CN114628768B - PEO polymer solid electrolyte with high safety performance, preparation method thereof and solid lithium battery - Google Patents
PEO polymer solid electrolyte with high safety performance, preparation method thereof and solid lithium battery Download PDFInfo
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- CN114628768B CN114628768B CN202111101426.2A CN202111101426A CN114628768B CN 114628768 B CN114628768 B CN 114628768B CN 202111101426 A CN202111101426 A CN 202111101426A CN 114628768 B CN114628768 B CN 114628768B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 106
- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000007787 solid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- 229910003480 inorganic solid Inorganic materials 0.000 claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 12
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000017 hydrogel Substances 0.000 claims description 16
- 238000003825 pressing Methods 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 229910000846 In alloy Inorganic materials 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000011858 nanopowder Substances 0.000 claims description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002228 NASICON Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- -1 imine lithium salt Chemical class 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical class [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 84
- 230000000052 comparative effect Effects 0.000 description 24
- 239000002002 slurry Substances 0.000 description 13
- 239000011268 mixed slurry Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- RZEQQEXIZXEASF-UHFFFAOYSA-N lithium trifluoro(sulfinato)methane Chemical compound [Li+].C(F)(F)(F)[S-](=O)=O RZEQQEXIZXEASF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of solid electrolytes for preparing solid lithium batteries, and particularly discloses a PEO polymer solid electrolyte with high safety performance, a preparation method thereof and a solid lithium battery; a PEO polymer solid electrolyte with high safety performance comprising three solid electrolyte layers: the first layer is a PAN layer and is prepared from PAN particles, inorganic solid electrolyte particles and lithium ion secondary battery lithium salt; the second layer is an inorganic composite layer and consists of a flame retardant, porous polyimide PI and lithium lanthanum zirconate LLZO nano particles; the third layer is a PEO layer and is composed of PEO particles, lithium bistrifluoro-methylsulfonylimi and LLZO nano particles; the oxidation-resistant PAN layer is contacted with a high-voltage positive electrode of the lithium battery, and the reduction-resistant PEO layer is contacted with a negative electrode of the lithium battery, so that the stability and the compatibility of an interface are effective, an electrochemical window is enlarged, and good connection is ensured to be formed at the interface; the high-strength lightweight PI bracket and the flame retardant improve the safety and the cycle life of the solid lithium battery.
Description
Technical Field
The invention relates to the technical field of solid electrolyte for preparing a solid lithium battery, in particular to PEO polymer solid electrolyte with high safety performance, a preparation method thereof and a solid lithium battery.
Background
The solid lithium battery is favored by a plurality of consumers by virtue of the advantages of high energy density and high charge and discharge efficiency, meanwhile, the safety performance of the solid lithium battery also brings great attention, the polymer solid electrolyte for manufacturing the solid lithium battery brings great attention by virtue of excellent high flexibility, easy processing property and good interface contact with an electrode, but the polymer solid electrolyte has poor high-voltage resistance, and can lead polymer molecules to be oxidized to reduce electrolyte performance when contacting with a high-voltage positive plate, so that the high-voltage resistance of the polymer solid electrolyte can be effectively improved by constructing the multi-layer heterogeneous polymer composite solid electrolyte, the electrochemical window of the solid battery is widened, and the comprehensive performance of the battery is improved.
Chinese patent CN202110271667.5 discloses a "double-layer composite solid electrolyte material, and preparation method and application thereof," which prepares double-layer polymers in a layered arrangement, matches a positive high-voltage polymer electrolyte layer and a lithium-philic polymer layer, and can be charged and discharged at room temperature; chinese patent CN202110027400.1 discloses a "preparation method of a multi-network structure polyamide-based gel polymer electrolyte", which comprises mixing polyamide-based monomer material and lithium ion battery liquid electrolyte, and polymerizing to form a film on a porous supporting material rich in hydroxyl and carboxyl groups, thus obtaining a multi-network structure high-strength interface-enhanced polyamide-based gel polymer electrolyte; chinese patent CN201811394930.4 discloses "a mixed ionic electronic conductive polymer based interface layer, a preparation method and use thereof", wherein the mixed ionic electronic conductive polymer based interface layer comprises a polymer material, a carbon material and/or a composite material of a carbon-based material and an alkali metal salt on an interface where a solid electrolyte contacts an alkali metal negative electrode of a battery; according to the technical scheme, the polymer solid electrolyte is compounded, so that the stability and electrochemical performance of the polymer solid electrolyte are improved, but the lithium battery is at high temperature risk in the working process, and the polymer solid composite electrolyte obtained by the prior art has certain combustibility and potential safety hazard in practical application.
Disclosure of Invention
Aiming at the defect of the prior technical scheme in the safety performance of the polymer solid composite electrolyte, the invention provides the PEO polymer solid electrolyte with high safety performance, which can obviously improve the safety performance of a solid lithium battery prepared by the electrolyte; the invention also aims to provide a preparation method of the PEO polymer solid electrolyte with high safety performance, and the prepared PEO polymer solid electrolyte can remarkably improve the safety performance of a solid lithium battery prepared by the PEO polymer solid electrolyte; another object of the present invention is to provide a solid lithium battery prepared with a PEO polymer solid electrolyte having high safety, which has the advantage of high safety.
The aim of the invention is realized by the following technical scheme:
a PEO polymer solid electrolyte with high safety performance comprises a PAN layer contacted with a positive plate, wherein the PAN layer consists of PAN particles, inorganic solid electrolyte particles and lithium salt of a lithium ion secondary battery; a PEO layer in contact with the negative electrode sheet, composed of PEO particles, lithium bistrifluoro-methylsulfonylimi and conductive particles; and an inorganic composite layer disposed between the PAN layer and the PEO layer, consisting of a flame retardant, porous polyimide PI, and LLZO nanoparticles; the oxidation-resistant PAN layer is contacted with the high-voltage positive electrode of the lithium battery, and the reduction-resistant PEO layer is contacted with the negative electrode of the lithium battery, so that the interface stability of the solid electrolyte is effectively improved, the electrochemical window is enlarged, the interface compatibility is also effectively improved, and good connection is ensured to be formed at the interface; meanwhile, the intermediate inorganic composite layer is added with the high-strength lightweight PI bracket and the flame retardant, so that the safety and the cycle life of the solid lithium battery are greatly improved.
Preferably, the inorganic solid electrolyte particles used in the PAN layer are one of LLZO nano powder, perovskite type particles and NASICON particles, and the lithium ion secondary battery lithium salt used is one of LiTFSI, chelate boron type lithium salt, chelate phosphorus type lithium salt, perfluor phosphine type lithium salt, alkyl type lithium salt, sulfonate type lithium salt, lithium aluminate salt, imine lithium and inorganic electrolyte lithium salt; the inorganic solid electrolyte particles and the lithium salt of the lithium ion secondary battery are beneficial to improving the lithium ion transmission performance and improving the lithium ion conductivity of the PAN layer.
Preferably, the conductive particles in the PEO layer are one of LLZO nanoparticles and lithium aluminum titanium phosphate LATP nanoparticles.
Preferably, the flame retardant in the inorganic composite layer is one of decabromodiphenylethane DBDPE, ferrite yellow, hollow glass microspheres, para-aramid fibers, graphene, transition metal dihalides and hexagonal boron nitride; flame retardants in nonflammable PI prevent the combustion of PEO and LiTFSI.
Preferably, the PAN layer is 25-100 μm thick, the PEO layer is 5-150 μm thick, the inorganic composite layer is 30-100 μm thick, and the total PEO polymer solid electrolyte thickness is 100-350 μm thick.
A method for preparing PEO polymer solid electrolyte with high safety performance, which comprises the following steps:
step one, preparing a PAN layer: adding PAN particles, inorganic solid electrolyte particles and lithium ion secondary battery lithium salt into Dimethylsulfoxide (DMSO) to form a mixed solution, ball-milling the mixed solution, placing the slurry at normal temperature and under the pressure of 0.005-0.02MPa for a period of time, pouring the mixed solution into a mould, and vacuum drying to obtain a solidified film, namely a first PAN layer;
step two, preparing an inorganic composite layer: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to the mass ratio of 50-70:3-8:4-8, wherein the mass of NMP is 30-60% of the mass of the mixed solution, stirring to obtain uniform mixed solution, dripping the mixed solution on the surface of hydrogel immersed in silicone oil to obtain a porous PI-flame retardant film, separating the PI-flame retardant film from the surface of the hydrogel, washing with water, and drying in air;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethyl sulfoxide DMSO with the mass ratio of 50-65:5-10:3-6, stirring to obtain a mixed solution, pouring the mixed solution into a mould, and vacuum drying to obtain a solidified film which is the PEO layer;
and step four, superposing the three solid electrolyte layers prepared in the steps one to three in one to three order, applying 10 to 20MPa, and carrying out vacuum heat treatment to obtain the PEO polymer solid electrolyte.
Preferably, the ball milling time of the mixed liquor in the first step is 1-3 hours, the mixed liquor is placed under low pressure for 12-24 hours, and the mixed liquor is dried in a mould at the temperature of 100-120 ℃ for 1-3 hours; step two, stirring the mixed solution for 2 to 6 hours, dripping the mixed solution on the surface of the hydrogel at the temperature of 30 to 60 ℃, flushing the obtained PI-flame retardant film with deionized water for 3 to 5 times, and drying the PI-flame retardant film in air at the temperature of 20 to 35 ℃ for 24 to 48 hours; stirring the mixed solution for 2-6 hours, and vacuum drying in a mould at 60-100 ℃ for 2-6 hours; and step four, the vacuum heat treatment temperature is 150-300 ℃ and the time is 30-60 minutes.
In the first step, the mixed solution is placed under low pressure for a period of time to remove bubbles generated in the ball milling process, if the mixed solution contains bubbles, the transmission of lithium ions and the internal resistance of a battery can be influenced, the lithium ions can only be transmitted along solids, the inside of the bubbles is in a hollow state, and a lithium ion transmission path is cut off, so that the internal resistance of the battery is increased, and the cycle life is reduced;
in the second step, the PAA generates PI molecules in the stirring process, the PI molecules are dripped into silicone oil to form a porous structure, the silicone oil can permeate into a hydrophobic layer on the surface of the hydrogel through hydrophobic-hydrophobic interaction, so that a double-layer hydrophobic layer is formed on the surface of the hydrogel, PAA-DBDPE micelle is aggregated at the interface between NMP solvent and the hydrogel to generate PI-DBDPE, meanwhile, the rotation and precipitation of polymer chains in the ultra-thin double-layer hydrophobic layer on the surface of the hydrogel are accelerated, so that bigger and bigger pores are formed at two sides, the size of the pores is increased along with the increase of the reaction temperature, and after the reaction in the medium is finished, the obtained porous PI-DBDPE film; PI is nonflammable, the critical temperature can be remarkably improved, the porous PI bracket can provide a high-strength bracket structure, more channels are provided for lithium ion transmission, the internal resistance of a solid battery is reduced, the battery polarization loss in the circulation process is reduced, the circulation life is prolonged, meanwhile, PI is a high-strength lightweight material, the volume change of a pole piece and an electrolyte in the charge and discharge process can be buffered, the lithium dendrite resistance is improved, and the circulation life of the battery is prolonged.
A solid lithium battery prepared from PEO polymer solid electrolyte with high safety performance comprises a positive plate, a negative plate and PEO polymer solid electrolyte, wherein the positive plate and the negative plate are positioned on two sides of the PEO polymer solid electrolyte, the positive plate is connected with one side of a PAN layer, and the negative plate is connected with one side of the PEO layer.
The preparation method of the solid lithium battery prepared by PEO polymer solid electrolyte with high safety performance comprises the following steps:
step one, preparing a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are ball-milled at normal temperature according to the mass ratio of 60-75:3-6:5-10:2-5, and the mixed powder is transferred into a die to be pressed into a positive plate;
step two, selecting a lithium-indium alloy sheet as the negative electrode sheet, and pressing the lithium sheet and the indium sheet to form the lithium-indium alloy sheet
Step three, preparing a solid lithium battery: and respectively pressing the positive and negative plates at 10-30MPa on two sides of the PEO polymer composite solid electrolyte, wherein the lithium surface of the negative plate faces the PEO polymer composite solid electrolyte.
Preferably, the active material in the first step is one of nickel cobalt manganese oxide NCM or lithium cobaltate, the conductive agent is one of carbon black, carbon nano tube, conductive graphite, carbon nano fiber or ketjen black, and the binder is one of polyvinylidene fluoride PVDF or polyurethane; ball milling time is 30-60 minutes; the pressing pressure is 20-30MPa; the thickness of the positive plate is 50-250 mu m; preparing a lithium indium alloy sheet in the second step: polishing the metal lithium sheet in vacuum, overlapping the lithium sheet and the indium sheet with the thickness ratio of 6:4, and pressing for 40-80 minutes under 2000-4000MPa to obtain a lithium-indium alloy sheet as a negative electrode sheet, wherein the thickness of the negative electrode sheet is 50-250 mu m.
The invention has the beneficial effects that: (1) The middle inorganic composite layer of the three solid electrolyte layers is added with the high-strength lightweight porous PI bracket and the flame retardant DBDPE, so that the safety and the cycle life of the all-solid battery are greatly improved; (2) The oxidation-resistant PAN is contacted with the high-voltage positive electrode, the reduction-resistant PEO is contacted with the lithium metal negative electrode, so that the interface stability and electrochemical window of the solid electrolyte are effectively improved, the interface compatibility is also effectively improved, and good connection is ensured to be formed at the interface.
Detailed Description
Example 1
Step one, preparing a PAN layer: adding PAN particles, lanthanum lithium zirconate LLZO nano powder and bis (trifluoromethanesulfonyl) lithium LiTFSI into a dimethyl sulfoxide DMSO solvent, adding the mixed solution into a high-energy vibration ball mill together, ball milling for 1.5 hours to obtain uniformly mixed slurry, and keeping the slurry for 24 hours under normal temperature vacuum for removing bubbles generated in the ball milling process, wherein the vacuum degree is 0.005MPa; PAN, LLZO, liTFSI and DMSO in a mass ratio of 15:2:0.8:65; immediately pouring the slurry with the bubbles removed into a mold, drying in vacuum at 110 ℃ for 3 hours, and pulling out the cured film from the mold to obtain a first PAN layer with the thickness of 75 mu m;
step two, preparing an inorganic composite layer: polyimide prepolymer PAA particles, DBDPE and LLZO nano particles are added into N-methylpyrrolidone NMP as solvent according to the mass ratio of 60:5:6 at normal temperature, stirring is continued for 4 hours to obtain uniform mixed solution, and the mixed solution is dripped onto the surface of hydrogel immersed in silicone oil at 50 ℃; after the reaction in the medium is finished, taking out the PI-DBDPE film from the silicone oil, washing 3 times with deionized water at normal temperature to remove residual silicone oil, drying in air at 35 ℃ for 35 hours, and removing redundant solvent to obtain the PI-DBDPE film with the thickness of 75 mu m;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethyl sulfoxide (DMSO) solvent according to the mass ratio of 55:8:5, stirring at normal temperature for 6 hours to obtain uniformly mixed slurry, pouring the slurry into a mold, drying in vacuum at 100 ℃ for 5 hours, and pulling out the cured film from the mold to obtain a third PEO layer with the thickness of 80 mu m;
and fourthly, after the prepared three-layer solid electrolyte is sequentially overlapped, applying 20MPa, and placing the three-layer solid electrolyte in a vacuum oven at 200 ℃ for heat treatment for 45 minutes, so that the interfacial compatibility of the three-layer solid electrolyte is improved, good connection is ensured to be formed at the interface, and finally the PEO polymer composite solid electrolyte is obtained, wherein the total thickness of the electrolyte is 200 mu m.
Example 2
Unlike example 1, the PEO polymer composite solid electrolyte of example 2 had a total thickness of 300 μm, a PAN layer thickness of 100 μm, a PI-DBDPE film thickness of 150 μm, and a PEO layer of 100 μm, with the remaining conditions being the same as in example 1.
Example 3
The difference from example 1 is that the mass ratio of the first layer electrolyte PAN, LLZO, liTFSI and DMSO in example 5 is 20:1:0.5:60, and the other conditions are the same as in example 1.
Example 4
The difference from example 1 is that the second layer electrolyte polyimide prepolymer PAA particles, DBDPE and LLZO nanoparticles in example 6 were in a mass ratio of 65:7:8, and the other conditions were the same as in example 1.
Example 5
The difference from example 1 is that the third layer electrolyte LLZO particles in example 7 were replaced with lithium aluminum titanium phosphate LATP, and the other conditions were the same as in example 1.
Example 6
Step one, preparing a PAN layer: adding PAN particles, inorganic solid electrolyte particles and lithium salt of a lithium ion secondary battery into Dimethylsulfoxide (DMSO) to form a mixed solution, ball-milling the mixed solution for 1 hour according to the mass ratio of PAN to inorganic solid electrolyte particles to lithium salt of the lithium ion secondary battery to DMSO of 10:1:0.5:60 to obtain a uniformly mixed slurry, placing the slurry at normal temperature and low pressure for 12 hours under the low pressure of 0.005MPa, pouring the slurry into a mould, and vacuum-drying at 100 ℃ for 1 hour to obtain a cured film which is a first PAN layer with the thickness of 25 mu m;
step two, preparing an inorganic composite layer: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to a mass ratio of 50:3:4, stirring for 2 hours to obtain a uniform mixed solution, dripping the mixed solution onto the surface of hydrogel immersed in silicone oil at 30 ℃, washing the PI-flame retardant film with deionized water for 3 times, and drying in air at 20 ℃ for 24 hours to obtain a PI-flame retardant film with a thickness of 50 mu m;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethyl sulfoxide DMSO according to a mass ratio of 50:5:3, stirring for 2 hours to obtain uniformly mixed slurry, pouring the slurry into a mold, and vacuum drying at 60 ℃ for 2 hours, wherein the cured film is the PEO layer with a thickness of 40 μm;
and fourthly, sequentially superposing the three solid electrolyte layers prepared in the first to third steps, applying 10MPa, and then placing the three solid electrolyte layers at 150 ℃ for vacuum heat treatment for 30 minutes to obtain the PEO polymer solid electrolyte with the total thickness of 100 mu m.
Example 7
Step one, preparing a PAN layer: adding PAN particles, inorganic solid electrolyte particles and lithium salt of a lithium ion secondary battery into Dimethylsulfoxide (DMSO) to form a mixed solution, ball-milling the mixed solution for 3 hours to obtain a uniformly mixed slurry, placing the slurry at normal temperature and low pressure for 24 hours, and at low pressure for 0.02MPa, pouring the slurry into a mould, and vacuum-drying at 120 ℃ for 3 hours to obtain a cured film which is a first PAN layer, wherein the thickness of the film is 30 mu m;
step two, preparing an inorganic composite layer: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to a mass ratio of 70:8:8, stirring for 6 hours to obtain a uniform mixed solution, dripping the mixed solution onto the surface of hydrogel immersed in silicone oil at 60 ℃, washing the PI-flame retardant film with deionized water for 5 times, and drying in air at 35 ℃ for 48 hours to obtain a PI-flame retardant film with a thickness of 40 mu m;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethylsulfoxide DMSO according to the mass ratio of 65:10:6, stirring for 6 hours to obtain uniformly mixed slurry, pouring the slurry into a mold, and vacuum drying at 100 ℃ for 6 hours, wherein the cured film is the PEO layer with the thickness of 60 mu m;
and fourthly, sequentially superposing the three solid electrolyte layers prepared in the first to third steps, applying 10 to 20MPa, and then placing the three solid electrolyte layers in a vacuum heat treatment at 300 ℃ for 60 minutes to obtain the PEO polymer solid electrolyte with the total thickness of 100 mu m.
Example 8
Step one, preparing a PAN layer: adding PAN particles, inorganic solid electrolyte particles and lithium salt of a lithium ion secondary battery into Dimethylsulfoxide (DMSO) to form a mixed solution, ball-milling the mixed solution for 2 hours to obtain a uniformly mixed slurry, placing the slurry at normal temperature and low pressure for 18 hours, and at low pressure for 0.0125MPa, pouring the slurry into a mould, and vacuum-drying at 110 ℃ for 2 hours to obtain a solidified film which is a first PAN layer with the thickness of 70 mu m;
step two, preparing an inorganic composite layer: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to a mass ratio of 60:5.5:6, stirring for 4 hours to obtain a uniform mixed solution, dripping the mixed solution onto the surface of hydrogel immersed in silicone oil at 45 ℃, washing the PI-flame retardant film with deionized water for 4 times, and drying in air at 27.5 ℃ for 36 hours to obtain a PI-flame retardant film with a thickness of 60 mu m;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethyl sulfoxide DMSO according to the mass ratio of 57.5:7.5:4.5, stirring for 2-6 hours to obtain uniformly mixed slurry, pouring the slurry into a mold, and vacuum drying at 80 ℃ for 4 hours, wherein the cured film is the PEO layer with the thickness of 70 mu m;
and fourthly, sequentially superposing the three solid electrolyte layers prepared in the first to third steps, applying 15MPa, and then placing the three solid electrolyte layers at 225 ℃ for vacuum heat treatment for 45 minutes to obtain the PEO polymer solid electrolyte with the total thickness of 150 mu m.
Example 9
Solid lithium batteries were assembled using the PEO polymer solid electrolyte prepared in example 1:
preparation of a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are put into a high-energy vibration ball mill according to the mass ratio of 65:5:8:3, ball milling is carried out for 60 minutes at normal temperature, the mixed powder is transferred into a die, and the positive plate is pressed under 30MPa, wherein the thickness of the positive plate is 150 mu m. Wherein the active material is a layered ternary material, the conductive agent is a carbon nanotube, and the binder is polyvinylidene fluoride PVDF;
preparing a negative plate: polishing a metal lithium sheet in a vacuum box by adopting lithium indium alloy (the atomic percent of lithium is 60%), overlapping the lithium sheet and the indium sheet with the thickness ratio of 6:4, and pressing for 60 minutes under 3000MPa to obtain a lithium indium alloy sheet as a negative electrode sheet, wherein the thickness of the negative electrode sheet is 100 mu m;
and (3) battery assembly: the positive and negative electrode plates are respectively pressed at two sides of the PEO polymer composite solid electrolyte under 25MPa, wherein the positive electrode plate is contacted with the PAN side, and the negative electrode plate is contacted with the PEO side, so that the 2032 button type all-solid battery is prepared.
Example 10
Except for the difference from example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 2, and the other conditions were the same as in example 9.
Example 11
Except for the difference from example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 3, and the other conditions were the same as in example 9.
Example 12
Except for the difference from example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 4, and the other conditions were the same as in example 9.
Example 13
Except for the difference from example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 5, and the other conditions were the same as in example 9.
Example 14
Unlike example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 6: preparation of a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are ball-milled for 30 minutes at normal temperature according to the mass ratio of 60:3:5:2, the mixed powder is transferred into a die, and the positive plate is pressed under 20 MPa;
preparing a negative plate: polishing a metal lithium sheet in vacuum, overlapping the lithium sheet and the indium sheet with the thickness ratio of 6:4, and pressing for 40 minutes under 2000MPa to obtain a lithium-indium alloy sheet as a negative electrode sheet;
preparation of a solid lithium battery: respectively pressing the positive and negative plates on two sides of the PEO polymer composite solid electrolyte under 10MPa, wherein the lithium surface of the negative plate faces the PEO polymer composite solid electrolyte;
the other conditions were the same as in example 9.
Example 15
Unlike example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 7: preparation of a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are ball-milled for 60 minutes at normal temperature according to the mass ratio of 75:6:10:5, the mixed powder is transferred into a die, and the positive plate is pressed under 30MPa;
preparing a negative plate: polishing a metal lithium sheet in vacuum, overlapping the lithium sheet and the indium sheet with the thickness ratio of 6:4, and pressing for 80 minutes under 4000MPa to obtain a lithium-indium alloy sheet as a negative electrode sheet;
preparation of a solid lithium battery: respectively pressing the positive and negative plates at 30MPa on two sides of the PEO polymer composite solid electrolyte, wherein the lithium surface of the negative plate faces the PEO polymer composite solid electrolyte;
the other conditions were the same as in example 9.
Example 16
Unlike example 9, a solid lithium battery was assembled using the PEO polymer solid electrolyte prepared in example 8: preparation of a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are ball-milled for 45 minutes at normal temperature according to the mass ratio of 67.5:4.5:7.5:3.5, and the mixed powder is transferred into a die and pressed into a positive plate under 25 MPa; preparing a negative plate: polishing a metal lithium sheet in vacuum, overlapping the lithium sheet and the indium sheet with the thickness ratio of 6:4, and pressing for 60 minutes under 3000MPa to obtain a lithium-indium alloy sheet as a negative electrode sheet;
preparation of a solid lithium battery: respectively pressing the positive and negative plates at 20MPa on two sides of the PEO polymer composite solid electrolyte, wherein the lithium surface of the negative plate faces the PEO polymer composite solid electrolyte;
the other conditions were the same as in example 9.
Example 17
Solid lithium batteries were assembled using the PEO polymer solid electrolyte prepared in example 1:
the difference from example 9 is that the thicknesses of the positive and negative electrode sheets in example 3 are 250 μm, respectively, and the other conditions are the same as in example 9.
Example 18
Solid lithium batteries were assembled using the PEO polymer solid electrolyte prepared in example 1:
the difference from example 9 is that the active material used for the positive electrode in example 4 is lithium cobaltate, and the other conditions are the same as those in example 9.
Comparative example 1
The remainder of the conditions for comparative example 1 using a single layer PEO polymer solid electrolyte (same composition as the third PEO layer of step c) were the same as in example 9, except that example 9 was followed.
Comparative example 2
Unlike example 9, the PAN side of the sandwich polymer composite solid electrolyte of comparative example 2 was in contact with lithium metal, and the PEO side was in contact with the positive electrode sheet, with the remaining conditions being the same as in example 9.
Comparative example 3
The difference from example 9 is that the second layer electrolyte of comparative example 3 does not contain porous polyimide PI, and the other conditions are the same as example 9.
Comparative example 4
The second layer electrolyte of comparative example 4 did not contain DBDPE, except for the difference from example 9, and the other conditions were the same as in example 9.
Comparative example 5
Unlike example 9, comparative example 5 was prepared in the PAN layer without exposing the mixed solution to low pressure for a while to remove bubbles, and the other conditions were the same as in example 9.
Comparative example 6
In contrast to example 9, the inorganic composite layer was prepared in comparative example 6 by directly coating the mixed solution on a silicone oil-free hydrogel, and the other conditions were the same as in example 9.
Solid lithium cell Performance test of examples and comparative examples
1. Critical temperature test: placing the battery in a hot box, and heating the temperature in the box according to the heating rate of 5 ℃/min until the battery has open fire, and marking the failed temperature as critical temperature;
2. cycle life test: and (3) carrying out cycle test by taking 0.3C as a charge-discharge multiplying power in different voltage ranges at 30 ℃, and stopping the experiment when the battery is obviously shorted, wherein the service life of the battery is considered to be ended.
The solid lithium battery performance test data for each of examples 9 to 18 and comparative example are shown in table 1 below:
table 1: critical temperature and cycle life data for solid lithium batteries
As can be seen from the data in table 1, the critical temperatures of comparative examples 1 to 4 are lower than those of examples, the cycle lives of comparative examples 1 to 3 and 5 are far lower than those of examples, the comparative example 1 adopts a single-layer PEO polymer solid electrolyte, the PI support and the flame retardant of the inorganic composite layer are absent, the safety performance is greatly reduced, and the interface contact with positive and negative pole pieces is not sufficiently improved, so that the cycle life is also reduced; comparative example 2 the three-layer polymer solid electrolyte was pressed in reverse between the positive and negative plates, so that the electrochemical stability window was limited, the critical temperature was lowered, the interfacial stability was far lower than that of the example, the resistance increased, and the cycle life of the battery was reduced; comparative example 3 does not contain a PI bracket, has lower critical temperature and has a cycle life which is nearly twice that of the example; comparative example 4 has no flame retardant, and therefore the critical temperature is significantly reduced, only slightly higher than comparative example 1, but does not affect the cycle life; in comparative example 5, the mixed solution for preparing the PAN layer was not subjected to low pressure for a period of time to remove bubbles, and the critical temperature was not affected, but resulted in a significant reduction in cycle life; comparative example 6 when preparing inorganic composite layer, the mixed solution is directly coated on the surface of hydrogel without silicone oil, PI has no porous structure, the influence of critical temperature and cycle life under low voltage of the prepared battery is not great, but the cycle life under high cut-off voltage is obviously reduced; although the preparation conditions of each of examples 9 to 18 are different, the preparation conditions are all within the scope of the claims, so that the performances are similar, wherein the critical temperature of example 9 and the cycle life in different voltage ranges are remarkably improved compared with those of a comparative example, the main reason is that the three-layer structure polymer composite solid electrolyte of the invention remarkably improves the interface stability with positive and negative plates, the oxidation-resistant PAN layer is contacted with a high-voltage positive electrode, the reduction-resistant PEO is contacted with a lithium metal negative electrode, the electrochemical stability window is expanded, meanwhile, the intermediate layer PI provides high mechanical strength, and the higher cycle life is still maintained even if the electrolyte is charged to about 4.8V; the addition of the flame retardants PI and DBDPE can greatly reduce the flammability of the polymer solid electrolyte, so that the safety of the solid battery is obviously improved.
Claims (10)
1. The PEO polymer solid electrolyte with high safety performance is characterized by comprising a PAN layer contacted with a positive plate, wherein the PAN layer consists of PAN particles, inorganic solid electrolyte particles and lithium salt of a lithium ion secondary battery; a PEO layer in contact with the negative electrode sheet, composed of PEO particles, lithium bistrifluoro-methylsulfonylimi and conductive particles; and an inorganic composite layer disposed between the PAN layer and the PEO layer, consisting of a flame retardant, porous polyimide PI, and LLZO nanoparticles;
the preparation method of the inorganic composite layer comprises the following steps: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to the mass ratio of 50-70:3-8:4-8, stirring to obtain a mixed solution, dripping the mixed solution to the surface of hydrogel immersed in silicone oil, washing the PI-flame retardant film with water, and drying in air.
2. The PEO polymer solid electrolyte of claim 1 wherein the inorganic solid electrolyte particles used in the PAN layer are one of lanthanum lithium zirconate LLZO nano-powder, perovskite type lithium salt, NASICON particles, and the lithium ion secondary battery lithium salt used is one of LiTFSI, chelate boron type lithium salt, chelate phosphorus type lithium salt, perfluoro phosphine type lithium salt, alkyl type lithium salt, sulfonate type lithium salt, lithium aluminate salt, imine lithium salt, and inorganic electrolyte lithium salt.
3. The high safety PEO polymer solid electrolyte of claim 1 wherein the conductive particles in the PEO layer are one of LLZO nanoparticles and lithium aluminum titanium phosphate LATP nanoparticles.
4. The high safety PEO polymer solid electrolyte of claim 1 wherein the flame retardant in the inorganic composite layer is one of decabromodiphenylethane DBDPE, ferrite yellow, hollow glass microspheres, para-aramid fibers, graphene, transition metal dihalides, and hexagonal boron nitride.
5. A PEO polymer solid electrolyte with high safety according to claim 1, wherein the PAN layer thickness is 25-100 μm, the PEO layer thickness is 5-150 μm, the inorganic composite layer thickness is 30-100 μm, and the PEO polymer solid electrolyte total thickness is 100-350 μm.
6. The method for preparing a PEO polymer solid electrolyte with high safety according to claim 1, comprising the steps of:
step one, preparing a PAN layer: adding PAN particles, inorganic solid electrolyte particles and lithium ion secondary battery lithium salt into Dimethylsulfoxide (DMSO) to form a mixed solution, ball-milling the mixed solution, placing the mixed solution at normal temperature and under the pressure of 0.005-0.02MPa for a period of time, pouring the mixed solution into a mould, and vacuum-drying to obtain a film, namely a first PAN layer;
step two, preparing an inorganic composite layer: adding polyimide prepolymer PAA particles, a flame retardant and LLZO nano particles into N-methylpyrrolidone (NMP) according to the mass ratio of 50-70:3-8:4-8, stirring to obtain a mixed solution, dripping the mixed solution to the surface of hydrogel immersed in silicone oil, washing the PI-flame retardant film with water, and drying in air;
step three, preparation of PEO layer: adding PEO particles, liTFSI and LLZO nano particles into dimethyl sulfoxide DMSO according to the mass ratio of 50-65:5-10:3-6, stirring for 2-6 hours to obtain mixed solution, pouring the mixed solution into a mould, and vacuum drying to obtain a solidified film which is the PEO layer;
and fourthly, sequentially superposing the three solid electrolyte layers prepared in the first step to the third step, pressing at 10MPa to 20MPa, and performing vacuum heat treatment to obtain the PEO polymer solid electrolyte.
7. The method for preparing a PEO polymer solid electrolyte with high safety according to claim 6, wherein the mixed solution in the first step is ball-milled for 1-3 hours, placed under low pressure for 12-24 hours, and dried in a mold at 100-120 ℃ for 1-3 hours; step two, stirring the mixed solution for 2 to 6 hours, dripping the mixed solution on the surface of the hydrogel at the temperature of 30 to 60 ℃, flushing the obtained PI-flame retardant film with deionized water for 3 to 5 times, and drying the PI-flame retardant film in air at the temperature of 20 to 35 ℃ for 24 to 48 hours; stirring the mixed solution for 2-6 hours, and vacuum drying in a mould at 60-100 ℃ for 2-6 hours; and step four, the vacuum heat treatment temperature is 150-300 ℃ and the time is 30-60 minutes.
8. The solid lithium battery prepared by the PEO polymer solid electrolyte with high safety performance according to claim 1, comprising a positive plate, a negative plate and the PEO polymer solid electrolyte, wherein the positive plate and the negative plate are positioned on two sides of the PEO polymer solid electrolyte, the positive plate is connected with the PAN layer, and the negative plate is connected with the PEO layer.
9. The method for preparing a solid lithium battery prepared from PEO polymer solid electrolyte with high safety performance according to claim 8, comprising the following steps:
step one, preparing a positive plate: the active material, the conductive agent, the binder and the LLZO inorganic solid electrolyte particles are ball-milled at normal temperature according to the mass ratio of 60-75:3-6:5-10:2-5, and the mixed powder is transferred into a die to be pressed into a positive plate;
step two, selecting a lithium-indium alloy sheet as a negative electrode sheet, and pressing the lithium sheet and the indium sheet to form the lithium-indium alloy sheet;
step three, preparing a solid lithium battery: and respectively pressing the positive and negative plates at 10-30MPa on two sides of the PEO polymer composite solid electrolyte, wherein the lithium surface of the positive plate faces the PEO layer to be connected.
10. The method for preparing a solid lithium battery prepared from PEO polymer solid electrolyte with high safety performance according to claim 9, wherein the active material in the first step is one of nickel cobalt manganese oxide NCM or lithium cobaltate, the conductive agent is one of carbon black, carbon nanotube, conductive graphite, carbon nanofiber and ketjen black, and the binder is one of polyvinylidene fluoride PVDF and polyurethane; ball milling time is 30-60 minutes; the pressing pressure is 20-30MPa;
and in the second step, the thickness ratio of the lithium sheet to the indium sheet used for pressing the lithium indium alloy sheet is 6:4.
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| JP2020136125A (en) * | 2019-02-21 | 2020-08-31 | 時空化学株式会社 | Polymer ceramic composite electrolyte membrane |
| CN113299985A (en) * | 2021-05-20 | 2021-08-24 | 杭州阳名新能源设备科技有限公司 | Preparation method and application of butanedinitrile double-layer composite polymer electrolyte |
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| CN113299985A (en) * | 2021-05-20 | 2021-08-24 | 杭州阳名新能源设备科技有限公司 | Preparation method and application of butanedinitrile double-layer composite polymer electrolyte |
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