CN117096273A - Protective layer modified lithium metal composite negative electrode, preparation method thereof and battery - Google Patents
Protective layer modified lithium metal composite negative electrode, preparation method thereof and battery Download PDFInfo
- Publication number
- CN117096273A CN117096273A CN202311360156.6A CN202311360156A CN117096273A CN 117096273 A CN117096273 A CN 117096273A CN 202311360156 A CN202311360156 A CN 202311360156A CN 117096273 A CN117096273 A CN 117096273A
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- CN
- China
- Prior art keywords
- protective layer
- lithium
- lithium metal
- framework material
- dimensional framework
- Prior art date
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- 239000011241 protective layer Substances 0.000 title claims abstract description 107
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- 150000002641 lithium Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 90
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- 239000011148 porous material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 53
- 239000002002 slurry Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 28
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- -1 poly-p-styrene Polymers 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 15
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- 239000003999 initiator Substances 0.000 claims description 9
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004528 spin coating Methods 0.000 claims description 3
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- VOEUMFXKYRCDKK-UHFFFAOYSA-N FS(=N)F.FS(=N)F.[Li] Chemical compound FS(=N)F.FS(=N)F.[Li] VOEUMFXKYRCDKK-UHFFFAOYSA-N 0.000 claims description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
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- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 2
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- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000007614 solvation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a protective layer modified lithium metal composite negative electrode, a preparation method thereof and a battery, and relates to the technical field of new energy. The pore structure of the three-dimensional framework material of the anode provides a space for deposition of lithium metal, so that the volume expansion of the lithium metal anode is relieved, and uniform deposition of lithium metal is promoted; the conductive agent reduces the contact resistance of the electrode, accelerates the movement speed of electrons, promotes the wettability between electrolyte and the pole piece, and improves the charge and discharge efficiency of the electrode; the protective layer is coated on the surface of lithium metal, so that uneven deposition of lithium ions on an electrode/electrolyte interface under high current density can be inhibited, direct contact of electrolyte and lithium metal is isolated, side reaction is reduced, loss of electrolyte is reduced, meanwhile, protective layer substances can permeate into a three-dimensional framework material, ion conducting channels are formed by gap filling of the three-dimensional framework material, ions can be conducted more rapidly, interface contact is enhanced, interface compatibility is improved, and stable SEI generation is improved.
Description
Technical Field
The application relates to the technical field of new energy, in particular to a lithium metal composite negative electrode modified by a protective layer, a preparation method thereof and a battery.
Background
Lithium ion batteries using graphite as the negative electrode have failed to meet the equipment requirements for pursuing high energy density. Lithium metal anodes with high specific capacities (3860 mAh/g) and low standard electrode potentials (-3.040V) are the most promising alternatives. However, lithium is used as an alkali metal, and has high chemical and electrochemical reactivity because the outer layer has only one electron, so that the lithium is easy to react with electrolyte to generate a Solid Electrolyte Interface (SEI) film, and the SEI film is broken and recombined to continuously consume additional electrolyte, so that irreversible capacity loss and side reaction occur. When the interface of lithium metal in contact with the electrolyte is extremely unstable, uneven lithium deposition may be caused, eventually producing lithium dendrites. As lithium dendrites further grow, the separator may be pierced to cause internal short circuits in the battery, or "dead lithium" may occur, resulting in a large capacity loss. In addition, the lithium metal anode has the problems of poor coulombic efficiency and cycle stability caused by volume expansion.
Constructing an artificial SEI film with ion conduction and electronic insulation is an effective strategy for protecting a lithium metal negative electrode, and the artificial SEI film can induce lithium ions to be deposited uniformly, so that the non-uniformity in spatial structure and distribution is avoided compared with a SEI film formed spontaneously. However, the mass transfer effect of components and structures of the artificial SEI film on charges in the film remains a problem to be solved in the research to construct a stable SEI film for a long period of time.
Disclosure of Invention
The application aims to provide a lithium metal composite anode modified by a protective layer, a preparation method thereof and a battery, so as to solve the problems.
In order to achieve the above purpose, the application adopts the following technical scheme:
the application firstly provides a lithium metal composite anode modified by a protective layer, which comprises the following components: the lithium battery comprises a three-dimensional framework material current collector, lithium metal compounded on the three-dimensional framework material current collector and a protective layer coated on the surface of the lithium metal;
the three-dimensional framework material is of a porous structure, and a conductive agent exists in the pores of the three-dimensional framework material;
the protective layer is a multicomponent polymer including any one of an ether oxygen polymer, a polycarbonate polymer, a vinylidene fluoride polymer, an acrylonitrile polymer, and a methyl methacrylate-based polymer.
Preferably, the protective layer satisfies at least one of the following conditions:
a. the hardness of the three-dimensional framework material current collector and lithium metal compounded on the three-dimensional framework material current collector is a, and the hardness of the lithium metal composite anode modified by the protective layer is b, wherein a and b satisfy the following conditions: 1 HA b-a is less than or equal to 1 and less than or equal to 50HA;
b. the Young modulus E of the lithium metal composite anode modified by the protective layer is 1GPa-70GPa;
c. the ionic conductivity sigma of the protective layer is 1×10 -6 ≤σ≤1×10 -3 。
Preferably, the protective layer satisfies at least one of the following conditions:
d. the thickness of the protective layer is 1-100 mu m;
e. the substances of the protective layer penetrate into the three-dimensional framework material, and the penetration depth is 50% -100% of the thickness of the three-dimensional framework material;
f. the combination mode of the protective layer and the lithium metal comprises any one of spraying, spin coating, wet coating, casting and dripping.
The protective layer is coated on the surface of lithium metal containing the three-dimensional framework material by adopting the modes of spraying, spin coating, wet coating, casting or dripping, and the reaction occurs in the modes of in-situ polymerization and solidification, so that the substances of the protective layer can permeate into the three-dimensional framework material. If the protective layer is made into a film and then contacted with lithium metal, or the lithium sheet is soaked in a polymer electrolyte, or the lithium metal is directly compounded with copper foil, no three-dimensional framework material exists, and the effect cannot be achieved.
Preferably, the three-dimensional framework material is a high polymer material and has a multi-level pore structure;
the three-dimensional scaffold material meets at least one of the following conditions:
A. the multistage holes are sunflower-shaped, and the multistage holes are distributed from dense to loose in the sequence of micropores, mesopores and macropores from inside to outside;
B. the hierarchical pore structure is formed by crosslinking and assembling nano sheets;
C. performing BET test on 10% R-80R% region of the three-dimensional framework material, wherein the average pore diameter D1 is 3-500 nm;
D. the pore diameter difference between the mesopores and macropores of the outer layer and the micropores and mesopores of the inner layer is 10-500nm;
E. the D50 of the three-dimensional framework material is 1-100 mu m;
F. the specific surface area of the three-dimensional framework material is 10-1000 m 2 /g；
G. The porosity of the three-dimensional framework material is 10% -95%;
more preferably, the three-dimensional framework material has a porosity of 60% to 90%.
Preferably, the protective layer modified lithium metal composite anode satisfies at least one of the following conditions:
H. the three-dimensional framework material is an organic polymer, and the organic polymer is selected from any one of polyaniline, polypyrrole, polythiophene, polyacetylene, poly-p-styrene, polyacetylene, phenolic resin, formaldehyde resin, epoxy resin, urea-formaldehyde resin, melamine resin, alkyl phenolic resin, furfural resin, acrylic resin and polyester resin;
I. the conductive agent comprises any one or more of SP, graphite, acetylene black, carbon nanotubes, graphene and Keqin black;
J. the particle size of the conductive agent is 1-100 nm;
K. the lithium metal is selected from any one of lithium particles, lithium sheets, lithium strips, lithium ingots and lithium powder;
and L, the thickness d1 of the lithium metal is 10-100 mu m.
The application also provides a preparation method of the lithium metal composite anode modified by the protective layer, which comprises the following steps:
compounding a three-dimensional framework material current collector with lithium metal to obtain a lithium metal anode;
dissolving protective layer active substances in an organic solvent, adding a cross-linking agent, stirring to form uniform protective layer solution, and coating the protective layer solution on the surface of the lithium metal negative electrode to obtain the lithium metal composite negative electrode modified by the protective layer;
the protective layer active material is selected from lithium salts, and the lithium salts comprise one or two of inorganic lithium salts and organic lithium salts.
Preferably, the preparation method satisfies at least one of the following conditions:
(1) The lithium salt comprises one or more of lithium tetrafluoroborate, lithium nitrate, lithium chloride, lithium sulfate, lithium carbonate, lithium acetate, lithium formate, lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium bisdifluorosulfimide and lithium bistrifluoromethylsulfonimide;
(2) The addition amount of the protective layer active substance is 10% -40% of the total mass of the protective layer solution;
(3) The organic solvent includes one or more of DME, DMC, DEC, FEC, FEMC, EC, PC, EMC, DMSO, NMP, DMF;
(4) The addition amount of the organic solvent is 2-30 times of the mass of the active substance of the protective layer;
(5) The cross-linking agent comprises one of DCP, BPO, DTBP, PEGDA, DTA, DAP, DBHP;
(6) The adding amount of the cross-linking agent is 1-10 times of the mass of the active substance of the protective layer.
Preferably, the adding of the cross-linking agent and stirring to form a uniform protective layer solution simultaneously comprise adding an electrolyte additive and an initiator;
the electrolyte additive satisfies at least one of the following conditions:
(7) The electrolyte additive comprises VC, PS, HFE, liNO 3 In DTD, BEP, TPP, TEP, BTFE, VEC, TFPCOne or more of;
(8) The addition amount of the electrolyte additive is 0.5% -10% of the total mass of the protective layer solution;
the initiator satisfies at least one of the following conditions:
(9) The initiator comprises one of dibenzoyl peroxide, di-tert-butyl peroxide, cyclohexanone peroxide, azodiisobutyronitrile, azodiisoheptonitrile, ammonium persulfate and sodium persulfate;
(10) The mass ratio of the initiator to the cross-linking agent is (1:1) - (1:50).
Preferably, the preparation method of the three-dimensional framework material comprises the following steps:
adding the first monomer and the second monomer into water, mixing and dissolving, adding a catalyst to adjust pH, and reacting to obtain a high polymer material;
and adding water into the high polymer material, the conductive agent and the dispersing agent, mixing, and reacting to obtain the three-dimensional framework material.
Preferably, the preparation method satisfies at least one of the following conditions:
(11) The first monomer comprises one or more of phenol, cresol, nonylphenol, xylenol, urea, melamine, decaphenol propane, aralkyl phenol, furfuryl alcohol, acrylic acid and phthalic acid;
(12) The second monomer comprises one or more of formaldehyde, pentanediamine, ethylene, propylene, chloroethylene, acrylonitrile, methacrylic acid, acetaldehyde and vinyl alcohol;
(13) The mass ratio of the first monomer to the second monomer is (0.1:1) - (1:1); the mass ratio of the water to the first monomer is 5-100;
(14) The catalyst is one or more selected from hydrochloric acid, formic acid, sulfurous acid, citric acid, oxalic acid, carbonic acid and acetic acid;
(15) The pH is in the range of 1-4;
(16) The dispersing agent is selected from any one of polyacrylate, polyvinyl alcohol, polyvinyl acid ester, sodium tripolyphosphate, sodium pyrophosphate, sodium citrate, cellulose, polyvinylpyrrolidone and ethanol;
(17) The mass ratio of the high polymer material to the dispersing agent is 1:1-1:3;
(18) The consumption of the conductive agent is 1% -30% of the mass of the three-dimensional framework material;
(19) The addition amount of the conductive agent is 0.3% -10% of the water mass.
Preferably, the preparation method of the three-dimensional framework material current collector comprises the following steps:
preparing a three-dimensional framework material, an adhesive and a solvent into slurry, coating the slurry on a current collector by adopting a coating method, and drying to obtain the three-dimensional framework material current collector;
the slurry meets at least one of the following conditions:
(20) The binder is any one of polyvinylidene fluoride, polyacrylic acid, polyamide, polytetrafluoroethylene, polyvinyl alcohol, polyethyleneimine, polyimide, polyethylene and styrene butadiene rubber;
(21) The solvent is any one of NMP, DMF, DMSO and water;
(22) The three-dimensional framework material accounts for 60% -90% of the slurry, and the binder accounts for 10% -30% of the slurry.
The application also provides a battery, which comprises the lithium metal composite anode modified by the protective layer.
Compared with the prior art, the application has the beneficial effects that:
according to the lithium metal composite anode modified by the protective layer, lithium metal is composited on the surface of the three-dimensional framework material current collector, the protective layer is arranged on the surface of the lithium metal, and the pore structure of the three-dimensional framework material provides a space for deposition of the lithium metal, so that the volume expansion of the lithium metal anode is relieved, and uniform deposition of the lithium metal is promoted; the conductive agent in the three-dimensional framework material reduces the contact resistance of the electrode, accelerates the movement speed of electrons, promotes the wettability between electrolyte and the pole piece, and improves the charge and discharge efficiency of the electrode; the multi-component polymer protective layer with good mechanical deformation resistance and compactness is coated on the surface of lithium metal, SEI with an organic-inorganic double-layer structure can be obtained, the organic layer on the surface of the SEI can adapt to the problem of volume expansion of lithium metal in the circulation process, the inorganic layer close to the surface of the lithium metal can inhibit uneven deposition of lithium ions on an electrode/electrolyte interface under high current density, direct contact of electrolyte and the lithium metal is isolated, side reaction is reduced, loss of the electrolyte is reduced, meanwhile, protective layer substances can permeate into a three-dimensional framework material, ion conducting channels are formed by filling gaps of the three-dimensional framework material, so that ions can be conducted more quickly, interface contact is enhanced, interface compatibility is improved, and stable SEI generation is improved. The combined action of the composite structure avoids the growth of dendrites to pierce through the diaphragm, inhibits the direct contact of lithium metal and electrolyte and the volume expansion of the lithium metal cathode, and improves the cycle life and coulombic efficiency of the battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an SEM image of a polymer material prepared in example 1;
FIG. 2 is the resistivity of the coated pole pieces before and after etching of the three-dimensional framework material of example 1;
FIG. 3 is a surface scanning electron microscope image of the protective layer modified lithium metal anode of example 1;
FIG. 4 is an SEM image of a commercial activated carbon of example 2;
FIG. 5 is a pore size distribution curve of the three-dimensional framework material of example 3;
fig. 6 is a cycle performance chart of the assembled battery of example 4;
fig. 7 is a cycle performance chart of the assembled battery of example 5;
FIG. 8 is a graph of the cycling performance of the assembled full cell of example 6;
fig. 9 is a cycle performance chart of the assembled battery of comparative example 1;
FIG. 10 is a graph of the cycling performance of the assembled full cell of comparative example 3;
fig. 11 is a protective layer modified lithium metal anode cross-sectional EDS diagram of example 6.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Adding 30g of acrylic acid and 70g of formaldehyde into 1L of water, stirring until the acrylic acid and the formaldehyde are completely dissolved, and adding a certain amount of acetic acid to adjust the pH to 2; and (3) uniformly stirring the mixed solution, standing, filtering, washing to neutrality, and drying to obtain the polymer material, wherein an SEM (scanning electron microscope) diagram is shown in figure 1. Then adding 15g of carbon nano tube and 75g of high polymer material, adding a proper amount of polyvinylpyrrolidone, stirring for a certain time, separating and washing to obtain the three-dimensional framework material, wherein the average pore diameter of the three-dimensional framework material is 15-20nm measured by BET.
90g of three-dimensional framework material and 10g of polyvinylidene fluoride are mixed, and then an appropriate amount of NMP is added and stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. The resistivity tests are respectively carried out on the pole pieces coated by the three-dimensional framework material before etching and the three-dimensional framework material with the depth of 10% etching, and the result is shown in figure 2, the resistivity of the pole pieces after etching is reduced, which shows that the content of the conductive agent in the area is higher, and the resistivity of the pole pieces is slightly higher because the conductive agent is distributed on the surface of the material before etching.
Then 20g LiTFSI was dissolved in 60g mixed solution of FEC and EMC (1:2 in vol), and then 30g DTA and 6g AIBN were added and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 1, wherein the surface scanning electron microscope image is shown in figure 3.
Cutting the pole piece decorated by the protective layer into a pole piece with the diameter of 12mm, taking the pole piece as a working electrode, taking an ultrathin lithium piece of 1mm as a counter electrode, and taking 1 mol/L LiPF (lithium ion battery power) 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Example 2
Mixing 80g of commercial activated carbon (SEM image of which is shown in figure 4) and 16g of conductive carbon black in water, adding appropriate amount of polyvinylpyrrolidone, stirring for a certain time, separating, and washing to obtain three-dimensional skeleton material of example 2 with BET test specific surface of 1500-2000m 2 And/g, the average pore diameter is 1-2nm. 90g of three-dimensional framework material and 10g of polyvinylidene fluoride are mixed, and then an appropriate amount of NMP is added and stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode.
Then 20g LiTFSI was dissolved in 60g mixed solution of FEC and EMC (1:2 in vol), and then 30g DTA and 6g AIBN were added and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 2.
Cutting the pole piece decorated by the protective layer into a pole piece with the diameter of 12mm, taking the pole piece as a working electrode, taking an ultrathin lithium piece of 1mm as a counter electrode, and taking 1 mol/L LiPF (lithium ion battery power) 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Example 3
56g of phenol and 100g of ethylene are added into 2L of water, stirred until the mixture is completely dissolved, and then a certain amount of hydrochloric acid is added to adjust the pH to 2; and uniformly stirring the mixed solution, standing, filtering, washing to neutrality, and drying to obtain the high polymer material. Then adding 20g SP and 80g polymer material, adding proper amount of ethanol, stirring, separating, and washing to obtain the three-dimensional framework material, wherein FIG. 5 is a pore size distribution curve of the three-dimensional framework material of example 3, and the micropore size test result of FIG. 5 shows that the pore size of the framework material is mainly about 15 nm.
95g of three-dimensional framework material and 5g of styrene-butadiene rubber are mixed, and then a proper amount of water is added, and the mixture is stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 15g LiBF 4 Dissolved in 50g of DEC, 100g of PEGDA and 8g of azobisisoheptonitrile were added and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 3.
A protective layer modified pole piece with the diameter of 12mm is used as a working electrode, an ultrathin lithium piece with the diameter of 1mm is used as a counter electrode, and a LiPF with the diameter of 1 mol/L is used 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Example 4
A three-dimensional scaffold material was prepared in the same manner as in example 2.
95g of three-dimensional framework material and 5g of styrene-butadiene rubber are mixed, and then a proper amount of water is added, and the mixture is stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 15g LiBF 4 Dissolved in 50g of DEC, 100g of PEGDA and 8g of azobisisoheptonitrile were added and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 4.
LiPF with diameter of 12mm and modified electrode plate as working electrode and counter electrode and 1 mol/L 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Example 5
36g of furfuryl alcohol and 72g of propylene are added into 1L of water, stirred until the furfuryl alcohol and the 72g of propylene are completely dissolved, and then a certain amount of carbonic acid is added to adjust the pH to 2; and uniformly stirring the mixed solution, standing, filtering, washing to neutrality, and drying to obtain the high polymer material. Then adding 10g of conductive graphite and 90g of high polymer material, adding a certain amount of cellulose, stirring, separating and washing to obtain the three-dimensional framework material.
90g of three-dimensional framework material and 10g of styrene-butadiene rubber are mixed, and then a proper amount of water is added and stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 100 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 30g LiFSI was dissolved in a mixture of 65g FEC and DME (1:3 in vol), and then 0.5g VEC,20g BPO and 8g AIBN were added and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 5.
A protective layer modified pole piece with the diameter of 12mm is used as a working electrode, an ultrathin lithium piece with the diameter of 1mm is used as a counter electrode, and a LiPF with the diameter of 1 mol/L is used 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Example 6
The three-dimensional framework material was synthesized in the same manner as in example 3.
90g of the three-dimensional framework material and 10g of polyethyleneimine are mixed, a proper amount of water is added, and the mixture is stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 10g LiFSI was dissolved in a mixture of 58 g FEC and DEC (1:3 in vol) and 1g LiNO was added 3 2g of VC,52 g of DBHP and 10g of ammonium persulfate were stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in the embodiment 6.
LiPF with diameter of 12mm and protection layer modified pole piece as negative electrode and lithium iron phosphate as positive electrode, and 1 mol/L 6 /EC+DMC+EMC (v/v=1:1:1) was assembled as an electrolyte for a coin cell and was subjected to charge and discharge tests.
Comparative example 1
A three-dimensional scaffold material was prepared in the same manner as in example 3.
95g of three-dimensional framework material and 5g of styrene-butadiene rubber are mixed, and then a proper amount of water is added, and the mixture is stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 100 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode.
1 mol/L LiPF (lithium ion battery) with a composite lithium anode with a diameter of 12mm as a working electrode and a 1mm ultrathin lithium sheet as a counter electrode 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Comparative example 2
32g of melamine and 60g of acrylonitrile are added into 1.2 of L water, stirred until the melamine and the acrylonitrile are completely dissolved, and then a certain amount of oxalic acid is added to adjust the pH to 2; and uniformly stirring the mixed solution, standing, filtering, washing to neutrality, and drying to obtain the high polymer material. Then adding 18g of graphene and 70g of high polymer material, adding a certain amount of sodium tripolyphosphate, stirring, separating and washing to obtain the three-dimensional framework material.
80g of three-dimensional framework material and 20g of polyimide are mixed, and then a proper amount of water is added and stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 50 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. 10g of PVDF was then dissolved in 100g of DMAc and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in comparative example 2.
The protective layer modified pole piece with the diameter of 12mm is used as a working electrode, the ultrathin lithium piece with the diameter of 1mm is used as a counter electrode, and the LiPF with the diameter of 1 mol/L is used 6 The assembled button half cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Comparative example 3
A50 μm lithium foil was compounded on a copper foil, and then 10g LiFSI was dissolved in 5To a mixed solution (1:3 in vol) of 8g of FEC and DEC, 1g of LiNO was further added 3 2g of VC,52 g of DBHP and 10g of ammonium persulfate were stirred to form a homogeneous solution. And coating the solution on the surface of a lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal negative electrode modified by the protective layer in comparative example 3. Lithium metal cathode modified by protective layer with diameter of 12mm is used as working electrode, lithium iron phosphate is used as positive electrode, and 1 mol/L LiPF is used 6 The assembled button cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Comparative example 4
Adding 50g of urea and 50g of formaldehyde into 800 mL water, stirring until the urea and the formaldehyde are completely dissolved, and adding a certain amount of citric acid to adjust the pH to 5; and uniformly stirring the mixed solution, standing, filtering, washing to neutrality, and drying to obtain the high polymer material. Then adding 8g of conductive carbon black, 2g of carbon nano tube and 80g of high polymer material, adding a proper amount of ethanol, stirring for a certain time, then separating and washing to obtain the three-dimensional framework material.
60g of the three-dimensional framework material and 8g of polyacrylic acid are mixed, and then a proper amount of water is added, and the mixture is stirred to form uniform slurry. And then coating the slurry on a copper foil by using a scraper, placing a 20 mu m lithium foil on the surface of a pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 10g LiFSI was dissolved in a mixture of 60g FEC and DEC (1:3 in vol) and 1g LiNO was added 3 30g of BPO and 5g of azobisisobutyronitrile were stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in comparative example 4.
The protective layer modified pole piece with the diameter of 12mm is used as a negative electrode, the ultrathin lithium piece with the diameter of 1mm is used as a counter electrode, and the LiPF with the diameter of 1 mol/L is used 6 The assembled button cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Comparative example 5
A three-dimensional scaffold material was prepared in the same manner as comparative example 2.
90g of the three-dimensional framework material and 10g of polyimide are mixed, and then a proper amount of water is added and stirred to form uniform slurry. The slurry is then applied with a doctor bladeAnd (3) placing the 50 mu m lithium foil on the surface of the pole piece after the copper foil is dried, and carrying out rolling compounding to obtain the composite lithium metal negative electrode. Then 7g of Al 2 O 3 And 3g PVDF were dissolved in the appropriate amount of DMF and stirred to form a homogeneous solution. And coating the solution on the surface of the composite lithium metal negative electrode, and heating at 80 ℃ for 3 hours to obtain the lithium metal composite negative electrode modified by the protective layer in comparative example 5.
LiPF with diameter of 12mm and protection layer modified pole piece as negative electrode and lithium iron phosphate as positive electrode, and 1 mol/L 6 The assembled button cell was assembled for electrolyte with/ec+dmc+emc (v/v=1:1:1) and tested for charge and discharge.
Performance testing
The lithium metal negative electrode modified by the protective layer obtained in the above examples and comparative examples was measured for ion conductivity by an ac impedance spectroscopy, the thickness of the electrode sheet before and after deposition of the metal lithium was measured by a micrometer, and the expansion ratio was calculated, and electrochemical performance test was performed after preparing batteries respectively.
The specific button half cell is prepared by methods well known in the art: lithium metal cathode modified by protective layer is used as working electrode, lithium metal or lithium metal cathode modified by protective layer is used as counter electrode, liPF of 1 mol/L 6 Ec+dmc+emc (v/v=1:1:1) as electrolyte and Celgrad2400 as separator, the housing was 2032 button cell housing, assembled button half cell.
The specific button cell is prepared by methods known in the art: lithium iron phosphate or lithium cobalt oxide is used as an anode, a protective layer is used for modifying a lithium metal pole piece as a cathode, and 1 mol/L LiPF is used 6 and/EC+DMC+EMC (v/v=1:1:1) is electrolyte, celgard2400 membrane and 2032 button cell casing is adopted as the casing, and the button cell is assembled.
The half cell coulombic efficiency and cycle performance of the lithium metal negative electrode modified by the protective layer prepared in each example and comparative example were tested with button half cells, and specific test conditions are as follows: tested on the LAND battery test system of Wuhan Jinno electronics Inc., first 0.5 mA/cm 2 Constant-current discharge with area specific capacity of 1 mAh/cm 2 Then 0.5. 0.5 mA/cm 2 Constant current charging, cut-off voltage 0.2V.
The button type full battery is used for testing the cycle performance of the lithium metal cathode full battery modified by the protective layers prepared in each example and comparative example, and the specific testing conditions are as follows: the test is carried out on the LAND battery test system of the Wuhan Jinno electronic Co., ltd.0.05C charge-discharge activation is carried out for 2 weeks, then the charge-discharge multiplying power is increased to 0.5C, and the cycle performance test is carried out for 300 weeks under the normal temperature condition.
The test results are shown in tables 1 and 2, and it can be seen from table 2 that the protective layer modified lithium metal negative electrodes prepared in examples 1 to 5 show higher cycle stability and lower expansion rate in the assembled half cell test, which suggests that uniform deposition of lithium can be achieved under the synergistic effect of the protective layer and the three-dimensional framework material, the occurrence of side reactions is suppressed, and the volume expansion is reduced. Meanwhile, beneficial components such as LiF and the like are generated by adding lithium salt, the stability of SEI is enhanced, and the growth of lithium dendrites is effectively inhibited. As shown in fig. 7, the cycle performance of the assembled battery of example 5 is shown in fig. 7, and the assembled battery has poor cycle stability due to volume expansion of the negative electrode caused by occurrence of side reaction during the cycle as the thickness of lithium metal increases in example 5 relative to example 1.
The surface scanning electron microscope image of the lithium metal negative electrode modified by the protective layer in embodiment 1 is shown in fig. 3, and as can be observed from fig. 3, the artificial SEI film has a smooth and compact surface, can effectively isolate lithium metal from electrolyte, reduce the decomposition of the electrolyte on the surface of the lithium metal and the consumption of active lithium, and prolong the cycle life of the lithium metal battery. The cycle performance of the assembled battery of example 4 is shown in fig. 6, and it can be seen from the comparison of example 1 and example 3, and the comparison of example 2 and example 4 that the cycle performance of the battery is better and the expansion ratio is lower when the electrolyte additive is added to the protective layer. The electrolyte additive is added to form a solvation structure with lithium ions more easily, so that the electrolyte additive on the lithium metal side is more easily reacted with lithium metal to generate an SEI film containing LiF and other components, the interface stability is improved, and meanwhile, the Li is reduced + Diffusion resistance, promoting uniform deposition of lithium and inhibiting dendrite growth. The protective layer is an organic component, has good flexibility and mechanical strength,has certain effect on inhibiting dendrite growth and volume expansion of lithium metal cathode. As can be seen from a comparison of example 1 and example 2, the protective layer plays the same role even if the three-dimensional framework material is changed, indicating that the protective layer has a general role in a matrix having a three-dimensional porous structure.
The cycle performance of the assembled full cell of example 6 is shown in fig. 8, the cycle performance of the assembled cell of comparative example 1 is shown in fig. 9, and the cycle performance of the assembled full cell of comparative example 3 is shown in fig. 10. At 0.5C, the capacity retention rate of the battery at 100 cycles was about 88%, whereas the capacity was attenuated to about 40% at 80 cycles of the full battery assembled with the protective layer of the uncoated scaffold of comparative example 3, since no three-dimensional scaffold provided lithium storage space, the volume expansion of the negative electrode was more remarkable during continuous charge and discharge, resulting in the growth of lithium dendrites and thus poor cycle performance. While comparative example 4 has a skeleton and a protective layer, the skeleton exhibits an irregular structure, which results in less or even non-uniform space for storing lithium, and in a charge and discharge process, uneven deposition of lithium is more likely to occur, and dendrite growth is finally caused, which affects cycle performance. As shown in FIG. 11, the electrode sheet modified by the protective layer in the EDS of the protective layer in example 6 contains electrolyte components in the protective layer in the skeleton, further illustrating that the protective layer modified on the surface of lithium metal permeates into the skeleton, and gel is formed between the skeleton and the skeleton during heating due to the components such as initiator and monomer, thereby improving the ionic conductivity of the skeleton layer and being more beneficial to the transmission of lithium ions and the cycle performance of the battery.
From a comparison of tables 1 and 2, it was found that comparative example 1 has a higher expansion rate and inferior electrochemical performance as compared with example 3, because the electrode sheet without the protective layer has inferior ionic conductivity, and the continuous reaction of the electrolyte with lithium metal causes the consumption of active lithium, thereby affecting the cycle performance of the electrode. The single polymer protective layer of comparative example 2 exhibited poor cycle performance and higher expansion rate compared to example 6 due to the problems of poor ionic conductivity and high interfacial resistance at long cycles. The oxide protective layer of comparative example 5 can also improve the cycling stability to a certain extent, inhibit the side reaction of the electrolyte and metallic lithium, but with the volume expansion of the negative electrode in the cycling process, the oxide protective layer cannot adapt to the volume expansion of lithium metal due to insufficient flexibility, and eventually, the battery performance is also reduced.
Table 1 ionic conductivity of the pole pieces prepared in examples and comparative examples
Table 2 expansion ratio, first coulombic efficiency and cycle stability of the pole pieces prepared in examples and comparative examples
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (12)
1. A protective layer modified lithium metal composite anode, comprising: the lithium battery comprises a three-dimensional framework material current collector, lithium metal compounded on the three-dimensional framework material current collector and a protective layer combined on the surface of the lithium metal;
the three-dimensional framework material is of a porous structure, and a conductive agent exists in the pores of the three-dimensional framework material;
the protective layer is a multicomponent polymer including any one of an ether oxygen polymer, a polycarbonate polymer, a vinylidene fluoride polymer, an acrylonitrile polymer, and a methyl methacrylate-based polymer.
2. The protective layer-modified lithium metal composite anode according to claim 1, wherein the protective layer satisfies at least one of the following conditions:
a. the hardness of the three-dimensional framework material current collector and lithium metal compounded on the three-dimensional framework material current collector is a, and the hardness of the lithium metal composite anode modified by the protective layer is b, wherein a and b satisfy the following conditions: 1 HA b-a is less than or equal to 1 and less than or equal to 50HA;
b. the Young modulus E of the lithium metal composite anode modified by the protective layer is 1GPa-70GPa;
c. the ionic conductivity sigma of the protective layer is 1×10 -6 ≤σ≤1×10 -3 。
3. The protective layer-modified lithium metal composite anode according to claim 2, wherein the protective layer satisfies at least one of the following conditions:
d. the thickness of the protective layer is 1-100 mu m;
e. the substances of the protective layer penetrate into the three-dimensional framework material, and the penetration depth is 50% -100% of the thickness of the three-dimensional framework material;
f. the combination mode of the protective layer and the lithium metal comprises any one of spraying, spin coating, wet coating, casting and dripping.
4. The protective layer-modified lithium metal composite anode according to any one of claims 1 to 3, wherein the three-dimensional framework material is a high molecular material having a hierarchical pore structure;
the three-dimensional scaffold material meets at least one of the following conditions:
A. the multistage holes are sunflower-shaped, and the multistage holes are distributed from dense to loose in the sequence of micropores, mesopores and macropores from inside to outside;
B. the hierarchical pore structure is formed by crosslinking and assembling nano sheets;
C. performing BET test on the three-dimensional framework material, wherein the average pore diameter D1 is 3-500 nm;
D. the pore diameter difference between the mesopores and macropores of the outer layer and the micropores and mesopores of the inner layer is 10-500nm;
E. the D50 of the three-dimensional framework material is 1-100 mu m;
F. the specific surface area of the three-dimensional framework material is 10-1000 m 2 /g；
G. The porosity of the three-dimensional framework material is 10% -95%.
5. The protective layer-modified lithium metal composite anode of claim 4, wherein the protective layer-modified lithium metal composite anode meets at least one of the following conditions:
H. the three-dimensional framework material is an organic polymer, and the organic polymer is selected from any one of polyaniline, polypyrrole, polythiophene, polyacetylene, poly-p-styrene, polyacetylene, phenolic resin, formaldehyde resin, epoxy resin, urea-formaldehyde resin, melamine resin, alkyl phenolic resin, furfural resin, acrylic resin and polyester resin;
I. the conductive agent comprises any one or more of SP, graphite, acetylene black, carbon nanotubes, graphene and Keqin black;
J. the particle size of the conductive agent is 1-100 nm;
K. the lithium metal is selected from any one of lithium particles, lithium sheets, lithium strips, lithium ingots and lithium powder;
and L, the thickness of the lithium metal is 10-100 mu m.
6. The preparation method of the lithium metal composite anode modified by the protective layer is characterized by comprising the following steps of:
compounding a three-dimensional framework material current collector with lithium metal to obtain a lithium metal anode;
dissolving protective layer active substances in an organic solvent, adding a cross-linking agent, stirring to form uniform protective layer solution, and coating the protective layer solution on the surface of the lithium metal negative electrode to obtain the lithium metal composite negative electrode modified by the protective layer;
the protective layer active material is selected from lithium salts, and the lithium salts comprise one or two of inorganic lithium salts and organic lithium salts.
7. The method for producing a protective layer-modified lithium metal composite anode according to claim 6, wherein the production method satisfies at least one of the following conditions:
(1) The lithium salt comprises one or more of lithium tetrafluoroborate, lithium nitrate, lithium chloride, lithium sulfate, lithium carbonate, lithium acetate, lithium formate, lithium hexafluorophosphate, lithium perchlorate, lithium difluorooxalato borate, lithium bisdifluorosulfimide and lithium bistrifluoromethylsulfonimide;
(2) The addition amount of the protective layer active substance is 10% -40% of the total mass of the protective layer solution;
(3) The organic solvent includes one or more of DME, DMC, DEC, FEC, FEMC, EC, PC, EMC, DMSO, NMP, DMF;
(4) The addition amount of the organic solvent is 2-30 times of the mass of the active substance of the protective layer;
(5) The cross-linking agent comprises one of DCP, BPO, DTBP, PEGDA, DTA, DAP, DBHP;
(6) The adding amount of the cross-linking agent is 1-10 times of the mass of the active substance of the protective layer.
8. The method for preparing a protective layer modified lithium metal composite anode according to claim 6 or 7, wherein the adding of the crosslinking agent and stirring to form a uniform protective layer solution simultaneously comprises adding an electrolyte additive and an initiator;
the electrolyte additive satisfies at least one of the following conditions:
(7) The electrolyte additive comprises VC, PS, HFE, liNO 3 One or more of DTD, BEP, TPP, TEP, BTFE, VEC, TFPC;
(8) The addition amount of the electrolyte additive is 0.5% -10% of the total mass of the protective layer solution;
the initiator satisfies at least one of the following conditions:
(9) The initiator comprises one of dibenzoyl peroxide, di-tert-butyl peroxide, cyclohexanone peroxide, azodiisobutyronitrile, azodiisoheptonitrile, ammonium persulfate and sodium persulfate;
(10) The mass ratio of the initiator to the cross-linking agent is (1:1) - (1:50).
9. The method for preparing a protective layer modified lithium metal composite anode according to claim 6, wherein the method for preparing a three-dimensional framework material comprises the following steps:
adding the first monomer and the second monomer into water, mixing and dissolving, adding a catalyst to adjust pH, and reacting to obtain a high polymer material;
and adding water into the high polymer material, the conductive agent and the dispersing agent, mixing, and reacting to obtain the three-dimensional framework material.
10. The method for producing a protective layer-modified lithium metal composite anode according to claim 9, wherein the production method satisfies at least one of the following conditions:
(11) The first monomer comprises one or more of phenol, cresol, nonylphenol, xylenol, urea, melamine, decaphenol propane, aralkyl phenol, furfuryl alcohol, acrylic acid and phthalic acid;
(12) The second monomer comprises one or more of formaldehyde, pentanediamine, ethylene, propylene, chloroethylene, acrylonitrile, methacrylic acid, acetaldehyde and vinyl alcohol;
(13) The mass ratio of the first monomer to the second monomer is (0.1:1) - (1:1); the mass ratio of the water to the first monomer is 5-100;
(14) The catalyst is one or more selected from hydrochloric acid, formic acid, sulfurous acid, citric acid, oxalic acid, carbonic acid and acetic acid;
(15) The pH is in the range of 1-4;
(16) The dispersing agent is selected from any one of polyacrylate, polyvinyl alcohol, polyvinyl acid ester, sodium tripolyphosphate, sodium pyrophosphate, sodium citrate, cellulose, polyvinylpyrrolidone and ethanol;
(17) The mass ratio of the high polymer material to the dispersing agent is 1:1-1:3;
(18) The consumption of the conductive agent is 1% -30% of the mass of the three-dimensional framework material;
(19) The addition amount of the conductive agent is 0.3% -10% of the water mass.
11. The method for preparing a protective layer modified lithium metal composite anode according to claim 6, wherein the method for preparing the three-dimensional framework material current collector comprises the following steps:
preparing a three-dimensional framework material, an adhesive and a solvent into slurry, coating the slurry on a current collector by adopting a coating method, and drying to obtain the three-dimensional framework material current collector;
the slurry meets at least one of the following conditions:
(20) The binder is any one of polyvinylidene fluoride, polyacrylic acid, polyamide, polytetrafluoroethylene, polyvinyl alcohol, polyethyleneimine, polyimide, polyethylene and styrene butadiene rubber;
(21) The solvent is any one of NMP, DMF, DMSO and water;
(22) The three-dimensional framework material accounts for 60% -90% of the slurry, and the binder accounts for 10% -30% of the slurry.
12. A battery comprising the protective layer-modified lithium metal composite anode of any one of claims 1 to 5.
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