CN114094042A - Liquid metal negative pole piece and preparation method and application thereof - Google Patents
Liquid metal negative pole piece and preparation method and application thereof Download PDFInfo
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- CN114094042A CN114094042A CN202111328572.9A CN202111328572A CN114094042A CN 114094042 A CN114094042 A CN 114094042A CN 202111328572 A CN202111328572 A CN 202111328572A CN 114094042 A CN114094042 A CN 114094042A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 80
- 239000000956 alloy Substances 0.000 claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000005518 polymer electrolyte Substances 0.000 claims description 12
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910003251 Na K Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
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- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 6
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910018131 Al-Mn Inorganic materials 0.000 claims description 5
- 229910018461 Al—Mn Inorganic materials 0.000 claims description 5
- -1 LLZTO Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910006639 Si—Mn Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910018507 Al—Ni Inorganic materials 0.000 claims description 2
- 229910007981 Si-Mg Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910008458 Si—Cr Inorganic materials 0.000 claims description 2
- 229910008316 Si—Mg Inorganic materials 0.000 claims description 2
- 229910020813 Sn-C Inorganic materials 0.000 claims description 2
- 229910020991 Sn-Zr Inorganic materials 0.000 claims description 2
- 229910018732 Sn—C Inorganic materials 0.000 claims description 2
- 229910009085 Sn—Zr Inorganic materials 0.000 claims description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 52
- 239000007784 solid electrolyte Substances 0.000 abstract description 29
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
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- 239000002223 garnet Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011165 3D composite Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000626 liquid-phase infiltration Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
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- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a liquid metal negative pole piece and a preparation method and application thereof. And the surface of the negative pole piece is coated with liquid alloy. The invention provides a liquid metal electrode with a liquid alloy coated on the surface of metal lithium, which is used for improving the interface contact between an electrolyte and a negative electrode, greatly improving the critical current density of a solid electrolyte, filling pores generated by lithium removal in a circulating process, realizing the self-healing of an interface, avoiding the formation and growth of lithium dendrites and effectively solving the problem of interface contact.
Description
Technical Field
The invention relates to a lithium ion battery, relates to a lithium ion solid-state battery, and particularly relates to a liquid metal negative electrode plate of the lithium ion solid-state battery, and a preparation method and application thereof.
Background
With the deep thought of the green environmental protection concept, the new energy lithium battery is widely applied from small and medium-sized electronic products such as mobile phones and computers to large-sized energy equipment such as electric automobiles in recent years by virtue of the advantages of high voltage, high energy density, long cycle life, wide electrochemical window and the like, and thus higher requirements are provided for the lithium battery, and the energy density of the single battery reaches 500 Wh/kg; in addition, there are higher demands for the life span, safety performance, etc. of the battery.
The solid-state lithium battery is considered as the development direction of the future lithium battery, the solid-state lithium battery adopts solid electrolyte to replace a diaphragm and electrolyte in the traditional lithium battery, the spontaneous combustion and explosion risks of the battery are obviously reduced, the battery cannot be obviously decomposed at high temperature, the safety is high, and the working temperature range is wide; the solid electrolyte is difficult to leak and volatilize, and the electrolyte cannot be dried up during long-term circulation, so that the cycle life is long, and the service life of the battery is long; and solid-state batteries may use a lithium metal negative electrode, lithium metal possessing a low electrochemical potential (-3.04V compared to a standard hydrogen electrode), low density (0.53 g/cm)3) And high theoretical capacity (3860 m A · h/g), are considered key materials for achieving high energy density batteries.
However, the existing solid electrolytes cannot be well matched with lithium metal for two main reasons: firstly, the interface between the solid electrolyte and the metal lithium is incompatible, and the chemical stability and the electrochemical stability of the interface between the solid electrolyte and the metal lithium are poor, such as solid sulfide electrolyte LGPS, solid polymer electrolyte PVDF, solid inorganic oxide electrolyte LATP, LLTO and the like; second, the formation and penetration of lithium dendrites at high current densities. When the current density is greater than the Critical Current Density (CCD), voids may form at the interface of the negative electrode and the electrolyte as the cycle progresses, further resulting in an increase in the local current density, eventually resulting in the formation of lithium dendrites inside the electrolyte to initiate short circuits.
Common methods to ameliorate the above problems include: firstly, constructing a semi-solid electrode, and coating molten metal lithium on the surface of solid electrolyte in a liquid form; secondly, a lithium-philic interface is added, and a layer of Al and Al is deposited on the surface of the solid electrolyte2O3And ZnO and other coatings, not only prevents the side reaction caused by the direct contact of lithium metal and solid electrolyte, but also improves the lithium phobicity of the electrolyte interface and promotes the uniform deposition of the lithium metal at the interface; thirdly, a multifunctional interface layer is constructed, polymer-based solid electrolyte is added to the interface, interface contact is improved, interface side reaction is prevented, such as PEO, or an artificial solid electrolyte interface film (SEI), such as LiPO, is introduced4Enhanced solid electrolyteStability with metallic lithium.
CN108933258A discloses a preparation method of an all-solid-state lithium ion battery of a three-dimensional composite metal lithium cathode, wherein metal lithium is loaded on a carrier material by a chemical or physical method of electrochemical deposition or melt infiltration to prepare the three-dimensional composite metal lithium cathode, and the carrier material is activated carbon fiber cloth; preparing a PMMA-PEI-based all-solid-state polymer electrolyte membrane; tearing the PMMA-PEI-based all-solid-state polymer electrolyte membrane from the surface of a poly tetrachloroethylene plate, and cutting the membrane into a proper size for later use; with LiFePO4And (3) assembling the positive electrode, the PMMA-PEI-based all-solid-state polymer electrolyte membrane and the three-dimensional composite metal lithium negative electrode in sequence to obtain the all-solid-state lithium ion button cell. But the active carbon fiber is used as a negative electrode carrier, and the prepared all-solid-state electrolyte has large interface resistance.
CN105470466A discloses an all-solid-state battery with a framework-supported alloy negative electrode and a preparation method thereof, wherein a lithium boron alloy foil is used as a negative electrode material of the all-solid-state lithium battery, but after the lithium boron alloy foil is alloyed with boron, the density of lithium ions in the negative electrode is reduced, and the lithium ion conductivity of the system is reduced.
CN113381055A discloses a lithium/garnet-based solid electrolyte interface with low interface impedance and a method for preparing the same, the lithium metal battery comprises: the lithium ion battery includes a substrate, a positive electrode disposed on the substrate, a garnet-based solid electrolyte disposed on the positive electrode, and a metallic lithium negative electrode disposed on the garnet-based solid electrolyte. Wherein, the discoloration layer sets up in the interface department of metal lithium negative pole and garnet base solid state electrolyte, and this discoloration layer includes: a first part and a second part, wherein the first part comprises a lithium-containing compound and the second part comprises a garnet-based solid-state electrolyte composition. The metallic lithium negative electrode can be lithium simple substance or/and lithium alloy. However, garnet solid electrolytes are expensive and not suitable for industrial production.
How to industrially produce a solid-state battery with high critical current density and good interface contact at low cost is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a liquid metal electrode with a liquid alloy coated on the surface of metal lithium, which effectively solves the problem of interface contact.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a liquid metal negative pole piece, wherein the surface of the negative pole piece is coated with liquid alloy.
According to the invention, the liquid alloy is coated on the surface of the metal lithium, so that a liquid metal electrode is constructed, the interface contact between the electrolyte and the negative electrode is improved, the Critical Current Density (CCD) of the solid electrolyte is greatly improved, the pores generated by lithium removal can be filled in the circulation process, the self-healing of the interface is realized, the formation and the growth of lithium dendrites are avoided, and the problem of interface contact is effectively solved.
As a preferred technical solution of the present invention, the liquid alloy includes any one of a tin-based alloy, an aluminum-based alloy, a silicon-based alloy, a silver-based alloy, an antimony-based alloy, and a sodium-based alloy.
Preferably, the alloy includes any one of Na-K alloy, Cu-Sn alloy, Sn-C alloy, Sn-Zr alloy, Al-Cu alloy, Al-Mn alloy, Al-Ni alloy, Si-Mn alloy, Si-Mg alloy, or Si-Cr.
The second purpose of the invention is to provide a preparation method of the liquid metal negative pole piece, which comprises the following steps:
heating the two metal simple substances to a single-phase liquid state, mixing, and cooling to obtain a liquid alloy;
and coating the liquid alloy on a substrate to obtain the liquid metal negative pole piece.
As a preferable technical scheme of the invention, the metal simple substance comprises any one of Na, K, Cu, Sn, C, Zr, Al, Mn, Ni, Si, Cr or Mg.
Preferably, the ratio of the two simple metals is 0.25-4, wherein the ratio can be 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4.
As a preferred embodiment of the present invention, the substrate includes lithium metal.
Preferably, the thickness of the lithium metal is 8 to 9mm, wherein the thickness may be 8mm, 8.1mm, 8.2mm, 8.3mm, 8.4mm, 8.5mm, 8.6mm, 8.7mm, 8.8mm, 8.9mm, or 9mm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the liquid alloy coating has a volume of 4 to 5 μ L, wherein the volume may be 4 μ L, 4.1 μ L, 4.2 μ L, 4.3 μ L, 4.4 μ L, 4.5 μ L, 4.6 μ L, 4.7 μ L, 4.8 μ L, 4.9 μ L, or 5 μ L, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, the liquid alloy is coated in a thickness of 1 to 100% of the thickness of the substrate, wherein the coating thickness may be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% in percentage by weight, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The invention also provides a solid-state battery, which comprises the liquid metal negative pole piece.
Preferably, the solid-state battery further comprises a positive electrode sheet and a solid-state electrolyte.
As a preferable technical scheme of the invention, the positive pole piece comprises any one of a ternary positive pole, a lithium iron phosphate positive pole, a lithium manganate positive pole, a lithium cobaltate positive pole or a lithium sulfur positive pole.
As a preferred embodiment of the present invention, the solid electrolyte includes any one of a PEO-based polymer electrolyte, a PVDF-based polymer electrolyte, a PMMA-based polymer electrolyte, LLZTO, LLTO, LATP, LGPS, or LPS.
Compared with the prior art, the invention has the following beneficial effects:
(1) the liquid metal negative pole piece prepared by the method can greatly improve the critical current density of the solid electrolyte, and the critical current density can reach 1.34mA/cm2Above, get togetherThe flow impedance can be reduced to below 19.9 omega, and the problem of interface contact is effectively solved.
(2) The preparation method of the liquid metal negative pole piece is simple and efficient, can be used for continuous large-scale production, and is suitable for industrialization.
(3) The liquid metal cathode of the present invention can be applied to a variety of different solid electrolytes, and has wide applicability.
Drawings
Fig. 1 is a structural diagram of a lithium battery in examples 1 to 14 of the present invention.
FIG. 2 is a graph showing the critical current densities in example 1 of the present invention, examples 10 to 14 and comparative example 3.
FIG. 3 is a graph of AC impedances in inventive example 1, examples 10-14, and comparative example 3.
In the figure: 1-a solid electrolyte; 2-liquid alloy; 3-lithium metal sheet.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with the thickness of about 1mm and the diameter of 10mm as a solid electrolyte 1, and removing LiCO by polishing, ultrasonic cleaning and heat treatment at 500 ℃ for 3h3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure sodium and pure potassium, transferring into a glass bottle according to the proportion of 1:1, heating to a single-phase liquid state, uniformly mixing, and cooling to prepare a Na-K alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 8mm, and coating 4 mu L of Na-K alloy, namely liquid alloy 2, on one surface of the lithium sheet uniformly;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Na-K alloy with the LLTO sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 2
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLZTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLZTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure tin and pure copper, transferring the melted pure tin and pure copper into a glass bottle according to the proportion of 4:1, heating the mixture until a single-phase liquid state is uniformly mixed, and cooling the mixture to prepare a Cu-Sn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Cu-Sn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Cu-Sn alloy with the LLZTO sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 3
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: PEO polymer electrolyte with the thickness of about 1mm and the diameter of 11mm is taken as the solid electrolyte 1, and LiCO is removed by grinding and polishing, ultrasonic cleaning and heat treatment at 500 ℃ for 3h3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure aluminum and pure copper, transferring the melted pure aluminum and pure copper into a glass bottle according to the proportion of 4:1, heating the mixture until a single-phase liquid state is uniformly mixed, and cooling the mixture to prepare an Al-Cu alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Al-Cu alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Al-Cu alloy with a PEO polymer electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 4
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure aluminum and pure magnesium, transferring the molten pure aluminum and pure magnesium into a glass bottle according to the ratio of 3:1, heating the molten pure aluminum and pure magnesium to a single-phase liquid state, uniformly mixing the single-phase liquid state and the liquid state, and cooling the mixture to prepare an Al-Mn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 4 mu L of Al-Mn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Al-Mn alloy with a solid electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 5
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure silicon and pure manganese, transferring the melted pure silicon and pure manganese into a glass bottle according to the ratio of 2:1, heating the mixture to a single-phase liquid state, uniformly mixing the mixture, and cooling the mixture to prepare a Si-Mn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Si-Mn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Si-Mn alloy with a solid electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 6
In this example, pure sodium and pure potassium in the second step were replaced with pure aluminum and pure nickel to prepare an Al — Ni alloy, and the other conditions were the same as in example 1.
Example 7
In this example, pure sodium and pure potassium in the second step were replaced with pure silicon and pure magnesium to prepare a Si — Mg alloy, and the other conditions were the same as in example 1.
Example 8
This example was carried out under the same conditions as in example 1 except that the coating volume of the Na-K alloy in step three was changed to 3. mu.L.
Example 9
This example was carried out under the same conditions as in example 1 except that the coating volume of the Na-K alloy in step three was changed to 6. mu.L.
Example 10
In this example, the ratio of pure sodium to pure potassium was changed to 7:3 instead of 1:1, and the other conditions were the same as in example 1.
Example 11
In this example, the ratio of pure sodium to pure potassium was changed to 6:4 instead of 1:1, and the other conditions were the same as in example 1.
Example 12
In this example, the ratio of pure sodium to pure potassium was changed to 4:6 instead of 1:1, and the other conditions were the same as in example 1.
Example 13
In this example, the ratio of pure sodium to pure potassium was changed to 3:7 instead of 1:1, and the other conditions were the same as in example 1.
Example 14
In this example, the ratio of pure sodium to pure potassium was changed to 2:8, and the other conditions were the same as in example 1.
Comparative example 1
In the comparative example, pure sodium in the step two is replaced by pure potassium with equal mass to prepare the potassium liquid metal, and other conditions are the same as those in the example 1.
Comparative example 2
In the comparative example, pure potassium in the second step is replaced by pure sodium with equal mass to prepare sodium liquid metal, and other conditions are the same as those in example 1.
Comparative example 3
This comparative example did not prepare a liquid alloy. Lithium pair batteries were made by combining metallic lithium sheets directly with LLTO solid-state electrolyte, wherein the critical current densities of examples 1, 10-14 and comparative example 3 are shown in FIG. 2 and the AC impedance plot is shown in FIG. 3.
The solid-state batteries of examples 1 to 14 and comparative examples 1 to 3 were subjected to critical current density tests, and the results are shown in table 1.
TABLE 1
The results show that: the critical current density of the solid electrolyte can be remarkably improved by coating a layer of liquid metal electrodes such as Na-K alloy, Cu-Sn alloy, Al-Cu alloy and the like on the surface of the metal lithium to construct the liquid metal electrodes, and compared with the embodiment 1, the critical current density is reduced and the alternating current impedance is increased in the comparative examples 1-3, so that the interface contact between the electrolyte and the negative electrode is improved by the liquid alloy, the internal resistance of the battery is greatly reduced, and the problem of poor interface contact between the solid electrolyte and a pole piece in the solid lithium battery is well solved. Compared with the embodiment 1, the embodiment 8 and the embodiment 9 have the advantage that the interface contact is better when the coating volume of the alloy is replaced and the coating volume of the alloy is 4-5 mu L. Comparing example 1 with examples 10-14, it can be seen that when the ratio of the two simple metals is 0.25-4, the critical current density is large and the AC impedance is small. Comparing examples 6-7 with example 1, it can be seen that the resistance values of pure sodium and pure potassium alloys are the smallest.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The liquid metal negative pole piece is characterized in that the surface of the negative pole piece is coated with liquid alloy.
2. The negative electrode plate as claimed in claim 1, wherein the liquid alloy comprises any one of tin-based alloy, aluminum-based alloy, silicon-based alloy, silver-based alloy, antimony-based alloy or sodium-based alloy;
preferably, the alloy includes any one of Na-K alloy, Cu-Sn alloy, Sn-C alloy, Sn-Zr alloy, Al-Cu alloy, Al-Mn alloy, Al-Ni alloy, Si-Mn alloy, Si-Mg alloy, or Si-Cr.
3. The preparation method of the liquid metal negative electrode plate as claimed in claim 1 or 2, wherein the preparation method comprises the following steps:
heating the two metal simple substances to a single-phase liquid state, mixing, and cooling to obtain a liquid alloy;
and coating the liquid alloy on a substrate to obtain the liquid metal negative pole piece.
4. The production method according to claim 3, wherein the elemental metal includes any one of Na, K, Cu, Sn, C, Zr, Al, Mn, Ni, Si, Cr, or Mg;
preferably, the ratio of the two metal simple substances is 0.25-4.
5. The production method according to claim 3 or 4, wherein the substrate comprises lithium metal;
preferably, the thickness of the lithium metal is 8-9 mm.
6. The method according to any one of claims 3 to 5, wherein the liquid alloy is applied in a volume of 4 to 5 μ L.
7. The method according to any one of claims 3 to 6, wherein the liquid alloy is applied to a thickness of 1 to 100% of the thickness of the substrate.
8. A solid-state battery comprising the liquid metal negative electrode sheet according to claim 1 or 2;
preferably, the solid-state battery further comprises a positive electrode sheet and a solid-state electrolyte.
9. The solid-state battery according to claim 8, wherein the positive electrode sheet includes any one of a ternary positive electrode, a lithium iron phosphate positive electrode, a lithium manganese oxide positive electrode, a lithium cobalt oxide positive electrode, or a lithium sulfur positive electrode.
10. The solid-state battery according to claim 8 or 9, wherein the solid-state electrolyte comprises any one of a PEO-based polymer electrolyte, a PVDF-based polymer electrolyte, a PMMA-based polymer electrolyte, LLZTO, LLTO, LATP, LGPS, or LPS.
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