CN111533851A - Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery - Google Patents
Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery Download PDFInfo
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- CN111533851A CN111533851A CN202010381309.5A CN202010381309A CN111533851A CN 111533851 A CN111533851 A CN 111533851A CN 202010381309 A CN202010381309 A CN 202010381309A CN 111533851 A CN111533851 A CN 111533851A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 150000003384 small molecules Chemical class 0.000 claims abstract description 13
- 230000000977 initiatory effect Effects 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 13
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
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- 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
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Abstract
The invention provides a preparation method of a polymer electrolyte polymerized in situ in a battery and application thereof in an all-solid-state battery, wherein the polymer electrolyte comprises a polymer matrix and lithium salt compounded in the polymer matrix; the polymer electrolyte is formed by in-situ polymerization of materials comprising a small molecule additive, a cross-linking agent and the lithium salt in a battery in a thermal initiation mode; the micromolecule additive is carbonate micromolecule containing olefinic unsaturated bonds, and the cross-linking agent is a substance containing polyethylene glycol acrylate structural units. The polymer electrolyte combines the high voltage resistance properties of carbonate polymers with the high ionic conductivity properties of polyethylene glycol segments. Meanwhile, due to the liquidity of the liquid, the liquid micromolecule additive and the cross-linking agent adopted by the invention are fully wetted at each interface of the solid-state battery and generate the polymer electrolyte through in-situ copolymerization, so that the compatibility of the solid-solid interface in the all-solid-state battery can be effectively enhanced, and the application is facilitated.
Description
Technical Field
The invention relates to the technical field of lithium secondary batteries, in particular to a preparation method of a polymer electrolyte polymerized in situ in a battery and application of the polymer electrolyte in an all-solid-state battery.
Background
With the rapid development of electric vehicles and energy storage industries, higher requirements are put on energy density, cost, cyclicity, safety and the like of secondary batteries represented by lithium ion batteries. The lithium ion battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and the like; the liquid lithium ion battery uses the traditional electrolyte as electrolyte, but has the safety problems of liquid leakage, fire, explosion and the like. The all-solid-state lithium battery comprises a solid electrolyte material, and the adopted solid electrolyte is non-volatile and non-flammable, so that the short circuit problem caused by lithium metal dendrites can be effectively prevented, the safety problem of the battery is expected to be fundamentally solved, and the energy density of the battery is improved. Therefore, all solid-state lithium batteries are currently the focus of research.
In recent years, all-solid-state batteries have been greatly developed in the research of solid electrolyte materials, and their ion conductivity has reached up to 10-2S/cm. However, the solid electrolyte does not have the wetting effect of the liquid electrolyte, and the solid particles in the positive electrode layer, the electrolyte layer and the negative electrode layer of the solid battery are in point contact and the gaps between the particles are easily causedThe unsmooth ion transmission channel in the battery system, so the solid-solid fixed contact inside the all-solid battery becomes a difficult point for research.
At present, solid electrolyte materials mainly include inorganic solid electrolytes and organic polymer electrolytes. Among them, the organic polymer electrolyte has good viscoelasticity and lightweight property, and can effectively improve the solid-solid interface contact performance, so that the organic polymer electrolyte becomes a preferred scheme for solving the all-solid battery interface compatibility. In the polymer electrolyte, the polymer matrix material mainly comprises polyethylene oxide (PEO), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and the like, wherein the polyethylene oxide is widely applied.
However, the ion conductivity of the polymer electrolyte at room temperature is generally low, and the PEO-based polymer electrolyte with high ion conductivity faces the limitation of narrower voltage window.
Disclosure of Invention
In view of the above, the present application provides a method for preparing a polymer electrolyte and an application of the polymer electrolyte in an all-solid battery, wherein the polymer electrolyte prepared by the method has high ionic conductivity and a wide voltage window.
The invention provides a polymer electrolyte polymerized in situ in a battery, which is formed by polymerizing materials comprising a small molecule additive, a cross-linking agent and a lithium salt in situ in the battery in a thermal initiation mode; the micromolecule additive is carbonate micromolecule containing olefinic unsaturated bonds, and the cross-linking agent is a substance containing polyethylene glycol acrylate structural units.
Preferably, the small molecule additive is one or two of vinylene carbonate and ethylene carbonate.
Preferably, the cross-linking agent is one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetra (ethylene glycol) diacrylate and tetra (ethylene glycol) dimethacrylate.
Preferably, the small molecule additive accounts for 1-90% of the mass of the polymer electrolyte; the cross-linking agent accounts for 1-90% of the mass of the polymer electrolyte; the lithium salt accounts for 0.1-10% of the mass of the polymer electrolyte.
Preferably, the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate.
The present invention provides a method for preparing the polymer electrolyte, which comprises the following steps:
after mixing the micromolecule additive, the cross-linking agent and the lithium salt, carrying out in-situ copolymerization in the solid-state battery in the presence of an initiator in a thermal initiation mode to obtain the polymer electrolyte.
Preferably, the initiator is selected from one or more of azo-type initiators and peroxide-type initiators; the mass fraction of the initiator in the copolymerization system is 0.1-3%.
Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide.
Preferably, the temperature of the copolymerization is 30 ℃ to 90 ℃.
The present invention provides an all-solid battery comprising the polymer electrolyte as described above at the internal voids and interfaces of the all-solid battery.
Compared with the prior art, the polymer electrolyte polymerized in situ in the battery is prepared, and the polymer matrix of the polymer electrolyte is mainly prepared by in-situ copolymerization of carbonate micromolecules containing olefinic unsaturated bonds and a cross-linking agent containing polyethylene glycol acrylate structural units in a thermal initiation mode. In the present invention, the prepared polymer electrolyte combines the high voltage resistance property of carbonate polymer and the high ion conductivity property of polyethylene glycol segment. Meanwhile, due to the liquidity of the liquid, the liquid micromolecule additive and the cross-linking agent adopted by the invention are fully wetted at each interface of the solid-state battery and generate the polymer electrolyte through in-situ copolymerization, so that the compatibility of the solid-solid interface in the all-solid-state battery can be effectively enhanced.
In addition, the preparation method of the polymer electrolyte is simple and rapid, is compatible with the existing battery process, and is beneficial to large-scale preparation.
Drawings
FIG. 1 is an SEM photograph of an electrode formed based on the VC in-situ polymerization method in example 1;
FIG. 2 is a charge-discharge curve diagram of an NCM 523-graphite solid-state battery formed based on the VC in-situ polymerization method in example 1;
FIG. 3 is a graph showing the charge and discharge curves of the comparative example 1, in which the NCM 523-graphite solid-state battery was formed by a PEO-direct film-forming method.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polymer electrolyte polymerized in situ in a battery, which comprises a polymer matrix and a lithium salt compounded in the polymer matrix; the polymer electrolyte is formed by in-situ polymerization of materials comprising a small molecule additive, a cross-linking agent and the lithium salt in a battery in a thermal initiation mode; the micromolecule additive is carbonate micromolecule containing olefinic unsaturated bonds, and the cross-linking agent is a substance containing polyethylene glycol acrylate structural units.
The polymer electrolyte provided by the application has excellent performances such as higher ionic conductivity, wider voltage window and the like, and is beneficial to application in all-solid-state batteries.
The polymer electrolyte polymerized in situ in the battery comprises a polymer matrix, wherein the polymer matrix is mainly prepared by in-situ copolymerization of a small-molecule additive and a cross-linking agent in the battery in a thermal initiation mode. Wherein, the small molecule additive is a carbonate small molecule containing olefinic unsaturated bonds, preferably one or two of Vinylene Carbonate (VC) and ethylene carbonate. The carbonic ester micromolecules containing olefinic unsaturated bonds are liquid micromolecule additives, the activity is moderate, the monomers can be polymerized within a certain time, the monomers can be polymerized after fully wetting positive and negative electrode phases, and the compatibility of the carbonic ester groups and a ternary system is good.
In the invention, the crosslinking agent polymerized in situ in the battery is a substance containing a polyethylene glycol acrylate structural unit, preferably one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetra (ethylene glycol) diacrylate and tetra (ethylene glycol) dimethacrylate, and more preferably one or two of polyethylene glycol diacrylate and polyethylene glycol dimethacrylate. In the embodiment of the invention, the molecular weight of the cross-linking agent is preferably 475-975.
The molecular structure aspect of the polymer matrix according to the embodiment of the present invention includes carbonate structural units and polyethylene glycol segments; the polymer matrix is compounded with lithium salt. The polymer electrolyte combines the high voltage resistance of the carbonate polymer and the high ion conductivity of the polyethylene glycol chain segment, and further has high ionic conductivity and a wide voltage window.
In the present invention, the polymer electrolyte is formed by in-situ polymerization of materials including the small molecule additive, the cross-linking agent and the lithium salt in the battery. Specifically, the lithium salt may be one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate; the product is commercially available. In the embodiment of the invention, the small molecule additive accounts for 1-90% of the mass of the polymer electrolyte; the cross-linking agent accounts for 1-90% of the mass of the polymer electrolyte; the lithium salt accounts for 0.1-10% of the mass of the polymer electrolyte.
The liquid micromolecule additive and the cross-linking agent adopted by the invention are fully wetted at each interface of the solid-state battery due to the liquidity of the liquid, and generate the polymer electrolyte through in-situ copolymerization, so that the compatibility of the solid-solid interface in the all-solid-state battery can be effectively enhanced.
The embodiment of the invention provides a preparation method of the polymer electrolyte, which comprises the following steps:
after mixing the micromolecule additive, the cross-linking agent and the lithium salt, carrying out in-situ copolymerization in the solid-state battery in the presence of an initiator in a thermal initiation mode to obtain the polymer electrolyte.
The polymer electrolyte prepared by the invention has excellent performance, is simple and quick to prepare, is compatible with the existing battery process, and is beneficial to large-scale preparation.
According to the embodiment of the invention, the liquid monomers of the small molecular additive and the cross-linking agent can be mixed and uniformly stirred, and then the lithium salt is dissolved in the mixed solution. Wherein, the structures and the types of the small molecule additive, the cross-linking agent and the lithium salt are as described in the foregoing. The mass ratio of the small molecule additive to the cross-linking agent is preferably 1: (1-5), more preferably 1: (2-3). The proportion of the lithium salt is preferably 2 wt%; the lithium salt content ratio refers to a ratio of a lithium salt to the total mass (total mass of a lithium salt and a monomer solution).
In the mixed solution of the raw materials, a certain amount of initiator is added to obtain a material solution. The mass fraction of the initiator in a copolymerization system (namely monomer solution) can be 0.1-3%, and preferably 0.5-2.5%; the initiator proportion refers to the proportion of initiator to monomer solution. The initiator can be selected from one or more of azo initiators and peroxide initiators; preferably selected from one or more of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide t-butyl peroxide and methyl ethyl ketone peroxide, more preferably azobisisobutyronitrile.
According to the embodiment of the invention, the obtained material solution is added into the all-solid-state battery, and after standing, the micromolecule additive and the cross-linking agent are polymerized in situ in the battery to form the polymer electrolyte at a certain temperature, so that an ion transmission channel is constructed in situ and the contact performance of each interface in the battery is enhanced.
The preparation method of the invention is that after the battery is assembled, liquid is directly injected to initiate polymerization in one step, which is completely different from the method that the battery is assembled by stacking after the metal lithium cathode coated by the polymer electrolyte is prepared. According to the invention, a polymer micromolecule solution is added into the battery core, and after each interface is fully wetted by using the fluidity of the precursor polymer micromolecule solution, in-situ polymerization is initiated to form a polymer electrolyte in the battery, and an ion transmission channel is constructed, so that the all-solid-state battery with lower interface impedance is formed.
In an embodiment of the present invention, the time for the standing may be 5 hours. The temperature of the in-situ polymerization is preferably 30-90 ℃, and more preferably 50-80 ℃. The embodiment of the invention can be subjected to heat treatment for 15 h-18 h at the temperature to obtain the polymer electrolyte polymerized in situ in the battery.
Accordingly, the present invention provides the use of the polymer electrolyte in an all-solid battery, i.e. an all-solid battery, wherein the polymer electrolyte as described hereinbefore is polymerized in situ at the internal voids and interfaces of the all-solid battery.
The positive electrode and the negative electrode in the all-solid-state battery are not particularly limited, and commercially available products can be adopted. In embodiments of the present invention, the battery positive electrode may employ a ternary positive electrode material, such as NCM523 (LiNi)0.5Co0.2Mn0.3O2) Etc.; the negative electrode is typically graphite. Experiments show that the all-solid-state battery formed by the embodiment of the invention has higher capacity.
For further understanding of the present application, the preparation method of the polymer electrolyte polymerized in situ in the battery and its application in the all-solid battery provided herein are specifically described below with reference to examples. In the following examples, all materials are commercially available.
Example 1
1) Vinylene carbonate and polyethylene glycol diacrylate (molecular weight is 475) are mixed and stirred uniformly, wherein the mass ratio of the vinylene carbonate to the polyethylene glycol diacrylate is 1: 2.
2) The LiTFSI salt was dissolved in the above mixed solution, and the ratio of the lithium salt was 2 wt%.
3) Adding an initiator AIBN accounting for 1 wt% of the total mass of the monomer solution into the mixed solution of the raw materials to obtain a material solution.
4) Adding the material solution into an all-solid-state battery, standing for 5h with the positive electrode of NCM523 and the negative electrode of graphite, and performing heat treatment at 60 ℃ for 15h to ensure that the polymer electrolyte is polymerized in situ in the internal gaps and interfaces of the all-solid-state battery.
The electrode of the solid-state battery is analyzed, and the scanning electron microscope analysis result is shown in figure 1, figure 1 is an SEM picture of the electrode formed based on the VC in-situ polymerization method in example 1, figure 1 shows that after VC in-situ polymerization, a uniform polymer electrolyte ionic conduction network is formed on the surface and bulk phase of the electrode, the contact is tight, the interface impedance is low, and the ionic conductivity of the polymer electrolyte is about 5.7 × 10-5S/cm。
The solid-state batteries were subjected to performance tests, and a comparative group of solid-state batteries, which were NCM 523-graphite solid-state batteries including a PEO-based polymer electrolyte directly film-formed (molecular weight of PEO was 600000 (number average molecular weight)), ionic conductivity of the electrolyte was 5.0 × 10-6S/cm。
The test results are shown in fig. 2 and fig. 3, respectively, and fig. 2 shows that the NCM 523-graphite solid-state battery formed based on the VC in-situ polymerization method can exert a normal capacity of the positive electrode 523 of 165mAh/g due to a high ionic conductivity and a uniform ionic conduction network construction. And, through CV test, the test result shows that its electrochemical window reaches 4.6V.
Fig. 3 shows that the NCM 523-graphite solid-state battery formed by a PEO-direct film-forming method has large polarization due to poor ionic conductivity and high interface impedance, and the positive electrode 523 can only exert partial capacity of 100 mAh/g.
Example 2
1) Vinylene carbonate and polyethylene glycol diacrylate (molecular weight is 975) are mixed and stirred uniformly, wherein the mass ratio of the vinylene carbonate to the polyethylene glycol diacrylate is 1: 3.
2) The LiTFSI salt was dissolved in the above mixed solution, and the ratio of the lithium salt was 2 wt%.
3) Adding an initiator AIBN accounting for 0.5 wt% of the total mass of the monomer solution into the mixed solution of the raw materials to obtain a material solution.
4) Adding the material solution into an all-solid-state battery, standing for 5h with the positive electrode of NCM523 and the negative electrode of graphite, and performing heat treatment at 60 ℃ for 18h to ensure that the polymer electrolyte is polymerized in situ in the internal gaps and interfaces of the all-solid-state battery.
The solid-state battery was subjected to performance test in the same manner as in example 1, and the results were: the battery discharge capacity of the formed NCM 523-graphite solid-state battery can reach 166 mAh/g.
Comparative example
This comparative example was a comparative solid-state battery, which was a NCM 523-graphite solid-state battery including a PEO-based polymer electrolyte directly film-formed (molecular weight of PEO was 600000 (number average molecular weight)), electrolyte ionic conductivity 5.0 × 10, prepared as described in example 1-6S/cm. The preparation process comprises the following steps:
(1) PEO-based polymer (molecular weight of PEO is 600000 (number average molecular weight)) and LiTFSI were dissolved in acetonitrile with solute mass fraction of 10 wt%, molar ratio of EO unit and lithium salt in PEO was 8:1, and stirred uniformly.
(2) The slurry is dripped on an NCM523 positive plate, the solvent is volatilized at room temperature for 12h, and the treatment is carried out at 60 ℃ for 12 h. Covering the positive plate with a graphite negative electrode, and assembling the button cell.
(3) The button cell was treated at 60 ℃ for 24h to increase the contact between the electrode and the electrolyte.
The solid-state battery was tested according to the method of example 1, and the results were (shown in fig. 3): based on a PEO-direct film forming method, the formed NCM 523-graphite solid-state battery has large polarization due to poor ionic conductivity and high interface impedance, and the positive electrode 523 can only exert partial capacity of 100 mAh/g.
From the above examples, it can be seen that the polymer electrolyte prepared by the present invention combines the high voltage resistance property of the carbonate polymer and the high ion conductivity property of the polyethylene glycol segment. Meanwhile, due to the liquidity of the liquid, the liquid micromolecule additive and the cross-linking agent adopted by the invention are fully wetted at each interface of the solid-state battery and generate the polymer electrolyte through in-situ copolymerization, so that the compatibility of the solid-solid interface in the all-solid-state battery can be effectively enhanced. In addition, the preparation method of the polymer electrolyte is simple and rapid, is compatible with the existing battery process, and is beneficial to large-scale preparation.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (9)
1. A method for preparing a polymer electrolyte, comprising the steps of:
mixing a small molecular additive, a cross-linking agent and a lithium salt, and carrying out in-situ copolymerization in a solid-state battery in the presence of an initiator in a thermal initiation manner to obtain a polymer electrolyte;
the micromolecule additive is carbonate micromolecule containing olefinic unsaturated bonds, and the cross-linking agent is a substance containing polyethylene glycol acrylate structural units.
2. The method according to claim 1, wherein the small molecule additive is one or both of vinylene carbonate and ethylene carbonate.
3. The method according to claim 1, wherein the crosslinking agent is one or more of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetra (ethylene glycol) diacrylate and tetra (ethylene glycol) dimethacrylate.
4. The preparation method according to claim 1, wherein the small molecule additive accounts for 1-90% of the mass of the polymer electrolyte; the cross-linking agent accounts for 1-90% of the mass of the polymer electrolyte; the lithium salt accounts for 0.1-10% of the mass of the polymer electrolyte.
5. The method according to claim 1, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium perchlorate, lithium bisoxalato borate, lithium difluorooxalato borate and lithium trifluoromethanesulfonate.
6. The production method according to claim 1, wherein the initiator is selected from one or more of azo-type initiators and peroxide-type initiators; the mass fraction of the initiator in the copolymerization system is 0.1-3%.
7. The method of claim 6, wherein the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, and methyl ethyl ketone peroxide.
8. The method according to any one of claims 1 to 7, wherein the temperature of the copolymerization is 30 ℃ to 90 ℃.
9. An all-solid battery comprising the polymer electrolyte obtained by the production method according to any one of claims 1 to 8 in the internal space and interface of the all-solid battery.
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