CN116565353A - Pole piece, preparation method and application thereof - Google Patents
Pole piece, preparation method and application thereof Download PDFInfo
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- CN116565353A CN116565353A CN202310621153.7A CN202310621153A CN116565353A CN 116565353 A CN116565353 A CN 116565353A CN 202310621153 A CN202310621153 A CN 202310621153A CN 116565353 A CN116565353 A CN 116565353A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 106
- 238000000576 coating method Methods 0.000 claims abstract description 106
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 75
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims description 111
- 229910019142 PO4 Inorganic materials 0.000 claims description 66
- 239000010452 phosphate Substances 0.000 claims description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 34
- 239000011247 coating layer Substances 0.000 claims description 24
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 23
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical group [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 22
- 239000002202 Polyethylene glycol Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000004386 diacrylate group Chemical group 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 5
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 5
- DOMLXBPXLNDFAB-UHFFFAOYSA-N ethoxyethane;methyl prop-2-enoate Chemical compound CCOCC.COC(=O)C=C DOMLXBPXLNDFAB-UHFFFAOYSA-N 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 229920001427 mPEG Polymers 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012985 polymerization agent Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 239000002253 acid Substances 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
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012722 thermally initiated polymerization Methods 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/13—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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to the technical field of lithium batteries, in particular to a pole piece, a preparation method and application thereof. According to the lithium battery, the solid electrolyte is mixed with the organic polymer solution with the thermal polymerization characteristic, the solid electrolyte is directly coated on the surface of the pole piece body, thermal polymerization is initiated through heating, a uniform organic/inorganic composite coating is obtained, the solid electrolyte and the pole piece body can be isolated, side reactions of reducing and inserting lithium are reduced, the solid electrolyte is uniformly distributed, precipitation of lithium dendrites is inhibited, the safety performance is further improved, meanwhile, the stability of the coating can be enhanced due to the flexibility and cohesiveness of the polymer, the coating effect is guaranteed, and the long cycle life of the lithium battery is further guaranteed.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a pole piece, a preparation method and application thereof.
Background
The lithium ion battery is a green and environment-friendly secondary battery, and has the advantages of high energy density, fast energy supplementing rate, long cycle life and the like compared with the traditional lead-acid battery and nickel-hydrogen battery, and has wide application in the field of new energy automobile power batteries nowadays. With the continuous development of new energy automobiles, the continuous voyage and safety anxiety of consumers on the new energy automobiles are more obvious, because the demands of people on energy density are continuously improved, however, the lithium ion batteries have hardly met the demands of increasingly improved specific energy. Therefore, the development of a power battery with high specific energy and high safety through a metal lithium negative electrode with high specific capacity natural advantages will become a great development trend of new energy automobiles.
In a power battery, metal lithium is a cathode material with high gram capacity, the theoretical gram capacity of the metal lithium reaches 3860mAh/g, which is ten times as much as that of the existing commercial graphite electrode (340 mAh/g), so that the metal lithium can greatly reduce the mass ratio of the cathode, reduce the weight of the battery and is a great core direction for developing a high specific energy battery. However, since lithium metal is very active and has low self potential, when the lithium metal is used as a negative electrode, serious side reactions exist with electrolyte, namely, a solid electrolyte layer (SEI) is continuously generated at a negative electrode/electrolyte interface, the process of forming the SEI layer is an irreversible process, and the electrolyte is continuously consumed to reduce the lithium content and deteriorate the cycle performance. Meanwhile, the metal lithium is different from a graphite electrode intercalation and deintercalation mechanism, is taken as a negative electrode and is separated through lithium deposition, current distribution is quite easy to be uneven, so that lithium dendrites are separated out, after the lithium dendrites reach a certain degree, dead lithium is formed, the capacity of the battery is reduced, the coulomb efficiency is reduced, and even the diaphragm is pierced, so that the internal short circuit of the lithium ion battery is caused, and safety problems such as thermal runaway and the like are caused.
The protection treatment of lithium negative electrode in lithium secondary battery disclosed in patent CN104617259a, wherein a silicon dioxide protection layer is deposited on the surface of lithium electrode in situ by growing silicon dioxide in situ protection layer on the metal lithium to isolate the metal lithium from electrolyte, so as to inhibit the problem of precipitation of lithium dendrite, thereby improving the cycle performance of lithium secondary battery. However, in the charging and discharging process of the metal lithium, the volume of the metal lithium is continuously expanded and contracted, and the fragile silicon dioxide protective layer is easy to break and fall off, so that the protective effect is lost.
In addition, replacing electrolyte with solid electrolyte is also a feasible method, such as oxide solid electrolyte disclosed in patent CN115799618A and a preparation method and application thereof, and a NASICON type solid electrolyte Lithium Aluminum Titanium Phosphate (LATP) which is easy to synthesize and has high purity is introduced, and the Lithium Aluminum Titanium Phosphate (LATP) has the advantages of high safety, high ion conductivity and the like, and can improve the multiplying power, the cycle and other electrochemical performances of a lithium ion battery. However, in practical application, ti element in LATP is +4 valent and is contacted with lithium-intercalated graphite, lithium-intercalated silicon or lithium cathode and other low potentials, and then Ti is 4+ Is extremely easy to be reduced to Ti 3+ The lithium intercalation characteristic is caused on the surface of the LATP, so that the safety is lowered.
Therefore, development of a surface modification layer of a lithium metal negative electrode with high safety and flexibility is needed to solve the problems of dendrite precipitation of lithium metal negative electrode and stability of the modification layer.
Disclosure of Invention
The purpose of the application is to provide a pole piece and a preparation method and application thereof, so as to solve the problems of precipitation and stability of metal lithium negative pole lithium dendrite of a lithium ion battery in the prior art, ensure that the lithium battery taking metal lithium as a negative pole has high safety and long cycle life, further improve the energy density and comprehensive performance of the lithium battery, and meet the requirements of consumers on the high-specific-energy lithium battery.
To achieve the above object and other related objects, the present application adopts the following technical solutions:
in a first aspect, the present application provides a pole piece, the pole piece includes a pole piece body and a coating layer located on the surface of the pole piece body, the coating layer includes a polymer skeleton with a three-dimensional network structure and phosphate type solid electrolyte distributed in the polymer skeleton, and the phosphate type solid electrolyte is titanium aluminum lithium phosphate or germanium aluminum lithium phosphate.
Further, the content of the phosphate type solid electrolyte in the coating is 78-95 wt%.
Further, the thickness of the coating is 10-30 μm.
Further, the coating comprises a first coating and a second coating, the first coating and the second coating both comprise a polymer framework and phosphate type solid electrolyte distributed in the polymer framework, the first coating is arranged on the surface of the pole piece body, and the second coating is arranged on the surface of the first coating.
Further, the content m of the phosphate type solid electrolyte in the first coating layer and the content n of the phosphate type solid electrolyte in the second coating layer satisfy the following relationship:
m＞n。
in the application, the content of the phosphate type solid electrolyte in the coating is adjusted, the first coating and the second coating are sequentially arranged on the surface of the pole piece, the content of the phosphate type solid electrolyte in the first coating is larger than that of the phosphate type solid electrolyte in the second coating, and meanwhile, the thicknesses of the first coating and the second coating are 5-15 mu m, so that gradient distribution of the content of the phosphate type solid electrolyte in the coating is realized, the uniformity of lithium ion transmission can be further improved, and the risk of precipitation of lithium dendrites is reduced.
In a second aspect, the present application provides a method for preparing a pole piece as described above, comprising the steps of:
s1, mixing a prepolymer, a thermal polymerization initiator and a polar solvent, and stirring to obtain an organic mixed solution, wherein the prepolymer is polyacrylate or acrylate monomer;
s2, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a mixed solution;
and S3, coating the mixed solution on the surface of the pole piece body, heating, and drying and performing thermal polymerization to obtain the pole piece.
In the application, in the step S1, the stirring speed is 50-500 rpm, and the stirring time is 0.5-1 h; in the step S2, the stirring speed is 50-500 rpm, the stirring time is 1-3 h, the viscosity of the obtained mixed solution is 200-1000 mPa.s by setting the stirring speed and the stirring time for two times and combining the proportion of the mixed solution, so that the mixed solution is coated on the surface of the pole piece, the thickness of the coated mixed solution is 20-50 mu m, and the pole piece with the coating thickness of 10-30 mu m is obtained through drying and thermal polymerization.
Further, in step S1, the ratio of the total mass of the prepolymer and the thermal polymerization initiator to the mass of the polar solvent is 2.5 to 7:93 to 97.5.
In the present application, the thermal polymerization initiator is azobisisobutyronitrile or methyl ethyl ketone peroxide; the polar solvent adopts N-methyl pyrrolidone or acetone.
Further, in step S1, the mass ratio of the prepolymer to the thermally initiated polymerization agent is 10 to 16:1.
in the application, polyacrylate and acrylate monomers in the prepolymer are provided with unsaturated carbon-carbon double bonds, wherein the viscosity average molecular weight of the polyacrylate is 100-1000, and the polyacrylate or the acrylate monomers can be heated to initiate polymerization reaction by a thermal initiation polymerization agent to obtain a polymer skeleton, wherein the prepolymer comprises at least one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate and poly (ethylene glycol) methyl ether acrylate; and the heating temperature is 60-80 ℃, at the temperature, the mixed solution positioned on the surface of the pole piece body is dried, and simultaneously, the thermal polymerization reaction is carried out, so that the polymer skeleton is obtained.
Further, in step S2, the mass ratio of the phosphate type solid electrolyte powder to the organic mixed solution is 20 to 30: 70-80.
In the application, the particle size of the phosphate type solid electrolyte powder is 10-50 nm, and the phosphate type solid electrolyte is obtained by grinding the phosphate type solid electrolyte and then is mixed with the organic mixed solution, so that the phosphate type solid electrolyte is uniformly dispersed in the organic mixed solution.
Further, in step S2, the mass ratio is 25-30: 70-75 (excluding 25:75) of phosphate type solid electrolyte powder into the organic mixed solution, stirring to obtain a first mixed solution, wherein the mass ratio of the first mixed solution to the second mixed solution is 20-25: and 75-80, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a second mixed solution.
Further, in step S3, the first mixed solution is coated on the surface of the pole piece body, and is heated, dried and thermally polymerized to obtain a first coating, and then the second mixed solution is coated on the surface of the first coating, and is heated, dried and thermally polymerized to obtain the pole piece.
According to the method, the first mixed solution and the second mixed solution are respectively obtained by adjusting the proportion of the mixed solutions, the content of the phosphate type solid electrolyte in the first mixed solution is larger than that of the phosphate type solid electrolyte in the second mixed solution, the first mixed solution, the drying and the thermal polymerization are sequentially coated on the surface of the pole piece, the second mixed solution is coated, the drying and the thermal polymerization are sequentially carried out, wherein the coating mode comprises but not limited to gravure coating, knife coating and spraying, the thickness of the first mixed solution coated on the surface of the pole piece body and the thickness of the second mixed solution coated on the surface of the first coating are 10-25 mu m, and the pole piece comprising the first coating and the second coating is obtained through the drying and the thermal polymerization, and the thickness of the first coating and the second coating is 5-15 mu m.
In a third aspect, the present application provides a solid state lithium battery comprising a pole piece as described above or a pole piece made according to a method of preparation as described above.
The beneficial effects of this application:
according to the lithium battery, the phosphate type solid electrolyte is mixed with the organic polymer solution with the thermal polymerization characteristic, the phosphate type solid electrolyte is directly coated on the surface of the pole piece body, thermal polymerization is initiated by heating, a polymer framework is formed to serve as a coating support, the flexibility of the phosphate type solid electrolyte can buffer huge volume expansion of a metal lithium negative electrode in the charge and discharge process, meanwhile, the phosphate type solid electrolyte is anchored to be distributed inside the polymer framework, further, a uniform organic/inorganic composite coating is obtained on the surface of the pole piece body, the solid electrolyte and the pole piece body can be isolated, side reactions of reducing and inserting lithium are reduced, the solid electrolyte is uniformly distributed, precipitation of lithium dendrites is restrained, the safety performance is further improved, meanwhile, the flexibility and cohesiveness of the polymer can enhance the stability of the coating, so that the coating effect is guaranteed, and the phosphate type solid electrolyte has the advantages of high ion conductivity and high safety, and long cycle life of the lithium battery can be ensured.
This application is further through setting up first coating at pole piece body surface, sets up the second coating at first coating surface, realizes that the content of phosphate type solid electrolyte is gradient distribution in the coating, can further improve lithium ion transmission's homogeneity, reduces the risk that lithium dendrite precipitated.
Drawings
Fig. 1 is a schematic structural view of a pole piece in embodiment 1 of the present application;
fig. 2 is a schematic structural view of a pole piece in embodiment 4 of the present application.
Description of the reference numerals
A-pole piece body; b-coating; 1-a polymer backbone; 2-phosphate type solid state electrolytes; b1-a first coating; b2-second coating.
Detailed Description
Further advantages and effects of the present invention will become readily apparent to those skilled in the art from the disclosure herein, by referring to the accompanying drawings and the preferred embodiments. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
The drawings provided in the following embodiments are merely to illustrate the basic concept of the present invention by way of illustration, and only the structures related to the present invention are shown in the drawings, not drawn according to the shape and size of the actual implementation.
The application provides a pole piece, which comprises a pole piece body and a coating layer positioned on the surface of the pole piece body, wherein the coating layer comprises a polymer framework with a three-dimensional network structure and phosphate type solid electrolyte distributed in the polymer framework, and the phosphate type solid electrolyte is lithium aluminum titanium phosphate or lithium aluminum germanium phosphate;
the content of the phosphate type solid electrolyte in the coating is 78-95 wt%;
the thickness of the coating is 10-30 mu m.
Further, the coating comprises a first coating and a second coating, wherein the first coating and the second coating both comprise a polymer framework and phosphate type solid electrolyte distributed in the polymer framework, the first coating is arranged on the surface of the pole piece body, and the second coating is arranged on the surface of the first coating.
Wherein the thickness of the first coating layer is 5-15 mu m, and the thickness of the second coating layer is 5-15 mu m.
The content m of the phosphate type solid electrolyte in the first coating layer and the content n of the phosphate type solid electrolyte in the second coating layer satisfy the following relationship:
m＞n。
the application also provides a preparation method of the pole piece, which comprises the following steps:
s1, according to the mass ratio of the total mass of the prepolymer and the thermal polymerization initiator to the mass of the polar solvent, the ratio is 2.5-7: 93 to 97.5, mixing a prepolymer, a thermal polymerization initiator and a polar solvent, and stirring to obtain an organic mixed solution, wherein the prepolymer is polyacrylate or acrylate monomer, and the mass ratio of the prepolymer to the thermal polymerization initiator is 10 to 16:1, a step of;
s2, according to the mass ratio of the phosphate type solid electrolyte powder to the organic mixed solution, the mass ratio is 20-30: 70-80, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a mixed solution;
and S3, coating the mixed solution on the surface of the pole piece body, heating, and drying and performing thermal polymerization to obtain the pole piece.
Wherein, in the step S1, the prepolymer comprises at least one of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate and poly (ethylene glycol) methyl ether acrylate; the thermal polymerization initiator adopts azodiisobutyronitrile or methyl ethyl ketone peroxide; the polar solvent adopts N-methyl pyrrolidone or acetone; the stirring speed is 50-500 rpm, and the stirring time is 0.5-1 h.
Wherein in step S2, phosphate type solid electrolyte powder is obtained by grinding phosphate type solid electrolyte, and the particle size of the phosphate type solid electrolyte powder is 10-50 nm; the stirring speed is 50-500 rpm, and the stirring time is 1-3 h.
Wherein, in the step S3, the thickness of the coating mixed solution is 20-50 mu m; the heating temperature is 60-80 ℃.
Further, in step S2, the mass ratio is 25-30: 70-75 (excluding 25:75) of phosphate type solid electrolyte powder into the organic mixed solution, stirring to obtain a first mixed solution, wherein the mass ratio of the first mixed solution to the second mixed solution is 20-25: and 75-80, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a second mixed solution.
Further, in step S3, the first mixed solution is coated on the surface of the pole piece body, and is heated, dried and thermally polymerized to obtain a first coating, and then the second mixed solution is coated on the surface of the first coating, and is heated, dried and thermally polymerized to obtain the pole piece.
Wherein the thickness of the first mixed solution is 10-25 mu m, and the thickness of the second mixed solution is 10-25 mu m.
The invention also provides a solid-state lithium battery, which comprises the pole piece or the pole piece manufactured according to the manufacturing method.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
In the application, the prepared pole piece is used as a negative electrode, and then the solid-state lithium battery is manufactured by matching with a high-nickel ternary positive electrode, and the method comprises the following steps: and directly performing Z-shaped lamination in a high-nickel ternary positive electrode/negative electrode mode, performing hot pressing, then putting into an aluminum film, assembling, drying and forming, dripping a trace amount of electrolyte into the high-nickel ternary positive electrode after drying, soaking and sealing, and forming the obtained soft-package battery to obtain the solid-state lithium battery.
Wherein the thickness of the prepared pole piece is 60-80 mu m.
Wherein the high nickel ternary anode is NCM811 or NCM9055.
Wherein the electrolyte comprises lithium salt and organic solvent, and the lithium salt is LiPF 6 Or LiBF 4 Or a combination of both, the organic solvent comprising at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), and dimethyl carbonate (DMC).
Wherein the electrolyte consumption is positive electrode surface capacity (Ah) and liquid injection coefficient (g/Ah), and the liquid injection coefficient is 0.1-0.2.
In the application, performance test is carried out on the prepared pole piece, and the test method comprises the following steps: (1) Laminating and assembling the obtained pole piece and a high-nickel ternary positive electrode NCM811, adding 0.1g of electrolyte to infiltrate the positive electrode, and performing 0.5C/0.5C cyclic charge-discharge test at 25 ℃ to obtain a soft-package battery core with the capacity of 1Ah after formation; (2) And assembling the obtained pole piece and the metal lithium negative electrode lamination to obtain a lithium symmetric battery, and performing 0.05C/0.05C cyclic charge and discharge test on the lithium symmetric battery.
Example 1
Referring to fig. 1, the present embodiment provides a pole piece.
As shown in fig. 1, the pole piece of the embodiment includes a pole piece body a and a coating layer B located on the surface of the pole piece body a, wherein the coating layer B includes a polymer skeleton 1 with a three-dimensional network structure and phosphate type solid electrolyte 2 distributed inside the polymer skeleton 1, and the phosphate type solid electrolyte 2 is lithium titanium aluminum phosphate.
The content of lithium aluminum titanium phosphate in the coating B was 90.9wt%.
The thickness of coating B was 10. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, according to the mass ratio of total mass of polyethylene glycol diacrylate and azodiisobutyronitrile to mass of N-methyl pyrrolidone of 2.5:97.5 respectively taking 18g of polyethylene glycol diacrylate, 1.125g of azobisisobutyronitrile and 745.875g of N-methylpyrrolidone, mixing, and stirring for 0.5h at a rotation speed of 500rpm to obtain an organic mixed solution, wherein the mass ratio of the polyethylene glycol diacrylate to the azobisisobutyronitrile is 16:1, a step of;
s2, according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution, the mass ratio is 30:70 adding 327.86g of lithium aluminum titanium phosphate powder with the particle size of 10nm into an organic mixed solution, stirring for 1h at the rotating speed of 500rpm to obtain a mixed solution, and measuring the viscosity of the mixed solution to be 300 mPas;
and S3, coating the mixed solution on the surface of the pole piece body with the thickness of 20 mu m, heating to 60 ℃, and drying and performing thermal polymerization to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Example 2
The embodiment provides a pole piece.
The pole piece of this embodiment differs from embodiment 1 in that: the content of the lithium aluminum titanium phosphate in the coating B is 87.0wt%; the thickness of coating B was 20. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, according to the mass ratio of total mass of polyethylene glycol dimethacrylate and azodiisobutyronitrile to mass of N-methyl pyrrolidone of 5:95 respectively taking 18g of polyethylene glycol dimethacrylate, 1.38g of azodiisobutyronitrile and 368.22g of N-methylpyrrolidone, mixing, and stirring for 0.8h at a rotating speed of 200rpm to obtain an organic mixed solution, wherein the mass ratio of the polyethylene glycol dimethacrylate to the azodiisobutyronitrile is 13:1, a step of;
s2, according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution, 25:75 adding 129.2g of lithium aluminum titanium phosphate powder with the particle size of 30nm into the organic mixed solution, stirring for 2 hours at a rotating speed of 200rpm to obtain a mixed solution, and measuring the viscosity of the mixed solution to be 567 mPa.s;
and S3, coating the mixed solution on the surface of the pole piece body with the thickness of 36 mu m, heating to 70 ℃, and drying and performing thermal polymerization to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Example 3
The embodiment provides a pole piece.
The pole piece of this embodiment differs from embodiment 1 in that: the phosphate type solid electrolyte is lithium aluminum germanium phosphate, and the content of the lithium aluminum germanium phosphate in the coating B is 78.1wt%; the thickness of coating B was 30. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, according to the mass ratio of the total mass of the ethoxylated trimethylolpropane triacrylate and the methyl ethyl ketone peroxide to the mass of the acetone, the ratio is 7:93 respectively taking 18g of ethoxylated trimethylolpropane triacrylate, 1.8g of methyl ethyl ketone peroxide and 263g of acetone, mixing, and stirring for 1h at a rotating speed of 50rpm to obtain an organic mixed solution, wherein the mass ratio of the ethoxylated trimethylolpropane triacrylate to the methyl ethyl ketone peroxide is 10:1, a step of;
s2, according to the mass ratio of the lithium aluminum germanium phosphate powder to the organic mixed solution, the mass ratio is 20:80 adding 70.7g of lithium aluminum germanium phosphate powder with the particle size of 20nm into the organic mixed solution, stirring for 3 hours at the rotating speed of 50rpm to obtain a mixed solution, and measuring the viscosity of the mixed solution to be 1000 mPa.s;
and S3, coating the mixed solution on the surface of the pole piece body at the thickness of 50 mu m, heating to 80 ℃, and drying and performing thermal polymerization to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Example 4
Referring to fig. 2, the present embodiment provides a pole piece.
As shown in fig. 2, the pole piece of the embodiment includes a pole piece body a, a first coating B1 located on the surface of the pole piece body a, and a second coating B2 located on the surface of the first coating B1, where the first coating B and the second coating B2 each include a polymer skeleton 1 with a three-dimensional network structure and phosphate type solid electrolyte 2 distributed inside the polymer skeleton 1, and the phosphate type solid electrolyte 2 is lithium aluminum titanium phosphate.
The content m of the phosphate type solid electrolyte in the first coating layer B1 was 94.5wt%, and the content n of the phosphate type solid electrolyte in the second coating layer B2 was 90.9wt%.
The thickness of the first coating layer B1 was 5. Mu.m, and the thickness of the second coating layer B2 was 5. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, according to the mass ratio of total mass of polyethylene glycol diacrylate and azodiisobutyronitrile to mass of N-methyl pyrrolidone of 2.5:97.5 respectively taking 18g of polyethylene glycol diacrylate, 1.125g of azobisisobutyronitrile and 745.875g of N-methylpyrrolidone, mixing, and stirring for 0.5h at a rotation speed of 500rpm to obtain an organic mixed solution, wherein the mass ratio of the polyethylene glycol diacrylate to the azobisisobutyronitrile is 16:1, a step of;
s2, according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution, the mass ratio is 30:70 adding 327.86g of lithium aluminum titanium phosphate powder with the particle size of 10nm into an organic mixed solution, stirring for 1h at a rotating speed of 500rpm to obtain a first mixed solution, measuring the viscosity of the first mixed solution to be 327 mPa.s, and according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution of 20:80 adding 191.25g of lithium aluminum titanium phosphate powder with the particle size of 10nm into the organic mixed solution, stirring for 1h at the rotating speed of 500rpm to obtain a second mixed solution, and measuring the viscosity of the second mixed solution to be 200 mPa.s;
s3, coating the first mixed solution on the surface of the pole piece body at the thickness of 10 mu m, heating to 60 ℃, drying and thermally polymerizing to obtain a first coating, coating the second mixed solution on the surface of the first coating at the thickness of 10 mu m, heating to 60 ℃, and drying and thermally polymerizing to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Example 5
The embodiment provides a pole piece.
The pole piece of this embodiment differs from that of embodiment 4 in that: the phosphate type solid electrolyte 2 is lithium titanium aluminum phosphate; the content m of the phosphate type solid electrolyte in the first coating B1 was 88.6wt%, and the content n of the phosphate type solid electrolyte in the second coating B2 was 85.0wt%; the thickness of the first coating layer B1 was 10. Mu.m, and the thickness of the second coating layer B2 was 10. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, the ratio of the total mass of poly (ethylene glycol) methyl ether acrylate and azodiisobutyronitrile to the mass of N-methyl pyrrolidone is 5:95 respectively taking 18g of poly (ethylene glycol) methyl ether acrylate, 1.38g of azodiisobutyronitrile and 368.22g of N-methylpyrrolidone, mixing, and stirring for 0.8h at a rotating speed of 200rpm to obtain an organic mixed solution, wherein the mass ratio of the poly (ethylene glycol) methyl ether acrylate to the azodiisobutyronitrile is 13:1, a step of;
s2, according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution, 28:72 adding 150.73g of lithium aluminum titanium phosphate powder with the particle size of 30nm into the organic mixed solution, stirring for 2 hours at the rotating speed of 200rpm to obtain a first mixed solution, measuring the viscosity of the first mixed solution to be 610 mPas, and according to the mass ratio of the lithium aluminum titanium phosphate powder to the organic mixed solution, obtaining a first mixed solution with the viscosity of 610 mPas: 78 adding 109.32g of lithium aluminum titanium phosphate powder with the particle size of 30nm into the organic mixed solution, stirring for 2 hours at a rotating speed of 200rpm to obtain a second mixed solution, and measuring the viscosity of the second mixed solution to be 523 mPa.s;
s3, coating the first mixed solution on the surface of the pole piece body at the thickness of 18 mu m, heating to 70 ℃, drying and thermally polymerizing to obtain a first coating, coating the second mixed solution on the surface of the first coating at the thickness of 18 mu m, heating to 70 ℃, and drying and thermally polymerizing to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Example 6
The embodiment provides a pole piece.
The pole piece of this embodiment differs from that of embodiment 4 in that: the phosphate type solid electrolyte 2 is lithium aluminum germanium phosphate; the content m of the phosphate type solid electrolyte in the first coating B1 was 83.4wt%, and the content n of the phosphate type solid electrolyte in the second coating B2 was 81.9wt%; the thickness of the first coating layer B1 was 15. Mu.m, and the thickness of the second coating layer B2 was 15. Mu.m.
The preparation method of the pole piece comprises the following steps:
s1, according to the mass ratio of total mass of tetraethylene glycol dimethacrylate and azodiisobutyronitrile to mass of N-methyl pyrrolidone of 7:93 respectively taking 18g of tetraethylene glycol dimethacrylate, 1.8g of azodiisobutyronitrile and 263g of N-methylpyrrolidone, mixing, and stirring for 1h at a rotating speed of 50rpm to obtain an organic mixed solution, wherein the mass ratio of the tetraethylene glycol dimethacrylate to the azodiisobutyronitrile is 10:1, a step of;
s2, according to the mass ratio of the lithium aluminum germanium phosphate powder to the organic mixed solution, 26:74 adding 99.36g of lithium aluminum germanium phosphate powder with the particle size of 50nm into the organic mixed solution, stirring for 3 hours at the rotating speed of 50rpm to obtain a first mixed solution, measuring the viscosity of the first mixed solution to be 941 mPa.s, and according to the mass ratio of the lithium aluminum germanium phosphate powder to the organic mixed solution, the mass ratio of the lithium aluminum germanium phosphate powder to the organic mixed solution is 24: adding 89.31g of lithium aluminum germanium phosphate powder with the particle size of 50nm into the organic mixed solution, stirring for 3 hours at the rotating speed of 50rpm to obtain a second mixed solution, and measuring the viscosity of the second mixed solution to be 887 mPa.s;
s3, coating the first mixed solution on the surface of the pole piece body at the thickness of 25 mu m, heating to 80 ℃, drying and thermally polymerizing to obtain a first coating, coating the second mixed solution on the surface of the first coating at the thickness of 25 mu m, heating to 80 ℃, and drying and thermally polymerizing to obtain the pole piece.
And performing performance test on the pole piece prepared in the embodiment.
Comparative example 1
This comparative example provides a pole piece that includes only the pole piece body and is not treated at all.
The performance test was performed on the pole pieces of this comparative example.
The results of the performance tests of examples 1 to 6 and comparative example 1 are shown in Table 1.
Table 1 results of performance tests of examples 1 to 6 and comparative example 1
| Source | 0.5C/0.5C cycle capacity retention | Cycle period of lithium symmetrical battery |
| Example 1 | 80％@300cycle | 500 |
| Example 2 | 80％@400cycle | 600 |
| Example 3 | 80％@375cycle | 580 |
| Example 4 | 80％@520cycle | 700 |
| Example 5 | 80％@560cycle | 720 |
| Example 6 | 80％@500cycle | 670 |
| Comparative example 1 | 80％@100cycle | 300 |
( And (3) injection: illustratively, "80% @300cycle" means that the battery capacity of the soft pack cell after 300 cycles of charge and discharge is 80% of the initial battery capacity; and taking the voltage dip point as the cycle end point in the cycle period of the lithium symmetrical battery, and separating out lithium dendrites at the moment. )
As can be seen from the analysis results of the performance tests of examples 1 to 3 and comparative example 1 in Table 1, the soft-pack battery cells prepared from the pole pieces prepared in examples 1 to 3 were subjected to a 0.5C/0.5C cycle charge-discharge test, and the number of cycles in which the battery capacity after the cycle was 80% of the initial battery capacity was 300 times or more; the prepared lithium-symmetric battery was subjected to 0.05C/0.05C cycle charge-discharge test, the cycle period was 500 and above, and it was apparent that the 0.5C/0.5C cycle capacity retention rate and the lithium-symmetric battery cycle period of comparative example 1 were lower than those of examples 1 to 3. The result shows that the phosphate type solid electrolyte is mixed with the organic polymer solution with the thermal polymerization characteristic, and is directly coated on the surface of the pole piece body, and the thermal polymerization is initiated by heating, so that a uniform organic/inorganic composite coating is obtained on the surface of the pole piece body, the precipitation of lithium dendrites is inhibited, and the cycle life of the lithium battery is prolonged.
As can be seen from the analysis results of the performance tests of examples 4 to 6 and examples 1 to 3 in Table 1, the soft-pack battery cells prepared from the pole pieces prepared in examples 4 to 6 were subjected to a 0.5C/0.5C cycle charge-discharge test, and the number of cycles in which the battery capacity after the cycle was 80% of the initial battery capacity was 500 times or more; the cycle period of the prepared lithium symmetrical battery subjected to the 0.05C/0.05C cycle charge and discharge test reaches 670 and above, and compared with the cycle capacity retention rate and the cycle period of the lithium symmetrical battery of examples 1-3,0.5C/0.5C, the cycle period of the lithium symmetrical battery is improved to a certain extent, and the lithium symmetrical battery is obviously superior to examples 1-3. This result shows that this application is further through setting up first coating at pole piece body surface, sets up the second coating at first coating surface, realizes that the content of phosphate type solid electrolyte is gradient distribution in the coating, and the content of phosphate type solid electrolyte is greater than the second coating in the first coating, has further improved lithium ion transmission's homogeneity, has reduced the risk that lithium dendrite precipitated, has prolonged lithium cell's cycle life.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. It is therefore intended that all equivalent modifications and changes made by those skilled in the art without departing from the spirit and technical spirit of the present invention shall be covered by the appended claims.
Claims (12)
1. A pole piece, characterized in that: the pole piece comprises a pole piece body and a coating layer positioned on the surface of the pole piece body, wherein the coating layer comprises a polymer framework with a three-dimensional network structure and phosphate type solid electrolyte distributed in the polymer framework, and the phosphate type solid electrolyte is lithium aluminum titanium phosphate or lithium aluminum germanium phosphate.
2. A pole piece according to claim 1, characterized in that: the content of the phosphate type solid electrolyte in the coating is 78-95 wt%.
3. A pole piece according to claim 1, characterized in that: the thickness of the coating is 10-30 mu m.
4. A pole piece according to claim 1, characterized in that: the coating comprises a first coating and a second coating, wherein the first coating and the second coating both comprise a polymer framework and phosphate type solid electrolyte distributed in the polymer framework, the first coating is arranged on the surface of the pole piece body, and the second coating is arranged on the surface of the first coating.
5. A pole piece according to claim 4, characterized in that: the content m of the phosphate type solid electrolyte in the first coating layer and the content n of the phosphate type solid electrolyte in the second coating layer satisfy the following relationship:
m＞n。
6. a method of manufacturing a pole piece according to any one of claims 1 to 5, comprising the steps of:
s1, mixing a prepolymer, a thermal polymerization initiator and a polar solvent, and stirring to obtain an organic mixed solution, wherein the prepolymer is polyacrylate or acrylate monomer;
s2, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a mixed solution;
and S3, coating the mixed solution on the surface of the pole piece body, heating, and drying and performing thermal polymerization to obtain the pole piece.
7. The method of manufacturing according to claim 6, wherein: in step S1, the ratio of the total mass of the prepolymer and the thermal polymerization initiator to the mass of the polar solvent is 2.5 to 7:93 to 97.5.
8. The method of manufacturing according to claim 7, wherein: in the step S1, the mass ratio of the prepolymer to the thermally initiated polymerizer is 10-16: 1.
9. the method of manufacturing according to claim 6, wherein: in the step S2, the mass ratio of the phosphate type solid electrolyte powder to the organic mixed solution is 20-30: 70-80.
10. The method of manufacturing according to claim 6, wherein: in the step S2, the mass ratio is 25-30: 70-75 (excluding 25:75) of phosphate type solid electrolyte powder into the organic mixed solution, stirring to obtain a first mixed solution, wherein the mass ratio of the first mixed solution to the second mixed solution is 20-25: and 75-80, adding phosphate type solid electrolyte powder into the organic mixed solution, and stirring to obtain a second mixed solution.
11. The method of manufacturing according to claim 10, wherein: in the step S3, the first mixed solution is coated on the surface of the pole piece body, heating is carried out, drying and thermal polymerization are carried out, a first coating is obtained, the second mixed solution is coated on the surface of the first coating, heating is carried out, and drying and thermal polymerization are carried out, so that the pole piece is obtained.
12. A solid state lithium battery comprising a pole piece according to any one of claims 1 to 5 or a pole piece produced according to the production method of any one of claims 6 to 11.
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