CN112993389A - Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof - Google Patents
Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN112993389A CN112993389A CN202110247698.7A CN202110247698A CN112993389A CN 112993389 A CN112993389 A CN 112993389A CN 202110247698 A CN202110247698 A CN 202110247698A CN 112993389 A CN112993389 A CN 112993389A
- Authority
- CN
- China
- Prior art keywords
- lithium
- perovskite oxide
- rich anti
- electrolyte
- composite electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 232
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 195
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000002131 composite material Substances 0.000 title claims abstract description 184
- 238000002360 preparation method Methods 0.000 title claims description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 49
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- 239000012528 membrane Substances 0.000 claims description 29
- 238000005266 casting Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 22
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000007731 hot pressing Methods 0.000 claims description 13
- 239000012943 hotmelt Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 150000003949 imides Chemical class 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 34
- 239000005518 polymer electrolyte Substances 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 37
- 239000007784 solid electrolyte Substances 0.000 description 25
- 239000011259 mixed solution Substances 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910003480 inorganic solid Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000010416 ion conductor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910009866 Ti5O12 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical group [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- H01M2300/0082—Organic polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium-rich anti-perovskite oxide composite electrolyte, wherein the material of the lithium-rich anti-perovskite oxide composite electrolyte comprises a polymer, a lithium salt and a filler, and the filler is a lithium-rich anti-perovskite oxide; wherein the structural formula of the lithium-rich anti-perovskite oxide is Li3‑xHxOA1‑yByWherein A and B are halogen elements, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. The lithium-rich anti-perovskite oxide electrolyte is used as a filler, so that the ionic conductivity and the electrochemical window of the composite polymer electrolyte can be improved, the mechanical property of the composite electrolyte can be improved, the interface impedance between the electrolyte and a lithium-based negative electrode is reduced, and the obtained composite electrolyte has high lithium ion conductivity, good bending mechanical property and high interface stability.
Description
The application is filed on 28.12.2018, and has the application number of 2018116259673, and the invention provides a divisional application named as 'a lithium-rich anti-perovskite oxide composite electrolyte and a preparation method and application thereof'.
Technical Field
The invention relates to the field of new energy materials, in particular to a lithium-rich anti-perovskite oxide composite electrolyte and a preparation method thereof, and an all-solid-state battery and a preparation method thereof.
Background
With the rapid development of the industries such as electronics, information, new energy automobiles and the like, a new energy storage device becomes the focus of scientific and technical development, and the research and development of a high-safety and high-capacity solid-state lithium ion battery becomes a research hotspot in the field of current new energy materials. Solid-state lithium ion batteries play an increasingly critical role in numerous fields due to the advantages of high energy density, safety, long service life, high working voltage, environmental friendliness and the like.
Solid electrolytes are key materials of solid ion batteries, and are ion conductors, generally requiring high ionic conductivity, low electronic conductivity, and low activation energy. Solid electrolytes are mainly classified into three categories: inorganic solid electrolytes, organic solid electrolytes, and composite solid electrolytes. The inorganic solid electrolyte, also called as a lithium fast ion conductor, is a solid material with high lithium ion conductivity in a working state, has the advantages of high safety, ultra-long service life, good ion conductivity, good electrochemical stability and the like, but has poor flexibility, large boundary impedance and interface resistance between the electrolyte and an electrode, and the practical application is limited by difficult processing. Organic solid electrolytes are classified into solid polymer electrolytes and gel polymer electrolytes. The solid polymer electrolyte is a polymer electrolyte material formed by compounding a lithium salt with a polymer. The polymer lithium ion battery is an all-solid-state structure with integrated electrodes, electrolyte and diaphragms, is easy to integrate and assemble, has high safety performance, but has poor mechanical strength and lower conductivity, and limits the application of the polymer lithium ion battery.
It is difficult for a single electrolyte to satisfy all the requirements, and thus, in addition to the above-mentioned inorganic or organic solid electrolytes in a pure phase or a single phase, composite solid electrolytes have been receiving wide attention. The composite solid electrolyte is mainly prepared by adding an inorganic solid electrolyte into an organic solid electrolyte as a filler, wherein the inorganic solid electrolyte permeates into a polymer matrix material through high lithium ions of the inorganic solid electrolyte, so that the lithium ion conductivity of the polymer electrolyte is improved, and the introduced solid electrolyte particle material improves the mechanical property of the composite electrolyte. At present, most of composite solid polymer electrolytes are modified by adding inorganic fillers. The composite solid polymer electrolyte comprises the composition of two inorganic lithium ion conductors, the composition of an organic lithium ion conductor and a lithium ion insulator, the composition of an inorganic lithium ion conductor and a lithium ion insulator and the composition of a lithium ion insulator and a lithium ion insulator. However, the composite solid electrolyte prepared at present still cannot have the characteristics of high ionic conductivity, wide electrochemical window, good mechanical properties, low interface impedance, high stability and the like.
Disclosure of Invention
The invention aims to provide a lithium-rich anti-perovskite oxide composite electrolyte and a preparation method thereof, and aims to enable the obtained electrolyte to have high ionic conductivity, wide electrochemical window, good mechanical property and high stability.
Another object of the present invention is to provide an all-solid-state battery containing a lithium-rich anti-perovskite oxide composite electrolyte and a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium-rich anti-perovskite oxide composite electrolyte is prepared from a polymer, a lithium salt and a filler, wherein the filler is a lithium-rich anti-perovskite oxide.
The preparation method of the lithium-rich anti-perovskite oxide composite electrolyte adopts a solution casting method or a melting hot pressing method to prepare the lithium-rich anti-perovskite oxide composite electrolyte.
And the all-solid-state battery is composed of a positive plate, a negative plate and an electrolyte between the positive plate and the negative plate, wherein the positive plate and the negative plate are oppositely arranged, the electrolyte adopts the lithium-rich anti-perovskite oxide composite electrolyte, or the electrolyte is the lithium-rich anti-perovskite oxide composite electrolyte prepared by the method, and the thickness of the lithium-rich anti-perovskite oxide composite electrolyte is 1 mu m-5 cm.
The preparation method of the all-solid-state battery comprises the steps of preparing the lithium-rich anti-perovskite oxide composite electrolyte according to the preparation method; heating and melting the lithium-rich anti-perovskite oxide composite electrolyte to obtain a lithium-rich anti-perovskite oxide composite electrolyte solution; and casting the lithium-rich anti-perovskite oxide composite electrolyte solution on a positive plate or a negative plate to form a composite electrolyte membrane, attaching the negative plate or the positive plate which are oppositely arranged on the composite electrolyte membrane, and cooling to normal temperature to obtain the lithium-rich anti-perovskite battery.
The lithium-rich anti-perovskite oxide composite electrolyte prepared by the invention comprises a polymer, lithium salt and a filler, wherein the filler is a lithium-rich anti-perovskite oxide. The lithium-rich anti-perovskite oxide electrolyte is used as a filler, so that the ionic conductivity and the electrochemical window of the composite polymer electrolyte can be improved, the mechanical property of the composite electrolyte can be improved, the interface impedance between the electrolyte and a lithium-based negative electrode is reduced, and the obtained composite electrolyte has high lithium ion conductivity, good bending mechanical property and high interface stability.
The preparation method of the lithium-rich anti-perovskite oxide composite electrolyte specifically adopts any one of a solution pouring method or a melt hot pressing method, the two preparation methods only need to mix materials and then respectively pour or hot press, the preparation process is simple, the operation is convenient, the conditions are controllable, and the large-scale production is facilitated.
The electrolyte of the all-solid-state battery prepared by the invention adopts the lithium-rich anti-perovskite oxide composite electrolyte or the lithium-rich anti-perovskite oxide composite electrolyte prepared by the method. The lithium-rich anti-perovskite oxide composite electrolyte has high conductivity, wide electrochemical window, good mechanical property and small interface impedance, so that the all-solid-state battery has small interface impedance, excellent charge-discharge cycle performance and rate capability.
According to the invention, the battery is prepared by adopting an in-situ hot melting casting method, on one hand, the molten electrolyte has better wettability with electrode plates (a positive plate and a negative plate), the contact area between the electrolyte and the electrode plates is increased, and the contact problem between the electrolyte and the electrodes is solved; on the other hand, the electrolyte in a molten state is directly poured on the electrode plate, the preparation method is simple and easy to implement, and the production efficiency is high.
Drawings
Fig. 1 is an LSV curve of a lithium-rich anti-perovskite composite electrolyte provided by an embodiment of the present invention.
Fig. 2 is an EIS curve of the lithium-rich anti-perovskite composite electrolyte provided by the embodiment of the invention.
Fig. 3 is an SEM photograph of the cross-sectional thickness of the lithium-rich anti-perovskite composite electrolyte provided by the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
The invention provides a lithium-rich anti-perovskite oxide composite electrolyte, which comprises a polymer, a lithium salt and a filler, wherein the filler is a lithium-rich anti-perovskite oxide. Specifically, the filler is a lithium-rich anti-perovskite oxide which is an inorganic solid electrolyte and has a structural formula of Li3-xHxOA1-yByWherein A and B are halogen elements, x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. Advantages of lithium-rich anti-perovskite oxides include: (1) the material has low melting point, is beneficial to directly synthesizing a film material and large-scale preparation and application; (2) the activation energy is lower, the conductivity is higher, particularly the structure is easy to adjust the crystal structure and the electronic structure, and after the structure, the components and the crystal form are regulated, the conductivity of the material can exceed that of other existing solid electrolytes and exceed that of part of liquid electrolytes; (3) extremely low electron conductance; (4) the density is small and the weight is light; (5) the lithium halide is decomposed into environment-friendly lithium halide by reacting with water, and is easy to recycle; (6) the cost is low; (7) stable with lithium metal electrodes; (8) has certain thermal stability; (9) an electrochemical window close to 5V meets the requirements of known high-voltage electrode materials. Therefore, the lithium-rich anti-perovskite oxide is used as an inorganic filler, can be well fused with a polymer and a lithium salt shell layer, improves the conductivity of lithium ions, widens the electrochemical window of the lithium ions, changes the property of the polymer, and improves the mechanical property of the composite electrolyte, and meanwhile, the interface impedance is reduced and the stability of the composite electrolyte is improved by fusing the polymer and the lithium-rich anti-perovskite oxide.
In the embodiment of the invention, the lithium-rich anti-perovskite oxide is particularly preferably Li3OCl、Li2OHCl、Li3OBr、Li2OHBr、Li3OCl0.5Br0.5、Li3OCl0.7Br0.3、Li3OCl0.3Br0.7、Li2OHCl0.9F0.1、Li3OCl0.8F0.2Etc. of
Preferably, in the prepared lithium-rich anti-perovskite oxide composite electrolyte, the mass fraction of the lithium-rich anti-perovskite oxide in the composite electrolyte is as follows: 1 to 80 percent.
In a preferred embodiment of the invention, the lithium-rich anti-perovskite oxide composite electrolyte is prepared by a solution casting method, wherein the mass fraction of the lithium-rich anti-perovskite oxide in the electrolyte is 2-80%, the mass fraction of the lithium salt in the composite electrolyte is 5-50%, and the mass fraction of the polymer in the composite electrolyte is 10-80%. In another preferred embodiment of the invention, the lithium-rich anti-perovskite oxide composite electrolyte is prepared by a hot-melt pressing method, wherein the mass fraction of the lithium-rich anti-perovskite oxide in the electrolyte is 1-80%, the mass fraction of the lithium salt in the composite electrolyte is 1-80%, and the mass fraction of the polymer in the composite electrolyte is 10-90%.
In the lithium-rich anti-perovskite oxide composite electrolyte, the lithium-rich anti-perovskite oxide can improve the mechanical property of the electrolyte, reduce the crystallinity of a polymer and improve the conductivity of the polymer; if the mass fraction of the lithium-rich anti-perovskite oxide in the electrolyte is too much and exceeds 80 percent, the composite electrolyte has poor flexibility and is easier to break; if the content is too low, the conductivity of the electrolyte cannot be improved, so that the conductivity is poor; the lithium salt is used as a relatively important substance in the electrolyte, the ionic conductivity is gradually increased along with the increase of the content of the lithium salt, however, if the content of the lithium salt is too high, the lithium ions and anions can form neutral molecules to block the migration of the lithium ions and reduce the conductivity of the lithium ions, and if the content of the lithium salt is too low, the ionic conductivity is low, the prepared electrolyte has poor conductivity and poor using effect; the polymer has certain flexibility and can adapt to certain deformation, and if the content of the polymer is too high, the prepared electrolyte has too high flexibility and is not beneficial to later use; if the content of the polymer is too low, the prepared electrolyte has too low flexibility, poor mechanical properties and easy cracking in the using process.
The composite solid electrolyte is mainly prepared by adding an inorganic solid electrolyte into an organic solid electrolyte as a filler, wherein the inorganic solid electrolyte permeates into a polymer matrix material through high lithium ions of the inorganic solid electrolyte, so that the lithium ion conductivity of the polymer electrolyte is improved, and the introduced solid electrolyte particle material improves the mechanical property of the composite electrolyte. Specifically, the embodiment of the invention adopts the lithium-rich anti-perovskite oxide as a filler, and adds the lithium-rich anti-perovskite oxide into the polymer and the lithium salt, wherein the polymer is one of main components of the lithium-rich anti-perovskite oxide composite electrolyte, and because the polymer has good flexibility, the battery can resist impact, vibration and deformation, and in an abuse state (overcharge, short circuit, acupuncture and the like), safety problems such as combustion, explosion and the like can not occur, so that the reactivity of the electrolyte and an electrode is reduced, meanwhile, the hidden danger of lithium dendrite formation and internal short circuit of the battery can be effectively relieved, and the cycle performance of the battery can be improved. In a preferred embodiment of the invention, the polymer is selected from one or more of Polycaprolactone (PCL), polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethacrylic acid (PMMA), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP).
In particular, lithium salts, which are key components of lithium battery electrolytes, are important factors in determining the performance of the electrolytes. In a preferred embodiment of the invention, the lithium salt is selected from lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bistrifluoromethylsulfonyl imide (LiTFSI), lithium bistrifluorosulfonimide (LiFSI), lithium trifluoromethanesulfonate (LiCF)3SO3) One or more of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiDFOB).
The lithium-rich anti-perovskite oxide composite electrolyte provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, the embodiment of the invention provides a preparation method of the lithium-rich anti-perovskite oxide composite electrolyte, and particularly, the lithium-rich anti-perovskite oxide composite electrolyte is prepared by adopting any one of a solution casting method and a melt hot pressing method.
In some embodiments, the lithium-rich anti-perovskite oxide composite electrolyte is prepared using a solution casting method. In a specific embodiment, the flow of preparing the lithium-rich anti-perovskite oxide composite electrolyte by adopting a solution casting method is as follows:
s01: dissolving the polymer and the lithium salt in an organic solvent to obtain a first solution;
s02: adding the lithium-rich anti-perovskite oxide into the first solution, and uniformly mixing to form a second solution;
s03: and pouring the second solution on a substrate, and drying in vacuum to obtain the lithium-rich anti-perovskite oxide composite electrolyte.
Specifically, the whole process of the solution casting method is operated in an inert gas glove box, the pollution of oxygen and other impurities can be fully isolated by operating in the glove box, the prepared electrolyte is ensured to have no impurities, and the performance of the battery cannot be influenced. In a preferred embodiment of the invention, the glove box can be selected from Mikrouna, Vigor, Etelux and Dellix.
Specifically, in the above S01 reaction step, the polymer and the lithium salt are dissolved in an organic solvent to obtain a first solution. In the preferred embodiment of the present invention, the addition ratio of the polymer to the lithium salt is (10-80): 5-50, and in the embodiment of the present invention, the mass ratio of the polymer to the lithium salt is particularly preferably 3:1, 4:1, 5: 1. When the content of the lithium salt is too low, the ionic conductivity of the electrolyte is low; when the content of the lithium salt is too high, the lithium ions and anions form neutral molecules, which hinder the migration of the lithium ions and reduce the conductivity thereof.
Preferably, the organic solvent is any one of acetonitrile, succinonitrile, etc., and the addition of the organic solvent can sufficiently dissolve the added polymer based on the principle of similar compatibility. In a preferred embodiment of the present invention, the polymer and the lithium salt may be mixed in a mass ratio and then dissolved in the organic solvent, and more preferably, the polymer may be dissolved in the organic solvent first and then the lithium salt may be added and mixed.
In the step of S02 reaction, the lithium-rich anti-perovskite oxide is added to the first solution and mixed uniformly to form a second solution. Specifically, the addition amount of the lithium-rich anti-perovskite oxide is 2 wt% to 80 wt% of the composite electrolyte, and in a preferred embodiment of the invention, the addition amount of the lithium-rich anti-perovskite oxide is 15 wt%. If the addition amount of the lithium-rich anti-perovskite oxide is too low, the crystallinity of the polymer cannot be effectively reduced, and the conductivity of the polymer is improved; too much lithium-rich anti-perovskite oxide deteriorates the flexibility of the composite electrolyte and is liable to crack. Preferably, the mixing means may include conventional techniques such as stirring. Further, the mixing time is 2-48 h, and the temperature is 40-80 ℃.
Specifically, in the S03 reaction step, the second solution is cast on a substrate and dried in vacuum to obtain the lithium-rich anti-perovskite oxide composite electrolyte. In a preferred embodiment of the invention, the substrate is preferably polytetrafluoroethylene, which is commonly referred to as a "non-stick coating" or "easy-to-clean material". The material has the characteristics of acid resistance, alkali resistance and various organic solvents resistance, and is almost insoluble in all solvents. Meanwhile, the polytetrafluoroethylene has the characteristics of high temperature resistance, acid and alkali resistance, corrosion resistance and the like. Therefore, polytetrafluoroethylene sheets are often chosen as the base material for lithium battery electrolytes. Specifically, the mixed solution of the polymer, the lithium salt and the lithium-rich anti-perovskite oxide is poured on a polytetrafluoroethylene plate and then is dried in vacuum, wherein the drying temperature is 30-70 ℃, and the drying time is 12-72 hours.
In some embodiments, the lithium-rich anti-perovskite oxide composite electrolyte is prepared using a hot melt pressing process. In a specific embodiment, the flow of preparing the lithium-rich anti-perovskite oxide composite electrolyte by using a hot-melt pressing method is as follows:
d01: mixing the lithium-rich anti-perovskite oxide, the polymer and the lithium salt, and heating and melting to form an electrolyte composite solution;
d02: and pouring the electrolyte composite solution on a first substrate, covering a second substrate on the surface of the electrolyte composite solution, which is away from the first substrate, hot-pressing to form a composite electrolyte membrane, and cooling to normal temperature to obtain the lithium-rich anti-perovskite oxide composite electrolyte.
Specifically, the whole process of the melting hot pressing method is operated in an inert gas glove box, the pollution of oxygen and other impurities can be fully isolated by operating in the glove box, and the prepared electrolyte is free of impurities and cannot affect the performance of the battery.
Specifically, in step D01, the lithium-rich anti-perovskite oxide, the polymer and the lithium salt are added in the following proportions: (1-80): (10-90): (1-80). When the addition amount of the lithium salt is too low, the ionic conductivity of the electrolyte is low; when the amount of the lithium salt added is too high, the lithium ions and anions form neutral molecules, which inhibit migration of the lithium ions and reduce the electrical conductivity thereof. When the content of the lithium-rich anti-perovskite oxide is too low, the crystallinity of the polymer cannot be effectively reduced, and the conductivity of the polymer is improved; too much lithium-rich anti-perovskite oxide deteriorates the flexibility of the composite electrolyte and is liable to crack. The right proportions ensure that the electrolyte has both high conductivity and good mechanical strength.
In the lithium-rich anti-perovskite oxide composite electrolyte obtained by the reaction according to the addition proportion, the mass fraction of the lithium-rich anti-perovskite oxide is 1-80%, the mass fraction of the polymer is 10-90%, and the mass fraction of the lithium salt in the electrolyte is 1-80%. Specifically, the lithium-rich anti-perovskite oxide, the polymer and the lithium salt are mixed, the mixing method comprises the methods of manual grinding, mechanical stirring, ball milling stirring and the like, the composite of the components is processed by the mixing method, the particle size of the material can be further crushed, the particle size of the obtained mixture is fine, and meanwhile, the stable property of the mixed material can be ensured. Further, the heating temperature of the heating and melting is 60-70 ℃, and the heating time is 2-48 hours. The specific heating temperature of the preferred heat melting in the present invention is 65 ℃.
Specifically, in step D02, a second substrate is covered on the surface of the electrolyte composite solution away from the first substrate, and a composite electrolyte membrane is formed by hot pressing; in a preferred embodiment of the invention, in the hot pressing step, the temperature is 50-200 ℃, the pressure is 5-100 MPa, and the time is 0.1-10 hours. Further, the formed composite electrolyte membrane is cooled to normal temperature, and the lithium-rich anti-perovskite oxide composite electrolyte is obtained.
The embodiment of the invention provides an all-solid-state battery which comprises a positive plate, a negative plate and an electrolyte, wherein the positive plate and the negative plate are oppositely arranged, and the electrolyte is arranged between the positive plate and the negative plate. The electrolyte is the lithium-rich anti-perovskite oxide composite electrolyte. Since the all-solid-state battery contains the lithium-rich anti-perovskite oxide composite electrolyte, the lithium ion conductivity of the lithium-rich anti-perovskite oxide composite electrolyte is high and can reach 10-6～10-3S cm-1(ii) a The electrochemical window is wide and stable in property, and the electrochemical window is 4-7V; the thickness of the electrolyte is controllable and is 1 mu m-5 cm; the all-solid-state battery has the advantages of good mechanical property and small interface impedance, so that the all-solid-state battery has small interface impedance, and excellent charge-discharge cycle performance and rate capability.
In a preferred embodiment of the invention, the active material of the positive plate is lithium manganate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Lithium iron phosphate (LiFePO)4) Lithium nickelate (LiNiO)2) Lithium manganese iron phosphate (LiFe)0.2Mn0.8PO4) Lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Or one or more of nickel-cobalt-manganese ternary materials; the negative plate active material is one or more of graphite, graphene, a metal lithium negative electrode, a lithium alloy, a silicon-carbon composite negative electrode, a tin-carbon composite negative electrode and lithium titanate.
Correspondingly, the embodiment of the invention provides a preparation method of an all-solid-state battery, which comprises the following steps:
g01: preparing a lithium-rich anti-perovskite oxide composite electrolyte according to any one of the preparation methods;
g02: heating and melting the lithium-rich anti-perovskite oxide composite electrolyte to obtain a lithium-rich anti-perovskite oxide composite electrolyte solution;
g03: casting the lithium-rich anti-perovskite oxide composite electrolyte solution on a positive plate or a negative plate to form a composite electrolyte membrane;
g04: and attaching a negative plate or a positive plate which is oppositely arranged on the composite electrolyte membrane, and cooling to normal temperature to obtain the lithium-rich anti-perovskite battery.
Specifically, the whole process of the solution casting method is operated in an inert gas glove box, the pollution of oxygen and other impurities can be fully isolated by operating in the glove box, the prepared electrolyte is ensured to have no impurities, and the performance of the battery cannot be influenced.
In the step G01, the preparation method of the lithium-rich anti-perovskite oxide composite electrolyte is as described above, and is not repeated here for saving space.
In the step G02, heating and melting the lithium-rich anti-perovskite oxide composite electrolyte to obtain a lithium-rich anti-perovskite oxide composite electrolyte solution; preferably, the specific operation method of heating and melting comprises: putting the lithium-rich anti-perovskite oxide composite electrolyte into a crucible, and then putting the crucible on a heating table for heating to completely melt the lithium-rich anti-perovskite oxide composite electrolyte; the preferable heating temperature is 50-200 ℃.
In the above steps G03 and G04, the lithium-rich anti-perovskite oxide composite electrolyte solution is cast on a positive electrode sheet or a negative electrode sheet to form a composite electrolyte membrane; and attaching a negative plate or a positive plate which is oppositely arranged on the composite electrolyte membrane, and cooling at normal temperature to obtain the lithium-rich anti-perovskite battery. In a preferred embodiment of the invention, the lithium-rich anti-perovskite oxide composite electrolyte solution can be cast in the positive plate to form a composite electrolyte membrane, and then the negative plate is attached to the positive plate and cooled to prepare the all-solid-state anti-perovskite battery. Furthermore, the lithium-rich anti-perovskite oxide composite electrolyte solution can be cast in a negative plate to form a composite electrolyte membrane, and then the positive plate is attached to the negative plate and cooled to obtain the all-solid-state anti-perovskite battery.
Specifically, the thickness of the electrolyte membrane prepared by the method is 1 mu m-5 cm. The composite electrolyte membrane is controlled in a proper thickness of 1-5 cm, if the thickness is less than 1 mu m, the obtained electrolyte membrane is too thin, and a battery assembled by the electrolyte membrane with too thin thickness is easy to cause short circuit, so that the quality of the battery is poor; if the thickness is more than 5cm, the obtained electrolyte membrane is too thick, and the internal resistance of the battery obtained by adopting the electrolyte assembly with too thick thickness is larger, which is not favorable for effectively exerting the performance of the battery.
Compared with the traditional lamination assembly method (stacking three layers of a negative plate, an electrolyte membrane and a positive plate), the application of the in-situ hot melting casting method mainly plays two roles, on one hand, the molten electrolyte and the electrode plate (the positive plate and the negative plate) have better wettability, the contact area between the electrolyte and the electrode plate is increased, and the contact problem between the electrolyte and the electrode is solved; on the other hand, the electrolyte in a molten state is directly poured on the electrode plate, so that the preparation of the all-solid-state battery is simple and feasible.
The lithium-rich anti-perovskite oxide composite electrolyte and the preparation method thereof are illustrated by the following examples.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Example 1:
a preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PCL), lithium salt (LiTFSI) and lithium-rich anti-perovskite oxide (Li)3OCl0.6Br0.4) Dissolving the materials in an organic solvent acetonitrile according to a mass ratio of 6:2:2, stirring the mixed solution to form a uniform solution, casting the uniform solution on a polytetrafluoroethylene plate, and drying the polytetrafluoroethylene plate in a vacuum drying oven at 60 ℃ for 12 hours to form the composite electrolyte.
Example 2
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of: mixing Polymer (PCL), lithium salt (LiFSI) and lithium-rich calcium-enriched transcalciumMineral oxide (Li)3OBr) is dissolved in an organic solvent succinonitrile according to the mass ratio of 5:1:1, the mixed solution is stirred to form a uniform solution, the uniform solution is cast on a polytetrafluoroethylene plate and is placed in a vacuum drying oven at 60 ℃ to be dried for 20 hours, and then the composite electrolyte is formed.
Example 3
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PEO), lithium salt (LiTFSI) and lithium-rich anti-perovskite oxide (Li)3OCl) is dissolved in an organic solvent acetonitrile according to the mass ratio of 4:1:1, the mixed solution is stirred to form a uniform solution, the uniform solution is cast on a polytetrafluoroethylene plate and is placed in a vacuum drying oven at 60 ℃ to be dried for 12 hours, and then the composite electrolyte is formed.
Example 4
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PEO), lithium salt (LiFSI) and lithium-rich anti-perovskite oxide (Li)3OCl0.5Br0.5) Dissolving the raw materials into an organic solvent succinonitrile according to the mass ratio of 6:2:2, stirring the mixed solution to form a uniform solution, casting the uniform solution on a polytetrafluoroethylene plate, and drying the polytetrafluoroethylene plate in a vacuum drying oven at 60 ℃ for 20 hours to form the composite electrolyte.
Example 5
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PCL), lithium-rich anti-perovskite oxide (Li)3OCl) and lithium salt (LiTFSI) according to a certain mass ratio (6:2:2) to form a uniform compound, then placing the compound into a crucible to be heated to 200 ℃ and preserving heat for 2 hours, finally casting the hot-melt mixed solution on a tetrafluoride film, then covering another compound film on a hot press, and placing the compound film on the hot press at 80 ℃ and 10MHot pressing under Pa pressure for a certain time to form the composite electrolyte membrane, and cooling to form the composite electrolyte.
Example 6
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PEO), lithium-rich anti-perovskite oxide (Li)3OBr) and lithium salt (LiFSI) are mixed into a uniform compound according to a certain mass ratio (7:3:1), then the uniform compound is placed into a crucible to be heated to 300 ℃ and insulated for 5 hours, finally the hot-melt mixed solution is cast on a tetrafluoride film, then another compound film is covered on a hot press to be hot-pressed for a certain time at 70 ℃ and 5MPa, and a compound electrolyte film can be formed after the compound electrolyte film is cooled.
Example 7
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PCL), lithium-rich anti-perovskite oxide (Li)3OCl) and lithium salt (LiTFSI) according to a certain mass ratio (6:2:2) to form a uniform compound, then placing the compound into a crucible to be heated to 200 ℃ and preserving heat for 2 hours, finally casting the hot-melt mixed solution on a tetrafluoride film, then covering another compound film on a hot press, hot-pressing the compound film for a certain time at 80 ℃ and 10MPa to form a compound electrolyte film, and cooling the compound electrolyte film to form the compound electrolyte.
Example 8
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PEO), lithium-rich anti-perovskite oxide (Li)3OBr) and lithium salt (LiFSI) are mixed into a uniform compound according to a certain mass ratio (7:3:1), then the uniform compound is put into a crucible and heated to 300 ℃ for heat preservation for 5 hours, finally the hot-melt mixed solution is cast on a tetrafluoride film,and then covering the other composite membrane on a hot press, hot-pressing for a certain time at 70 ℃ and 5MPa to form a composite electrolyte membrane, and cooling to form the composite electrolyte.
Example 9
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PCL), lithium-rich anti-perovskite oxide (Li)3OCl) and lithium salt (LiTFSI) according to a certain mass ratio (6:2:2) to form a uniform compound, then placing the compound into a crucible to be heated to 200 ℃ and preserving heat for 2 hours, finally casting the hot-melt mixed solution on a tetrafluoride film, then covering another compound film on a hot press, hot-pressing the compound film for 6 hours at 80 ℃ and 10MPa to form a compound electrolyte film, and cooling the compound electrolyte film to form the compound electrolyte.
Example 10
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing Polymer (PEO), lithium-rich anti-perovskite oxide (Li)3OBr) and lithium salt (LiFSI) are mixed into a uniform compound according to a certain mass ratio (7:3:1), then the uniform compound is placed into a crucible to be heated to 300 ℃ and insulated for 5 hours, finally the hot-melt mixed solution is cast on a tetrafluoride film, then another compound film is covered on a hot press and is hot-pressed for 2 hours at 70 ℃ and 5MPa to form a compound electrolyte film, and the compound electrolyte film can be formed after the compound electrolyte film is cooled.
Example 11
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing polymer (PVDF-HFP), lithium-rich anti-perovskite oxide (Li)3OCl0.5Br0.5) Mixing with lithium salt (LiTFSI) according to a certain mass ratio (7:2:1) to obtain a uniform composite, and placing the composite into a crucibleHeating to 300 ℃, preserving heat for 5h, finally casting the hot-melt mixed solution on a tetrafluoride film, then covering another composite film on a hot press, hot-pressing for 24h at 100 ℃ and 10MPa to form a composite electrolyte film, and cooling to form the composite electrolyte.
Example 12
A preparation method of a lithium-rich anti-perovskite oxide composite electrolyte is characterized by comprising the following steps of:
mixing polymer (PVDF-HFP), lithium-rich anti-perovskite oxide (Li)3OCl0.3Br0.7) Mixing the lithium salt (LiFSI) and lithium salt (LiFSI) according to a certain mass ratio (6:2:2) to form a uniform compound, then placing the compound into a crucible, heating the mixture to 300 ℃, preserving the heat for 5 hours, finally casting the hot-melted mixed solution on a tetrafluoride film, then covering another compound film on a hot press, hot-pressing the film for 12 hours at 100 ℃ and 10MPa to form a compound electrolyte film, and cooling the compound electrolyte film to form the compound electrolyte.
Example 13
A preparation method of an all-solid-state battery containing a lithium-rich anti-perovskite oxide composite electrolyte is characterized in that the all-solid-state battery containing the lithium-rich anti-perovskite oxide composite electrolyte is prepared by an in-situ casting method, and specifically comprises the following steps:
the prepared composite lithium-rich anti-perovskite oxide composite electrolyte is put into a crucible and heated to 300 ℃ to be completely melted into liquid state, then the liquid state is cast on a graphite (C) negative electrode plate to form a composite electrolyte membrane with the thickness of 50 mu m, and then lithium iron phosphate (LiFePO) is pasted on the membrane4) And cooling the positive plate to obtain the lithium-rich anti-perovskite battery.
Example 14
A preparation method of an all-solid-state battery containing a lithium-rich anti-perovskite oxide composite electrolyte is characterized in that the all-solid-state battery containing the lithium-rich anti-perovskite oxide composite electrolyte is prepared by an in-situ casting method, and specifically comprises the following steps:
the prepared composite lithium-rich anti-perovskite oxide composite electrolyte is put into a crucible and heated toCompletely melting at 400 deg.C to obtain liquid, casting on graphite (C) negative plate to form composite electrolyte membrane with thickness of 80 μm, and sticking lithium cobaltate (LiCoO) on the membrane4) And cooling the positive plate to obtain the lithium-rich anti-perovskite battery.
Example 15
A preparation method of an all-solid-state battery containing a lithium-rich anti-perovskite oxide composite electrolyte is characterized in that the all-solid-state battery containing the lithium-rich anti-perovskite oxide composite electrolyte is prepared by an in-situ casting method, and specifically comprises the following steps:
the prepared composite lithium-rich anti-perovskite oxide composite electrolyte is put into a crucible and heated to 400 ℃ to be completely melted into liquid state, and then the liquid is cast on lithium cobaltate (LiCoO)4) Forming a composite electrolyte membrane with the thickness of 80 mu m on the positive plate, and then pasting lithium titanate (Li) on the membrane4Ti5O12) And cooling the negative plate to obtain the lithium-rich anti-perovskite battery.
Example 16
A preparation method of an all-solid-state battery containing a lithium-rich anti-perovskite oxide composite electrolyte is characterized in that the all-solid-state battery containing the lithium-rich anti-perovskite oxide composite electrolyte is prepared by an in-situ casting method, and specifically comprises the following steps:
melting the prepared composite lithium-rich anti-perovskite oxide, and casting the melted composite lithium-rich anti-perovskite oxide on lithium iron phosphate (LiFePO)4) Forming a 60 μm composite electrolyte film on the positive electrode plate, and then attaching lithium titanate (Li) on the film4Ti5O12) And cooling the negative plate to obtain the lithium-rich anti-perovskite battery.
Comparative example
Other solid state lithium ion electrolytes are available in the market which do not contain lithium-rich anti-perovskite oxides.
The composite electrolyte prepared by the preparation method of the embodiment 1-12 of the invention and the all-solid-state battery selected by the comparative example are subjected to performance test and the decomposition voltage, the lithium ion conductivity and the thickness of the composite electrolyte are specifically analyzed, wherein the attached figure 1 is an LSV curve of the lithium-rich anti-perovskite composite electrolyte provided by the embodiment of the invention; FIG. 2 is an EIS curve of a lithium-rich anti-perovskite composite electrolyte provided by an embodiment of the invention; fig. 3 is an SEM photograph of the cross-sectional thickness of the lithium-rich anti-perovskite composite electrolyte provided by the embodiment of the present invention. The data analysis results are shown in table 1:
TABLE 1 results of performance tests of the electrolyte prepared according to the present invention and the solid electrolyte of comparative example
As can be seen from table 1, the lithium-rich anti-perovskite oxide electrolyte prepared by either the solution casting method or the hot melt pressing method according to the embodiment of the present invention has a decomposition voltage of 4.0 to 5.0V, a wide decomposition voltage window, and a high electrochemical stability. The obtained lithium ion has a conductivity of 10-6～10-3S cm-1And the lithium ion battery prepared by the composite electrolyte has more excellent performance. And the thickness of the composite electrolyte is controllable, the thickness of the prepared electrolyte is 50-500 mu m, the thickness is controllable, and the new energy of the battery can be fully exerted. The electrolyte of the comparative example has the decomposition voltage of 4.2-4.5V, and the decomposition voltage window is obviously smaller than that of the lithium-rich anti-perovskite oxide electrolyte prepared by the invention, so that the lithium-rich anti-perovskite oxide electrolyte prepared by the invention has higher electrochemical stability. Secondly, the lithium ion conductivity of the electrolyte described in the comparative example is not more than 10-4S cm-1The conductivity is low, and the working performance of the battery is fully influenced; in addition, the electrolyte prepared by the comparative example has the thickness of 30-100 mu m, and the thickness controllability is small, so that the performance of the battery is easily influenced.
In summary, the composite electrolyte prepared by any method of the present invention has the following advantages: high lithium ion conductivity (10)-6～10-3S cm-1) (ii) a The electrochemical stability is high and is 4-7V; the thickness is controllable and is 1 mu m-5 cm; the mechanical property is good; good electrolyte and electrode wettability, small interface impedance and stable circulationThe performance is good, and the rate capability is high; the preparation process is simple and the cost is low.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The lithium-rich anti-perovskite oxide composite electrolyte is characterized in that the material of the lithium-rich anti-perovskite oxide composite electrolyte consists of a polymer, a lithium salt and a filler, wherein the filler is a lithium-rich anti-perovskite oxide, and the mass fraction of the lithium-rich anti-perovskite oxide in the composite electrolyte is as follows: 1-80% of lithium salt, 1-80% of lithium salt and 10-90% of polymer.
2. The lithium-rich anti-perovskite oxide composite electrolyte as claimed in claim 1, wherein the lithium-rich anti-perovskite oxide has a general formula of Li3-xHxOA1-yByWherein A and B are halogen elements, 0<x≤1，0≤y≤1。
3. The lithium-rich anti-perovskite oxide composite electrolyte according to any one of claims 1 or 2, wherein the lithium-rich anti-perovskite oxide is selected from Li2OHCl、Li2OHBr、Li2OHCl0.9F0.1Any one of (1).
4. The lithium-rich anti-perovskite oxide composite electrolyte as claimed in any one of claims 1 or 2, wherein the polymer is selected from one or more of polycaprolactone, polyethylene oxide, polyacrylonitrile, polymethacrylic acid, polyvinylidene fluoride-hexafluoropropylene, and/or;
the lithium salt is selected from one or more of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, lithium difluorosulfonyl imide, lithium trifluoromethanesulfonate, lithium bisoxalato borate and lithium difluorooxalato borate.
5. A method for preparing a lithium-rich anti-perovskite oxide composite electrolyte, which is characterized in that the lithium-rich anti-perovskite oxide composite electrolyte as claimed in any one of claims 1 to 4 is prepared by a solution casting method or a hot-melt pressing method.
6. The method for preparing a lithium-rich anti-perovskite oxide composite electrolyte according to claim 5, wherein the lithium-rich anti-perovskite oxide composite electrolyte is prepared by a solution casting method, and comprises the following steps:
dissolving the polymer and the lithium salt in an organic solvent to obtain a first solution;
adding the lithium-rich anti-perovskite oxide into the first solution, and uniformly mixing to form a second solution;
and pouring the second solution on a substrate, and drying in vacuum to obtain the lithium-rich anti-perovskite oxide composite electrolyte.
7. The method for preparing a lithium-rich anti-perovskite oxide composite electrolyte according to claim 5, wherein the method for preparing the lithium-rich anti-perovskite oxide composite electrolyte by using a hot-melt pressing method comprises the following steps:
uniformly mixing the lithium-rich anti-perovskite oxide, the polymer and the lithium salt, and heating and melting to form an electrolyte composite solution;
and pouring the electrolyte composite solution on a first substrate, covering a second substrate on the surface of the electrolyte composite solution, which is away from the first substrate, hot-pressing to form a composite electrolyte membrane, and cooling to normal temperature to obtain the lithium-rich anti-perovskite oxide composite electrolyte.
8. An all-solid-state battery, which comprises a positive plate, a negative plate and an electrolyte between the positive plate and the negative plate, wherein the positive plate and the negative plate are oppositely arranged, and the all-solid-state battery is characterized in that the electrolyte adopts the lithium-rich anti-perovskite oxide composite electrolyte according to any one of claims 1 to 5, or the electrolyte is the lithium-rich anti-perovskite oxide composite electrolyte prepared by the method according to any one of claims 6 to 8, and the thickness of the lithium-rich anti-perovskite oxide composite electrolyte is 1 μm to 5 cm.
9. A preparation method of an all-solid-state battery is characterized by comprising the following steps:
preparing a lithium-rich anti-perovskite oxide composite electrolyte according to the preparation method of any one of the claims 5 to 7;
heating and melting the lithium-rich anti-perovskite oxide composite electrolyte to obtain a lithium-rich anti-perovskite oxide composite electrolyte solution;
casting the lithium-rich anti-perovskite oxide composite electrolyte solution on the positive plate or the negative plate to form a composite electrolyte membrane;
and attaching a negative plate or a positive plate which is oppositely arranged on the composite electrolyte membrane, and cooling to normal temperature to obtain the lithium-rich anti-perovskite battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110247698.7A CN112993389A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811625967.3A CN109786822A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
| CN202110247698.7A CN112993389A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811625967.3A Division CN109786822A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112993389A true CN112993389A (en) | 2021-06-18 |
Family
ID=66498740
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811625967.3A Pending CN109786822A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
| CN202110247698.7A Pending CN112993389A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811625967.3A Pending CN109786822A (en) | 2018-12-28 | 2018-12-28 | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN109786822A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110635113B (en) * | 2019-08-16 | 2021-09-03 | 南方科技大学 | Lithium cathode or sodium cathode, and preparation method and application of lithium cathode or sodium cathode |
| CN111211303B (en) * | 2020-01-13 | 2021-04-13 | 珠海冠宇电池股份有限公司 | Negative electrode active material and preparation method and application thereof |
| CN111952598B (en) * | 2020-07-03 | 2021-06-04 | 南方科技大学 | Negative plate, preparation method thereof and secondary battery |
| CN111725561B (en) * | 2020-07-31 | 2021-09-28 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN111799504B (en) * | 2020-08-06 | 2021-07-02 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN112062991B (en) * | 2020-08-19 | 2023-03-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of organic-inorganic solid electrolyte |
| CN112397770A (en) * | 2020-11-19 | 2021-02-23 | 华南理工大学 | Preparation method of organic-inorganic composite solid electrolyte and electrolyte thereof |
| CN112687945A (en) * | 2020-12-21 | 2021-04-20 | 南方科技大学 | Composite solid electrolyte slurry, thin film, preparation method and all-solid-state battery |
| CN112768754B (en) * | 2020-12-30 | 2022-06-17 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN113054245B (en) * | 2021-03-12 | 2022-08-19 | 南方科技大学 | Anti-perovskite solid electrolyte material, preparation method thereof, solid electrolyte sheet and all-solid-state battery |
| CN113363563A (en) * | 2021-05-21 | 2021-09-07 | 万向一二三股份公司 | Composite solid electrolyte and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150364788A1 (en) * | 2014-06-11 | 2015-12-17 | Los Alamos National Security, Llc | Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof |
| CN106602138A (en) * | 2017-01-17 | 2017-04-26 | 哈尔滨工业大学无锡新材料研究院 | Solid polymer electrolyte added with high-concentration lithium salt and preparation method thereof |
| US20170170515A1 (en) * | 2015-12-15 | 2017-06-15 | Sila Nanotechnologies Inc. | Solid state electrolytes for safe metal and metal-ion batteries |
| CN107492680A (en) * | 2017-07-26 | 2017-12-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of vinylene carbonate and polyethylene glycol（Methyl）Acrylate base polymer electrolyte and preparation method thereof |
| CN108155412A (en) * | 2017-12-26 | 2018-06-12 | 暨南大学 | A kind of inorganic-inorganic hybrid solid-state electrolyte ceramic membrane and preparation method thereof |
| WO2018106957A1 (en) * | 2016-12-07 | 2018-06-14 | Sepion Technologies, Inc. | Microstructured ion-conducting composites and uses thereof |
| CN108172784A (en) * | 2017-12-19 | 2018-06-15 | 成都亦道科技合伙企业（有限合伙） | A kind of lithium silicon-carbon composite cathode lithium battery structure and preparation method thereof |
| CN108336399A (en) * | 2018-02-08 | 2018-07-27 | 天津瑞晟晖能科技有限公司 | Solid electrolyte film and preparation method thereof and secondary cell and preparation method thereof |
| CN108428935A (en) * | 2018-01-25 | 2018-08-21 | 深圳市沃特玛电池有限公司 | A kind of solid electrolyte membrane preparation method and lithium battery |
| CN108511687A (en) * | 2018-02-28 | 2018-09-07 | 哈尔滨工业大学无锡新材料研究院 | A kind of lithium an- ode and preparation method thereof of cladding solid polymer electrolyte |
| CN108630996A (en) * | 2017-03-22 | 2018-10-09 | 福特全球技术公司 | Solid state battery |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
| CN109075390A (en) * | 2016-09-30 | 2018-12-21 | 株式会社Lg化学 | Rich lithium anti-perovskite compound, comprising its lithium secondary battery electrolyte and include its lithium secondary battery |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9246188B2 (en) * | 2011-02-14 | 2016-01-26 | Los Alamos National Security, Llc | Anti-perovskite solid electrolyte compositions |
| CN104466239B (en) * | 2014-11-27 | 2017-02-22 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN105811002A (en) * | 2016-03-16 | 2016-07-27 | 中国科学院青岛生物能源与过程研究所 | Organic and inorganic composite all-solid-state electrolyte and all-solid-state battery formed from same |
| WO2018062770A1 (en) * | 2016-09-30 | 2018-04-05 | 주식회사 엘지화학 | Lithium-rich antiperovskite compound, lithium secondary battery electrolyte comprising same, and lithium secondary battery comprising same |
| US11011796B2 (en) * | 2016-10-21 | 2021-05-18 | Quantumscape Battery, Inc. | Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride |
| US10700377B2 (en) * | 2017-01-17 | 2020-06-30 | Samsung Electronics Co., Ltd. | Solid electrolyte for a negative electrode of a secondary battery including first and second solid electrolytes with different affinities for metal deposition electronchemical cell and method of manufacturing |
| CN107403955B (en) * | 2017-08-04 | 2020-06-05 | 郑州新世纪材料基因组工程研究院有限公司 | Double-type anti-perovskite lithium ion solid electrolyte and preparation method and application thereof |
| CN108899579B (en) * | 2018-06-14 | 2021-03-05 | 北京工业大学 | Preparation of self-crosslinking composite solid electrolyte and all-solid-state lithium ion battery formed by same |
| CN109037774B (en) * | 2018-07-30 | 2020-10-09 | 哈尔滨工业大学无锡新材料研究院 | Crosslinked polymer electrolyte suitable for lithium secondary battery and preparation method thereof |
-
2018
- 2018-12-28 CN CN201811625967.3A patent/CN109786822A/en active Pending
- 2018-12-28 CN CN202110247698.7A patent/CN112993389A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150364788A1 (en) * | 2014-06-11 | 2015-12-17 | Los Alamos National Security, Llc | Methods for growth of lithium-rich antiperovskite electrolyte films and use thereof |
| CN108370060A (en) * | 2015-12-15 | 2018-08-03 | 新罗纳米技术有限公司 | solid electrolyte for safe metal and metal ion battery |
| US20170170515A1 (en) * | 2015-12-15 | 2017-06-15 | Sila Nanotechnologies Inc. | Solid state electrolytes for safe metal and metal-ion batteries |
| CN109075390A (en) * | 2016-09-30 | 2018-12-21 | 株式会社Lg化学 | Rich lithium anti-perovskite compound, comprising its lithium secondary battery electrolyte and include its lithium secondary battery |
| WO2018106957A1 (en) * | 2016-12-07 | 2018-06-14 | Sepion Technologies, Inc. | Microstructured ion-conducting composites and uses thereof |
| CN106602138A (en) * | 2017-01-17 | 2017-04-26 | 哈尔滨工业大学无锡新材料研究院 | Solid polymer electrolyte added with high-concentration lithium salt and preparation method thereof |
| CN108630996A (en) * | 2017-03-22 | 2018-10-09 | 福特全球技术公司 | Solid state battery |
| CN107492680A (en) * | 2017-07-26 | 2017-12-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of vinylene carbonate and polyethylene glycol（Methyl）Acrylate base polymer electrolyte and preparation method thereof |
| CN108172784A (en) * | 2017-12-19 | 2018-06-15 | 成都亦道科技合伙企业（有限合伙） | A kind of lithium silicon-carbon composite cathode lithium battery structure and preparation method thereof |
| CN108155412A (en) * | 2017-12-26 | 2018-06-12 | 暨南大学 | A kind of inorganic-inorganic hybrid solid-state electrolyte ceramic membrane and preparation method thereof |
| CN108428935A (en) * | 2018-01-25 | 2018-08-21 | 深圳市沃特玛电池有限公司 | A kind of solid electrolyte membrane preparation method and lithium battery |
| CN108336399A (en) * | 2018-02-08 | 2018-07-27 | 天津瑞晟晖能科技有限公司 | Solid electrolyte film and preparation method thereof and secondary cell and preparation method thereof |
| CN108511687A (en) * | 2018-02-28 | 2018-09-07 | 哈尔滨工业大学无锡新材料研究院 | A kind of lithium an- ode and preparation method thereof of cladding solid polymer electrolyte |
| CN108878959A (en) * | 2018-06-14 | 2018-11-23 | 北京工业大学 | A kind of preparation and its application of organo-mineral complexing solid electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109786822A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112993389A (en) | Lithium-rich anti-perovskite oxide composite electrolyte and preparation method and application thereof | |
| JP5458740B2 (en) | Sulfide solid electrolyte material | |
| CN113471442B (en) | Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same | |
| KR20180015841A (en) | All solid lithium secondary battery comprising gel polymer electrolyte and method for manufacturing the same | |
| CN110336073A (en) | A kind of solid electrolyte and preparation method thereof, solid state battery and electronic equipment | |
| CN113285118A (en) | Compound solid electrolyte based on MOF three-dimensional framework support and preparation method thereof | |
| CN112397762A (en) | Solid-state battery | |
| CN110808411B (en) | Electrolyte and lithium ion battery | |
| JP5522086B2 (en) | Ion conductor material, solid electrolyte layer, electrode active material layer and all solid state battery | |
| KR20070066453A (en) | Positive electrode active material, manufacturing method thereof and lithium secondary battery comprising the same | |
| CN114976263B (en) | Positive electrode and electrolyte integrated solid-state battery and preparation method thereof | |
| CN115986213A (en) | Nonaqueous electrolyte solution and nonaqueous electrolyte battery | |
| CN110676433A (en) | Composite lithium cathode, preparation method thereof and lithium battery | |
| CN112670450A (en) | Negative pole piece for solid-state battery and preparation method and application thereof | |
| CN111484247B (en) | Glass positive electrode material and preparation method and application thereof | |
| CN113270634A (en) | Composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and preparation method thereof | |
| KR100743982B1 (en) | Active material, manufacturing method thereof and lithium secondary battery comprising the same | |
| JP2017033858A (en) | Solid electrolyte material | |
| CN111799502A (en) | Garnet type solid composite electrolyte, preparation method and application | |
| JP2019200868A (en) | Nonaqueous secondary battery | |
| CN115642292A (en) | Zero-strain all-solid-state lithium-aluminum battery | |
| CN113363573B (en) | Preparation method of solid electrolyte, solid electrolyte and all-solid-state battery | |
| CN114976218A (en) | Composite isolating membrane, preparation method thereof and secondary battery | |
| KR102253763B1 (en) | Manufacturing method of solid-state composite electrolyte membrane for secondary battery having compact structure | |
| CN114512718A (en) | Composite solid electrolyte, preparation method thereof and high-performance all-solid-state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |