CN114520309A - Lithium-philic base material for metal lithium cathode and preparation method and application thereof - Google Patents
Lithium-philic base material for metal lithium cathode and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000004744 fabric Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910001960 metal nitrate Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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Abstract
The invention discloses a lithium-philic substrate material of a metal lithium cathode and a preparation method and application thereof; dissolving nickel salt and zinc salt in deionized water to obtain a metal salt aqueous solution 1; adding cetyl trimethyl ammonium bromide into the metal salt water solution 1, and stirring to obtain a solution 2; adding urea into the solution 2, and stirring to obtain a solution 3; carrying out hydrothermal reaction on the solution 3 to obtain a precursor mixed solution; filtering, washing and drying the precursor mixed solution to obtain precursor powder; and sintering the precursor powder in an ammonia atmosphere to obtain the lithium-philic material. The lithium-philic material has the advantages of simple preparation method, convenient control, high yield, easy industrialization and the like. The lithium-philic material prepared by the invention has high chemical stability, high conductivity and low cost, and shows good performance in the application aspect of lithium metal batteries.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium metal battery cathodes, and particularly relates to a lithium-philic substrate material for a lithium metal cathode, and a preparation method and application thereof.
Background
Along with the development of green energy, the demand of human beings for high energy density of energy storage devices is also increasing. Efficient and stable green energy storage and conversion are power for sustainable development of future technologies, and the appearance of batteries can help people to utilize energy more efficiently and conveniently. Since the last century, various battery forms have achieved commercial applications such as: lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, lithium ion batteries, and the like. The successful commercial application of lithium ion batteries changes the life style of people and promotes the rapid development of the fields of portable cameras, mobile phones, notebook computers, electric vehicles and the like.
However, despite the rapid development of lithium ion batteries, their energy density has been increasing slowly. Over the past 150 years, the energy density of batteries has only been from 40Wh kg of past lead-acid batteries-1The current lithium ion battery is improved to 200Wh kg-1. Such a growth rate is far from satisfying the demand of people for energy. As the actual energy density of the graphite cathode in the lithium ion battery is gradually close to the theoretical limit value, a more efficient electrode material is urgently needed to meet the development requirement of a new high-end energy storage device.
Lithium metal negative electrodes have an extremely high theoretical capacity (3860mAh g)-1) And the lowest (negative) potential (-3.04V vs standard hydrogen electrode), are widely regarded as the most promising next generation lithium ion battery anode materials and have received great attention from researchers. At present, the batteries that can use metallic lithium as a negative electrode mainly include: lithium-sulfur, lithium-air, lithium-oxide and lithium-ion batteries, all of which exhibit very high theoretical energy densities (lithium-air: 3500 Wh. kg. lithium battery)-12600 Wh.kg lithium-sulfur battery-11000-1500Wh kg of lithium-oxide cell-1. Therefore, a lithium metal battery using metal lithium as a negative electrode is likely to become a next-generation energy storage battery. However, these lithium metal batteries have serious safety problems (lithium dendrite growth causes short-circuiting of the battery) and are difficult to stably cycle (low coulombic efficiency). Lithium dendrite growth can cause short circuits in the battery, which can lead to thermal runaway, and risk of ignition and even explosion. This problem directly results in the failure of lithium metal secondary batteries to be commercially used. Since the commercial use of lithium ion batteries, most of the lithium metal battery products have been abandoned by the market. However, as a negative with extremely high energy densityThe search for metallic lithium has never been stopped by researchers for the electrode material. In recent years, various emerging strategies have been developed to inhibit the growth of lithium dendrites on metallic lithium negative electrodes, thereby improving the safety and service life of the batteries in anticipation of their ultimate practical use.
The method for utilizing the lithium-philic material as the current collector of the metal lithium negative electrode is an effective method, can effectively reduce the overpotential in the lithium deposition process, and can ensure the uniform deposition of the metal lithium, thereby greatly reducing the possibility of short circuit of the battery caused by the generation of lithium dendrites. The Lithium-philic materials reported so far mainly comprise pure Metal Lithium-philic materials, Lithium-philic alloy materials, Metal oxide Lithium-philic materials and Metal nitride Lithium-philic materials (Huang, K.; Li, Z.; Xu, Q.; Liu, H.; Li, H.; Wang, Y., LithiophilicuO nanofluoflower on Ti-Mesh Inducing Lithium Metal Plating intercalation Lithium Metal-hydrophilic metals with ultra high Rates and ultra Cycle life. ADVANCED ENERGY MATERIALS 2019,9 (29)). Since most of the lithium-philic materials of pure metals or metal alloys mainly comprise gold and silver, the price of the lithium-philic materials is high, and the battery production cost is increased by large-batch commercial application. The lithium-philic metal oxide and nitride materials have low electron conductivity and can undergo irreversible side reactions with lithium metal, so that the material of the interface transmission layer of the lithium metal cathode needs to be studied more deeply.
Disclosure of Invention
In order to overcome the above disadvantages of the prior art, the present invention provides a method for preparing a lithium-philic material with high chemical stability, high conductivity and low cost, which aims to improve the lithium-philic property of a base material, ensure high conductivity and high chemical stability of metal lithium, effectively ensure uniform deposition of the metal lithium and inhibit the formation of metal lithium dendrites.
The purpose of the invention is realized by at least one of the following technical solutions.
A preparation method of a lithium-philic substrate material for a lithium metal cathode comprises the following steps:
(1) dissolving nickel salt and zinc salt in deionized water to obtain a metal salt aqueous solution 1;
(2) adding hexadecyl trimethyl ammonium bromide into the metal salt water solution 1 in the step (1), and stirring to obtain a solution 2;
(3) adding urea into the solution 2 obtained in the step (2), and stirring to obtain a solution 3;
(4) carrying out hydrothermal reaction on the solution 3 obtained in the step (3) to obtain a precursor mixed solution;
(5) filtering, washing and drying the precursor mixed solution obtained in the step (4) to obtain precursor powder;
(6) and (5) sintering the precursor powder in the ammonia atmosphere to obtain the lithium-philic material.
Preferably, the molar ratio of the nickel salt to the zinc salt in the step (1) is (1:1) - (5: 1);
further preferably, the molar ratio of the nickel salt to the zinc salt in step (1) is 3: 1;
preferably, the nickel salt in step (1) is Ni (NO)3)2·6H2O, zinc salt being Zn (NO)3)2·6H2O。
Preferably, the total mass percentage concentration of the nickel salt and the zinc salt in the metal salt aqueous solution 1 in the step (1) is 5-30%;
further preferably, the total mass percentage concentration of the nickel salt and the zinc salt in the aqueous solution 1 of the metal salt in the step (1) is 10%;
preferably, the stirring treatment time in the step (1) is 10-30 min.
Further preferably, the stirring treatment time in the step (1) is 15 min.
Preferably, the mole ratio of the hexadecyl trimethyl ammonium bromide in the step (2) to the total amount of the nickel salt and the zinc salt in the step (1) is (1:5) - (1: 10);
further preferably, the molar ratio of the hexadecyl trimethyl ammonium bromide in the step (2) to the total amount of the nickel salt and the zinc salt in the step (1) is 1: 7;
preferably, the stirring treatment time in the step (2) is 60-180 min;
further preferably, the stirring treatment time in the step (2) is 120 min;
preferably, the temperature of the stirring treatment in the step (2) is 40-90 ℃.
Further preferably, the temperature of the stirring treatment in the step (2) is 60 ℃.
Preferably, the molar ratio of the urea to the total amount of the nickel salt and the zinc salt in the step (3) is (5:1) - (10: 1);
further preferably, the molar ratio of the urea to the total amount of the nickel salt and the zinc salt in the step (3) is 1: 1;
preferably, the stirring treatment time in the step (3) is 30-60 min.
Further preferably, the stirring treatment time in the step (3) is 30 min.
Preferably, the temperature of the hydrothermal reaction in the step (4) is 80-140 ℃ and the time is 3-16 h.
Further preferably, the temperature of the hydrothermal reaction in the step (4) is 120 ℃ and the time is 8 h.
Preferably, the washing in the step (5) is washing alternately by using ethanol and deionized water;
preferably, the drying treatment in the step (5) is vacuum drying; the temperature is 40-80 ℃ and the time is 6-24 h.
Further preferably, the temperature is 60 ℃ and the time is 12 h.
Preferably, the temperature of the sintering treatment in the step (6) is 300-800 ℃;
further preferably, the temperature of the sintering treatment in the step (6) is 450 ℃;
preferably, the time of the sintering treatment in the step (6) is 2-8 h;
further preferably, the time of the sintering treatment in the step (6) is 4 h;
preferably, the flow rate of the ammonia gas in the ammonia gas atmosphere in the step (6) is 0.1-1L/h.
The lithium-philic base material for the lithium metal cathode prepared by the preparation method.
The lithium-philic base material for the metal lithium negative electrode is applied to preparation of a current collector material of the metal lithium negative electrode and an interface material of the current collector of the metal lithium negative electrode.
According to the invention, according to two principles of lithium affinity of a lithium affinity material and chemical stability of the material and metal lithium, the anti-perovskite nitride containing nitrogen (N), nickel (Ni) and zinc (Zn) is used as the lithium affinity material of the metal lithium negative current collector for the first time, and a series of lithium affinity metal lithium negative current collectors are prepared.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention prepares the lithium-philic interface material/lithium-philic substrate material with high chemical stability and high conductivity, which can effectively ensure the uniform deposition of the metal lithium and inhibit the formation of the metal lithium dendrite. The method is easy to synthesize and good in repeatability, and the obtained electrode material or the modified electrode can be directly used as a metal lithium battery without dendrites and with high coulomb efficiency.
Drawings
FIG. 1 is a ZnNNi prepared in example 13The X-ray powder diffraction characterization result curve is obtained;
FIG. 2 is a ZnNNi preparation from example 13A chemical structure diagram of (a);
FIG. 3 is the ZnNNi prepared in example 13The nucleation overpotential and the polarization overpotential curve in the lithium deposition process;
FIG. 4 is a ZnNNi preparation of example 131.0mA/cm of long cycle test curve of lithium2,1.0mA h/cm2；
FIG. 5 is the ZnNNi prepared in example 23The X-ray powder diffraction characterization result curve is obtained;
fig. 6 is a cycle test curve of the lithium metal cathode prepared in example 2 in combination with lithium iron phosphate at a current density of 1C;
FIG. 7 is a ZnNNi prepared in example 331.0mA/cm of long cycle test curve of lithium2,1.0mA h/cm2；
Fig. 8 is a graph of the cycle test results of the lithium metal negative electrode prepared in example 3 with NMC (111) at 1C current density;
FIG. 9 is a graph showing the full cell rate test curves of NCM (111) prepared in example 3 (in which the current densities are 0.2C, 0.5C, 1.0C, 2.0C, 5.0C, 10.0C, 5.0C, 2.0C, 1.0C, 0.5C, 0.2C, and 1.0C, in that order);
FIG. 10 is the pure ZnNNi prepared in example 43CV stability test result graph of electrode to metal lithium;
FIG. 11 is the ZnNNi prepared in example 43Graph of electron conductivity test results for lithium-philic materials and ketjen black.
Detailed Description
The following examples are included to further illustrate the practice of the invention, but are not intended to limit the practice or protection of the invention. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Weighing 7.5mmol of Ni (NO)3)2·6H2O powder and 2.5mmol of Zn (NO)3)2·6H2Dissolving O powder in 100mL of deionized water, stirring for 15min at normal temperature until 2 metal nitrates are completely dissolved, adding 1.4mmol of CTAB powder, and continuously stirring at 60 ℃ for 2h until complete reaction and clear solution are formed. Then adding 10mmol of urea into the solution, continuously stirring for 1h, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate after uniform stirring, and carrying out hydrothermal treatment at 110 ℃ for 12 h. After the treatment, the obtained slurry is filtered, washed (absolute ethyl alcohol and deionized water) and dried (vacuum oven 60 ℃ for 12 hours). Then the obtained precursor powder is placed in a tube furnace containing ammonia gas atmosphere (flow rate is 25L/h) to be sintered for 4h at 450 ℃. Finally, the lithium-philic interface material/lithium-philic substrate material with high chemical stability and high electrical conductivity is obtained. And uniformly coating the lithium-philic material on the surface of the carbon cloth, and then putting the carbon cloth into a battery containing the lithium metal for lithium deposition. Then 2 carbon cloth/ZnNNi after lithium deposition3The pole pieces were again assembled into a "lithium on lithium" symmetric cell for stability testing (pure carbon cloth without lithium-philic coating as comparative example).
As shown in figure 1, the XRD powder diffraction characterization shows that the material can be completely preparedCorresponding to the simulated diffraction peak position, the ordered peak at a low angle can also indicate that the material has a structure with orderly atomic arrangement; FIG. 2 is a schematic diagram of the chemical structure of the material; FIG. 3 shows nucleation overpotential and polarization overpotential during lithium deposition; fig. 4 shows the results of the long lithium-to-lithium cycling test. Compared with pure carbon cloth electrode, through ZnNNi3The modified electrode has obvious stability advantage in lithium-to-lithium tests, and the uniform deposition of lithium metal can effectively reduce the side reaction of the lithium metal and improve the utilization efficiency of the lithium metal.
Example 2
Weighing 7.5mmol of Ni (NO)3)2·6H2O powder and 2.5mmol of Zn (NO)3)2·6H2Dissolving O powder in 100mL of deionized water, stirring for 15min at normal temperature until 2 metal nitrates are completely dissolved, adding 1.4mmol of CTAB powder, and continuously stirring at 60 ℃ for 2h until complete reaction and clear solution are formed. Then adding 10mmol of urea into the solution, continuously stirring for 1h, uniformly stirring, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene substrate, and carrying out hydrothermal treatment at 120 ℃ for 12 h. After the treatment, the obtained slurry is filtered, washed (absolute ethyl alcohol and deionized water) and dried (vacuum oven 60 ℃ for 12 hours). Then, the obtained precursor powder was placed in a tube furnace containing an ammonia gas atmosphere (flow rate 25L/h) and subjected to sintering treatment at 500 ℃ for 4 h. Finally, the lithium-philic interface material/lithium-philic substrate material with high chemical stability and high electrical conductivity is obtained. And (3) uniformly coating the surface of the carbon cloth with the lithium-philic material, and then putting the carbon cloth into a battery containing the lithium metal for lithium deposition. Then the carbon cloth/ZnNNi after lithium deposition3And (3) assembling the pole piece and the lithium iron phosphate pole piece again to form a full cell for cycle life test (pure carbon cloth without being coated with a lithium-philic material is taken as a comparative example).
As in fig. 5, X-ray powder diffraction test results for the material; fig. 6 shows the results of the lithium iron phosphate full cell cycle test. Compared with pure carbon cloth electrode, through ZnNNi3The modified electrode shows obvious stability advantage in lithium iron phosphate full-cell test, and the uniform deposition of lithium metal can be effectively reducedThe side reaction of the metallic lithium is reduced, and the utilization efficiency of the metallic lithium is improved.
Example 3
Weighing 7.5mmol of Ni (NO)3)2·6H2O powder and 2.5mmol of Zn (NO)3)2·6H2Dissolving O in 100mL of deionized water, stirring for 15min at normal temperature until 2 metal nitrates are completely dissolved, adding 1.2mmol of CTAB powder, and continuously stirring at 60 ℃ for 2h until complete reaction and clear solution are formed. Then adding 8mmol of urea into the solution, continuously stirring for 1h, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate after uniform stirring, and carrying out hydrothermal treatment at 110 ℃ for 12 h. After the treatment, the obtained slurry is filtered, washed (absolute ethyl alcohol and deionized water) and dried (vacuum oven 60 ℃ for 12 hours). Then the obtained precursor powder is placed in a tube furnace containing ammonia gas atmosphere (flow rate is 25L/h) to be sintered for 4h at 400 ℃. Finally, the lithium-philic interface material/lithium-philic substrate material with high chemical stability and high electrical conductivity is obtained. And uniformly coating the lithium-philic material on the surface of the carbon cloth, and then putting the carbon cloth into a battery containing the lithium metal for lithium deposition. Then the carbon cloth/ZnNNi after lithium deposition3And (3) assembling the pole piece and the ternary positive electrode NCM (111) pole piece again to form a full cell for cycle life test (pure carbon cloth without a lithium-philic material is used as a comparative example).
As in fig. 7, the lithium-to-lithium long cycle test results for the material; fig. 8 shows the NMC (111) full cell cycling test results. Fig. 9 shows the results of the NCM (111) full cell rate test. Compared with pure carbon cloth electrode, through ZnNNi3The modified electrode shows obvious stability advantage in NMC (111) full battery test, and the uniform deposition of lithium metal can effectively reduce the side reaction of the lithium metal and improve the utilization efficiency of the lithium metal.
Example 4
Weighing 7.5mmol of Ni (NO)3)2·6H2O powder and 2.5mmol of Zn (NO)3)2·6H2Dissolving O powder in 100mL deionized water, stirring at normal temperature for 15min, adding 1.2mmol of the solution after 2 metal nitrates are completely dissolvedCTAB powder, continued stirring at 60 ℃ for 2h until complete reaction and a clear solution formed. Then adding 8mmol of urea into the solution, continuously stirring for 1h, transferring the solution into a stainless steel reaction kettle with a polytetrafluoroethylene substrate after uniform stirring, and carrying out hydrothermal treatment at 110 ℃ for 12 h. After the treatment, the obtained slurry is filtered, washed (absolute ethyl alcohol and deionized water) and dried (vacuum oven 60 ℃ for 12 hours). Then the obtained precursor powder is placed in a tube furnace containing ammonia gas atmosphere (flow rate is 25L/h) to be sintered for 4h at 450 ℃. Finally, the lithium-philic interface material/lithium-philic substrate material with high chemical stability and high electrical conductivity is obtained. And (3) uniformly coating the lithium-philic material on the surface of the copper foil, then loading the copper foil into a battery containing lithium metal for LSV test, and analyzing the chemical stability of the lithium-philic material on the lithium metal or lithium ions.
Figure 10 shows CV cycle test results. The lithium-philic material has no irreversible side reaction in the process of converting lithium ions and metal lithium, which shows that the material has good chemical stability to the metal lithium/lithium ions.
Fig. 11 shows the results of the electron conductivity test. The lithium-philic material has good electronic conductivity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, and equivalents thereof are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a lithium-philic substrate material for a metal lithium cathode is characterized by comprising the following steps:
(1) dissolving nickel salt and zinc salt in deionized water to obtain a metal salt water solution 1;
(2) adding hexadecyl trimethyl ammonium bromide into the metal salt water solution 1 in the step (1), and stirring to obtain a solution 2;
(3) adding urea into the solution 2 obtained in the step (2), and stirring to obtain a solution 3;
(4) carrying out hydrothermal reaction on the solution 3 in the step (3) to obtain a precursor mixed solution;
(5) filtering, washing and drying the precursor mixed solution obtained in the step (4) to obtain precursor powder;
(6) and (5) sintering the precursor powder in the ammonia atmosphere to obtain the lithium-philic material.
2. The method for preparing a lithium-philic metallic lithium substrate material as in claim 1, wherein the molar ratio of the nickel salt to the zinc salt in step (1) is (1:1) - (5: 1);
the nickel salt is Ni (NO)3)2·6H2O, Zn (NO) as zinc salt3)2·6H2O。
3. The method for preparing the lithium-philic metal lithium substrate material as claimed in claim 1, wherein the total mass percent concentration of the nickel salt and the zinc salt in the aqueous solution 1 of the metal salt in the step (1) is 5-30%;
the stirring treatment time in the step (1) is 10-30 min.
4. The method of preparing a lithium-philic metallic lithium substrate material as in claim 1, wherein the molar ratio of cetyltrimethylammonium bromide in step (2) to the total amount of nickel and zinc salts in step (1) is (1:5) - (1: 10);
the stirring treatment time in the step (2) is 60-180 min;
the temperature of the stirring treatment in the step (2) is 40-90 ℃.
5. The method for preparing a lithium-philic metallic lithium substrate material as claimed in claim 1, wherein the molar ratio of the urea to the total amount of the nickel salt and the zinc salt in step (3) is (5:1) - (10: 1);
the stirring treatment time in the step (3) is 30-60 min.
6. The method for preparing the lithium-philic metallic lithium substrate material as claimed in claim 1, wherein the hydrothermal reaction in step (4) is carried out at a temperature of 80-140 ℃ for a time of 3-16 h.
7. The method for preparing a lithium-philic metal lithium substrate material as claimed in claim 1, wherein the washing in step (5) is an alternate washing with ethanol and deionized water;
the drying treatment in the step (5) is vacuum drying; the temperature is 40-80 ℃ and the time is 6-24 h.
8. The method for preparing the lithium-philic metal lithium substrate material as claimed in claim 1, wherein the sintering temperature in the step (6) is 300-800 ℃;
the sintering treatment time in the step (6) is 2-8 h;
and (4) the flow rate of ammonia in the ammonia atmosphere in the step (6) is 0.1-1L/h.
9. A lithium metal negative electrode lithium-philic substrate material prepared by the preparation method as set forth in any one of claims 1 to 8.
10. Use of the lithium metal negative electrode lithium philic substrate material of claim 9 in the preparation of a lithium metal negative electrode current collector material, a lithium metal negative electrode current collector interface material.
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