CN110828883A - Lithium ion battery, preparation method thereof and electric vehicle - Google Patents
Lithium ion battery, preparation method thereof and electric vehicle Download PDFInfo
- Publication number
- CN110828883A CN110828883A CN201810893618.3A CN201810893618A CN110828883A CN 110828883 A CN110828883 A CN 110828883A CN 201810893618 A CN201810893618 A CN 201810893618A CN 110828883 A CN110828883 A CN 110828883A
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- Prior art keywords
- polymer
- electrolyte layer
- ion battery
- lithium ion
- lithium
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 97
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 97
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 239000000919 ceramic Substances 0.000 claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005524 ceramic coating Methods 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 13
- 239000001989 lithium alloy Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims description 83
- 239000002002 slurry Substances 0.000 claims description 63
- 229920006254 polymer film Polymers 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 38
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 35
- 239000007773 negative electrode material Substances 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims description 24
- 159000000002 lithium salts Chemical class 0.000 claims description 24
- 239000002033 PVDF binder Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 23
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- 238000000034 method Methods 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
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- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 7
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 7
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910013188 LiBOB Inorganic materials 0.000 claims description 6
- 229910010941 LiFSI Inorganic materials 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
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- YZFWTZACSRHJQD-UHFFFAOYSA-N ciglitazone Chemical compound C=1C=C(CC2C(NC(=O)S2)=O)C=CC=1OCC1(C)CCCCC1 YZFWTZACSRHJQD-UHFFFAOYSA-N 0.000 claims description 4
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- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 229910012516 LiNi0.4Co0.2Mn0.4O2 Inorganic materials 0.000 claims description 3
- 229910012528 LiNi0.4Co0.4Mn0.2O2 Inorganic materials 0.000 claims description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 3
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 claims description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 claims description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 3
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 4
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention discloses a lithium ion battery, a preparation method thereof and an electric vehicle, wherein the lithium ion battery comprises a positive electrode, a negative electrode and a composite electrolyte layer positioned between the positive electrode and the negative electrode, wherein the composite electrolyte layer comprises a gel polymer electrolyte layer, a solid polymer electrolyte layer positioned on the surface of the gel polymer electrolyte layer and a porous ceramic coating positioned on the surface of the solid polymer electrolyte layer; the gel polymer electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode; the porous ceramic coating includes ceramic particles, a dispersant, and a first binder. When the negative electrode is metal lithium or lithium alloy, the composite electrolyte layer can reduce side reaction between the electrolyte and the negative electrode, and can effectively buffer the volume expansion effect of the negative electrode, so that the cycle performance and the safety performance of the whole battery are greatly improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium ion battery, a preparation method thereof and an electric vehicle adopting the lithium ion battery.
Background
With the continuous improvement of the energy density of the lithium ion battery, the traditional graphite material (the theoretical specific capacity is only 372mAh/g) is far from meeting the requirements of people, and people have developed a plurality of negative electrode materials with high specific capacity successively, wherein the specific capacity of a metal lithium negative electrode is 3860mAh/g, the potential is 3.04V (vs standard hydrogen electrode), and the negative electrode material is very suitable for being used as a battery negative electrode.
The gel polymer electrolyte has good machining performance and film forming property, and forms a stable interface with the metal lithium, so that the leakage of the electrolyte can be avoided, and the safety is high; however, when the gel polymer electrolyte is directly contacted with the lithium metal negative electrode, the electrolyte still exists in the gel polymer electrolyte, and reacts with the lithium metal, causing deterioration of electrolytic performance, and the metal lithium negative electrode has a large volume change (e.g., expansion and contraction) during charge and discharge, which not only deforms the solid electrolyte in contact with the lithium metal and destroys the solid electrolyte, but also causes defects such as cracking, pulverization, structural collapse of the negative electrode material, and the like; in addition, lithium metal batteries gradually generate lithium dendrites from lithium metal electrodes during repeated charge and discharge cycles, pass through an electrolyte, and finally contact with a positive electrode, causing internal short circuits of the batteries, which not only cause degradation of battery capacity but also adversely affect safety thereof.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a composite electrolyte layer positioned between the positive electrode and the negative electrode, and is characterized in that the composite electrolyte layer comprises a gel polymer electrolyte layer, a solid polymer electrolyte layer positioned on the surface of the gel polymer electrolyte layer and a porous ceramic coating positioned on the surface of the solid polymer electrolyte layer; the gel polymer electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode; the porous ceramic coating includes ceramic particles, a dispersant, and a first binder.
Preferably, the negative electrode includes a negative electrode active material, and the negative electrode active material is metallic lithium or a lithium alloy.
Preferably, the porosity of the porous ceramic coating is 30-50%.
Preferably, the average pore diameter of the porous ceramic coating is 50-400 nm.
Preferably, the average particle size of the ceramic particles is 100 to 500 nm.
Preferably, the ceramic particles comprise Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2The dispersant comprises one or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine; the first binder comprises one or more of polyvinylidene fluoride and copolymers thereof, styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene diene monomer, polyethylene oxide and copolymers thereof, polyacrylate, polyamide, polyacrylic acid, polyurethane, polyvinyl ethyl ether and polyacrylonitrile.
Preferably, the content of the ceramic particles is 90-96.8% by taking the total mass of the porous ceramic coating as a reference; the content of the dispersing agent is 0.2-2%, and the content of the first binder is 3-8%.
Preferably, the solid polyelectrolyte comprises a polymer matrix and a lithium salt dispersed in the polymer matrix.
Preferably, the polymer matrix is one or more of polyethylene oxide, polyvinylidene fluoride and polymethyl methacrylate; the lithium salt is selected from LiTFSI and LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI.
Preferably, the gel polymer electrolyte further comprises a polymer film and an electrolyte adsorbed in the polymer film.
Preferably, the polymer film comprises one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, isopropyl polycyanoacrylate, polyphenylene sulfide, and polyvinyl chloride.
Preferably, the thickness of the gel polymer electrolyte layer is 7 to 30 μm, the thickness of the solid polymer layer is 0.5 to 3 μm, and the thickness of the porous ceramic coating layer is 0.5 to 1.5 μm.
Preferably, the gel polyelectrolyte layer and/or the solid polymer electrolyte layer further comprise inorganic nanoparticles; the inorganic nanoparticles are selected from Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of (a).
Preferably, the inorganic nanoparticles in the gel polymer electrolyte layer account for 1-10% of the total mass of the gel polymer electrolyte layer; the inorganic nanoparticles in the solid polymer electrolyte layer account for 3-10% of the total mass of the solid polymer electrolyte layer.
Preferably, the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the surface of the positive electrode current collector; the positive electrode material comprises a positive electrode active material selected from LiFePO4、LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/ 3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.8Co0.15Al0.05O2One or more of (a).
The second object of the invention provides a preparation method of a lithium ion battery, which comprises the steps of coating a first polymer slurry on a support body, and drying to obtain a polymer film; sequentially coating the second polymer slurry and the ceramic slurry on the surface of the polymer film, and drying to obtain a composite electrolyte; and then pressing and molding the anode, the composite electrolyte and the cathode, and finally adsorbing electrolyte in a polymer film to obtain the lithium ion battery, wherein a gel polymer electrolyte layer in the composite electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode.
Preferably, the first polymer slurry comprises a first polymer and a first solvent, and the content of the first polymer is 5-20% by weight of the total weight of the first polymer slurry; the first polymer is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile system, poly (isopropyl cyanoacrylate) system, polyphenylene sulfide and polyvinyl chloride; the first solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile;
the second polymer slurry comprises a second polymer, a lithium salt and a second solvent, wherein the content of the second polymer is 1-30% and the content of the lithium salt is 0.2-5% based on the total weight of the second polymer slurry; the second polymer is one or more of polyethylene oxide, polyvinylidene fluoride and polymethyl methacrylate; the lithium salt is selected from LiTFSI and LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI; the second solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile;
the ceramic slurry comprises ceramic particles, a dispersing agent, a binder and a third solvent, wherein the ceramic particles account for 5-40% of the total weight of the ceramic slurry, the dispersing agent accounts for 0.2-2% of the total weight of the ceramic slurry, and the binder accounts for 3-8% of the total weight of the ceramic slurry; the ceramic particles are selected from Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of; the dispersing agent is selected from one or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine; the binder comprises polyvinylidene fluoride and its copolymer, styrene butadiene rubber, nitrile butadiene rubber, ethylene propylene diene monomer, polyethylene oxide and its copolymer, polyacrylate, and polyimideOne or more of amine, polyacrylic acid, polyurethane, polyvinyl ethyl ether and polyacrylonitrile; the third solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile.
Preferably, the support is selected from one of a polytetrafluoroethylene plate, a polyimide plate, a polyethylene terephthalate plate, a polyethylene plate, and a polypropylene plate.
Preferably, the first polymer paste and/or the second polymer paste further comprise inorganic nanoparticles; the inorganic nanoparticles are selected from Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of (a).
The third object of the invention is to provide an electric vehicle, which contains the lithium ion battery.
Compared with the prior art, the lithium ion battery has the beneficial effects that the capacity of the battery can be greatly improved by using the metal lithium or the lithium alloy as the cathode in the prior art, but the cycling performance of the battery is greatly reduced due to the fact that the metal lithium and the electrolyte are easy to generate side reaction, a solid polymer electrolyte layer and a porous ceramic coating are arranged between the gel polymer electrolyte and the lithium metal or the lithium alloy cathode and used as a barrier layer, and the barrier layer can prevent the electrolyte in the gel polymer electrolyte from corroding the metal lithium or the lithium alloy cathode; the porous ceramic coating in the barrier layer can also buffer the volume expansion effect of the metal lithium or lithium alloy cathode in the charging cycle process, and the two layers have a synergistic effect, so that the cycle performance and the safety performance of the battery are greatly improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention will be further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The lithium ion battery provided by the invention comprises a positive electrode, a negative electrode and a composite electrolyte layer positioned between the positive electrode and the negative electrode, and is characterized in that the composite electrolyte layer comprises a gel polymer electrolyte layer, a solid polymer electrolyte layer positioned on the surface of the gel polymer electrolyte layer and a porous ceramic coating positioned on the surface of the solid polymer electrolyte layer; the gel polymer electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode; the porous ceramic coating includes ceramic particles, a dispersant, and a first binder.
Preferably, the negative electrode comprises a negative electrode material, and the negative electrode material is metallic lithium or a lithium alloy.
In the invention, the negative electrode comprises a negative electrode current collector and a negative electrode material positioned on the surface of the negative electrode current collector; the negative electrode material includes a negative electrode active material including lithium metal or a lithium alloy. Specifically, the lithium metal negative active material comprises one of a lithium foil, a lithium film, stabilized lithium powder and a lithium ribbon; the lithium alloy comprises lithium-silicon-carbon or an alloy formed by one or more of boron, gallium, indium, aluminum, phosphorus, lead, germanium and tin and lithium; the lithium-silicon-carbon negative electrode active material comprises a silicon-carbon negative electrode which is pre-embedded with lithium, and a negative electrode active material which is compounded by the silicon-carbon negative electrode, a lithium belt, lithium powder, a lithium film and the like; the negative current collector comprises one of copper foil, copper mesh, nickel foil, foam copper, foam nickel, stainless steel mesh and stainless steel band. When the composite electrolyte layer is adopted, the electrolyte can be effectively prevented from corroding the negative electrode, and the volume expansion effect of the metal lithium or lithium alloy negative electrode in the charging cycle process can be buffered, so that the cycle performance and the safety performance of the battery are greatly improved.
Preferably, the porosity of the porous ceramic coating is 30-50%.
The porous ceramic coating arranged between the gel polymer electrolyte and the lithium metal or lithium alloy negative electrode has good chemical inertness, improves the compatibility between the gel polymer electrolyte and the negative electrode active material, and simultaneously, in the process of repeated lithium ion desorption, the porous structure can limit and buffer the volume expansion generated in the charge-discharge process of the negative electrode active material, reduce the pulverization and shedding of the negative electrode active material and prolong the service life of the battery. After a plurality of experiments, the inventor of the application finds that when the porosity of the porous ceramic coating is controlled in the range and the composite electrolyte layer is applied to a lithium ion battery, the composite electrolyte layer is beneficial to the transmission of lithium ions and can effectively regulate and control the volume expansion of a negative electrode active material, and further the safety performance and the cycle performance of the battery are improved.
Preferably, the average pore diameter of the porous ceramic coating is 50-400 nm, and after multiple experiments, the inventor of the application finds that the average pore diameter of the porous ceramic coating is too large, the volume expansion of the negative active material generated in the charging and discharging process cannot be effectively regulated, and on the contrary, the average pore diameter is too small, so that the transmission of lithium ions is not facilitated, the ion conductivity of the whole battery is further influenced, the average pore diameter is controlled to be 50-400 nm, and when the composite electrolyte layer is applied to a lithium ion battery, the transmission of the lithium ions is facilitated, the volume expansion of the negative active material can be effectively regulated, and the safety performance and the cycle performance of the battery are further improved.
Preferably, the average particle size of the ceramic particles is 100-500 nm, and multiple experiments show that when the average particle size of the ceramic particles is controlled within the range, a uniform ceramic coating can be obtained, the ceramic coating also has proper pore size and porosity, the volume expansion of the negative active material in the charge-discharge cycle process can be controlled effectively, and the cycle performance and the safety performance of the battery are improved.
Preferably, the ceramic particles comprise Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of; the ceramic particles exhibit good compatibility with a negative electrode active material and a polymer solid electrolyte; the dispersing agent comprises one or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine, and the dispersing agent has the function of uniformly dispersing ceramic particles so that the porous ceramic coating can be uniformly coated on the solid polymer electrolyte layerA surface; the first binder comprises one or more of polyvinylidene fluoride and copolymers thereof, styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene diene monomer, polyethylene oxide and copolymers thereof, polyacrylate, polyamide, polyacrylic acid, polyurethane, polyvinyl ethyl ether and polyacrylonitrile; the binder is used for improving the binding force between the ceramic coating and the solid polymer electrolyte layer; by taking the total mass of the porous ceramic coating as a reference, the content of the ceramic particles is 90-96.8%, the content of the dispersing agent is 0.2-2%, and the content of the first binder is 3-8%.
In the present invention, the solid polymer electrolyte layer is a solid polymer electrolyte layer well known in the battery field, and for example, specifically includes a polymer matrix and a lithium salt dispersed in the polymer matrix; the polymer matrix is selected from one or more of polyethylene oxide, polyvinylidene fluoride and polymethyl methacrylate; the polymer matrix may be a mixture of the above polymer matrices, or a copolymer based on the above polymers or a cross-linked polymer based on the above polymer system; the lithium salt is conventional in the battery field, and specifically, the lithium salt is selected from LiTFSI and LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI.
In the present application, a solid polymer electrolyte layer is disposed between a gel polymer electrolyte and a porous ceramic coating, and compared with the prior art in which an inorganic solid electrolyte is disposed between a gel polymer electrolyte and a negative electrode active material, since an ion conduction mechanism in the polymer electrolyte layer is that anions and lithium ions move simultaneously, and an ion conduction mechanism in the inorganic electrolyte layer is that only lithium ions move, the ion conduction mechanisms of the polymer electrolyte layer and the inorganic electrolyte layer are different, concentration polarization exists between the polymer electrolyte layer and the inorganic electrolyte layer, and the concentration polarization may affect the ion conductivity of a contact interface between the polymer electrolyte layer and the inorganic electrolyte layer. In the application, the lithium ion conduction mechanisms of the gel polymer electrolyte and the solid polymer electrolyte are the same, concentration polarization in the prior art can be avoided, the interface characteristic between the gel polymer electrolyte and the solid polymer electrolyte is better, lithium ions can be transmitted conveniently, the solid polymer electrolyte can react with lithium metal or lithium alloy deposited in the porous ceramic coating to generate a stable SEI layer, and therefore the electrolyte in the gel polymer electrolyte can be prevented from penetrating into the surface of a negative electrode active material to cause side reaction, lithium dendrites formed on the surface of the lithium metal can be prevented from puncturing the gel polymer electrolyte, and internal short circuit of a battery is avoided.
In the present invention, the gel polymer electrolyte is a polymer electrolyte layer well known in the battery field, and for example, specifically includes a polymer film and an electrolytic solution adsorbed in the polymer film for the above-mentioned gel polymer electrolyte; the polymer film material is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile system, polycyanoacrylate isopropyl system, polyphenylene sulfide and polyvinyl chloride, the polymer film can also be a mixture of the polymers, and can also be a copolymer based on the polymers or a cross-linked product of the polymers, and the like; the electrolyte is an electrolyte commonly used in the art, and specifically, the electrolyte includes a nonaqueous organic solvent and a lithium salt, the nonaqueous organic solvent is selected from one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethylene carbonate, 1.3-propyl sultone, 1.4-butyrolactone sulfonate, ethylene chlorocarbonate, propylene dichlorocarbonate, propylene trichlorocarbonate, fluoroethylene carbonate, propylene fluorocarbonate, propylene difluorocarbonate, propylene trifluorocarbonate, 1, 2-dimethoxyethane, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, tetrahydrofuran, and 4-methyl-1, 3-dioxolane, and the lithium salt can be various lithium salts commonly used in the art and added in the electrolyte, specifically, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorosilicate, lithium bis (oxalato) borate, lithium chloride, lithium bromide, LiCF3SO3, LiC (CF3SO2)3, LiB (C2O4)2, Li2Al (CSO3C14), LiP (C6H4O2)3, LiPF3(C2F5)3, LiN (CF3SO2)2, LiN (SiC3Hg) 2; the concentration of the lithium salt can vary within a wide range, and preferably, the concentration of the lithium salt is 0.5 to 2.0 mol/L; in addition, various functional additives such as film forming additives or flame retardants can be added into the electrolyte.
According to the lithium ion battery provided by the invention, the thickness of each layer in the composite electrolyte layer fluctuates in a large range, preferably, the thickness of the gel polymer electrolyte layer is 7-30 μm, the thickness of the solid polymer layer is 0.5-3 μm, and the thickness of the porous ceramic coating is 0.5-1.5 μm, after experiments, the applicant of the invention finds that the thickness of each layer is controlled in a reasonable range, the porous ceramic coating can effectively control and adjust the volume expansion of the negative electrode active material in the charge-discharge cycle process, the solid polymer layer can effectively isolate the side reaction between the electrolyte and the negative electrode active material in the gel polymer, can effectively inhibit the formation of lithium dendrite, and can form a stable SEI film at the position contacted with the negative electrode active material, and the gel polymer electrolyte layer can ensure the transmission of lithium ions, the three layers are compounded together, so that the charge-discharge cycle and the safety performance of the battery can be improved.
In order to improve the conductivity of the electrolyte layer of the gel polymer and the solid polymer electrolyte layer, the solid polymer electrolyte layer and/or the gel polymer electrolyte layer preferably further comprises inorganic nanoparticles; the inorganic nanoparticles are selected from nano-grade Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of (a). The specific addition amount of the inorganic nanoparticles varies within a wide range, and preferably, the inorganic nanoparticles in the gel polymer electrolyte layer account for the total mass of the gel polymer electrolyte layer3-10%; the inorganic nanoparticles in the solid polymer electrolyte layer account for 3-10% of the total mass of the solid polymer electrolyte layer.
In the present invention, the positive electrode is not particularly limited, and a positive electrode generally used in a conventional lithium battery may be specifically used. Specifically, the positive electrode comprises a positive electrode current collector and a positive electrode material positioned on the surface of the positive electrode current collector.
The kind of the positive electrode current collector is well known to those skilled in the art, and may be selected from, for example, an aluminum foil, a copper foil, or a stamped steel strip.
The positive electrode material includes a positive electrode active material, a conductive agent, and a second binder. Specifically, the positive electrode active material is selected from LiFePO4、LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.8Co0.15Al0.05O2One or more of (a).
The conductive agent is not particularly limited in the present invention, and may be a positive electrode conductive agent conventional in the art, such as at least one of b block black, carbon nanotube, HV, carbon black. Wherein the content of the conductive agent is 0.1-20 wt%, preferably 1-10 wt% based on the weight of the positive electrode active material.
The kind and content of the second binder are well known to those skilled in the art, for example, one or more of fluorine-containing resin and polyolefin compound such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), and styrene-butadiene rubber (SBR). Generally, the content of the second binder is 0.01 to 10 wt%, preferably 0.02 to 5 wt%, based on the weight of the positive electrode active material, depending on the kind of the binder used.
The second objective of the invention is to provide a preparation method of the lithium ion battery, which specifically comprises the steps of coating a first polymer slurry on a support body, and drying to obtain a polymer film; sequentially coating a second polymer slurry and a ceramic slurry on the surface of the polymer film to obtain a composite electrolyte; and then pressing and molding the anode, the composite electrolyte and the cathode, and finally adsorbing electrolyte in a polymer film to obtain the lithium ion battery, wherein a gel polymer electrolyte layer in the composite electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode.
In the preparation method, the polymer film is used as a precursor of the gel polymer electrolyte layer, and the gel polymer electrolyte layer can be obtained by activating the polymer film after the polymer film absorbs the electrolyte.
With the above-described production method, the order of lamination of the multilayer structure of the positive electrode, the gel polymer electrolyte layer, the solid polymer electrolyte layer, and the negative electrode, which are formed in a stack, cannot be reversed. However, the order of preparation may vary and is not intended to be limiting. For example, the lithium ion battery may be obtained by preparing a composite electrolyte layer, and then laminating a positive electrode, the composite electrolyte layer, and a negative electrode in a fixed order, or may be formed as a first composite having a two-layer structure, the first composite including a positive electrode and a polymer film on the surface of the positive electrode, then a solid polymer electrolyte layer and a porous ceramic coating are sequentially formed on the surface of the polymer film, finally the negative electrode is placed on the porous ceramic coating for compression molding, or the negative electrode, the solid polymer electrolyte layer and the porous ceramic coating can form a second complex body firstly, then the second complex body is laminated with the first complex body to make the gel polymer electrolyte layer contact with the solid polymer electrolyte layer, then compression molding is carried out, in different preparation methods, attention is paid to keeping the gel polymer electrolyte layer opposite to the positive electrode and the porous ceramic coating opposite to the negative electrode.
The following describes in detail a method of obtaining the composite electrolyte layer, and then laminating the positive electrode, the composite electrolyte layer, and the negative electrode in a fixed order to obtain the lithium ion battery.
Firstly, a polymer film is obtained, and a method for preparing the polymer film adopts a coating method, and specifically comprises the following steps: coating the first polymer slurry on a support, and drying at 40-100 ℃. The first polymer slurry specifically comprises a first polymer and a first solvent, and the content of the first polymer is 5-20% by mass fraction based on the total weight of the first polymer slurry; the first polymer is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile system, poly (isopropyl cyanoacrylate) system, polyphenylene sulfide and polyvinyl chloride; the first solvent is used to distribute the first polymer therein to form a slurry, facilitating coating. In the subsequent drying process, the first solvent is removed, and the specific substances and addition amount of the first solvent are known to those skilled in the art, such as one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether, and acetonitrile.
Preferably, the polymer film prepared by the above method has a thickness of 5 to 25 μm.
Secondly, obtaining a solid polymer electrolyte layer on the surface of the polymer film, wherein the method for preparing the solid polymer electrolyte layer adopts a coating method, and specifically comprises the following steps: coating the second polymer slurry on the surface of the dried polymer film, and then drying at 40-100 ℃. The second polymer slurry comprises a second polymer, a lithium salt and a second solvent, wherein the second polymer is one or more of polyethylene oxide, polyvinylidene fluoride and polymethyl methacrylate; the lithium salt may be any one known to those skilled in the art for transporting lithium ions, and may be, for example, LiTFSI or LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI; the second solvent has the same function as the first solvent, and the specific material and the addition amount used are the same, and are not described herein, but the first solvent and the second solvent may be the same or different, and the content of the second polymer and the lithium salt in the second polymer slurry is known by those skilled in the art, preferably, the second polymer slurry is based on the total weight of the second polymer slurryThe content is 1-30% by mass, and the content of lithium salt is 0.5-5% by mass.
And thirdly, obtaining a porous ceramic coating, specifically coating ceramic slurry on the surface of the dried solid electrolyte layer, and drying at 40-100 ℃. The ceramic slurry includes ceramic particles, a dispersant, a first binder, and a third solvent. The ceramic particles are selected from Al2O3、TiO2、SiO2、ZrO2、ZnO、SnO2One or more of the above-mentioned materials, dispersing agent can be added in the ceramic slurry, for example, one or several of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine, for uniformly dispersing the ceramic particles in the third solvent, a first binder, such as polyvinylidene fluoride, is also added to the ceramic slurry, preferably, a third solvent with dispersion function, such as N, N-dimethylformamide, can be directly selected, the type and content of the third solvent are the same as those of the first solvent and the second solvent, and are not described herein again, the porous ceramic coating is left after the third solvent is removed in the subsequent drying process, based on the total weight of the ceramic slurry, the content of the ceramic particles is 5-40% by mass, the content of the first binder is 3-8% by mass, and the content of the dispersant is 0.2-2%.
In the preparation of the above composite electrolyte layer, the support is used to assist spreading of the electrolyte slurry, adhesion between the support and the electrolyte slurry is not strong, and the electrolyte can be removed from the surface of the support after drying the electrolyte slurry, and the support is conventionally used in the art, for example, the support is one selected from a polytetrafluoroethylene plate, a polyimide plate, a polyethylene terephthalate plate, a polyethylene plate, and a polypropylene plate.
Next, a positive electrode is obtained, which includes a positive electrode current collector and a positive electrode material on a surface of the positive electrode current collector. The positive electrode can be obtained directly or prepared by itself. When self-prepared, the concrete preparation method is well known to those skilled in the art, and the self-prepared positive electrode paste is prepared by coating a positive electrode slurry on a positive electrode current collector, drying and rolling. The positive electrode slurry comprises a positive electrode active material, a conductive agent, a second binder and a solvent. The materials and the respective addition amounts of the positive electrode active material, the conductive agent and the second binder are as described above, and are not described herein again. The solvent is used for distributing the positive electrode active material, the conductive agent and the second binder in the solvent to form slurry, so that coating is facilitated. During the subsequent drying process, the above solvent is removed. The specific materials and amounts of addition of the solvents are known to those skilled in the art and will not be described further herein.
Next, a negative electrode is obtained comprising lithium metal, lithium-silicon-carbon, other negative electrode materials that can be alloyed with lithium. The lithium metal negative active material includes lithium foil, lithium thin film, stabilized lithium powder, lithium ribbon, etc. The lithium-silicon-carbon negative electrode active material comprises a silicon-carbon negative electrode which is pre-embedded with lithium, and a negative electrode active material which is compounded by the silicon-carbon negative electrode, a lithium belt, lithium powder, a lithium film and the like. Negative active materials that can be alloyed with lithium include boron, gallium, indium, aluminum, phosphorus, lead, germanium, tin. The negative electrode also comprises a current collector such as a copper foil, a copper mesh, a nickel foil, a foam copper, a foam nickel, a stainless steel mesh, a stainless steel belt and the like. When self-prepared, the specific preparation method is well known to those skilled in the art, for example, a lithium negative electrode is prepared by pressing a lithium thin film on a copper foil current collector.
And finally, sequentially laminating the positive electrode, the composite electrolyte layer and the negative electrode according to the sequence that the polymer film is opposite to the positive electrode and the porous ceramic coating is opposite to the negative electrode, pressing and forming, and adsorbing electrolyte in the polymer film to obtain the electrolyte. The method for pressing and forming is hot rolling.
In the above method, inorganic nanoparticles may also be added to the first polymer slurry or the second polymer, and the types and content of the inorganic nanoparticles are the inorganic nanoparticles described above, and are not described herein again.
The third object of the invention is to provide an electric vehicle which contains the lithium ion battery provided above.
The present invention will be further described below by way of examples.
Example 1
Preparation of polymer film:
0.1g of nano Al2O3Dissolved in 20g of N, N-Dimethylformamide (DMF) and stirred at room temperature until a uniformly dispersed solution is obtained. Then 2g of PEO powder is added into the solution which is just prepared, the mixture is stirred evenly until the mixture is dissolved to obtain first polymer slurry, then the first polymer slurry is coated on a grinding tool made of a polytetrafluoroethylene plate and is dried for 24 hours at the temperature of 60 ℃, the moisture and the solvent in the first polymer slurry are fully removed, and the thickness of a polymer film is controlled to be 5 mu m.
Manufacturing a solid electrolyte layer:
1g of PEO powder was dissolved in 20g of DMF and stirred at 60 ℃ before adding 0.1g of lithium salt LiTFSI and 0.05g of Al2O3And continuously stirring the powder until the solution is uniformly dispersed to obtain a second polymer slurry. And then the second polymer slurry is uniformly coated on the surface of the polymer film prepared above, the coating thickness is controlled to be 0.5 mu m, and then the polymer film is placed in an oven at 60 ℃ for 24h to remove the solvent and the water.
Preparing a porous ceramic coating:
mixing 6g of Al2O3Adding the nano powder (with the particle size of 200nm) and 0.06g of sodium polyacrylate powder into 20g of DMF solvent, and stirring at normal temperature to uniformly disperse the solution to obtain the ceramic slurry. And then coating the slurry on the surface of the solid polymer electrolyte layer, controlling the coating thickness to be 0.5 mu m, then placing the solid polymer electrolyte layer in an oven, baking the solid polymer electrolyte layer for 24h at 60 ℃, and removing the solvent and the water to obtain a composite electrolyte layer, which is recorded as C1, wherein the average pore diameter of the ceramic coating is 100nm, and the porosity is 40%. And cutting the prepared composite electrolyte into electrolyte sheets with the diameter of 19 mm.
And (3) manufacturing a positive electrode:
3g of LiFePO as a positive electrode active material41.5g of PVDF as a binder and 0.35g of Sup-p as a conductive agent were added to 23g of DMF as a solvent, and the mixture was stirred in a vacuum stirrer to form a stable and uniform positive electrode slurry. Uniformly coating the anode slurry on a single surface of an aluminum foil, drying at 60 ℃, tabletting by a roller press to obtain an anode, and cutting the anode by a slicerThe sheet was cut into a positive electrode sheet having a diameter of 13 mm.
And (3) manufacturing a negative electrode:
a 200 μm lithium film was pressed on a copper foil current collector, and the lithium sheet was cut into a lithium negative electrode wafer having a diameter of 17mm using a cutting piece.
Assembling the battery:
the button cells were assembled using a CR2025 battery cell. The positive electrode is placed in the positive electrode shell in the middle, then the composite electrolyte layer and the negative electrode are sequentially placed, the polymer is opposite to the positive electrode side, the porous ceramic coating is opposite to the negative electrode, after the porous ceramic coating is sequentially placed, 0.3ml of electrolyte (1mol/LLIPF6/EC: DMC: EMC: 1:1:1) is injected into the polymer film, a stainless steel sheet with the diameter of 16.2mm and the thickness of 0.5mm is placed on the negative electrode, a spring piece with the diameter of 15.4mm is placed on the stainless steel sheet, and then the negative electrode shell is placed. A button cell was thus prepared, as S1.
Example 2
A composite electrolyte C2 and a button cell S2 were prepared according to the method of example 1, except that PEO in the first polymer syrup was replaced with P (VDF-HFP) when the polymer film was manufactured.
Example 3
A composite electrolyte C3 and a button cell S3 were prepared as in example 1, except that the PEO in the first polymer slurry was replaced with PMMA when the polymer film was made.
Example 4
A composite electrolyte C4 and a button cell S4 were prepared as in example 1, except that in the preparation of the polymer film, PEO in the first polymer slurry was replaced with PAN.
Example 5
A composite electrolyte C5 and a button cell S5 were prepared as in example 1, except that the PEO in the first polymer slurry was replaced with PVC in the preparation of the polymer film.
Example 6
A composite electrolyte C6 and button cell S6 were prepared as in example 1, except that Al in the ceramic slurry was added to the ceramic slurry to form the porous ceramic layer2O3Replacement ofTo SiO2The ceramic coating had an average pore diameter of 50nm and a porosity of 50%.
Example 7
A composite electrolyte C7 and button cell S7 were prepared as in example 1, except that Al in the ceramic slurry was added to the ceramic slurry to form the porous ceramic layer2O3By substitution with TiO2The ceramic coating had an average pore diameter of 400nm and a porosity of 30%.
Example 8
A composite electrolyte C8 and button cell S8 were prepared as in example 1, except that Al in the ceramic slurry was added to the ceramic slurry to form the porous ceramic layer2O3By substitution into ZrO2The ceramic coating had an average pore diameter of 225nm and a porosity of 40%.
Example 9
A composite electrolyte C9 and button cell S9 were prepared as in example 1, except that Al in the ceramic slurry was added to the ceramic slurry to form the porous ceramic layer2O3Instead of ZnO, the ceramic coating had an average pore size of 90nm and a porosity of 50%.
Example 10
A composite electrolyte C10 and a button cell S10 were prepared as in example 1, except that polyethylene oxide (PEO) in the second polymer slurry was replaced with polyvinylidene fluoride (PVDF) in the preparation of the solid electrolyte layer.
Example 11
A composite electrolyte C11 and a button cell S11 were prepared as in example 1, except that polyethylene oxide (PEO) in the second polymer slurry was replaced with Polyacrylonitrile (PAN) in the preparation of the solid electrolyte layer.
Example 12
A composite electrolyte C12 and a button cell S12 were prepared as in example 1, except that polyethylene oxide (PEO) in the second polymer slurry was replaced with poly isopropyl cyanoacrylate (PMCA) in the preparation of the solid electrolyte layer.
Example 13
A composite electrolyte C13 and a button cell S13 were prepared as in example 1, except that the thickness of the polymer film was controlled to 25 μm, the thickness of the solid electrolyte layer was controlled to 3 μm, and the thickness of the porous ceramic layer was controlled to 1.5. mu.m.
Example 14
A composite electrolyte C14 and a button cell S14 were prepared as in example 1, except that the thickness of the polymer film was controlled to 15 μm, the thickness of the solid electrolyte layer was controlled to 1.7 μm, and the thickness of the porous ceramic layer was controlled to 1 μm.
Example 15
A composite electrolyte C15 and a button cell S15 were prepared as in example 1, except that the inorganic nanoparticles Al were not added in the preparation of the polymer film and the solid electrolyte layer2O3。
Comparative example 1
The polymer film, the positive electrode and the negative electrode were prepared in the same manner as in example 1, except that the positive electrode, the polymer film and the negative electrode were directly stacked in order to prepare a button cell, and an electrolyte was injected to obtain a button cell DS1, wherein the polymer film was designated as DC 1.
Comparative example 2
A composite electrolyte DC2 and a button cell DS2 were prepared in the same manner as in example 1, except that, in the preparation of the composite electrolyte, the ceramic slurry was not coated on the surface of the solid electrolyte layer, and the composite electrolyte layer consisted only of the polymer film and the solid polymer electrolyte.
Performance testing
1) Testing of lithium efficiency for composite electrolytes
With reference to the test method for lithium efficiency in the literature [ adv. energy. mater.2018,8,1702097], the efficiency (CE) of metallic lithium, i.e. the percentage of metallic lithium remaining during each cycle, can be obtained when using different composite electrolytes; conversely, (1-CE) is the percentage of lithium metal consumed during each cycle.
Cutting the composite electrolyte into circular sheets with the diameter d of 19mm, placing the circular sheets between a copper sheet with the diameter d of 17mm and a lithium sheet with the diameter d of 16mm and the thickness h of 590 mu m, and absorbing enough quantity of the composite electrolyte in the gel polymer electrolyte layerSealing electrolyte (electrolyte is lithium hexafluorophosphate with concentration of 1mol/L, organic solvent is EC, EMC and DEC are mixed according to mass ratio of 1:1:1) in 2025 type button cell, charging with 0.33mA for 20h at 25 + -1 deg.C on LAND CT 2001C secondary cell performance detection device to deposit certain amount of metal lithium Q on copper sheetTThen, a charge-discharge test was carried out at 3.3mA with a capacity of Q per cycleCThe number of cycles was 10 at 3.3mAh, and all lithium on the copper current collector was extracted at 3.3mA at 11 th, and the cut-off voltage was set to 1V, and the capacity of extraction was QS。The calculation formula for lithium efficiency (CE) is as follows: CE ═ nQ (nQ)C+QS)/(nQC+QT) The test results are shown in Table 1.
TABLE 1
The test results show that the composite electrolyte of the present application has an overall lithium efficiency of more than 99%, whereas in comparative example 1, when the electrolyte is only the gel polymer electrolyte DC1, the lithium efficiency is 85.12%, and in comparative example 2, when the composite electrolyte is the solid-state non-polymer electrolyte and the gel polymer electrolyte, the lithium efficiency is 92.52%, which indicates that the composite electrolyte of the present application can significantly protect metallic lithium, improve the lithium efficiency, and reduce side reactions.
2) Test of button cell cycle performance
The button cell batteries S1-S15 and DS1-DS2 were subjected to a charge-discharge cycle test at 0.1C on a LAND CT 2001C secondary battery performance testing device at 25 + -1 ℃. The method comprises the following steps: standing for 10 min; charging to 3.7V by constant current; standing for 10 min; constant current discharge to 2.5V, i.e. 1 cycle. The steps are repeated, the circulation is terminated when the circulation is carried out for 200 times, and the ratio of the residual value of the battery capacity to the initial capacity value when the circulation is carried out for 200 times is the battery capacity retention rate for 200 times. The test results are reported in table 2.
TABLE 2
The test result shows that after the composite electrolyte of the application is used in a button cell, the capacity retention rate of the cell after 200 cycles is greater than or equal to 96%, while in comparative example 1, when the electrolyte is only gel polymer electrolyte DC1, the capacity retention rate is 69%, and in comparative example 2, when the composite electrolyte is solid-state absolute polymer electrolyte and gel polymer electrolyte, the capacity retention rate is 81%, which shows that the cycling performance of the cell adopting the composite electrolyte of the application is obviously improved.
Claims (20)
1. A lithium ion battery comprises a positive electrode, a negative electrode and a composite electrolyte layer positioned between the positive electrode and the negative electrode, and is characterized in that the composite electrolyte layer comprises a gel polymer electrolyte layer, a solid polymer electrolyte layer positioned on the surface of the gel polymer electrolyte layer and a porous ceramic coating positioned on the surface of the solid polymer electrolyte layer; the gel polymer electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode; the porous ceramic coating includes ceramic particles, a dispersant, and a first binder.
2. The lithium ion battery of claim 1, wherein the negative electrode comprises a negative active material that is metallic lithium or a lithium alloy.
3. The lithium ion battery according to claim 1, wherein the porosity of the porous ceramic coating is 30-50%.
4. The lithium ion battery according to claim 1, wherein the porous ceramic coating has an average pore size of 50 to 400 nm.
5. The lithium ion battery according to claim 1, wherein the ceramic particles have an average particle diameter of 100 to 500 nm.
6. According to the rightThe lithium ion battery of claim 1, wherein the ceramic particles comprise Al2O3、 TiO2、SiO2、ZrO2、ZnO、SnO2The dispersant comprises one or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine; the first binder comprises one or more of polyvinylidene fluoride and copolymers thereof, styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene diene monomer, polyethylene oxide and copolymers thereof, polyacrylate, polyamide, polyacrylic acid, polyurethane, polyvinyl ethyl ether and polyacrylonitrile.
7. The lithium ion battery according to claim 6, wherein the content of the ceramic particles is 90 to 96.8% based on the total mass of the porous ceramic coating; the content of the dispersing agent is 0.2-2%, and the content of the first binder is 3-8%.
8. The lithium ion battery of claim 1, wherein the solid state polyelectrolyte comprises a polymer matrix and a lithium salt dispersed in the polymer matrix.
9. The lithium ion battery of claim 8, wherein the polymer matrix is one or more of polyethylene oxide, polyvinylidene fluoride, and polymethyl methacrylate; the lithium salt is selected from LiTFSI and LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI.
10. The lithium ion battery of claim 1, wherein the gel polymer electrolyte further comprises a polymer film and an electrolyte adsorbed in the polymer film.
11. The lithium ion battery of claim 10, wherein the polymer film comprises one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, isopropyl polycyanoacrylate, polyphenylene sulfide, and polyvinyl chloride.
12. The lithium ion battery of claim 1, wherein the gel polymer electrolyte layer has a thickness of 7 μm to 30 μm, the solid polymer layer has a thickness of 0.5 μm to 3 μm, and the porous ceramic coating has a thickness of 0.5 μm to 1.5 μm.
13. The lithium ion battery of claim 1, wherein the gel polyelectrolyte layer and/or the solid polymer electrolyte layer further comprises inorganic nanoparticles; the inorganic nanoparticles are selected from Al2O3、 TiO2、 SiO2、ZrO2、ZnO、SnO2One or more of (a).
14. The lithium ion battery of claim 13, wherein the inorganic nanoparticles in the gel polymer electrolyte layer account for 1-10% of the total mass of the gel polymer electrolyte layer; the inorganic nanoparticles in the solid polymer electrolyte layer account for 3-10% of the total mass of the solid polymer electrolyte layer.
15. The lithium ion battery according to claim 1, wherein the positive electrode comprises a positive electrode current collector and a positive electrode material on the surface of the positive electrode current collector; the positive electrode material comprises a positive electrode active material selected from LiFePO4、LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.4Co0.2Mn0.4O2、LiNi0.4Co0.4Mn0.2O2、LiNi0.8Co0.15Al0.05O2One or more of (a).
16. The preparation method of the lithium ion battery is characterized in that a first polymer slurry is coated on a support body and dried to obtain a polymer film; sequentially coating the second polymer slurry and the ceramic slurry on the surface of the polymer film, and drying to obtain a composite electrolyte; and then pressing and molding the anode, the composite electrolyte and the cathode, and finally adsorbing electrolyte in a polymer film to obtain the lithium ion battery, wherein a gel polymer electrolyte layer in the composite electrolyte layer is opposite to the anode, and the porous ceramic coating is opposite to the cathode.
17. The method for preparing the lithium ion battery according to claim 16, wherein the first polymer slurry comprises a first polymer and a first solvent, and the content of the first polymer is 5-20% by weight based on the total weight of the first polymer slurry; the first polymer is selected from one or more of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile system, poly (isopropyl cyanoacrylate) system, polyphenylene sulfide and polyvinyl chloride; the first solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile;
the second polymer slurry comprises a second polymer, a lithium salt and a second solvent, wherein the content of the second polymer is 1-30% and the content of the lithium salt is 0.2-5% based on the total weight of the second polymer slurry; the second polymer is one or more of polyethylene oxide, polyvinylidene fluoride and polymethyl methacrylate; the lithium salt is selected from LiTFSI and LiPF6、LiBF4、LiClO4One or more of LiBOB and LiFSI; the second solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile;
the ceramic slurry comprises ceramic particles, a dispersing agent, a binder and a third solvent, wherein the total weight of the ceramic slurry is taken as a reference, and the content of the ceramic particles is 5-40Percent, the content of the dispersant is 0.2-2 percent, and the content of the binder is 3-8 percent; the ceramic particles are selected from Al2O3、 TiO2、 SiO2、ZrO2、ZnO、SnO2One or more of; the dispersing agent is selected from one or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol, ammonium polymethacrylate, polyethylene oxide and polyethyleneimine; the binder comprises one or more of polyvinylidene fluoride and copolymers thereof, styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene diene monomer, polyethylene oxide and copolymers thereof, polyacrylate, polyamide, polyacrylic acid, polyurethane, polyvinyl ethyl ether and polyacrylonitrile; the third solvent is one or more of acetone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran, diethyl ether and acetonitrile.
18. The method for manufacturing a lithium ion battery according to claim 16, wherein the support is one selected from a polytetrafluoroethylene plate, a polyimide plate, a polyethylene terephthalate plate, a polyethylene plate, and a polypropylene plate.
19. The method for preparing a lithium ion battery according to claim 16, wherein the first polymer paste and/or the second polymer paste further comprises inorganic nanoparticles; the inorganic nanoparticles are selected from Al2O3、 TiO2、SiO2、ZrO2、ZnO、SnO2One or more of (a).
20. An electric vehicle comprising the lithium ion battery of any of claims 1-15.
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