) is added, magnetic stirring is carried out for 10 minutes to obtain a uniform solution, the solution is coated on the prepared composite solid electrode in a blade mode, the monomer is polymerized into a solid electrolyte to cover the composite solid electrode by vacuum heating at 60 ℃ for 8 hours, and finally the solid electrode and the Li foil lamination method are used for preparing and assembling the solid battery.
The solid-state battery is subjected to battery internal resistance test and charge and discharge test at room temperature of 25 ℃, and the charge and discharge test multiplying power is 0.1, 0.2, 0.5 and 1C.
In conclusion, the all-solid-state battery containing the solid electrode can obtain higher specific capacity, lower internal resistance and better rate performance at 25 ℃.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
The following examples illustrate the porosity of the solid electrode, the molecular weight of the copolymer solid electrolyte, and the influence of the two copolymers and the pure ionic liquid monomer homopolymer on the electrochemical performance of the solid electrode with the lithium iron phosphate cathode material. The active material of the solid electrode may be not only a lithium iron phosphate material, but also a positive electrode material such as lithium manganate, lithium cobaltate, a ternary material, and the like, and may also be a negative electrode material such as graphite, hard carbon, soft carbon, lithium titanate, a silicon/carbon material, a silicon/silicon oxide material, and the like. In the examples, the electrochemical performance of the solid electrode was evaluated by assembling a solid electrode | solid state electrolyte | Li cell, in which a lithium iron phosphate electrode | solid state electrolyte | Li cell, a lithium manganate electrode | solid state electrolyte | Li cell, and a ternary material electrode | solid state electrolyte | Li cell were charged and discharged at a window of 2.5 to 4.2V at room temperature, and the assembled graphite electrode | solid state electrolyte | Li cell was charged and discharged at 0.1 to 3.0V at room temperature.
Example 1
Solid electrolyte precursor solution composition: monomer A: vinyl imidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: acrylate monomer (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing lithium iron phosphate, a conductive agent-conductive carbon black, a binder PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 70: 10, blade-coating the dispersion solution on the surface of an aluminum foil, coating the aluminum foil with the thickness of 200 mu m, and heating the aluminum foil in vacuum at 50 ℃ for 24h to polymerize monomers in the solid electrolyte precursor and remove the solvent NMP, so as to obtain a solid lithium iron phosphate electrode with the porosity of 3%, wherein the average molecular weight of the contained solid electrolyte is about 200000. Fig. 1 is a schematic view of the internal structure of the solid electrode obtained in this embodiment.
Example 2
Solid electrolyte precursor solution composition: monomer A: allyl pyrrole-containing ionic liquid monomer (50 wt%), monomer B: acrylate monomer (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azobisisobutyronitrile (0.5% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing lithium iron phosphate, a conductive agent-conductive carbon black, a binder PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 85: 5: 0: 10, blade-coating the dispersion solution on the surface of an aluminum foil, coating the aluminum foil with the thickness of 200 mu m, and heating the aluminum foil in vacuum at 80 ℃ for 4h to polymerize monomers in the solid electrolyte precursor and remove the solvent NMP, so as to obtain a solid lithium iron phosphate electrode with the porosity of 5%, wherein the average molecular weight of the contained solid electrolyte is about 100000.
Example 3
Solid electrolyte precursor solution composition: monomer A: piperidine bistrifluoromethanesulfonylimide salt containing an amine group (50 wt%), monomer B: two-stage glycidyl group-containing polyethylene glycol (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azobisisobutyronitrile (5% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate material, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 88: 5: 3: 4, blade-coating the dispersion solution on the surface of an aluminum mesh, coating the surface of the aluminum mesh with the thickness of 200 mu m, and heating the aluminum mesh in vacuum at 60 ℃ for 12h to polymerize monomers in the solid electrolyte precursor and remove the NMP solvent, thereby obtaining a solid electrode with the porosity of 10%, wherein the average molecular weight of the contained solid electrolyte is about 50000.
Example 4
Solid electrolyte precursor solution composition: monomer A: vinyl imidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: acrylonitrile monomer (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate positive electrode material, a conductive agent, conductive carbon black, a binder, PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 88: 5: 3: 4, blade-coating the dispersion liquid on the surface of an aluminum mesh, wherein the coating thickness is 200 mu m, and vacuum heating is carried out at 60 ℃ for 12h to polymerize monomers in the solid electrolyte precursor and remove the NMP solvent at the same time, so as to obtain a solid electrode with the porosity of 10%, wherein the average molecular weight of the contained solid electrolyte is about 100000.
Example 5
Solid electrolyte precursor solution composition: monomer A: vinyl imidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: diacrylate monomer (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate material, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 95: 2: 1, coating the dispersion liquid on the surface of an aluminum foil in a blade mode, wherein the coating thickness is 200 mu m, and heating in vacuum at 60 ℃ for 24h to polymerize monomers in the solid electrolyte precursor and remove the solvent NMP, so that a solid electrode with the porosity of 20% is obtained, and the average molecular weight of the contained solid electrolyte is about 200000.
Example 6
Solid electrolyte precursor solution composition: monomer A: vinylimidazole bistrifluoromethanesulfonylimide salt (95 wt%), monomer B: diacrylate monomer (0 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (5 wt%), thermal initiator: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing graphite, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 91: 3: 2: 4, coating the dispersion solution on the surface of an aluminum foil in a blade mode, wherein the coating thickness is 200 mu m, and heating in vacuum at 60 ℃ for 8h to polymerize monomers in the solid electrolyte precursor and remove the NMP solvent at the same time, so that a solid electrode with the porosity of 10% is obtained, and the average molecular weight of the contained solid electrolyte is about 50000.
Example 7
Solid electrolyte precursor solution composition: monomer A: aminopyrrole bis (trifluoromethanesulfonyl) imide salt (50 wt%), monomer B: two-stage glycidyl end group-containing polyethylene oxide (10 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (40 wt%), a thermal initiator was additionally added: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate material, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 88: 5: 3: 4, blade-coating the dispersion solution on the surface of a copper mesh, coating the copper mesh with the thickness of 200 mu m, and heating the copper mesh in vacuum at 60 ℃ for 8h to polymerize monomers in the solid electrolyte precursor and remove the NMP solvent, thereby obtaining a solid electrode with the porosity of 10%, wherein the average molecular weight of the contained solid electrolyte is about 50000.
Example 8
Solid electrolyte precursor solution composition: monomer A: allylimidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: acrylate monomer (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), photoinitiator: bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate material, a conductive agent, conductive carbon black, a binder, PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 88: 5: 3: 4, blade-coating the dispersion liquid on the surface of an aluminum foil, coating the dispersion liquid with the thickness of 200 mu m, carrying out ultraviolet curing for 2min in a glove box filled with argon, carrying out vacuum heating for 12h at 60 ℃, removing the NMP solvent, and obtaining a solid electrode with the porosity of 10%, wherein the average molecular weight of the solid electrolyte is 10000.
Example 9
Solid electrolyte precursor solution composition: monomer A: vinylpiperidine bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: acrylonitrile monomer (40 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (10 wt%), photoinitiator: bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing a lithium iron phosphate material, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 90: 3: 4, blade-coating the dispersion liquid on the surface of an aluminum foil, coating the aluminum foil with the thickness of 200 mu m, carrying out ultraviolet curing for 60min in a glove box filled with argon, heating in vacuum at 60 ℃ for 12h to remove a solvent NMP, and obtaining a solid electrode with the porosity of 10%, wherein the molecular weight of the solid electrolyte is 200000.
Example 10
In this example, the present inventors further performed the same experiment by replacing the thermal initiator azobisisobutyronitrile with azobisisoheptonitrile, dibenzoyl peroxide, dialkyl peroxide, potassium persulfate, cumene hydroperoxide, tert-butyl hydroperoxide, etc., according to the procedure of example 1, and the structure and performance of the obtained solid electrode substantially agreed with those of example 1.
Example 11
In this embodiment, the inventors further replaced lithium iron phosphate as the positive electrode active material particles, respectively, with lithium manganate, lithium cobaltate, and the like, replaced conductive carbon black as the conductive additive, respectively, with SUPER-P, KS-6, carbon nanotubes, graphene, carbon fibers VGCF, and the like, and replaced PVDF as the binder, respectively, with polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyethylene imine, polyimide, and the like, according to the procedure of example 1, and performed the same experiment, and the structure and performance of the obtained solid electrode were substantially the same as those of example 1.
Example 12
In this example, the present inventors further replaced the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide with 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, etc., respectively, according to the procedure of example 9, and conducted the same experiment, and the ultraviolet curing time was 1min, and the structure and properties of the obtained solid electrode were substantially identical to those of example 1.
Example 13
In this embodiment, the inventors further replaced the lithium iron phosphate as the positive active material particles with graphite as the negative active material particles, hard carbon, soft carbon, lithium titanate, silicon/carbon material, silicon/silicon oxide, and the like according to the procedure in example 9, and performed the same experiment, and the obtained solid negative electrode could obtain higher specific capacity, lower internal resistance, and better rate capability at 25 ℃.
Comparative example 1
Preparation of solid electrode: uniformly dispersing lithium iron phosphate, a conductive agent, conductive carbon black and a binder, namely PVDF in NMP according to the mass ratio of 90: 5, blade-coating the dispersion on the surface of an aluminum foil, coating the surface of the aluminum foil with the thickness of 200 mu m, heating the aluminum foil in vacuum at 60 ℃ for 8 hours, and removing the solvent NMP. The solid electrode has a porosity of 35% and does not contain a solid electrolyte to form a continuous ion channel. The results are shown in Table 1, which shows that the solid electrode containing no solid electrolyte has a large internal resistance, a low capacity exertion and a poor rate capability. A schematic view of the internal structure of the solid electrode obtained in this comparative example can be seen from fig. 2.
Comparative example 2
Solid electrolyte precursor solution composition: monomer A: vinylimidazole bistrifluoromethanesulfonylimide salt (45 wt%), monomer B: diacrylate (15 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), thermal initiator: azodiisobutyronitrile (1% of the total mass of the monomer A and the monomer B), and 1-ethyl-3-butylimidazole bistrifluoromethanesulfonylimide ionic liquid (10 wt%) as a plasticizer.
Preparation of solid electrode: uniformly dispersing active substance-graphite, conductive agent-conductive carbon black, binder-PVDF and solid electrolyte precursor solution in NMP according to the mass ratio of 91: 2: 3: 4, blade-coating the dispersion on the surface of a copper mesh, coating the surface of the copper mesh with the thickness of 200 mu m, and heating the copper mesh in vacuum at 60 ℃ for 8h to polymerize monomers in the solid electrolyte precursor and remove the NMP solvent at the same time, thereby obtaining the solid electrode with the porosity of 10%, wherein the average molecular weight of the solid electrolyte is about 50000. The results are shown in Table 1, which shows that the battery cannot be normally charged and discharged although the internal resistance is small in the case of the graphite electrode, and that the ionic liquid may be co-intercalated in the graphite.
Comparative example 3
Solid electrolyte precursor solution composition: monomer A: vinylimidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: diacrylate (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), a thermal initiator was additionally added: azobisisobutyronitrile (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing active substance-lithium iron phosphate, conductive agent-conductive carbon black, binder-PVDF and solid electrolyte precursor solution in NMP according to the mass ratio of 88: 5: 3: 4, blade-coating the dispersion on the surface of an aluminum foil, coating the surface of the aluminum foil with the thickness of 200 mu m, and heating the aluminum foil in vacuum at 60 ℃ for 48 hours to polymerize monomers in the solid electrolyte precursor and remove NMP solvent at the same time, thereby obtaining a solid electrode with the porosity of 10%, wherein the average molecular weight of the solid electrolyte is about 300000. The results are shown in Table 1, which shows that too large molecular weight results in too low ionic conductivity of the polymer electrolyte, resulting in large internal resistance of the battery, low capacity exertion, and poor rate capability.
Comparative example 4
Solid electrolyte precursor solution composition: monomer A: vinylimidazole bistrifluoromethanesulfonylimide salt (50 wt%), monomer B: diacrylate (20 wt%), lithium salt: lithium bistrifluoromethanesulfonimide (30 wt%), photoinitiator: bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (1% of the total mass of monomer A and monomer B).
Preparation of solid electrode: uniformly dispersing lithium iron phosphate, a conductive agent-conductive carbon black, a binder-PVDF and a solid electrolyte precursor solution in NMP according to the mass ratio of 90: 3: 4, blade-coating the dispersion solution on the surface of an aluminum foil, coating the aluminum foil with the thickness of 200 mu m, carrying out ultraviolet curing for 90min in a glove box filled with argon, carrying out vacuum heating for 12h at 60 ℃, removing the NMP solvent, and obtaining a solid electrode with the porosity of 10%, wherein the molecular weight of the solid electrolyte is 250000. The results are shown in Table 1, which shows that too large molecular weight results in too low ionic conductivity of the polymer electrolyte, resulting in large internal resistance of the battery, low capacity exertion, and poor rate capability.
TABLE 1 internal resistance and specific capacity at different rates at 25 ℃ of solid electrode | solid electrolyte | Li cell
As can be seen from the test results of table 1 above: 1. the molecular weight of the polymer can be regulated and controlled by regulating the polymerization time, so that the ionic conductivity of the solid polymer electrolyte, the internal resistance and the electrochemical performance of the solid battery are influenced. 2. The porosity of the solid pole piece can be regulated and controlled by adjusting the proportion of the active substance, the conductive carbon black and the solid electrolyte, so that the impedance and the rate performance of the solid battery are influenced. 3. From comparative example 1, the total impedance of the battery was large because no solid electrolyte inside the positive electrode constructed an ion transmission channel, resulting in failure to exert the capacity of the battery. 4. It can be seen from comparative example 2 that with the addition of an ionic liquid as a plasticizer, the ionic liquid co-intercalates into the graphite, resulting in failure of the graphite to function properly. 5. Comparative examples 3 and 4 show that too long polymerization time results in too large a polymer molecular weight, resulting in too low an ionic conductivity of the polymer electrolyte, large internal resistance of the battery, low capacity exertion, and poor rate performance.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A solid electrode, characterized by comprising: the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles, and the polyion liquid-based solid electrolyte is a copolymer electrolyte obtained by in-situ polymerization reaction of an ionic liquid monomer with at least one reactive active group and a polymer monomer with at least one reactive active group.
2. The solid electrode according to claim 1, characterized in that: the porosity of the solid electrode is 0-20%, preferably 3-20%, and particularly preferably 5-15%; and/or the content of active material particles in the solid electrode is 70-95 wt%, the content of conductive additives is 3-10 wt%, and the content of polyion liquid-based solid electrolyte is 1-10 wt%; preferably, the solid electrode further comprises a binder, and the content of the binder in the solid electrode is 0-10 wt%.
3. The solid electrode according to claim 1, characterized in that: in the polyion liquid-based solid electrolyte, the content of a polymer formed by an ionic liquid monomer is 50-95 wt%, the content of a polymer formed by a polymer monomer is 0-40 wt%, and the content of lithium salt is 5-40 wt%; and/or the number average molecular weight of the polyion liquid-based solid electrolyte is 10000-200000, preferably 10000-100000.
4. The solid electrode according to claim 1, characterized in that: the ionic liquid monomer is a cationic ionic liquid and/or an anionic ionic liquid, and preferably comprises any one or a combination of more than two of imidazole ionic liquid, pyrrole ionic liquid, pyridine ionic liquid and piperidine ionic liquid; preferably, the reactive group comprises any one or a combination of more than two of vinyl, allyl, epoxypropyl, amine and hydroxyl;
and/or, the polymer monomer comprises a soft segment; preferably, the polymer monomer comprises any one or a combination of more than two of acrylate monomers, acrylonitrile monomers and ethylene oxide monomers, wherein the acrylate monomers at least have one reactive group; preferably, the reactive group comprises any one or a combination of more than two of vinyl, allyl, epoxypropyl, amine and hydroxyl;
and/or the lithium salt comprises any one or the combination of more than two of lithium bis (trifluoromethane sulfonyl) imide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium difluoro (oxalato) borate.
5. The solid electrode according to claim 1, characterized in that: the active material particles include positive electrode active material particles or negative electrode active material particles; preferably, the positive electrode active material particles include any one or a combination of two or more of lithium iron phosphate, lithium manganate and lithium cobaltate; preferably, the negative active material particles include any one or a combination of two or more of graphite, hard carbon, soft carbon, lithium titanate, silicon/carbon material, and silicon/silicon oxide material;
and/or the conductive additive comprises any one or a combination of more than two of conductive carbon black, SUPER-P, KS-6, carbon nanotubes, graphene and carbon fiber VGCF;
and/or the binder comprises one or a combination of more than two of polyvinylidene fluoride, polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyethylene imine and polyimide;
and/or, the current collector comprises a foil or a porous conductive material having a three-dimensional structure.
6. A method for producing a solid electrode according to any one of claims 1 to 5, comprising:
providing a uniformly mixed reaction system containing active material particles, a conductive additive, a solid electrolyte precursor solution, a binder and a dispersant, wherein the solid electrolyte precursor solution comprises a mixture of an ionic liquid monomer having at least one reactive active group, a polymer monomer having at least one reactive active group, an initiator and a lithium salt;
applying the uniformly mixed reaction system on a current collector, and carrying out heating or illumination treatment to enable ionic liquid monomers and polymer monomers in the uniformly mixed reaction system to carry out in-situ polymerization reaction on the surfaces of the active material particles, so as to coat the surfaces of the active material particles to form polyion liquid-based solid electrolyte; and the number of the first and second groups,
and removing the dispersing agent to ensure that the conductive additive and the polyion liquid-based solid electrolyte are uniformly and densely coated on the surface of the active material particles to obtain the solid electrode.
7. The method of claim 6, wherein: the mass ratio of the active material particles, the conductive additive, the binder and the solid electrolyte precursor solution is 70-95: 3-10: 0-10: 1-10;
and/or the content of ionic liquid monomer in the solid electrolyte precursor solution is 50-95 wt%, the content of polymer monomer is 0-40 wt%, and the content of lithium salt is 5-40 wt%; preferably, the mass ratio of the initiator to the combination of the ionic liquid monomer and the polymer monomer is 0.5-5: 100.
8. The method of claim 6, wherein: the initiator comprises a thermal initiator and/or a photoinitiator; preferably, the thermal initiator comprises any one or a combination of more than two of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dialkyl peroxide, potassium persulfate, cumene hydroperoxide and tert-butyl hydroperoxide; preferably, the photoinitiator comprises any one or the combination of more than two of 2-hydroxy-methylphenyl propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone and bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide;
and/or the dispersant comprises any one or the combination of more than two of N-methyl pyrrolidone, water and N, N-dimethylformamide, and preferably N-methyl pyrrolidone;
and/or, the preparation method comprises the following steps: applying the uniformly mixed reaction system on a current collector, wherein the coating thickness is 10-1000 mu m, and then heating or irradiating;
and/or the temperature of the heating treatment is 50-80 ℃, and the time is 4-24 hours;
and/or the illumination treatment time is 1-60 min.
9. Use of the solid electrode according to any one of claims 1 to 5 for the preparation of a lithium battery; preferably, the lithium battery comprises a solid state lithium battery.
10. A solid-state lithium battery characterized by comprising the solid electrode according to any one of claims 1 to 5.
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