CN112086678A - Solid electrolyte, preparation method thereof and solid battery - Google Patents
Solid electrolyte, preparation method thereof and solid battery Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 57
- 239000007787 solid Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000010416 ion conductor Substances 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 229920005601 base polymer Polymers 0.000 claims abstract description 13
- 239000002019 doping agent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 4
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 4
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 4
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910010252 TiO3 Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003292 glue 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
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 3
- BXPLEMMFZOKIHP-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-3-fluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=CC(=C(C#N)C#N)C=CC1=C(C#N)C#N BXPLEMMFZOKIHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical compound C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 claims description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910010942 LiFP6 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910009160 xLi2S Inorganic materials 0.000 claims description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000000306 component Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- -1 lithium nickel cobalt manganese oxide transition metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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- General Physics & Mathematics (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a solid electrolyte and a preparation method thereof, wherein the solid electrolyte comprises the following components: a ceramic-based ionic conductor, a polymeric ionic conductor, and a lithium salt; the polymeric ion conductor includes a base polymer and a dopant. The invention also discloses a solid-state battery. According to the invention, the components of the solid electrolyte are improved and optimized, and the ionic conductivity of the solid electrolyte is improved by the combined use of the ceramic-based ionic conductor, the polymer ionic conductor and the lithium salt, so that the solid electrolyte has smaller interface impedance and good mechanical property; in addition, the stability is good. According to the invention, by adding a trace amount of electrolyte into the positive electrode plate, the interface contact impedance can be effectively reduced, and the diffusion rate of lithium ions in a solid phase is improved. The solid-state battery prepared by the invention has excellent performance, the maximum working voltage is more than 4V, the safety performance is good, and the solid-state battery has good application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a solid electrolyte, a preparation method thereof and a solid battery.
Background
The solid-state battery has better safety performance, is considered as a next-generation lithium ion battery, can replace a liquid lithium ion battery in the future, and has a prospect of large-scale application on new energy automobiles.
Currently, a number of problems limit further applications of solid-state batteries. The solid electrolyte is a core component of the solid battery, and the contact interface between the solid electrolyte and the polar plate is a solid interface, so that how to reduce the interface impedance of the solid interface is always a key problem to be solved because the interface impedance of the solid interface is very high. The ceramic-based solid electrolyte is a commonly used solid electrolyte, and the interface impedance between the ceramic-based solid electrolyte and the positive electrode plate is large, and the mechanical property is also poor. There is a technology (CN108336402A) that improves the interface contact and mechanical properties by mixing a ceramic-based solid electrolyte with a high molecular polymer. The impedance of the high molecular polymer on the interface is superior to that of a ceramic solid electrolyte due to the viscoelasticity of the high molecular polymer, but the high molecular polymer is not a polymer solid ion conductor after all, and the ionic conductivity of the solid electrolyte cannot be improved. In addition, the mixing of the polymer and the solid electrolyte has stability problems, such as the instability of the traditional polyethylene oxide (PEO) polymer under high voltage (which is also the reason that the existing PEO polymer cannot be compounded with the ceramic composite electrolyte), and the ion conductivity of the polymer is not high (1 × 10) at room temperature-6S/cm), there are many problems faced in modifying a solid electrolyte with a high molecular weight polymer.
On the other hand, the existing plate of the liquid lithium ion battery is not suitable for the design concept of the solid battery. The electrode plate of the liquid lithium ion battery is a porous electrode, which is beneficial to the wetting of liquid electrolyte. The multiplying power performance is improved, the electrode plate is also thinner, and the electrode plate which is too thick cannot obtain good cycle performance and multiplying power performance. The solid-state battery is in solid-solid contact, and the electrode plate developed according to the traditional solid-liquid interface theory cannot exert the maximum benefit of the solid-state battery when being applied to the solid-state battery.
Disclosure of Invention
In view of the above-described drawbacks, an object of the present invention is to provide a solid electrolyte having good stability and having small interfacial resistance by improving and optimizing the composition of the solid electrolyte to improve the ionic conductivity and mechanical properties thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the solid electrolyte comprises the following components in percentage by mass: 10% -60% of ceramic-based ion conductor, 40% -90% of polymer ion conductor and 0.5% -10% of lithium salt; the polymeric ion conductor includes a base polymer and a dopant; the polymer ion conductor is a glassy super ion conductor containing thio and phenyl functional groups; the glass transition temperature of the polymer ion conductor is high.
As a preferable technical scheme, the mass ratio of the base polymer to the dopant is 1: (1-8); the base polymer is one of poly-p-phenylene sulfide (PPS), poly-m-phenylene sulfide (PMPS) and poly-dibenzothiophene sulfur (PDTS); the dopant is one of tetrachloro-p-benzoquinone (chloranil), 2, 3-dichloro-5, 6-dicyano-p-benzoquinone (DDQ), 2-fluoro-7, 7,8, 8-tetracyano-quinodimethane (FTCNQ) and 7,7,8, 8-tetracyano-p-benzoquinodimethane (TCNQ).
As a preferred technical scheme, the ceramic-based ion conductor is Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3(LATP)、LiAlO2(LAO)、Li7-xLa3Zr2-xMx012(M＝Ta，Nb)(0.25＜x＜2)(LLZMO)、Li7+xGeP3-xS11(LGPS)、xLi2S·(100-x)P2S5(LPS). The grain diameter of the ceramic-based ionic conductor is between 50nm and 10 mu m. In the prior art, if a single ceramic-based ionic conductor is formed into a film, a high-molecular binder such as polyvinylidene fluoride is added, and the film is formed by tape casting after a solvent is mixed. If the particle diameter of the ceramic-based ion conductor is too large, uniformity of film formation is not favorable, but if it is too smallThe active lithium ion channel tends to be aggregated and the specific surface area is too large, so that the active lithium ion channel is lost much, and it is preferable to use a ceramic-based ion conductor of about 500 nm. Although the present invention uses a polymer ion conductor in place of the polymer binder, the particle size range is still applicable.
As a preferred technical solution, the lithium salt is LiFP6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4、LiAsO4At least one of (1). The lithium salt can further improve the transference number of lithium ions in the solid electrolyte, is beneficial to improving the electric conductivity, and researches find that the performance improvement effect of the solid electrolyte by adopting the multi-component lithium salt is better than that of a single-component lithium salt. Preferably, the lithium salt is LiBF4And a mixed lithium salt of LiDFOB in a mass ratio of 1: 1.
Another object of the present invention is to provide the above method for preparing a solid electrolyte, comprising the steps of:
(1) heating a mixture of a base polymer and a doping agent at the heating temperature of 150-280 ℃, wherein the heating temperature can be in an argon environment or in an air environment, the heating temperature needs to be close to the melting point of the base polymer, generating sites for transmitting and transferring lithium ions through heating reaction to form a polymer ion conductor, and cooling and grinding the polymer ion conductor into powder with the particle size of below 100 mu m for later use; preferably, the heating temperature may be 150 ℃, 180 ℃, 200 ℃, 250 ℃, 280 ℃ or the like, and may be selected according to the type of the base polymer to be actually selected.
(2) Adding lithium salt, a polymer ion conductor and a ceramic-based ion conductor into a polar solvent for dissolving to obtain a slurry-like glue solution; and coating the slurry-like glue solution on a base material, and drying to form a film-like material on the base material, namely the solid electrolyte. Further, the polar solvent is one of tetrahydrofuran, acetone and isopropanol; the base material is a metal film, and the material of the metal film is copper or aluminum.
The solid electrolyte exists in a film form, and the thickness thereof has a certain influence on the performance of the solid battery, and when the thickness is large, the battery impedance becomes large, and when the thickness is low, the mechanical strength of the solid electrolyte is reduced, and preferably 20 μm. The solid electrolyte is electronically insulated and ion conducted to realize the shuttle of lithium ions between the anode plate and the cathode plate. And the contact between the positive and negative electrode plates is blocked, resulting in short circuit failure of the battery.
A third object of the present invention is to provide a solid-state battery comprising a positive electrode plate, a negative electrode plate, and the solid-state electrolyte of any one of claims 1 to 4, the solid-state electrolyte being located between the positive electrode plate and the negative electrode plate, the solid-state electrolyte having a thickness of 15 to 70 μm, a room-temperature conductivity of more than 1 x 10 "4S/cm, and a young' S modulus of more than 3 mPa.
The solid-state battery consists of the solid electrolyte, the positive electrode plate and the negative electrode plate. The negative pole plate is a pole plate which is commonly used in the field, and metal lithium is generally selected; the silicon negative electrode can be selected as a negative electrode material with higher specific capacity to prepare a negative electrode plate, so that the silicon negative electrode has more advantages in energy density. In a liquid battery, when metal lithium is selected to act as a negative electrode, lithium dendrite is generated due to uneven current density, and the cycle and safety performance of the battery are affected. In the solid-state battery, the mechanical strength of the solid-state electrolyte can inhibit the generation of lithium dendrite, so that the metal lithium negative electrode plate has better matching property with the solid-state electrolyte.
As a preferred technical solution, the positive electrode plate includes a current collector and a positive active material loaded on the current collector; the positive active material comprises a conductive agent, a binder, electrolyte and a positive material with a ceramic-based ion conductor coated on the surface. In the solid-state battery, since there is no electrolyte for the migration of lithium ions, the excessive gap in the positive electrode plate generates high contact resistance, which is not favorable for the rate performance of the battery. In the present invention, the positive electrode plate is designed to be a plate with low porosity, so that the contact resistance between material particles can be reduced to the maximum extent. For a solid-state battery, the lower the porosity is, the better the porosity is, but the porosity close to zero has certain difficulty in the preparation process and causes the stress inside the material to be larger, and the porosity of the positive electrode plate is less than 10%. Low porosity plates are generally obtained by rolling the plates with a temperature, generally selected between 100 and 150 c, and in order to obtain a lower porosity, in some embodiments, 2-3 repeated rolls are required in addition to increasing the rolling pressure.
As a preferred technical scheme, the ceramic-based ion conductor is Li7La3Zr2O12(LLZO)、LixLa2/3-xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3(LATP)、LiAlO2(LAO)、Li7-xLa3Zr2-xMx012(M ═ Ta, Nb) (0.25 < x < 2) (LLZMO); the ceramic-based ionic conductor is a commercially available material.
The positive electrode material is a lithium metal oxide capable of being extracted and inserted with lithium, is mostly nanoparticles and is lithium iron phosphate, lithium manganese oxide, lithium cobalt phosphate or lithium manganese nickel oxide, lithium cobalt oxide or LiNiO2At least one of (a); the coating thickness of the ceramic-based ionic conductor on the surface of the anode material is 10-100 nm. When the surface of the anode material particle is coated with the ceramic-based ion conductor, the transference number of lithium ions is increased, and the diffusion rate is increased. Can also prevent the dissolution of some high-voltage anode materials such as lithium nickel cobalt manganese oxide transition metals. Therefore, the invention can make the positive plate very thick, generally more than 300 μm, without changing the rate performance of the battery. However, for cylindrical or wound cells, the thickness of the positive electrode plate is generally not more than 1mm in this type of cell, considering the bending of the plate in the cell and the mechanical properties of the thick electrode and the load-bearing capacity of the current collector.
As a preferred technical solution, the current collector is aluminum; the electrolyte accounts for 0.1-3% of the total mass of the positive active material, can properly relieve stress, can moisten the material, and can effectively reduce interface impedance when contacting with a solid electrolyte, and the electrolyte with the proportion less than 3% of the mass of the positive electrode plate can not influence the safety performance of the solid battery; the positive active material is cast into a film by a solvent-free method and is loaded on at least one surface of a current collector. The solvent-free method is also called a dry process, that is, the positive active material is dissolved without using a solvent in the process of loading the positive active material on a current collector. Although solvent-containing slurries are more viscous for film coating, the solvent cannot be completely removed from the material, and the solvent is not balanced against the electrical properties of the cell. However, the slurry viscosity of the dry process is very high, and the coating process is more difficult to realize than the wet coating process with the solvent.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the components of the solid electrolyte are improved and optimized, and the ionic conductivity of the solid electrolyte is improved by the combined use of the ceramic-based ionic conductor, the polymer ionic conductor and the lithium salt, so that the solid electrolyte has smaller interface impedance and good mechanical property; in addition, the polymer ion conductor has good stability under high voltage, and the problem of insufficient stability of the solid electrolyte in a high-voltage environment is remarkably improved by introducing the polymer ion conductor into the solid electrolyte. According to the invention, by adding a trace amount of electrolyte into the positive electrode plate, the interface contact impedance can be effectively reduced, and the diffusion rate of lithium ions in a solid phase is improved; meanwhile, the thick positive plate with low porosity enables the energy density of the solid-state battery to be higher. The solid-state battery prepared by the invention has excellent performance, the maximum working voltage is more than 4V, the safety performance is good, and the solid-state battery has good application prospect.
Drawings
FIG. 1 is a schematic diagram of an assembly structure of a positive electrode plate, a solid electrolyte and a negative electrode plate;
fig. 2 is a first charge and discharge curve of the solid-state batteries manufactured in example 1, comparative example 1, and comparative example 6;
fig. 3 is a graph showing cycle performance of the solid-state batteries manufactured in example 1, comparative example 2, comparative example 3, and comparative example 5;
fig. 4 is an SEM image of the surface of a lithium metal negative electrode of example 1 after 200 cycles;
reference numerals: 1-positive electrode plate, 2-solid electrolyte and 3-negative electrode plate.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few 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. It should be noted that the raw materials or processes used in the following preparation methods are those conventionally used in the art, unless otherwise specified.
The solid electrolyte comprises the following components in percentage by mass: 10% -60% of ceramic-based ion conductor, 40% -90% of polymer ion conductor and 0.5% -10% of lithium salt; the polymeric ion conductor includes a base polymer and a dopant; the polymer ion conductor is a glassy super ion conductor containing thio and phenyl functional groups; the glass transition temperatures of the polymer ion conductors are all higher, and the following table 1 shows the comparison between the glass transition temperatures of the three polymer ion conductors proposed by the present invention and the glass transition temperature of PEO, which indicates that the glass transition temperature of the polymer ion conductor in the present invention is significantly higher than that of the conventional high molecular polymer. In addition, compared with PEO, the polymer ion conductor provided by the invention has stronger polarity and larger dielectric constant, and indirectly reflects that the carrier decoupling motion released from the polymer greatly improves the dissociation degree of the salt. These structures and properties result in the polymeric ionic conductors of the present invention having higher ionic conductivity at room temperature.
TABLE 1 glass transition temperature of Polymer ion conductor
| Polymer ion conductor | Ratio of | Glass transition temperature/. degree.C |
| PPS + chloranil | 4:1 | 230 |
| PMPS + chloranil | 4:1 | 143 |
| PPS+DDQ | 4:1 | 260 |
| PMPS+DDQ | 4:1 | 155 |
| PDTS+DDQ | 4:1 | 254 |
| PEO | / | -25 |
1. Preparation of solid electrolyte:
according to the composition design in table 2, the base polymer and the dopant are mixed in a mass ratio of 5: 1, then placing the mixture in an argon environment, heating at 200 ℃ for 24h, cooling, and grinding to reduce the particle size of the material to about 50 mu m to obtain a polymer ion conductor for later use;
and putting the ceramic-based ionic conductor into a ball mill, and ball-milling for 8 hours at the rotating speed of 1000 revolutions per minute to enable the particle size to be smaller to about 500 nm. And dissolving a mixture consisting of the ceramic-based ionic conductor, the polymer ionic conductor and the lithium salt in DMF (dimethyl formamide), uniformly stirring, and coating on the surface of the aluminum foil. After the solvent is volatilized, a solid electrolyte with the thickness of 50 mu m is obtained; table 2 gives the solid state electrolyte composition and performance parameters, wherein for the lithium salt composition, the mass ratio of LiTFSI and litdob in the lithium salt jointly consisting of LiTFSI and litdob is 3: 1.
Table 2 solid state electrolyte composition and performance
2. Preparation of positive electrode plate
Uniformly mixing 1% of conductive agent single-walled carbon nanotube and 2% of binding agent (mixture of polytetrafluoroethylene and polyvinylidene fluoride in a mass ratio of 1: 1) by a planetary screw rod dispersion machine, then forming slurry by high-speed shearing, and then adding electrolyte (the electrolyte is 1.2mol/L LiPF) accounting for 0.5% of the total mass of the positive active material6The solvent is a mixture of EC and EMC according to a volume ratio of 1: 1), the balance is a single crystal lithium nickel cobalt manganese oxide positive electrode material (NCM811, the coating method is a conventional solid phase sintering method) with the surface coated with 50nmLATP, high-speed dispersion is carried out for 4 hours, the mixture is coated on the surface of a 12 mu m aluminum foil, hot rolling is carried out, and positive electrode plates with different porosities are prepared by changing the rolling conditions.
To better illustrate the advantages of the positive electrode plate of the present invention, comparative positive electrode plates of different compositions were prepared in the same manner, and information on the positive electrode plate is shown in table 3.
TABLE 3 Positive electrode plate and comparative positive electrode plate compositions and parameters
3. Preparation of solid-state batteries
The solid electrolyte, the positive electrode plate and the metallic lithium negative electrode (with the thickness of 50 mu m) are assembled to assist some common lugs for leading external current and external packing sealing materials to manufacture the solid battery. Fig. 1 is a schematic view of an assembly structure of a positive electrode plate 1, a solid electrolyte 2, and a negative electrode plate 3.
Comparative example
The solid-state cell had PEO (molecular weight > 600000) with a thickness of 50 μm as the solid-state electrolyte, and the others remained unchanged;
the solid-state battery takes LLZTO/polyvinylidene fluoride with the thickness of 50 mu m as a solid electrolyte, the mass ratio of the LLZTO to the polyvinylidene fluoride is 3:1, and the others are kept unchanged;
1M LiPF for liquid lithium ion battery6EC and EMC were dissolved as electrolytes, and others were kept unchanged.
The solid-state battery had the comparative positive electrode plate in table 2 as the positive electrode plate, and the others remained unchanged.
Table 4 shows the information of the positive electrode plate, the negative electrode plate, the electrolyte or the electrolyte of the medium-state batteries of each example and each comparative example.
TABLE 4 solid-state battery compositions and Performance
The test method of the above performances is as follows:
1. testing of solid electrolyte ionic conductivity
The solid electrolyte is cut into 2cm multiplied by 2cm, and is placed between 2 steel sheets with the thickness of 1mm and the diameter of 1cm of SUS304, and the upper steel sheet and the lower steel sheet are respectively connected with a working electrode and a counter electrode of an electrochemical workstation. Electrochemical AC impedance spectrum is selected for testing, and the frequency range is 10mHz-100 kHz. After reading the resistance value R, the ionic conductivity (: ionic conductivity; A cross-sectional area: d thickness of solid electrolyte) was determined from d/AR
2. Porosity testing
The porosity of the positive electrode plate at a certain area density was calculated from the true density of each material to be 0Volume V1, the actual measured volume of the positive electrode plate at a certain areal density is V2。V2-V1/V2X 100% is the porosity.
3. Energy density and Clay of discharge capacity calibration
The solid-state battery is charged and discharged for the first time at 0.1C in a range of 3.0-4.2V. And the second time of charging and discharging at 0.1C, and the energy of discharging divided by the weight of the battery is the energy density of the battery. The discharged capacity of the battery is the gram-discharge capacity of the battery when the weight of the positive electrode active material (NCM811) is the weight of the positive electrode active material. Similarly, the gram discharge capacity of 1C was also measured.
4. Solid state battery cycling performance testing
The solid-state battery is placed in an environment with the temperature of 25 ℃ and is subjected to charge-discharge circulation at the temperature of 0.5C/1C and between 3.0 and 4.3V. The decay of the discharge capacity was recorded.
As can be seen from table 2, the ion conductivity will be improved by about 1 fold after the lithium salt is changed from a single component to a multi-component. The proportion of the LLZTO ceramic-based ionic conductor is increased in the solid electrolyte, and the ionic conductivity of the LLZTO ceramic-based ionic conductor is further improved; but the mechanical properties of the solid electrolyte are affected because the ratio of the polymer ion conductor is too low. The combination of PMPS basic polymer and chloro jade can improve the ionic conductivity of the solid electrolyte to 10-3And S/cm grade. As can be seen from comparative examples 3, 4, and 5, the addition of the electrolyte, the decrease in porosity, and the coating of the positive electrode 811 all improve the discharge performance and capacity of the solid-state battery.
Table 4 shows that after increasing the discharge current, the solid-state batteries of examples 1 and 2 containing the solid-state electrolyte proposed by the present invention exhibited significantly higher capacity than the solid-state batteries of comparative examples 1 and 2 containing other solid-state electrolytes, the PEO solid-state electrolyte was unstable at high voltage, consumed more active Li at the positive electrode, and the LLZTO/polyvinylidene fluoride interfacial resistance was large, affecting the discharge capacity at large current.
Fig. 2 is a first charge-discharge curve of the batteries prepared in example 1, comparative example 1 and comparative example 6, and it can be seen that the first gram capacity of the PEO solid electrolyte discharged is only 178mAh/g, and the first coulombic efficiency is about 78%, which indicates that the PEO solid electrolyte is unstable at high voltage, and part of lithium extracted from the positive electrode participates in the side reaction, thereby affecting the exertion of the discharge capacity. From the charge and discharge curves of example 1 and comparative example 6, the positive electrode plate and the conventional positive electrode plate were substantially identical. Particularly, the time of the constant voltage stage shows that the electrical property of the positive electrode plate of the solid-state battery reaches the same level as that of the conventional positive electrode plate.
Fig. 3 is a comparison of cycle performances of the batteries manufactured in example 1, comparative example 2, comparative example 3, and comparative example 4, and it can be seen that the battery manufactured in example 1 can achieve less degradation in 200 cycles of charge and discharge cycles. While the cell prepared in comparative example 2 initially decayed relatively normally with cycling, but then suddenly experienced a capacity "jump", mainly due to the increase in interfacial resistance of the ceramic-based solid electrolyte. The cell prepared in comparative example 3 shows no water jump, but shows a rapid decay, since the uncoated 881 positive electrode material has significantly weaker lithium ion transport and transport ability than the 881 positive electrode active material coated with LATP of example 1. In contrast, the battery of comparative example 5, because the positive electrode plate had no effect of wetting with a trace amount of electrolyte and relieving internal stress, the cycle was also rapidly attenuated after a certain number of cycles.
Fig. 4 is an SEM image of the surface of the negative electrode of lithium metal of the solid-state battery manufactured in example 1 after 200 cycles, and it can be seen that lithium dendrites are not generated on the surface of lithium metal.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. A solid state electrolyte characterized by: the composite material comprises the following components in percentage by mass: 10% -60% of ceramic-based ion conductor, 40% -90% of polymer ion conductor and 0.5% -10% of lithium salt; the polymeric ion conductor includes a base polymer and a dopant; the polymer ion conductor contains sulfenyl and phenyl functional groups.
2. The solid electrolyte of claim 1, wherein: the mass ratio of the base polymer to the dopant is 1: (1-8); the base polymer is one of poly-p-phenylene sulfide, poly-m-phenylene sulfide and poly-dibenzothiophene sulfur; the dopant is one of tetrachloro p-benzoquinone, 2, 3-dichloro-5, 6-dicyan p-benzoquinone, 2-fluoro-7, 7,8, 8-tetracyanoquinodimethane and 7,7,8, 8-tetracyanoterephthalquinodimethane.
3. The solid electrolyte of claim 1, wherein: the ceramic-based ion conductor is Li7La3Zr2O12、LixLa2/3-xTiO3、Li1+xAlxTi2-x(PO4)3、LiAlO2、Li7-xLa3Zr2-xMx012、Li7+xGeP3-xS11、xLi2S·(100-x)P2S5At least one of; wherein: li7-xLa3Zr2-xMx012Wherein M is Ta or Nb, and 0.25 < x < 2.
4. The solid electrolyte of claim 1, wherein: the lithium salt is LiFP6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4、LiAsO4At least one of (1).
5. The method for producing a solid electrolyte according to any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) heating a mixture of a base polymer and a doping agent, melting the material by heating to generate sites for transporting and migrating lithium ions, forming a polymer ion conductor, cooling and grinding into powder for later use;
(2) adding lithium salt, a polymer ion conductor and a ceramic-based ion conductor into a polar solvent for dissolving to obtain a slurry-like glue solution; and coating the slurry-like glue solution on a base material, and drying to form a film-like material on the base material, namely the solid electrolyte.
6. The method of claim 5, wherein: the heating temperature is 150-280 ℃; the polar solvent is one of tetrahydrofuran, acetone and isopropanol; the base material is a metal film, and the material of the metal film is copper or aluminum.
7. A solid-state battery characterized by: comprising a positive electrode plate, a negative electrode plate and a solid-state electrolyte according to any one of claims 1 to 4, which is located between the positive electrode plate and the negative electrode plate.
8. The solid-state battery according to claim 7, characterized in that: the positive electrode plate comprises a current collector and a positive active material loaded on the current collector; the positive active material comprises a conductive agent, a binder, electrolyte and a positive material with a ceramic-based ion conductor coated on the surface.
9. The solid-state battery according to claim 8, characterized in that: the ceramic-based ion conductor is Li7La3Zr2O12、LixLa2/3-xTiO3、Li1+xAlxTi2-x(PO4)3、LiAlO2、Li7-xLa3Zr2-xMx012At least one of, wherein: li7- xLa3Zr2-xMx012Wherein M is Ta or Nb, and x is more than 0.25 and less than 2; the anode material is lithium iron phosphate, lithium manganese oxide, lithium cobalt phosphate or lithium manganese nickel oxide, lithium cobalt oxide, LiNiO2At least one of (a); the coating thickness of the ceramic-based ionic conductor on the surface of the anode material is 10-100 nm.
10. The solid-state battery according to claim 8, characterized in that: the current collector is aluminum; the electrolyte accounts for 0.1-3% of the total mass of the positive active material.
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Application publication date: 20201215 |