CN117650244B - Structure and method for protecting lithium metal anode material and application thereof - Google Patents
Structure and method for protecting lithium metal anode material and application thereof Download PDFInfo
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- CN117650244B CN117650244B CN202410115144.5A CN202410115144A CN117650244B CN 117650244 B CN117650244 B CN 117650244B CN 202410115144 A CN202410115144 A CN 202410115144A CN 117650244 B CN117650244 B CN 117650244B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 lanthanide metal halide Chemical class 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 125000005250 alkyl acrylate group Polymers 0.000 claims abstract description 24
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011241 protective layer Substances 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- 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 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- JAPGBCYHMJSRNG-UHFFFAOYSA-N 3-oxo-1,2-dihydroindazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2NN=C(O)C2=C1 JAPGBCYHMJSRNG-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- MUKJDVAYJDKPAG-UHFFFAOYSA-N 2,3-dibromopropyl prop-2-enoate Chemical compound BrCC(Br)COC(=O)C=C MUKJDVAYJDKPAG-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 claims description 5
- 229910020187 CeF3 Inorganic materials 0.000 claims description 4
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 4
- 229910008069 Cerium(III) iodide Inorganic materials 0.000 claims description 4
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 4
- 229910002319 LaF3 Inorganic materials 0.000 claims description 4
- 229910016859 Lanthanum iodide Inorganic materials 0.000 claims description 4
- 229910017544 NdCl3 Inorganic materials 0.000 claims description 4
- 229910017557 NdF3 Inorganic materials 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 claims description 4
- KYKBXWMMXCGRBA-UHFFFAOYSA-K lanthanum(3+);triiodide Chemical compound I[La](I)I KYKBXWMMXCGRBA-UHFFFAOYSA-K 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- DKSXWSAKLYQPQE-UHFFFAOYSA-K neodymium(3+);triiodide Chemical compound I[Nd](I)I DKSXWSAKLYQPQE-UHFFFAOYSA-K 0.000 claims description 4
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 23
- 210000001787 dendrite Anatomy 0.000 abstract description 13
- 238000007086 side reaction Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- 239000011889 copper foil Substances 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 11
- 229910001290 LiPF6 Inorganic materials 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 229910017768 LaF 3 Inorganic materials 0.000 description 7
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical class CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- AOUSBQVEVZBMNI-UHFFFAOYSA-N 2-bromoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCBr AOUSBQVEVZBMNI-UHFFFAOYSA-N 0.000 description 3
- GXAZFDDOJOCXLO-UHFFFAOYSA-N 3,3-dibromopropyl prop-2-enoate Chemical compound BrC(Br)CCOC(=O)C=C GXAZFDDOJOCXLO-UHFFFAOYSA-N 0.000 description 3
- NDGDRYSROJEHNM-UHFFFAOYSA-N ethyl 3-bromo-2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=CBr NDGDRYSROJEHNM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- CDZAAIHWZYWBSS-UHFFFAOYSA-N 2-bromoethyl prop-2-enoate Chemical compound BrCCOC(=O)C=C CDZAAIHWZYWBSS-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
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Abstract
The invention provides a structure, a method and application for protecting a lithium metal anode material. The structure for protecting the lithium metal anode material comprises a multifunctional protection layer, wherein the raw materials of the multifunctional protection layer comprise 3 wt-10 wt% of polyhalogenated alkyl acrylate and 5-15% by weight of lanthanide metal halide. The structure can regulate the uniform deposition growth of lithium, promote the rapid transmission of lithium ions, reduce the side reaction of metal lithium and electrolyte and effectively relieve the formation of lithium dendrites; the method for protecting the lithium metal anode material is simple and easy to operate, high in controllability, low in cost and suitable for large-scale and industrialized operation; the lithium metal battery containing the protective structure has excellent cycle stability and safety.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a structure and a method for protecting a lithium metal negative electrode material, an application of the structure and the method, the lithium metal negative electrode material and a lithium metal battery.
Background
Modern society is highly dependent upon high performance electrochemical energy storage systems, and batteries that can be used in portable electronic devices, renewable energy sources, and electrified traffic are receiving significant attention. Metallic lithium is considered the most promising battery negative electrode material due to its ultra-high theoretical specific capacity (3830 mAh g -1), light weight (6.94 g mol -1) and lower redox potential (3.04V compared to standard hydrogen electrode). However, the lithium metal anode has two major problems of safety (dendrite growth) and cycle stability, which are application-oriented bottlenecks. During battery cycling, a Solid Electrolyte (SEI) film is formed at the lithium negative electrode interface, and the interface dendrite growth and side reactions are very related to the negative electrode SEI interfacial film properties. The non-uniform SEI film is easy to break in the battery cycle, so that the electrolyte is in direct contact with the negative electrode, and side reaction is initiated. In addition, the uneven structure of the interface can induce the local aggregation of the surface negative charge, the polarization of the interface is enhanced, the concentration of the interface ions is unevenly distributed, the growth of dendrites is accelerated, and the safety problem of the battery is caused.
To overcome the chemical and mechanical instability of the electrode/electrolyte interface, thereby developing a stable and high performance lithium metal negative electrode (LMA), precise control of the composition and characteristics of the SEI is required. Surface and interface engineering plays a key role in improving the interfacial physicochemical and electrochemical properties of LMA because of its strong ability to build a variety of functional artificial SEI. Therefore, development of an artificial interface multifunctional protective layer with functions of inhibiting lithium dendrite and uniform deposition of lithium and excellent cycle performance is particularly critical to development of lithium metal batteries.
Disclosure of Invention
In order to solve all or part of the technical problems, the invention provides the following technical scheme:
The invention aims to provide a structure for protecting a lithium metal anode material, which comprises a multifunctional protection layer, wherein the raw materials of the multifunctional protection layer comprise 3 wt-10-wt% of polyhalogenated alkyl acrylate and 5-15 wt% of lanthanide metal halide.
The lanthanide metal halide and lithium in the structure for protecting the lithium metal anode material form inorganic components such as lanthanide metal, lithium alloy, lithium halide and the like, can induce uniform deposition and growth of lithium, provide higher mechanical strength and lower lithium ion diffusion barrier, and inhibit dendrite growth from two aspects of mechanical stress and chemical diffusion; the polyhalogenated alkyl acrylate organic component not only has better flexibility and ion permeability, can buffer the volume change of lithium metal, but also can promote the dispersibility and film forming property of lanthanide metal halide and inhibit the dissolution of lanthanide metal halide and the interfacial side reaction of free solvent; under the synergistic effect of the multi-component protective layer interface, the occurrence of side reactions is effectively reduced, and the lithium intercalation/exfoliation cycle is kept under a stable interface, which greatly reduces the formation of lithium dendrites and the volume expansion effect.
In some embodiments, the polyalkyl halide acrylate is a polymerized reaction of a halogenated alkyl acrylate monomer with methacryloyl fluoride, azobisisobutyronitrile.
Further, the halogenated alkyl acrylate monomer comprises one or more of ethyl 2-bromomethacrylate, ethyl 2-chloromethacrylate, 2-chloroethyl methacrylate, 2, 3-dibromopropyl acrylate, methyl 2-bromomethacrylate, and 2, 3-dibromopropyl acrylate.
In some embodiments, the lanthanide metal halide includes a combination of one or more of LaF3、CeF3、NdF3、LaCl3、CeCl3、 NdCl3、CeI3、LaI3、NdI3.
In some embodiments, the raw material of the multifunctional protective layer further includes an organic solvent, where the organic solvent includes one or a combination of several of tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, and 1, 3-dioxolane.
In some embodiments, the structure for protecting a lithium metal anode material further includes a substrate, and the multifunctional protective layer is bonded to a surface of the substrate.
Further, the substrate comprises copper foil and/or aluminum foil.
In some embodiments, the weight average molecular weight of the polyalkyl halide acrylate is 7000 to 9000.
In some embodiments, the thickness of the multifunctional protective layer is 2-5 μm. If the protective layer is too thick, the capacity of the battery is reduced, the conductivity is poor, the internal resistance of the battery is increased, the charging speed is also reduced, in addition, the internal pressure of the battery is increased due to the excessive film thickness, and even the expansion and leakage of the battery are possibly caused, so that the safety risk is increased; if the protective layer is too thin, it may lead to a shortened battery life, and internal short circuits and leakage may be easily generated, and at the same time, the risk of overcharge and overdischarge of the battery may be increased. The inventors found that the battery has excellent comprehensive performance when the thickness of the multifunctional protective layer is 2-5 mu m.
Another object of the present invention is to provide a method for protecting a lithium metal anode material, the method comprising:
Providing a coating liquid, wherein the coating liquid comprises 3 wt-10 wt% of polyhalogenated alkyl acrylate, 5-15 wt% of lanthanide metal halide and an organic solvent;
Preparing the coating liquid into a film, and drying to form a multifunctional protective layer;
And bonding the multifunctional protective layer on the surface of the metal lithium.
The addition amount of the polymer and the lanthanide metal halide provided by the invention can effectively relieve the formation of lithium dendrite, and further improve the safety and the cycle performance of the lithium ion battery. If the concentration of the polyalkyl halide acrylate or the lanthanide metal halide in the coating liquid is low or high, the cycle performance of the battery is significantly reduced, and the polarization voltage and the internal resistance are increased.
In some embodiments, the method of preparing the polyalkyl halide acrylate includes: and (3) under the inert atmosphere condition, carrying out polymerization reaction on a mixed reactant containing halogenated alkyl acrylate monomer, methacryloyl fluoride and azodiisobutyronitrile to obtain the poly halogenated alkyl acrylate.
Further, in the mixed reactant, the mass fractions of the halogenated alkyl acrylate monomer, the methacryloyl fluoride and the azodiisobutyronitrile are 30-60 wt%, 10-wt-40 wt% and 5-wt-10 wt% respectively.
Further, the reaction temperature of the polymerization reaction is 50-80 ℃ and the reaction time is 8-16 h.
Further, the preparation method further comprises the following steps: and after the polymerization reaction is finished, drying the reaction product, wherein the drying temperature of the drying treatment is 80-100 ℃ and the drying time is 3-6 hours, and the polyhalogenated alkyl acrylate is obtained.
Further, the halogenated alkyl acrylate monomer comprises one or more of ethyl 2-bromomethacrylate, ethyl 2-chloromethacrylate, 2-chloroethyl methacrylate, 2, 3-dibromopropyl acrylate, methyl 2-bromomethacrylate, and 2, 3-dibromopropyl acrylate.
In some embodiments, the lanthanide metal halide includes a combination of one or more of LaF3、CeF3、NdF3、LaCl3、CeCl3、 NdCl3、CeI3、LaI3、NdI3.
In some embodiments, the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide, dimethylsulfoxide, ethylene glycol dimethyl ether, 1, 3-dioxolane.
In some embodiments, the method for preparing the coating solution includes: and adding the poly-halogenated alkyl acrylate and the lanthanide metal halide into the organic solvent, and stirring for 3-6 hours at the rotating speed of 500-800 r/min.
In some embodiments, the method specifically includes: and coating the coating liquid on the surface of the substrate, and drying to obtain the multifunctional protective layer.
In some embodiments, the drying comprises: and (3) vacuum drying the coating liquid at the temperature of 60-80 ℃ for 6-10 hours to form the multifunctional protective layer.
In some embodiments, the bonding the multifunctional protective layer to the metallic lithium surface specifically includes: and laminating the multifunctional protective layer with the metal lithium, and then carrying out rolling treatment. The method of combining the multifunctional protective layer on the surface of the metal lithium through rolling treatment can enable the formation of the protective layer to be more uniform, and if the coating liquid is directly coated on the lithium foil, the protective layer can have uneven phenomenon due to the fact that the lithium foil is too soft and has higher technological requirements.
In some embodiments, the thickness of the multifunctional protective layer is 2-5 μm.
The third object of the present invention is to provide a lithium metal anode material, which comprises metal lithium, and further comprises a structure for protecting the lithium metal anode material as defined in any one of the above technical solutions, which is bonded to the surface of the metal lithium.
The fourth object of the present invention is to provide a structure for protecting a lithium metal anode material according to any one of the above-mentioned aspects, a method for protecting a lithium metal anode material according to any one of the above-mentioned aspects, or use of a lithium metal anode material according to any one of the above-mentioned aspects in the preparation of a lithium metal battery.
The fifth object of the invention is to provide a lithium metal battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises the lithium metal negative electrode material in the technical scheme.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) In the structure for protecting the lithium metal anode material, the lanthanide metal halide can form inorganic components such as lanthanide metal, lithium alloy, lithium halide and the like with lithium, so that uniform deposition growth of the lithium is induced, higher mechanical strength and lower lithium ion diffusion barrier are provided, and dendrite growth is inhibited from two aspects of mechanical stress and chemical diffusion; the polyhalogenated alkyl acrylate organic component can promote the dispersibility and film forming property of lanthanide metal halide and inhibit the dissolution of lanthanide metal halide and the interfacial side reaction of free solvent, and on the other hand, the organic component can enable the protective structure to have better flexibility and ion permeability and buffer the volume change of lithium metal; under the synergistic effect of the multi-component protective layer interface, the occurrence of side reaction is effectively reduced, and the lithium intercalation/exfoliation cycle is kept under a stable interface, so that the formation of lithium dendrites and the volume expansion effect are greatly reduced;
(2) The method for protecting the lithium metal anode material is simple and easy to operate, high in controllability, low in cost and suitable for large-scale and industrialized operation;
(3) The secondary battery having the protective structure has excellent cycle stability and safety.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is an SEM image of the surface of a modified metallic lithium anode of a protective structure prepared in example 1 of the present invention;
Fig. 2 is an SEM image of the protective structure prepared in example 1 of the present invention after lithium deposition.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Example 1
Preparation of polybrominated ethyl methacrylate: dispersing 40g of 2-bromoethyl methacrylate monomer, 25g of methacryloyl fluoride and 5g of azodiisobutyronitrile in 30g of deionized water under an inert atmosphere, carrying out polymerization reaction at 80 ℃ for 12 h, and drying the obtained product at 80 ℃ for 6 h to obtain polybromoethyl methacrylate;
Under a dry environment, adding 10g of polybromoethyl methacrylate and 10g of LaF 3 into 80g of tetrahydrofuran, and stirring 8h at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer in the embodiment is 3.5 mu m;
the protective structure is attached to the surface of a metal lithium sheet through rolling, so that a lithium metal battery cathode is obtained, scanning electron microscope shooting is carried out on the lithium metal battery cathode, and as shown in fig. 1, fig. 1 shows that the protective layers are uniformly distributed.
A CR2016 coin cell was assembled in an argon-filled glove box, a copper foil with a protective layer was used as the cathode, celgard 2400 was used as the separator, a conventional carbonate electrolyte (1M LiPF 6, EC/DMC/FEC (v/v/v=3/7/0.5), lithium foil was used as the anode, 2 h was deposited at 1mA cm 2, and the cell was then removed in an argon-filled glove box, and was subjected to scanning electron microscopy, as shown in fig. 2, the lithium deposition exhibited a flat smooth sheet structure and a dense morphology, without dendrite growth.
The prepared negative electrode containing the protective structure, celgard2400 separator, NCM811 positive electrode and conventional carbonate electrolyte (1M LiPF 6, EC/DMC/FEC (v/v/v=3/7/0.5) were assembled into a 3.8 Ah soft pack battery, and electrochemical performance test was performed on the battery under the conditions of 3-4.3V, 0.2C/0.5C charge and discharge 100 times, and test data are shown in Table 1.
Example 2
Preparation of polybromoethyl acrylate: dispersing 40g of 2-bromoethyl acrylate monomer, 25g of methacryloyl fluoride and 5g of azodiisobutyronitrile in 30g of deionized water under inert atmosphere, carrying out polymerization reaction at 80 ℃ for 12 h, and drying the obtained product at 80 ℃ for 6h to obtain polybromoethyl acrylate;
Under a dry environment, 5g of polybromoethyl acrylate and 15g of CeF 3 are added into 80g of tetrahydrofuran, and 8 h is stirred at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6 h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer in the embodiment is 3.7 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The prepared negative electrode containing the protection structure and Celgard2400 diaphragm, NCM811 positive electrode and conventional carbonate electrolyte (1M LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5) are assembled into a 3.8 Ah soft package battery, and electrochemical performance test is carried out under the test conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 3
Preparation of poly (chloromethyl ethyl acrylate): under inert atmosphere, 35g of 2-chloromethyl ethyl acrylate monomer, 25g of methacryloyl fluoride and 10g of azobisisobutyronitrile are dispersed in 30g of deionized water, polymerization reaction is carried out at 70 ℃ for 10 h, and the obtained product is dried at 100 ℃ for 5h to obtain polychloromethyl acrylate;
Under a dry environment, adding 8g of poly (chloromethyl) ethyl acrylate and 15g of LaCl 3 into 77g of N, N-dimethylformamide, and stirring for 6h at 500r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 60 ℃ for 10 h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer is 4.2 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The prepared negative electrode containing the protective structure, celgard2400 separator, NCM811 positive electrode and conventional carbonate electrolyte (1M LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5) were assembled into a 3.8 Ah soft pack battery, and electrochemical performance test was performed on the battery under the conditions of 3-4.3V and 0.2C/0.5C charge and discharge 100 times, and test data are shown in Table 1.
Example 4
Preparation of polychloroethyl methacrylate: dispersing 40g of 2-chloroethyl methacrylate monomer, 23g of methacryloyl fluoride and 7g of azodiisobutyronitrile in 30g of deionized water under inert atmosphere, carrying out polymerization reaction at 60 ℃ for 16 h, and drying the obtained product at 100 ℃ for 6h to obtain the polychloroethyl methacrylate;
Under a dry environment, adding 6g of polychloroethyl methacrylate and 14g of CeCl 3 into 80g of ethylene glycol dimethyl ether, and stirring at 600 r/min for 8 h to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6 h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer in the embodiment is 3.7 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 5
Preparation of polydibromopropyl acrylate: dispersing 40g of 2, 3-dibromopropyl acrylate monomer, 23g of methacryloyl fluoride and 7g of azodiisobutyronitrile in water under an inert atmosphere, carrying out polymerization reaction at 60 ℃ for 16 h, and drying the obtained product at 80 ℃ for 6 h to obtain the poly dibromopropyl acrylate;
Under a dry environment, 10g of poly dibromopropyl acrylate and 10g of NdCl 3 are added into 80g of dimethyl sulfoxide, and the mixture is stirred for 8 h at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer in the embodiment is 3.4 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 6
Preparation of polybrominated methyl methacrylate: 50g of 2-bromomethyl methacrylate monomer, 15g of methacryloyl fluoride and 5g of azodiisobutyronitrile are dispersed in 30g of deionized water under inert atmosphere, polymerization reaction is carried out for 12 hours at 70 ℃, and the obtained product is dried at 80 ℃ for 6h to obtain polybromomethyl methacrylate;
Under a dry environment, adding 3g of polybromomethyl methacrylate and 5g of NdF 3 into 92g of 1, 3-dioxolane, and stirring for 8 h at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 8 h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer is 2 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 7
Preparation of polydibromopropyl acrylate: dispersing 40g of 2, 3-dibromopropyl acrylate monomer, 20g of methacryloyl fluoride and 5g of azodiisobutyronitrile in 30g of deionized water under inert atmosphere, carrying out polymerization reaction for 12 hours at 80 ℃, and drying the obtained product at 80 ℃ for 6h to obtain the polydibromopropyl acrylate;
Under a dry environment, adding 8g of poly dibromopropyl acrylate and 8g of NdF 3 into 84g of tetrahydrofuran, and stirring at 600 r/min for 8 h to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 8 h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer is 2.6 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 8
Preparation of polybrominated ethyl methacrylate: dispersing 40g of 2-bromoethyl methacrylate monomer, 20g of methacryloyl fluoride and 5g of azodiisobutyronitrile in 30g of deionized water under inert atmosphere, carrying out polymerization reaction for 12h at 80 ℃, and drying the obtained product at 80 ℃ for 6h to obtain polybromoethyl methacrylate;
Under a dry environment, 5g of polybromoethyl methacrylate and 15g of LaI 3 are added into 80g of tetrahydrofuran, and the mixture is stirred for 8h at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6h to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer in the embodiment is 3.8 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Example 9
Preparation of polybrominated ethyl methacrylate: dispersing 40g of 2-bromoethyl methacrylate monomer, 25g of methacryloyl fluoride and 5g of azodiisobutyronitrile in 30g of deionized water under an inert atmosphere, carrying out polymerization reaction at 80 ℃ for 12 h, and drying the obtained product at 80 ℃ for 6 h to obtain polybromoethyl methacrylate;
10g of polybrominated ethyl methacrylate and 15g of LaF 3 are added into 75g of tetrahydrofuran under a dry environment, and stirred for 8 h at 600 r/min to obtain a uniform dispersion; coating the prepared dispersion on the surface of a copper foil, and drying at 80 ℃ for 6 h ℃ to obtain a protective layer which is dried and formed on the surface of the copper foil, wherein the thickness of the protective layer is 5 mu m;
the protective structure is attached to the surface of a metal lithium sheet by rolling, so that a lithium metal anode is obtained;
The negative electrode containing the protective structure prepared above was assembled with a Celgard2400 separator, an NCM811 positive electrode, a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v/v=3/7/0.5)) to form a 3.8 Ah pouch battery, and subjected to electrochemical performance test under the conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Comparative example 1
The difference between comparative example 1 and examples 1 to 8 is that the lithium metal negative electrode does not contain the improved structure of the present invention, and the lithium metal negative electrode without the protection structure is used for preparing a soft-pack battery according to the preparation method of the soft-pack battery of example 1, namely, an unmodified lithium sheet is used as a negative electrode, an NCM811 is used as a positive electrode, a conventional carbonate electrolyte (1M LiPF6, EC/DMC/FEC (v/v=3/7/0.5)) is used as an electrolyte, and the soft-pack battery of 3.8 Ah is assembled, and the electrochemical performance test is performed on the soft-pack battery under the test conditions: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
Comparative example 2
The procedure of example 1 was repeated except that 20g of poly (bromomethacrylic acid) ethyl ester was added to 80g of tetrahydrofuran in a dry environment, and 8 h was stirred at 600 r/min to obtain a uniform dispersion, which was coated on the surface of copper foil to a protective layer thickness of 3 μm, and the remaining procedure was repeated as in example 1 to obtain battery properties as shown in Table 1.
Comparative example 3
The procedure of example 1 was repeated except that 20g of LaF 3 was added to 80g of tetrahydrofuran in a dry environment, and 8. 8h was stirred at 600: 600 r/min to obtain a uniform dispersion, which was applied to the surface of a copper foil to give a protective layer having a thickness of 3.7. Mu.m, and the remaining procedure was repeated in the same manner as in example 1 to obtain battery properties as shown in Table 1.
Comparative example 4
The difference from example 1 was that, under a dry environment, 2g of poly (bromomethacrylic acid) ethyl ester and 3g of LaF 3 were added to 95g of tetrahydrofuran, and 8 h was stirred at 600: 600 r/min to obtain a uniform dispersion, which was coated on the surface of a copper foil, the thickness of the protective layer was 1.5. Mu.m, and the remaining operations were carried out in the same manner as in example 1, and the obtained battery properties were shown in Table 1.
Comparative example 5
The procedure of example 1 was repeated except that 12g of poly (bromomethacrylic acid) ethyl ester and 18g of LaF 3 were added to 70g of tetrahydrofuran in a dry environment, and 8.8 h was stirred at 600: 600 r/min to obtain a uniform dispersion having a protective layer thickness of 5.5. Mu.m, and the remaining steps were performed in the same manner as in example 1 to obtain battery properties as shown in Table 1.
Comparative example 6
The difference from example 1 is only that the polybrominated ethyl methacrylate and LaF 3 are directly added to the electrolyte, the amount of added polybrominated ethyl methacrylate is 1wt% of the electrolyte, the amount of added LaF 3 is 1wt% of the electrolyte, the negative electrode is not modified, a soft-pack battery is prepared according to the soft-pack battery preparation method of example 1 for a lithium metal negative electrode without a protective structure, namely, an unmodified lithium sheet is used as the negative electrode, the positive electrode is NCM811, the electrolyte adopts a conventional carbonate electrolyte (1 m LiPF6, EC/DMC/FEC (v/v=3/7/0.5))+polybrominated ethyl methacrylate, laF 3, and a 3.8 Ah soft-pack battery is assembled, and electrochemical performance test is performed on the same, test conditions are: 3-4.3V, 0.2C/0.5C charge and discharge 100 times. The test data are shown in table 1.
It can be seen that the protective layer based on fluoroalkyl ethyl methacrylate polymer and lanthanide metal halide can more effectively improve battery performance than the method of directly adding in the electrolyte, which may be due to poor mechanical stability and not having high modulus of the protective layer formed in situ of the electrolyte, and difficulty in mechanically suppressing dendrite growth.
Table 1 battery voltage, internal resistance battery, and cycle performance measurement results of examples and comparative examples
As can be seen from comparing the test results of examples 1 to 8 and comparative examples 1 to 6, the battery composed of the metal lithium negative electrode having the multifunctional protection structure of 3 wt% to 10% wt% of the polyalkyl halide and 5% to 15% by weight of the lanthanide metal halide can significantly improve the polarization voltage and the cycle stability of the lithium metal battery, which is mainly because the protection structure provided by the present invention can uniformly deposit and grow lithium, promote rapid lithium ion transport, and reduce side reactions between the metal lithium and the electrolyte, while the structure has good flexibility, and can suppress dendrite growth and alleviate volume changes in the cycle, so that the lithium metal battery including the negative electrode exhibits more excellent performance.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely 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.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, 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 the scope thereof. 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 (13)
1. The structure for protecting the lithium metal anode material is characterized by comprising a multifunctional protection layer, wherein the raw material of the multifunctional protection layer consists of 3 wt-10% wt% of polyhalogenated alkyl acrylate, 5-15% by weight of lanthanide metal halide and the balance of organic solvent, and the thickness of the multifunctional protection layer is 2-5 mu m;
the poly-halogenated alkyl acrylate is obtained by the polymerization reaction of halogenated alkyl acrylate monomer and methacryloyl fluoride and azodiisobutyronitrile; wherein the halogenated alkyl acrylate monomer comprises one or more of ethyl 2-bromomethacrylate, ethyl 2-chloromethacrylate, 2-chloroethyl methacrylate, 2, 3-dibromopropyl acrylate, methyl 2-bromomethacrylate, and 2, 3-dibromopropyl acrylate.
2. The structure for protecting a lithium metal anode material according to claim 1, wherein: the lanthanide metal halide includes a combination of one or more of LaF3、CeF3、NdF3、LaCl3、CeCl3、 NdCl3、CeI3、LaI3、NdI3.
3. The structure for protecting a lithium metal anode material according to claim 1, wherein: the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether and 1, 3-dioxolane.
4. The structure for protecting a lithium metal anode material according to claim 1, wherein: the structure for protecting the lithium metal anode material further comprises a substrate, and the multifunctional protection layer is combined on the surface of the substrate.
5. A method of protecting a lithium metal anode material, comprising:
Providing a coating liquid, wherein the coating liquid consists of 3 wt-10 wt% of polyhalogenated alkyl acrylate, 5-15% by weight of lanthanide metal halide and the balance of organic solvent;
preparing the coating liquid into a film, and drying to form a multifunctional protective layer, wherein the thickness of the multifunctional protective layer is 2-5 mu m;
bonding the multifunctional protective layer on the surface of the metal lithium;
The preparation method of the poly halogenated alkyl acrylate comprises the following steps: under the inert atmosphere condition, carrying out polymerization reaction on a mixed reactant containing halogenated alkyl acrylate monomer, methacryloyl fluoride and azodiisobutyronitrile to obtain the poly halogenated alkyl acrylate; the halogenated alkyl acrylate monomer comprises one or more of ethyl 2-bromomethacrylate, ethyl 2-chloromethacrylate, 2-chloroethyl methacrylate, 2, 3-dibromopropyl acrylate, methyl 2-bromomethacrylate and 2, 3-dibromopropyl acrylate.
6. The method according to claim 5, wherein: the lanthanide metal halide includes a combination of one or more of LaF3、CeF3、NdF3、LaCl3、CeCl3、 NdCl3、CeI3、LaI3、NdI3.
7. The method according to claim 5, wherein: the organic solvent comprises one or more of tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether and 1, 3-dioxolane.
8. The method according to claim 5, wherein: in the mixed reactant, the mass fractions of the halogenated alkyl acrylate monomer, the methacryloyl fluoride and the azodiisobutyronitrile are 30-wt-60-wt%, 10-wt-40-wt% and 5-wt-10-wt% respectively.
9. The method according to claim 5, wherein: the reaction temperature of the polymerization reaction is 50-80 ℃ and the reaction time is 8-16 h.
10. The method of claim 5, wherein the method of preparing the polyalkyl halide acrylate further comprises: and after the polymerization reaction is finished, drying the reaction product, wherein the drying temperature of the drying treatment is 80-100 ℃ and the drying time is 3-6 hours, and the polyhalogenated alkyl acrylate is obtained.
11. A lithium metal negative electrode material comprising lithium metal, further comprising the structure of any one of claims 1-4 bonded to a surface of the lithium metal to protect the lithium metal negative electrode material.
12. The structure for protecting a lithium metal anode material according to any one of claims 1 to 4, the method for protecting a lithium metal anode material according to any one of claims 5 to 10, or the use of a lithium metal anode material according to any one of claims 11 in the preparation of a lithium metal battery.
13. A lithium metal battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that: the negative electrode comprises the lithium metal negative electrode material of any one of claim 11.
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| EP3123543A1 (en) * | 2014-03-28 | 2017-02-01 | Basf Se | Overcharge protection electrolyte additive for lithium ion batteries |
| CN107305950B (en) * | 2016-04-19 | 2019-11-05 | 宁德新能源科技有限公司 | Polymeric protective film, lithium anode piece, lithium secondary battery |
| CN112216817A (en) * | 2019-07-12 | 2021-01-12 | 华为技术有限公司 | Metal negative electrode, preparation method thereof and secondary battery |
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