CN117535572A - Gallium-based alloy and preparation method and application thereof - Google Patents
Gallium-based alloy and preparation method and application thereof Download PDFInfo
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- CN117535572A CN117535572A CN202311594891.3A CN202311594891A CN117535572A CN 117535572 A CN117535572 A CN 117535572A CN 202311594891 A CN202311594891 A CN 202311594891A CN 117535572 A CN117535572 A CN 117535572A
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- based alloy
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 66
- 239000000956 alloy Substances 0.000 title claims abstract description 66
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 229910052744 lithium Inorganic materials 0.000 claims description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 239000010405 anode material Substances 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 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 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 230000017525 heat dissipation Effects 0.000 abstract description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 etc.) Chemical compound 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a gallium-based alloy and a preparation method and application thereof, wherein the preparation method comprises the following steps: the gallium-based alloy prepared by the method can inhibit continuous growth of negative dendrites in the battery when used for manufacturing the negative electrode and further applied to the battery, so that ions are uniformly deposited, the contact area of the electrode and electrolyte is increased, the critical current density is increased, meanwhile, the heat dissipation of the battery is accelerated, the safety is improved, the cycle performance of the battery is further improved, the problem of short cycle life of the metal secondary battery is effectively solved, and the method is simple and effective, and has the advantages of simple process, high efficiency and mild condition.
Description
Technical Field
The invention relates to the field of electrochemical devices, in particular to a gallium-based alloy and a preparation method and application thereof.
Background
With the increasing shortage of traditional resources and energy sources and the increasing serious environmental problems, the development of new energy storage and conversion technologies has become an important point of energy strategy in various countries. Energy storage devices, typified by metal secondary batteries such as lithium metal batteries and sodium metal batteries, play an extremely important role in energy storage and conversion. Metallic lithium, metallic sodium, are considered to be preferred materials for significantly increasing the energy density of the battery due to their high specific capacity and low electrode potential. However, the metal lithium and sodium negative electrode continuously form dendrites in the battery cycle process, which can continuously consume electrolyte, so that the battery coulomb efficiency is low, the cycle life is reduced, and more serious, the dendrites continuously grow to puncture the diaphragm, so that the internal short circuit of the battery is caused, and the safety accident of the battery is easily caused by the accumulated generated heat.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved method for preparing a gallium-based alloy, wherein the gallium-based alloy prepared by the method can inhibit continuous growth of negative dendrites in a battery when being used for preparing the negative electrode and being applied to the battery, can accelerate heat dissipation of the battery, and can improve the cycle performance of the battery while providing a negative electrode with high safety and uniform ion deposition.
The invention also provides the gallium-based alloy prepared by the method.
The invention also provides a gallium-based alloy anode material containing the gallium-based alloy prepared by the method and application of the gallium-based alloy anode material serving as an anode in preparation of batteries.
In order to achieve the above purpose, the invention adopts a technical scheme that: a method of preparing a gallium-based alloy, the method comprising: mixing and grinding metal gallium and one or more of other metals except the metal gallium, forming an alloy, and then annealing at the temperature of 30-400 ℃.
According to some preferred aspects of the invention, the annealing treatment is carried out at a temperature of 50-350 ℃. Further, the annealing treatment is performed at a temperature of 80-200 ℃.
In some embodiments of the invention, the annealing treatment is performed at a temperature of 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, or 200 ℃.
In some preferred and specific embodiments of the present invention, the annealing time of the annealing treatment is controlled to be 0.5-2h, for example, may be 0.5h, 0.6h, 0.8h, 1h, 1.5h, 1.8h, etc.
According to some preferred aspects of the invention, the mixed grinding and the annealing treatment are performed separately under a protective atmosphere formed by the passage of nitrogen and/or inert gas.
According to some preferred aspects of the present invention, the other metal includes, but is not limited to, one, two or more combinations of metals that may be selected from lithium, sodium, potassium, calcium, magnesium, indium, iron, copper, manganese, gold, silver, zinc, platinum, cobalt, tin, nickel, antimony, ruthenium, aluminum, titanium, tungsten.
In the invention, after electrons are reduced into lithium atoms by the negative electrode, a certain diffusion path is needed to be combined with the alloy negative electrode to form an alloy or solid solution, so that the molar ratio of gallium to other metals is limited, the formation of a path for lithium diffusion is facilitated, and the formation of dendrites on the surface of the negative electrode is further facilitated to be inhibited. According to some preferred aspects of the invention, the molar ratio of the gallium metal to the other metal is 0.1-10:1, for example, 0.1:1, 2:1, 3:1, 5:1, 7:1, 8:1, 9:1, 10:1, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Still more preferably, in some embodiments of the present invention, the molar ratio of the gallium metal to the other metal is 0.5-10:1. In some other embodiments, the molar ratio of the gallium metal to the other metal may be 1-10:1.
In some preferred embodiments of the present invention, embodiments of preparing the gallium-based alloy include:
mixing and grinding metallic gallium and one or more metals selected from the group consisting of other metals except the metallic gallium in a protective atmosphere until the metallic gallium and the one or more metals are completely fused to form an alloy;
then annealing the grinded alloy under protective atmosphere at 30-400 ℃ and preserving heat.
The invention provides another technical scheme that: the gallium-based alloy prepared by the preparation method of the gallium-based alloy.
The invention provides another technical scheme that: a gallium-based alloy anode material comprising the gallium-based alloy described above.
In the present invention, the gallium-based alloy anode material may be composed of a gallium-based alloy alone, or may further contain an inactive substance that does not participate in the lithium deposition reaction and form a composite with the gallium-based alloy, and in some embodiments, the inactive substance includes one or more selected from oxides (for example, magnesium oxide, calcium oxide, zirconium oxide, etc.), carbon, and chlorides (for example, magnesium chloride, calcium chloride, sodium chloride, etc.).
In some embodiments of the present invention, the gallium-based alloy anode material further comprises an ion conductive agent (for example, may be a halide electrolyte, a sulfide electrolyte, an oxide electrolyte, etc.), for example, when the gallium-based alloy anode material is used in a solid-state battery, the above-mentioned gallium-based alloy and the ion conductive agent may be mixed to prepare the electrode material, wherein the type and the content of the ion conductive agent may be regulated and selected according to different battery systems.
The invention provides another technical scheme that: the gallium-based alloy anode material is applied to battery preparation as an anode.
In some embodiments of the invention, the battery comprises a solid state battery, a liquid battery, or a flow battery;
among them, the solid-state battery is a battery using a solid electrode and a solid electrolyte, and is generally low in power density and high in energy density; solid state batteries include, but are not limited to, lithium batteries, sodium batteries, magnesium batteries, calcium batteries, potassium batteries, and the like;
the liquid battery consists of a battery formed by immersing an electrochemically active electrode in a glass container filled with electrolyte;
the flow battery is composed of a pile unit, electrolyte, an electrolyte storage and supply unit, a management control unit and the like. The flow battery is a high-performance storage battery which is separated by positive and negative electrolyte and circulates respectively. It has the characteristics of high capacity, wide application field (environment) and long cycle service life. The flow battery realizes the mutual conversion of electric energy and chemical energy through the reversible oxidation-reduction reaction (namely the reversible change of valence state) of the active substances of the electrolyte solution of the positive electrode and the negative electrode. During charging, the anode generates oxidation reaction to raise the valence state of the active material, the cathode generates reduction reaction to lower the valence state of the active material, and the discharging process is opposite to the oxidation reaction.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
through a great deal of experimental study, the inventor of the invention prepares the gallium-based alloy, firstly mixes all metals to form the alloy through grinding, and then carries out annealing treatment in a relatively low specific temperature interval, and discovers that the alloy can obtain pure Xiang Jiaji alloy, can effectively inhibit the growth of negative dendrites, has unexpected inhibition effect, realizes uniform deposition of ions, reduces potential safety hazard of the battery, ensures better safety of the battery and improves the cycle performance of the battery; the practice shows that when the gallium-based alloy prepared by the invention is applied to the negative electrode of a lithium battery, the critical current density of the battery, such as an all-solid-state battery, can reach 10mA/cm 2 The device can stably circulate for more than five hundred times;
further, according to research and analysis of the inventor, the gallium-based alloy prepared by the method has relatively low chemical potential, and can enable alkali metal ions to form an alloy or a solid solution during negative electrode deposition, so that growth of negative electrode dendrites is effectively inhibited, electrode-electrolyte contact area can be increased, critical current density of a battery is improved, and cycle life of the battery is prolonged while high safety and uniform ion deposition are provided.
In addition, the invention not only effectively solves the problem of short cycle life of the metal secondary battery, but also has simple and effective method, simple and convenient process, high efficiency and mild condition.
Drawings
FIG. 1 is an X-ray diffraction chart of a lithium gallium alloy prepared according to example 1 of the invention;
fig. 2 is a first charge-discharge curve of an all-solid-state battery (commercial high-nickel ternary NCM811 is positive electrode) prepared in example 1 of the present invention;
fig. 3 is a cycle performance test chart of an all-solid-state battery (commercial high nickel ternary NCM811 is the positive electrode) prepared in example 1 of the present invention;
fig. 4 is a constant current charge-discharge test chart of the all-solid-state symmetrical battery prepared in example 1 of the present invention;
fig. 5 is a charge-discharge curve of an all-solid battery (lithium metal is a counter electrode) prepared in example 2 of the present invention;
FIG. 6 is an X-ray diffraction chart of the lithium gallium alloy prepared in comparative example 1 of the invention;
fig. 7 is a first charge-discharge curve of an all-solid-state battery (commercial high-nickel ternary NCM811 is positive) prepared in comparative example 1 of the present invention;
fig. 8 is a first charge-discharge curve of an all-solid-state battery (commercial high-nickel ternary NCM811 is positive) prepared in comparative example 2 of the present invention;
FIG. 9 is an X-ray diffraction chart of the lithium gallium alloy prepared in comparative example 3 of the invention;
fig. 10 is a first charge-discharge curve of an all-solid-state battery (commercial high-nickel ternary NCM811 is positive) prepared in comparative example 4 of the present invention.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
Example 1
The embodiment provides a lithium gallium alloy, a preparation method thereof and a lithium gallium alloy anode material prepared further.
The preparation method of the lithium gallium alloy comprises the following steps:
weighing 0.7g of gallium metal and 0.1g of lithium metal respectively, manually grinding in a glove box by using an agate mortar until the gallium metal and the lithium metal are completely fused together to form an alloy, then annealing the ground material in an argon atmosphere at the temperature of 180 ℃ for 2 hours to form Li 3 Ga 2 An alloy having an X-ray diffraction pattern as shown in figure 1.
Li obtained after the heat preservation 3 Ga 2 And (3) after the alloy is subjected to standing, cooling and pressing, the standing process is carried out for 1h, and the lithium gallium alloy anode material is obtained.
Assembling an all-solid-state battery with the lithium gallium alloy anode material obtained in the example, and performing constant-current charge and discharge test, wherein the lithium gallium alloy anode material obtained in the example is taken as an anode, and Li is 6 PS 5 Cl is used as electrolyte, commercial high nickel ternary is used as positive electrode, and charge-discharge current density is 0.5mA/cm 2 As shown in fig. 2, the average voltage of the all-solid-state battery is about 3.8V, which is a normal operating voltage value of the high-nickel ternary positive electrode, and the battery cycle performance is good, and as shown in fig. 3, the capacity retention rate is still high after 500 cycles, almost no drop, and the retention rate is above 98%.
The lithium gallium alloy negative electrode material obtained in the example is assembled into an all-solid-state symmetrical battery, and a constant-current charge and discharge test is carried out, and as can be seen from FIG. 4, the battery is at 25mA/cm 2 Can be stably cycled at a current density of (2), exhibits an extremely high critical current density and reaches at least 10mA/cm 2 The above.
Example 2
The embodiment provides a sodium-gallium alloy, a preparation method thereof and a sodium-gallium alloy anode material prepared further.
The preparation method of the sodium-gallium alloy comprises the following steps:
weighing 0.7g of gallium metal and 0.33g of sodium metal respectively, manually grinding in a glove box by using an agate mortar until the gallium metal and the sodium metal are completely fused together to form an alloy, then annealing the ground material in an argon atmosphere at 120 ℃ for 2 hours to form Na 3 Ga 2 And (3) alloy.
Na obtained after heat preservation 3 Ga 2 And (3) after the alloy is subjected to standing, cooling and pressing, the standing process is carried out for 1h, and the sodium-gallium alloy anode material is obtained.
Assembling an all-solid-state battery with the sodium-gallium alloy anode material obtained in the embodiment, and performing constant-current charge-discharge test, wherein metal sodium is used as a counter electrode, and Na 3 PS 4 As electrolyte, the sodium-gallium alloy anode material obtained in the embodiment is a working electrode, and the charge-discharge current is 3mA/cm 2 The charge-discharge time was set to 1h, and the charge-discharge curve of the all-solid battery was as follows with reference to fig. 5: the sodium intercalation potential of the battery is less than 0.3V, which indicates that the negative electrode can well display lower potential when being applied to a sodium battery.
Comparative example 1
The comparative example provides a lithium gallium alloy, a preparation method thereof and a lithium gallium alloy anode material prepared further.
The preparation method of the lithium gallium alloy comprises the following steps:
mixing 0.7g gallium metal and 0.1g metal lithium, directly heating the mixture under argon atmosphere at 800 ℃ for 2h to form Li x Ga y And (3) alloy. FIG. 6 is Li prepared in comparative example 1 x Ga y As can be seen from the X-ray diffraction pattern of the alloy, the lithium gallium alloy prepared by the method has obvious impurity phase.
Li obtained after the heat preservation x Ga y And (3) standing the alloy block, cooling, grinding into powder, and pressing to obtain the lithium gallium alloy anode material, wherein the standing time is 1 h.
The lithium gallium alloy negative electrode material obtained in comparative example 1 was assembled into an all-solid-state battery, and the battery was assembledCharge and discharge test in which the negative electrode material of lithium gallium alloy in this comparative example 1 was used as the negative electrode, li 6 PS 5 Cl is used as electrolyte, commercial high nickel ternary is used as positive electrode, and current density is 0.5mA/cm 2 The first charge-discharge curve of the all-solid-state battery is shown in fig. 7, and the potential of the negative electrode of the all-solid-state battery is found to be higher, the voltage platform of the whole battery is lower, and analysis shows that the all-solid-state battery is caused by more impurity phases in the lithium gallium alloy.
Comparative example 2
The same as in example 1, but without grinding.
Assembling an all-solid-state battery with the lithium gallium alloy anode material obtained in comparative example 2, and performing constant-current charge-discharge test, wherein the lithium gallium alloy anode material obtained in comparative example 2 is used as an anode, li 6 PS 5 Cl is used as electrolyte, commercial high nickel ternary is used as positive electrode, and charge-discharge current density is 0.5mA/cm 2 As can be seen from fig. 8, the first charge-discharge curve of the all-solid-state battery is shown in fig. 8, and the potential of the negative electrode is also higher, the voltage plateau of the whole battery is lower, and analysis is considered to be caused by insufficient purity of the lithium gallium alloy obtained by the method of comparative example 2, so that more impurity phases should exist, and the electrical performance is affected.
Comparative example 3
Substantially the same as in example 1, the only difference is that: the annealing temperature was 420 ℃.
The X-ray diffraction pattern of the lithium gallium alloy obtained in this comparative example 3 is shown in fig. 9, and it is clear from fig. 9 that a pure lithium metal phase appears, which indicates that the lithium gallium alloy prepared by the method in this comparative example also has an obvious impurity phase, and the purity of the obtained lithium gallium alloy is obviously not high.
Comparative example 4
Substantially the same as in example 1, the only difference is that: the sequence of grinding and annealing treatment is adjusted, specifically, heating and smelting are carried out at 180 ℃ and then grinding is carried out.
Assembling all solid-state batteries with the lithium gallium alloy anode material obtained in the comparative example, and performing constant-current charging and dischargingElectric test in which the negative electrode material of lithium gallium alloy obtained in this comparative example was used as a negative electrode, li 6 PS 5 Cl is used as electrolyte, commercial high nickel ternary is used as positive electrode, and charge-discharge current density is 0.5mA/cm 2 As can be seen from fig. 10, the potential of the negative electrode is also higher, and the voltage plateau of the whole battery is lower, and analysis shows that the purity of the lithium gallium alloy prepared by the method of the comparative example is not high.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (16)
1. A method for preparing a gallium-based alloy, comprising: mixing and grinding metal gallium and one or more of other metals except the metal gallium, forming an alloy, and then annealing at the temperature of 30-400 ℃.
2. The method of producing a gallium-based alloy according to claim 1, wherein the annealing treatment is performed at a temperature of 50 to 350 ℃.
3. The method of producing a gallium-based alloy according to claim 2, wherein the annealing treatment is performed at a temperature of 80 to 200 ℃.
4. The method of producing a gallium-based alloy according to claim 1, wherein the annealing time of the annealing treatment is controlled to be 0.5 to 2 hours.
5. The method according to claim 1, wherein the mixed grinding and the annealing treatment are performed in a protective atmosphere, respectively, the protective atmosphere being formed by introducing nitrogen and/or an inert gas.
6. The method of producing a gallium-based alloy according to claim 1, wherein the other metal comprises a combination of one, two or more selected from lithium, sodium, potassium, calcium, magnesium, indium, iron, copper, manganese, gold, silver, zinc, platinum, cobalt, tin, nickel, antimony, ruthenium, aluminum, titanium, tungsten.
7. The method of producing a gallium-based alloy according to claim 1, wherein the molar ratio of the metallic gallium to the other metal is 0.1-10:1.
8. The method of producing a gallium-based alloy according to claim 7, wherein the molar ratio of the metallic gallium to the other metal is 0.5-10:1.
9. The method of producing a gallium-based alloy according to claim 1, wherein an embodiment of producing the gallium-based alloy includes:
mixing and grinding metallic gallium and one or more metals selected from the group consisting of other metals except the metallic gallium in a protective atmosphere until the metallic gallium and the one or more metals are completely fused to form an alloy;
then annealing the grinded alloy under protective atmosphere at 30-400 ℃ and preserving heat.
10. A gallium-based alloy made by the method of making a gallium-based alloy of any one of claims 1-9.
11. A gallium-based alloy anode material, characterized in that the gallium-based alloy anode material comprises the gallium-based alloy according to claim 10.
12. The gallium-based alloy anode material according to claim 11, further comprising an inactive substance that does not participate in a lithium deposition reaction.
13. The gallium-based alloy negative electrode material according to claim 12, wherein the inactive substance comprises one or a combination of more selected from the group consisting of oxides, carbons, chlorides.
14. The gallium-based alloy anode material according to claim 11, further comprising an ion-conducting agent.
15. Use of a gallium-based alloy negative electrode material according to any one of claims 11-14 as a negative electrode in the preparation of a battery.
16. The use of claim 15, wherein the battery is a solid state battery, a liquid battery or a flow battery.
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