CN116487679A - Composite solid electrolyte, preparation method and battery - Google Patents
Composite solid electrolyte, preparation method and battery Download PDFInfo
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- CN116487679A CN116487679A CN202310518618.6A CN202310518618A CN116487679A CN 116487679 A CN116487679 A CN 116487679A CN 202310518618 A CN202310518618 A CN 202310518618A CN 116487679 A CN116487679 A CN 116487679A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 83
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000007654 immersion Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 125000003636 chemical group Chemical group 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 PEGDMA Polymers 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000002203 sulfidic glass Substances 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000001513 hot isostatic pressing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 238000002490 spark plasma sintering Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- 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)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a composite solid electrolyte, a preparation method and a battery, and relates to the technical field of secondary battery materials. The composite solid electrolyte comprises porous particles and solid electrolyte coated on the surfaces of the porous particles, wherein the solid electrolyte is adsorbed on the surfaces of the porous particles through chemical groups. The preparation method comprises the following steps: and soaking the porous particles in a solid electrolyte precursor solution to obtain immersion porous particles. And carrying out solid-state treatment on the immersion liquid porous particles to obtain solid-state porous particles. And (3) carrying out composite treatment on the solid porous particles and the polymer solid electrolyte to obtain the composite solid electrolyte. The composite electrolyte can effectively improve the electrochemical performance of the solid-state battery and effectively improve the circulation stability at room temperature.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to a composite solid electrolyte, a preparation method and a battery.
Background
With the rise and development of the fields of electric automobiles, large-scale energy storage, smart grids, energy Internet and the like, new energy storage devices are deeply changing the development of human society, influencing the energy generation, acquisition and utilization modes and providing new requirements for the performance of the energy storage devices. As a representative of clean energy, lithium ion batteries are one of the most competitive electrochemical energy storage devices due to their high specific energy/power, environmental friendliness, long service life, and the like. Higher energy density, higher power density, longer cycle life, and safer lithium batteries are important directions for the development of the energy storage industry for the next few years, but the energy density of traditional lithium ion batteries based on oxide positive electrodes and graphite negative electrodes is getting closer to its theoretical upper limit. Meanwhile, the current commercial lithium ion battery mainly adopts organic liquid electrolyte as a medium for transporting anions and cations between anode and cathode, so that side reactions are inevitably generated in the process of charging and discharging the lithium ion battery, and phenomena such as volatilization, leakage and the like of the electrolyte in the process of battery circulation can cause irreversible attenuation of battery capacity, and the service life of the lithium ion battery is influenced. In addition, safety problems caused by organic combustible electrolytes raise public concerns about the safety of lithium ion batteries.
The solid electrolyte is adopted to replace the solid lithium battery of the liquid organic electrolyte, and the positive electrode material and the negative electrode material with higher specific capacity are hopeful to be used, so that a battery system with higher specific energy is realized, the safety problem of the battery can be thoroughly solved, the development direction of a secondary battery in the future is met, and the battery is an ideal power supply for electric automobiles and large-scale energy storage. The existing solid electrolyte mainly comprises inorganic solid electrolyte, polymer or composite solid electrolyte, but the lower ionic conductivity becomes a difficult problem for restricting the application of the solid electrolyte.
Disclosure of Invention
In order to solve the technical problems, the present disclosure provides a composite solid electrolyte, a preparation method and a battery.
The technical problems of the present disclosure are solved by adopting the following technical schemes.
A first aspect of the present disclosure provides a composite solid electrolyte comprising porous particles and a solid electrolyte coated on the surfaces of the porous particles, wherein the solid electrolyte is adsorbed on the surfaces of the porous particles through chemical groups.
A second aspect of the present disclosure provides a method for preparing a composite solid electrolyte as described above, comprising:
s1, soaking porous particles in a solid electrolyte precursor solution to obtain immersion porous particles;
s2, carrying out solid-state treatment on the immersion liquid porous particles to obtain solid-state porous particles;
and S3, carrying out composite treatment on the solid porous particles and the polymer solid electrolyte to obtain the composite solid electrolyte.
Further, in a preferred embodiment of the present disclosure, the porous particles are subjected to a pretreatment, which is one or more of atmospheric sintering, plasma surface treatment, magnetron sputtering treatment, and vacuum evaporation treatment, prior to step S1.
Further, in a preferred embodiment of the present disclosure, in step S1, the solid electrolyte precursor is selected from one or more of an oxide solid electrolyte precursor, a sulfide solid electrolyte precursor, and a halide solid electrolyte precursor.
Further, in a preferred embodiment of the present disclosure, in step S2, the solid-stating process is a sintering process.
Further, in a preferred embodiment of the present disclosure, the sintering process is an atmospheric sintering process, a hot press sintering process, a hot isostatic pressing sintering process, or a plasma sintering process; the atmosphere of the sintering treatment is inert gas, air or oxygen.
Further, in a preferred embodiment of the present disclosure, the sintering process is performed at a temperature of 100 ℃ to 1000 ℃ for a time of 1 to 12 hours.
Further, in a preferred embodiment of the present disclosure, in step S3, the composite treatment of the solid-state porous particles and the polymer solid electrolyte includes:
dispersing the solid porous particles, the polymer matrix and lithium salt in a solvent, and mixing to obtain mixed slurry;
and removing the solvent in the dispersion liquid to obtain the composite solid electrolyte.
Further, in preferred embodiments of the present disclosure, the polymer matrix is selected from one or more of PEO, PVDF, PEG, PMMA, PVDF-HFP, PEGDMA, PVA, PPC, PAN and composites of the foregoing materials.
A third aspect of the present disclosure provides a solid-state battery comprising: a positive electrode, a negative electrode, and a composite solid electrolyte as described, the composite solid electrolyte being disposed between the positive electrode and the negative electrode.
The composite solid electrolyte, the preparation method and the battery have the beneficial effects that:
the porous particles are used as base materials, solid electrolyte precursor solution is immersed and solid-state treatment is carried out, so that the solid electrolyte coated porous composite material is prepared, then the porous composite material is compounded with polymer electrolyte with high ion conductivity, and finally the composite solid electrolyte material with high ion transmission rate, good mechanical strength and stable chemical property is prepared. Based on the characteristics of high porosity and uniform pore size distribution of the porous material, the surface of the porous material is coated with the solid electrolyte, so that more contact area with the polymer electrolyte can be provided, and the ion transmission rate is improved. Meanwhile, the special structure of the porous material can also improve the mechanical strength and chemical stability of the composite solid electrolyte material. The prepared composite solid electrolyte material has high ion transmission rate, good mechanical strength and stable chemical property, and can be applied to electrochemical devices such as lithium ion batteries, sodium ion batteries, lithium sulfur batteries, super capacitors and the like. Meanwhile, the preparation method has the advantages of simple preparation process and low cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM image of a composite solid electrolyte of example 1 of the present disclosure;
fig. 2 is a battery cycle diagram of the composite solid electrolyte of example 1 of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The composite solid electrolyte, the preparation method and the battery according to the embodiment of the invention are specifically described below.
The implementation provides a composite solid electrolyte, which comprises porous particles and a solid electrolyte coated on the surfaces of the porous particles, wherein the solid electrolyte is adsorbed on the surfaces of the porous particles through chemical groups.
The present embodiment also provides a method for preparing the above composite solid electrolyte, which includes the steps of:
s1, soaking porous particles in a solid electrolyte precursor solution to obtain immersion porous particles;
s2, carrying out solid-state treatment on the immersion liquid porous particles to obtain solid-state porous particles;
and S3, carrying out composite treatment on the solid porous particles and the polymer solid electrolyte to obtain the composite solid electrolyte.
Specifically, in one embodiment of the present disclosure, in step S1, the porous particles are an inorganic material having high porosity and uniform pore size distribution, and may be zeolite porous particles, porous ceramic particles, or the like, for example, and the present disclosure is not particularly limited.
Further, the porous particles have a particle diameter of 500nm to 30000nm, more preferably, 500nm to 10000nm. Through the hole structure of the porous particles, the adsorption area of the product can be increased, and more solid electrolyte precursors can be adsorbed.
Further, in a preferred embodiment of the present disclosure, the porous particles are subjected to a pretreatment, which is one or more of atmospheric pressure sintering, spark plasma sintering, plasma surface treatment, magnetron sputtering treatment, and vacuum evaporation treatment, prior to step S1.
Specifically, normal pressure sintering is to sinter a material at atmospheric pressure without pressurizing it. The spark plasma sintering is performed in a plasma sintering furnace. For example, porous particles are placed in a graphite mold and sintered using a spark plasma sintering furnace. Specifically, the plasma surface treatment may be, for example, placing porous particles in a plasma generating apparatus, with CF 4 、N 2 、CCl 4 And the like as a reaction gas, and treating the porous particles. Specifically, the magnetron sputtering treatment is to place porous particles in a magnetron sputtering device, vacuumize, introduce argon with a certain pressure, introduce argon plasma gas to bombard a target material, and sputter elements on the surfaces of the porous particles. Specifically, the vacuum evaporation process heats and plates the modified material onto the porous particles in a vacuum environment.
Through the pretreatment process, the structure of the porous particles is improved, or special chemical groups are formed on the surfaces of the porous particles, so that the surface modification of the porous particles is realized, the interface performance of the solid electrolyte can be improved, and the electrochemical performance of the battery is improved.
Preferably, in one embodiment, the step of pre-treating the porous particles comprises: porous particlesImmersing in Kh550 or other coupling agent for 10-60 min, and loading in plasma generator 4 Is a reaction gas. The reaction pressure is 10-15 Pa, the reaction power is 100-200W, and the reaction time is 5-15 min, so as to obtain the pretreated porous particles. By plasma surface modification, the surface of the porous particles is collided with the plasma to form high active groups on the surfaces of the particles.
Further preferably, in step S1, the solid electrolyte precursor is selected from one or more of an oxide solid electrolyte precursor, a sulfide solid electrolyte precursor, and a halide solid electrolyte precursor.
Preferably, the lithium oxide solid electrolyte is Li x La y TiO 3 ，Li a Al b M1 2-b P 3 O g Or Li (lithium) c La d M2 e Zr f One or more of Og, wherein 0.1 < x < 1, 0 < y < 1, 0.1 < a < 2, 0 < b < 2, 5 < c < 8, 1.5 < d < 4, 0.1 < e < 2, 0 < f < 2, 10 < g < 13, M1 is selected from one or two of Ge and Ti, and M2 is selected from one or more of Nb, ta, ga and Al.
Preferably, the lithium sulfide solid electrolyte is one or more of LiPSX (x=cl, br, I), liSiPSX (x=cl, br, I), lisgps, and LiPS;
in the present invention, the concentration of the precursor solution of the solid electrolyte is in the range of 0.5mol/L to 10mol/L, preferably 1mol/L to 3mol/L. For example, 1mol/L, 2mol/L, 3mol/L, etc.
Further, in a preferred embodiment of the present disclosure, in step S2, the solid-stating process is a sintering process. Specifically, the sintering treatment is normal pressure sintering treatment, hot pressing sintering treatment, hot isostatic pressing sintering treatment or plasma sintering treatment; the atmosphere of the sintering treatment is inert gas, air or oxygen.
Further, in a preferred embodiment of the present disclosure, in step S2, the sintering treatment is performed at a temperature of 100 ℃ to 1000 ℃ for a time of 1 to 12 hours. Further, the temperature of the sintering treatment is preferably 200 ℃ to 700 ℃; the sintering treatment time is 3-8 h. The solid-state porous particles are obtained by densifying porous particles impregnated with the solid electrolyte precursor by sintering treatment.
Further, in a preferred embodiment of the present disclosure, in step S3, the composite treatment of the solid-state porous particles and the polymer solid electrolyte includes: dispersing the solid porous particles, the polymer matrix and lithium salt in a solvent, and mixing to obtain mixed slurry; and removing the solvent in the dispersion liquid to obtain the composite solid electrolyte.
Further, the solvent may be acetonitrile, ethanol, methanol, or the like.
Further, in preferred embodiments of the present disclosure, the polymer matrix is selected from one or more of PEO (polyethylene oxide), PVDF (polyvinylidene fluoride), PEG (polyethylene glycol), PMMA (polymethyl methacrylate), PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene), PEGDMA (polyethylene glycol dimethacrylate), PVA (polyvinyl alcohol), PPC (polymethyl ethylene carbonate), PAN (polyacrylonitrile), and composites of the above materials.
Further, in an embodiment of the present disclosure, the lithium salt is selected from LiTFSI, liCF 3 SO 3 、LiN(SO z CF 3 ) One or more of LiBOB.
Further, in a preferred embodiment of the present disclosure, the weight ratio of solid-stating porous particles, polymer matrix, and lithium salt is 0.05-0.5:1:0.2-0.5. More preferably, the weight ratio of solid-stating porous particles to polymer matrix is 0.1 to 0.2:1. The above-described optimized arrangement can provide a solid electrolyte having a more excellent effect.
According to the preparation method of the composite solid electrolyte, coating is realized by utilizing the high surface area of the porous particles and the chemical action between the solid electrolyte, and the interface of high-conductivity lithium is constructed by further combining with the seepage effect between the polymer solid electrolyte and the solid-state porous particles, so that synergy can be realized, and the capacity, high pressure and long-cycle stability at room temperature of the solid electrolyte can be synergistically improved.
The disclosed embodiments also provide a solid-state battery including: a positive electrode, a negative electrode, and a composite solid electrolyte as described above, the composite solid electrolyte being disposed between the positive electrode and the negative electrode. The construction of the solid-state battery may be referred to the prior art, and the present disclosure is not described in detail herein. The solid-state battery may have a known structure, components and materials other than the composite solid electrolyte according to the present invention.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The composite solid electrolyte provided by the embodiment is obtained according to the following steps:
(1) According to LLZTO (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 ) Is to weigh LiOH.H 2 O、La 2 O 3 、ZrO 2 、Ta 2 O 5 Then adding 12wt% LiOH H in excess 2 O, adding a proper amount of isopropanol as a solvent, and performing high-energy ball milling and mixing for 2 hours at a rotating speed of 800 revolutions per minute to obtain uniformly mixed slurry. And (3) drying the slurry, presintering for 12 hours at 800 ℃, and grinding to obtain the LLZTO precursor. The LLZTO precursor is dispersed in ethanol to prepare a LLZTO precursor solution with the concentration of 1 mol/L.
(2) Dispersing zeolite porous particles in the LLZTO precursor solution obtained in the step (1), stirring and mixing for 60min at the temperature of an oil bath of 100 ℃ to completely volatilize the solvent, thereby obtaining the immersion liquid porous particles coated with the solid electrolyte precursor.
(3) And (3) heating the immersion liquid porous particles obtained in the step (2) to 700 ℃ at a speed of 2 ℃/min under an oxygen atmosphere, and preserving heat for 3 hours to densify the electrolyte, so as to obtain solid-state porous particles.
(4) 0.1g of the solid-state porous particles obtained in the step (3), 1g of PEO (polyethylene oxide; molecular weight 10) 6 Ara Ding Shiji), 0.36g LiTFSI (lithium bistrifluoromethane sulfonimide, ara Ding Shiji) was dissolved in anhydrous acetonitrile, and after stirring and mixing, slowly dropped into a polytetrafluoroethylene mold to obtain a homogeneous mixture.
(5) Volatilizing the uniform mixture at room temperature for 12h to remove the solvent in the mixture, and drying at 60 ℃ to remove the residual solvent in the mixture to obtain the composite solid electrolyte.
Example 2
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: the concentration of LLZTO precursor solution was 0.5mol/L.
Example 3
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: the concentration of LLZTO precursor solution is 2mol/L.
Example 4
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: the concentration of the LLZTO precursor solution is 5mol/L.
Example 5
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: in the step (3), the temperature is raised to 500 ℃ at 2 ℃/min, and the heat is preserved for 3 hours, so that the electrolyte is densified, and solid porous particles are obtained.
Example 6
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: in the step (3), the temperature is raised to 900 ℃ at 2 ℃/min, and the temperature is kept for 3 hours, so that the electrolyte is densified, and solid porous particles are obtained.
Example 7
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: in the step (4), the amount of the solid-state porous particles was 0.05g.
Example 8
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: in the step (4), the amount of the solid-state porous particles used was 0.3g.
Example 9
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: in the step (3), the sintering atmosphere is air.
Example 10
The present embodiment provides a composite solid electrolyte, which is different from embodiment 1 in that: the zeolite porous particles were subjected to the following pretreatment prior to use: the porous particles are immersed in a Kh550 coupling agent for 30min and then placed in a plasma generating device, and CCl4 is used as a reaction gas. The reaction pressure is 12Pa, the reaction power is 150W, and the reaction time is 12min, so as to obtain the pretreated zeolite porous particles.
Comparative example 1
The composite solid electrolyte provided in the embodiment is obtained according to the following steps:
(1) According to LLZTO (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 ) Is to weigh LiOH.H 2 O、La 2 O 3 、ZrO 2 、Ta 2 O 5 Then adding 12wt% LiOH H in excess 2 O, adding a proper amount of isopropanol as a solvent, and performing high-energy ball milling and mixing for 2 hours at a rotating speed of 800 revolutions per minute to obtain uniformly mixed slurry. And (3) drying the slurry, presintering for 12 hours at 800 ℃, and grinding to obtain the LLZTO precursor. The LLZTO precursor is dispersed in ethanol to prepare a LLZTO precursor solution with the concentration of 1 mol/L.
(2) And (3) drying the LLZTO precursor solution obtained in the step (1), and then heating to 700 ℃ at 2 ℃/min under the oxygen atmosphere, and preserving heat for 3 hours to obtain the solid electrolyte.
(3) 0.1g of the solid electrolyte obtained in step (2), 1g of PEO (polyethylene oxide; molecular weight 10) 6 Ara Ding Shiji), 0.36g LiTFSI (lithium bistrifluoromethane sulfonimide, ara Ding Shiji) was dissolved in anhydrous acetonitrile, and after stirring and mixing, slowly dropped into a polytetrafluoroethylene mold to obtain a homogeneous mixture.
(4) Volatilizing the uniform mixture at room temperature for 12h to remove the solvent in the mixture, and drying at 60 ℃ to remove the residual solvent in the mixture to obtain the composite solid electrolyte.
Comparative example 2
(1) 0.1g of zeolite porous particles, 1g of PEO (polyethylene oxide; molecular weight 10) 6 Ara Ding Shiji), 0.36g LiTFSI (lithium bistrifluoromethane sulfonyl imide, ara Ding Shiji) was dissolved in anhydrous acetonitrile, and the mixture was stirred and mixed slowlyDripping into polytetrafluoroethylene mould to obtain uniform mixture.
(2) Volatilizing the uniform mixture at room temperature for 12h to remove the solvent in the mixture, and drying at 60 ℃ to remove the residual solvent in the mixture to obtain the composite solid electrolyte.
Test example 1
The composite solid electrolytes obtained in examples 1 to 10 and comparative examples 1 to 2 were each used as LiFeO 4 The positive electrode plate and the metal lithium plate are assembled into an all-solid-state battery, and a LAND battery test system (Wuhan blue electric electronic Co., ltd.) is used for constant-current charge and discharge performance test at 30 ℃, the charge and discharge range is 2.75-4.0V, and the test results are shown in the following table 1:
the capacity of the solid-state battery reaches 156mAh/g, and after 200 circles of stable circulation, the capacity retention rate is 86%.
The measurement was performed, and the results are shown in table 1:
TABLE 1
A TEM image of the composite solid electrolyte provided in example 1 is shown in fig. 1; fig. 2 is a cycle chart of a composite solid electrolyte provided in example 1.
The composite solid electrolyte provided in this example realizes coating by the high surface area of the porous particles and the chemical action between the solid electrolytes. Then the solid porous particles and the polymer solid electrolyte are matched, and a high-conductivity lithium interface is constructed by the seepage effect between the solid porous particles and the polymer solid electrolyte, so that the coordination can be realized unexpectedly, and the capacity, high pressure and long-cycle stability at room temperature of the solid electrolyte can be improved synergistically.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. A composite solid electrolyte, comprising porous particles and a solid electrolyte coated on the surfaces of the porous particles, wherein the solid electrolyte is adsorbed on the surfaces of the porous particles through chemical groups.
2. A method of producing the composite solid electrolyte according to claim 1, comprising:
s1, soaking porous particles in a solid electrolyte precursor solution to obtain immersion porous particles;
s2, carrying out solid-state treatment on the immersion liquid porous particles to obtain solid-state porous particles;
and S3, carrying out composite treatment on the solid porous particles and the polymer solid electrolyte to obtain the composite solid electrolyte.
3. The method for producing a composite solid electrolyte according to claim 2, wherein the porous particles are subjected to a pretreatment before step S1, the pretreatment being one or more of normal pressure sintering, plasma surface treatment, magnetron sputtering treatment, and vacuum evaporation treatment.
4. The method for producing a composite solid electrolyte according to claim 2, wherein in step S1, the solid electrolyte precursor is one or more selected from the group consisting of an oxide solid electrolyte precursor, a sulfide solid electrolyte precursor, and a halide solid electrolyte precursor.
5. The method for producing a composite solid electrolyte according to claim 2, wherein in step S2, the solid-state treatment is a sintering treatment.
6. The method for producing a composite solid electrolyte according to claim 5, wherein the sintering treatment is an atmospheric pressure sintering treatment, a hot press sintering treatment, a hot isostatic pressing sintering treatment, or a plasma sintering treatment; the atmosphere of the sintering treatment is inert gas, air or oxygen.
7. The method for producing a composite solid electrolyte according to claim 5, wherein the sintering treatment is performed at a temperature of 100 ℃ to 1000 ℃ for a time of 1 to 12 hours.
8. The method for producing a composite solid electrolyte according to claim 2, wherein in step S3, the solid-state porous particles and the polymer solid electrolyte are subjected to a composite treatment, comprising:
dispersing the solid porous particles, the polymer matrix and lithium salt in a solvent, and mixing to obtain mixed slurry;
and removing the solvent in the dispersion liquid to obtain the composite solid electrolyte.
9. The method of preparing a composite solid electrolyte according to claim 8, wherein the polymer matrix is selected from one or more of PEO, PVDF, PEG, PMMA, PVDF-HFP, PEGDMA, PVA, PPC, PAN and composites of the foregoing materials.
10. A solid-state battery, characterized by comprising:
a positive electrode, a negative electrode, a positive electrode,
negative electrode
The composite solid electrolyte according to claim 1, which is arranged between the positive electrode and the negative electrode.
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