CN114551813B - Metal lithium composite electrode, preparation method, application and battery - Google Patents
Metal lithium composite electrode, preparation method, application and battery Download PDFInfo
- Publication number
- CN114551813B CN114551813B CN202210189864.7A CN202210189864A CN114551813B CN 114551813 B CN114551813 B CN 114551813B CN 202210189864 A CN202210189864 A CN 202210189864A CN 114551813 B CN114551813 B CN 114551813B
- Authority
- CN
- China
- Prior art keywords
- lithium
- dimensional
- metal
- sheet
- composite electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 146
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 103
- 239000000843 powder Substances 0.000 claims abstract description 61
- -1 transition metal nitride Chemical class 0.000 claims abstract description 44
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 42
- 238000005096 rolling process Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims abstract description 6
- 230000007480 spreading Effects 0.000 claims abstract description 4
- 238000003892 spreading Methods 0.000 claims abstract description 4
- 239000002905 metal composite material Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 21
- 210000001787 dendrite Anatomy 0.000 abstract description 17
- 230000006911 nucleation Effects 0.000 abstract description 12
- 238000010899 nucleation Methods 0.000 abstract description 12
- 238000001291 vacuum drying Methods 0.000 abstract description 3
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 46
- 239000000463 material Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 5
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 5
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a metal lithium composite electrode, a preparation method, application and a battery. The preparation method comprises the following steps: (1) Performing ball milling and dispersing on the two-dimensional transition metal nitride nanosheet powder, and then performing vacuum drying and drying; (2) Uniformly spreading two-dimensional transition metal nitride nano-sheet powder on the surface of a metal lithium foil, and rolling to obtain a composite sheet; (3) folding the composite sheet and rolling the composite sheet; and (4) repeatedly repeating the step (3) to obtain the composite electrode. The method provided by the invention can avoid the problems of 'lithium dendrite' and 'dead lithium' caused by uneven lithium deposition and stripping which are easy to occur on the surface of the lithium metal negative electrode, thereby improving the coulomb efficiency of the electrode and prolonging the cycle life of the electrode. The two-dimensional transition metal nitride has excellent lithium-philic characteristic, can induce the two-dimensional nucleation and growth of metal lithium, can provide larger specific surface area for metal lithium deposition, reduce local current density and further inhibit the growth of metal lithium dendrite.
Description
Technical Field
The invention belongs to the technical field of metal lithium electrodes, and particularly relates to a metal lithium composite electrode, a preparation method, application and a battery.
Background
The lithium ion battery is used as a main power source of products such as electric vehicles, electronic equipment, unmanned aerial vehicles and the like, and the energy density of the lithium ion battery is continuously improved. Compared with the traditional lithium ion battery cathode material (graphite cathode), the metal lithium has lower reduction potential (-3.04V, vs H) + /H 2 ) And a higher theoretical specific capacity (3860 mAh g -1 ) The energy density of the battery can be greatly improved. However, lithium metal is prone to form "lithium dendrite" and "dead lithium" on the surface during the charge and discharge of the battery, resulting in low coulomb efficiency, short battery cycle life, and even thermal runaway or explosion safety problems due to battery short circuit. The above problems greatly limit the application of metallic lithium cathodes in high specific energy batteries. Construction of high-performance lithium metal composite electrode is to realize uniform lithiumDeposition/exfoliation behavior, one of the important methods to inhibit lithium dendrite growth.
The commonly used skeleton materials for preparing the lithium-containing composite electrode mainly comprise carbon materials such as copper foam, nickel foam, carbon fibers and the like, and the surfaces of the materials are often non-lithium-philic, so that uneven deposition and high deposition overpotential of metallic lithium on the surfaces of the materials are caused; thus, it is generally necessary to modify the surface with a layer of a lithium-philic substance, e.g. Au, ag, znO 2 、SnO 2 Etc., which adds both to the cost and makes the process cumbersome. In addition, in the process of compounding with metal lithium, two methods of molten lithium leaching or electrochemical lithium deposition are generally adopted, and a lithium-philic layer on the surface of a framework material is easy to fall off, so that the electrochemical performance is invalid. In addition, the process is complicated, the former needs to be performed at a relatively high temperature, and the latter needs to undergo additional complicated battery assembling and disassembling processes. Based on the two points, the design of a novel lithium-philic skeleton and the development of a simpler composite method are key to the application of the high-performance metal lithium composite electrode.
Pressing an additive into a metal lithium sheet, and adopting a rolling method to prepare a metal lithium anode (such as a preparation method of a layered composite for a secondary metal lithium battery anode, china patent No. 106654232B) has also been reported, wherein the additive is one or more of metal nano powder, nonmetal nano powder, a layered structure compound and a two-dimensional nano sheet; wherein the two-dimensional nano-sheet is selected from reduced graphene oxide, boron nitride nano-sheet, molybdenum disulfide nano-sheet, tungsten disulfide nano-sheet, ti 3 C 2 One or more of the MXene nanoplatelets. Compared with the preparation of the composite electrode by rolling the granular material, the two-dimensional material has larger specific surface area, can reduce the nucleation current density of lithium, and can more effectively inhibit the growth of lithium dendrites. The use of non-conductive two-dimensional materials (graphene oxide, boron nitride, etc.) as additives can lead to problems such as slower reaction kinetics, lithium ion aggregation, and uneven lithium deposition induction. If the conductive material is less lithium-philic (reduced graphene oxide), the metallic lithium will be more prone to non-uniform deposition on the upper surface of the material, growing lithium dendrites. For having a certainThe lithium-philic conductive two-dimensional material can only realize uniform nucleation to a certain extent, but lithium dendrites are still easy to grow under the high-current and high-capacity circulation condition.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a metal lithium composite electrode, a preparation method, application and a battery, and aims to combine transition metal nitride with a metal lithium sheet by a rolling method, fully utilize the advantages of the transition metal nitride, such as large specific surface area, high electronic conductivity, strong lithium-philicity, rapid ion transmission and promotion of epitaxial tiling growth of the metal lithium, and realize dendrite-free lithium deposition/stripping under large current and large capacity.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a lithium metal composite electrode, comprising the steps of:
(1) Ball milling or ultrasonic treatment is carried out on the two-dimensional transition metal nitride nanosheet powder, and then vacuum drying and drying are carried out;
(2) Uniformly spreading the two-dimensional transition metal nitride nano-sheet powder on the surface of a metal lithium foil, and rolling to obtain a composite sheet;
(3) Folding the composite sheet and rolling the composite sheet;
(4) And (3) repeating the step (3) to obtain the lithium composite electrode with a certain thickness.
Preferably, the pretreatment process in the step (1) is ball milling or ultrasonic treatment. The ball milling is carried out for 0.5-3h at 500-1500rpm by ZrO with diameter of 0.5-2mm 2 And (3) particles. The specific parameters of ultrasonic treatment are that the ultrasonic time is 0.5-2h and the ultrasonic frequency is 40kHZ.
Preferably, the two-dimensional transition metal nitride nanosheet powder is a two-dimensional molybdenum nitride nanosheet powder, a two-dimensional titanium nitride nanosheet powder, a two-dimensional vanadium nitride nanosheet powder, a two-dimensional chromium nitride nanosheet powder, a two-dimensional zirconium nitride nanosheet powder, a two-dimensional niobium nitride nanosheet powder, a two-dimensional tantalum nitride nanosheet powder or a two-dimensional tungsten nitride nanosheet powder.
Preferably, the thickness of the two-dimensional transition metal nitride nano-sheet is 5-8nm, and the average size of the two-dimensional plane of the two-dimensional transition metal nitride nano-sheet powder is 0.5-10 mu m.
Preferably, the mass ratio of the two-dimensional transition metal nitride nano-sheet powder to the metal lithium foil is 0.6:1-1.2:1.
Preferably, the number of rolling is 2 to 12.
Preferably, the steps (2) - (4) are performed under an Ar protective atmosphere.
In another aspect, the invention provides a lithium metal composite electrode.
In yet another aspect, the invention provides the use of a lithium metal composite electrode in a negative electrode of a lithium metal battery.
In yet another aspect, the present invention provides a lithium metal battery comprising the metal lithium composite electrode.
In general, the above technical solutions conceived by the present invention can achieve at least the following advantageous effects compared to the prior art.
(1) In the invention, two-dimensional transition metal nitride nano-sheets and lithium sheets are combined, wherein the two-dimensional transition metal nitride is a lithium-philic material, and in general, metal lithium and transition metal nitride (titanium nitride, vanadium nitride, chromium nitride, molybdenum nitride, zirconium nitride, niobium nitride, tantalum nitride or tungsten nitride) are subjected to mechanical rolling process at room temperature, and the metal lithium is easy to react with the surface of the metal nitride to generate Li 3 N and the corresponding transition metal exhibit a lithium-philic character. Therefore, the metal lithium and the transition metal nitride have stronger binding capacity, so that the metal lithium can be induced to uniformly nucleate on the surface of the metal lithium, and then be uniformly deposited. Thus, the problems of a large amount of lithium dendrites and dead lithium caused by uneven lithium deposition and stripping on the surface of the lithium metal negative electrode can be avoided, and the coulomb efficiency of the battery is improved and the cycle life of the battery is prolonged.
The two-dimensional transition metal nitride has the characteristics of large specific surface area, high electronic conductivity and strong lithium affinity, and can reduce the effective current density, accelerate the reaction kinetics, reduce the nucleation overpotential and realize uniform nucleation; furthermore, two-dimensional passingThe reaction of the transition metal nitride with the metallic lithium can produce Li with very good ionic conductivity 3 N and the corresponding transition metals, li 3 N can promote rapid ion transmission, high rate performance is realized, strong interaction is also realized between transition metal and Li, and lower lattice mismatch exists between the transition metal and lithium, so that epitaxial tiling growth of metal lithium can be induced, and high capacity cycle performance is further realized.
(2) In the invention, the two-dimensional transition metal nitride nanosheets are subjected to ball milling or ultrasonic dispersion treatment to obtain the monodisperse nanosheets.
(3) Compared with bulk materials, the two-dimensional sheet shape can provide larger specific surface area, thereby providing more lithium nucleation sites and promoting uniform lithium nucleation; meanwhile, part of special two-dimensional surfaces (such as a MoN (002) crystal surface) can induce the epitaxial horizontal growth of metallic lithium on a plane, so that the vertical growth of lithium dendrites is prevented from penetrating through a diaphragm. On the other hand, the two-dimensional material has large surface area, can reduce nucleation current density, and further inhibit lithium dendrite growth.
(4) The two-dimensional transition metal nitride nanosheets are preferably two-dimensional molybdenum nitride, and have the advantages of rich Mo ore resources in China, and in addition, the plane (002) crystal face of the two-dimensional MoN can induce the epitaxial parallel growth of the metal lithium.
(5) The transition metal nitride nano-sheet/lithium metal composite electrode is prepared by using the physical operation of mechanical rolling/folding for a plurality of times. The preparation method is operated at room temperature, avoids the high-temperature melting process, is safer, and is more beneficial to industrial production and application.
Drawings
Fig. 1 is a schematic diagram of a method for preparing a metal lithium composite electrode according to an embodiment of the present invention;
fig. 2 (a) is a schematic diagram of a deposition stripping mechanism of metallic lithium on a pure lithium electrode, and fig. 2 (b) is a schematic diagram of a deposition stripping mechanism of metallic lithium on a two-dimensional molybdenum nitride nano-sheet/lithium composite electrode;
FIG. 3 (a) is a TEM image of two-dimensional molybdenum nitride nanoplates; fig. 3 (c) is a Mapping spectrum of Mo element in the two-dimensional molybdenum nitride nanosheets; fig. 3 (d) shows a Mapping graph of element N in the two-dimensional molybdenum nitride nano-sheet, and fig. 3 (b) shows a TEM graph corresponding to the Mapping graph;
fig. 4 (a) is an XPS spectrum of a two-dimensional molybdenum nitride nanosheet Mo3d, and fig. 4 (b) is an XPS spectrum of a two-dimensional molybdenum nitride nanosheet N1 s;
fig. 5 (a) is an optical photograph of the composite electrode prepared by example 7, fig. 5 (b) is a cross-sectional view of an SEM of the composite electrode, and fig. 5 (c) is an SEM of an upper surface of the composite electrode;
FIG. 6 is an XRD contrast pattern of pure molybdenum nitride and a composite electrode, wherein MoN@Li is prepared by example 7, moN is two-dimensional molybdenum nitride nano-sheet powder Li PDF#15-0401 used in example 7, and MoN PDF#25-1367 are standard cards;
FIG. 7 (a) shows a current of 1mA/cm for a composite electrode assembled symmetrical cell prepared by example 7 -2 With a capacity of 1mAh/cm -2 Cycling performance under conditions, FIG. 7 (b) is a graph of current 1mA/cm -2 Capacity 3mAh/cm -2 Cyclic performance graph under conditions;
fig. 8 (a) is an SEM image after the cycle of the composite electrode mon@li assembled symmetric battery prepared by example 7, and fig. 8 (b) is an SEM image after the cycle of the pure Li electrode assembled symmetric battery;
fig. 9 is a graph of full cell performance assembled using the composite electrode prepared in example 7 as the negative electrode and lithium iron phosphate as the positive electrode;
fig. 10 (a) is an SEM image of the negative electrode after the full-cell charge-discharge cycle in which the composite electrode mon@li prepared in example 7 was used as the negative electrode, and the lithium iron phosphate was used as the positive electrode, and fig. 10 (b) is an SEM image of the negative electrode after the full-cell charge-discharge cycle in which the pure Li electrode was used as the negative electrode, and the lithium iron phosphate was used as the positive electrode.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention adopts a mechanical rolling method. Firstly, the rolled materials are required to have good electronic conductivity, and the introduction of materials with poor conductivity (boron nitride nanosheets, molybdenum disulfide, tungsten disulfide nanosheets and graphene oxide) into an electrode can cause uneven charge accumulation on the surface of the electrode, so that uneven lithium deposition is caused; secondly, the material should have good lithium-philic properties to induce uniform nucleation of lithium, while the surface nucleation overpotential of the material with poor lithium-philic properties (e.g., graphene) is high, and thus non-uniform deposition, producing lithium dendrites. Ti (Ti) 3 C 2 the-MXene material has excellent electronic conductivity, the surface of the material contains abundant-F, -OH and other lithium-philic functional groups, and uniform lithium deposition can be realized to a certain extent, however, ti 3 C 2 The preparation process of the-MXene is complex, medicines with high harmfulness such as HF and the like are required to be used, and on the other hand, the amount of functional groups such as F, OH and the like on the surface of the medicines is difficult to accurately control. The invention adopts the two-dimensional MoN nano-sheet, has excellent electronic conductivity and good lithium-philic property, and the Li reacts with MoN on the surface, and the products are metal Mo and Li 3 N, wherein Li 3 The N has extremely high ion transmission rate, can greatly promote the rapid transmission of lithium ions, has small lattice mismatch between a MoN two-dimensional plane (002) crystal face and a metal Mo (100) crystal face and metal lithium, can induce the planar epitaxial growth of the metal lithium, and effectively inhibits lithium dendrites; thus, compared with Ti 3 C 2 The introduction of two-dimensional MoN in the present invention allows to induce uniform lithium deposition to a greater extent, inhibit lithium dendrites, and realize long cycling at high capacity/high current, for conventional materials such as MXene. In addition, the metal lithium prepared by rolling is stable in network structure penetrated by MoN, and the volume change of the electrode is small in the Li deposition stripping process, so that the high-rate and long-cycle performance can be realized.
According to the invention, the two-dimensional transition metal nitride nano-sheet is taken as a metal lithium deposition framework, and the composite electrode formed by stacking the two-dimensional transition metal nitride nano-sheet and lithium is prepared by a simple mechanical rolling method. The preparation process of the two-dimensional transition metal nitride nano-sheet/metal lithium composite electrode is simple and feasible, and the commercial production is easy. The two-dimensional transition metal nitride nano sheet/metal lithium composite electrode is applied to a metal lithium negative electrode, can reduce the nucleation overpotential of metal lithium and induce the uniform nucleation of the metal lithium, further realizes dendrite-free lithium deposition, and provides possibility for the commercial application of the metal lithium.
In some embodiments, the preparation method of the metal lithium composite electrode provided by the invention comprises the following steps:
(1) Ball milling is carried out on the two-dimensional transition metal nitride nanosheet powder, and then vacuum drying and drying are carried out;
(2) Uniformly spreading the two-dimensional transition metal nitride nano-sheet powder on the surface of a metal lithium foil, and rolling to obtain a composite sheet;
(3) Folding the composite sheet and rolling the composite sheet;
(4) Repeating the step (3), and preparing the circular electrode plate with a certain diameter.
The two-dimensional transition metal nitride nano-sheet/metal lithium composite electrode prepared by the method is a composite electrode formed by stacking two-dimensional transition metal nitride nano-sheets and metal lithium layer by layer.
The invention prepares the composite electrode by stacking the two-dimensional transition metal nitride nano-sheets and the metal lithium layer by layer through a plurality of simple mechanical rolling/folding/rolling methods. Fig. 1 is a flowchart of a method for preparing a composite electrode by stacking two-dimensional transition metal nitride nano-sheets and lithium metal layer by layer, which is provided by the embodiment of the invention, and takes two-dimensional molybdenum nitride nano-sheets as an example.
A comparison of the deposition mechanisms of metallic lithium on different substrate materials as shown in fig. 2 (a) and (b), the metallic lithium surface is prone to uneven lithium deposition, which will produce significant amounts of lithium dendrites and dead lithium during the cycling process; in the two-dimensional molybdenum nitride nano-sheet/metal lithium composite electrode, metal lithium can be uniformly nucleated on the surface of the nano-sheet and further spread on the surface of the nano-sheet, so that uniform lithium deposition is realized.
In some embodiments, the two-dimensional molybdenum nitride nanoplatelets to metallic lithium usage ratio is 0.8:1.
In some embodiments, the number of times the two-dimensional molybdenum nitride nanosheets are rolled with the lithium metal during the rolling process is 2.
In the embodiment, a mechanical rolling method is adopted to prepare the two-dimensional molybdenum nitride nano-sheet/metal lithium composite electrode.
Various examples detailed analyses are given below to illustrate the technical solution of the present embodiment.
The preparation method of the two-dimensional molybdenum nitride nanosheet powder in the following examples is shown in the application number: CN202110079625.1, entitled: patent literature on a method for preparing a two-dimensional transition metal nitride with the aid of a decomposable alkali metal compound.
Example 1
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder, wherein the ball milling conditions are as follows: the ball milling time is 3h, the ball milling rotating speed is 500rpm, and ZrO with the diameter of 2mm is adopted for ball milling 2 Particles; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 2 times according to the mass ratio of 0.6:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 2
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 2 times according to the mass ratio of 0.8:1;
step (3): and then the round electrode plate with the diameter of 12mm is formed by blundering.
Example 3
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 2 times according to the mass ratio of 1:1;
step (3): and then the round electrode plate with the diameter of 12mm is formed by blundering.
Example 4
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 2 times according to the mass ratio of 1.2:1;
step (3): and then the round electrode plate with the diameter of 12mm is formed by blundering.
Example 5
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 4 times according to the mass ratio of 1:1;
step (3): and then the round electrode plate with the diameter of 12mm is formed by blundering.
Example 6
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 6 times according to the mass ratio of 1:1;
step (3): and then the round electrode plate with the diameter of 12mm is formed by blundering.
Example 7
Step (1): ball milling is carried out on the two-dimensional molybdenum nitride nanosheet powder; drying the two-dimensional molybdenum nitride nano-sheet, and transferring to a glove box;
step (2): rolling/folding the two-dimensional molybdenum nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 8
Step (1): ball milling is carried out on the two-dimensional titanium nitride nanosheet powder; drying the two-dimensional titanium nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional titanium nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 9
Step (1): ball milling is carried out on the two-dimensional vanadium nitride nanosheet powder; drying the two-dimensional vanadium nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional vanadium nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 10
Step (1): ball milling is carried out on the two-dimensional chromium nitride nanosheet powder; drying the two-dimensional chromium nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional chromium nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 11
Step (1): ball milling is carried out on the two-dimensional zirconium nitride nano-sheet powder; drying the two-dimensional zirconium nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional zirconium nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 12
Step (1): ball milling is carried out on the two-dimensional niobium nitride nano-sheet powder; drying the two-dimensional niobium nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional niobium nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 13
Step (1): ball milling is carried out on the two-dimensional tantalum nitride nano-sheet powder; drying the two-dimensional tantalum nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional tantalum nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Example 14
Step (1): ball milling is carried out on the two-dimensional tungsten nitride nanosheet powder; drying the two-dimensional tungsten nitride nano-sheet powder, and transferring to a glove box;
step (2): rolling/folding the two-dimensional tungsten nitride nano-sheet powder and metal lithium for 8 times according to the mass ratio of 1:1;
step (3): then preparing the circular electrode plate with the diameter of 12 mm.
Results and analysis
XPS results of the raw material molybdenum nitride used in examples 1 to 7 described above are shown in FIGS. 4 (a) and (b), XRD patterns are shown in FIG. 6, TEM patterns, and individual element Mapping patterns are shown in FIGS. 3 (a) to (d). XPS results and XRD results show that no other impurities exist in the two-dimensional molybdenum nitride, the crystallinity of the material is high, TEM results show that the molybdenum nitride presents a two-dimensional plane morphology, the diameter of a single piece is about 1 mu m, and the crystallinity of the synthesized molybdenum nitride is good.
In example 7, the optical photographs and SEM of the finally prepared composite electrode are shown in (a) to (c) of fig. 5. The result shows that the molybdenum nitride and the lithium metal are in a stacked morphology.
In example 7, the XRD result of the finally prepared composite electrode is shown in fig. 6. The result shows that after the molybdenum nitride and the metal lithium are rolled and compounded, the (002) plane peak intensity of the molybdenum nitride and the metal lithium is obviously weakened, and the molybdenum nitride and the metal lithium are in a plane surface state, and the metal lithium grows in two dimensions along the nano sheet.
Fig. 7 (a) - (b) are graphs showing the cycle performance of the assembled symmetric battery using the composite electrode prepared in example 7. The result shows that the pure metal lithium electrode has poor cycle performance and obvious voltage polarization, the cycle performance of the composite electrode is obviously improved, and the cycle performance is still improved under the conditions of high current and high capacity.
Fig. 8 (a) is an SEM image of a symmetric battery assembled using the composite electrode prepared in example 7 after a cycle. Comparison of the results in fig. 8 (b) shows that the pure metallic lithium forms lithium dendrites and dead lithium on the surface after a certain number of cycles, while the composite electrode surface is very flat and no dendrites are generated.
Fig. 9 is a graph of the performance of a full cell assembled using the composite electrode prepared in example 7 as the negative electrode and lithium iron phosphate as the positive electrode. The results show that the composite electrode as a negative electrode improves the battery capacity and cycle performance under the same positive electrode material.
Fig. 10 (a) is an SEM image of the negative electrode after full battery cycle in which the composite electrode prepared in example 7 was used as the negative electrode and lithium iron phosphate was used as the positive electrode. Comparison of the results in fig. 10 (b) shows that no obvious dendrites and dead lithium are found on the surface of the composite negative electrode, but that dead lithium accumulates more on the surface of the pure lithium sheet.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The preparation method of the metal lithium composite electrode is characterized by comprising the following steps of:
(1) Pretreating two-dimensional transition metal nitride nanosheet powder, and then drying in vacuum;
(2) Uniformly spreading the two-dimensional transition metal nitride nano-sheet powder on the surface of a metal lithium foil, and rolling to obtain a composite sheet;
(3) Folding the composite sheet and rolling the composite sheet;
(4) Repeating the step (3) to obtain a composite electrode; the composite electrode is a composite electrode formed by stacking two-dimensional transition metal nitride nano sheets and metal lithium layer by layer;
wherein the two-dimensional transition metal nitride nanosheet powder is a two-dimensional MoN nanosheet powder; correspondingly, in the obtained composite electrode, the metallic lithium grows in two dimensions along the (002) crystal face of MoN.
2. The method of claim 1, wherein the pretreatment in step (1) is ball milling or ultrasonic treatment.
3. The method of manufacturing as claimed in claim 1 or 2, wherein the thickness of the two-dimensional transition metal nitride nano-sheet powder is 5-8nm and the average two-dimensional plane size of the two-dimensional transition metal nitride nano-sheet powder is 0.5-10 μm.
4. The method of claim 1 or 2, wherein the mass ratio of the two-dimensional transition metal nitride nanosheet powder to the metallic lithium foil is 0.6:1-1.2:1.
5. The method of claim 1, wherein the number of rolls is 2 to 12.
6. The method of claim 1, wherein steps (2) - (4) are performed under Ar atmosphere.
7. A lithium metal composite electrode prepared by the method of any one of claims 1-6.
8. Use of the lithium metal composite electrode according to claim 7 in a negative electrode of a lithium metal battery.
9. A lithium metal battery comprising the lithium metal composite electrode of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210189864.7A CN114551813B (en) | 2022-02-28 | 2022-02-28 | Metal lithium composite electrode, preparation method, application and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210189864.7A CN114551813B (en) | 2022-02-28 | 2022-02-28 | Metal lithium composite electrode, preparation method, application and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114551813A CN114551813A (en) | 2022-05-27 |
| CN114551813B true CN114551813B (en) | 2024-02-02 |
Family
ID=81662215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210189864.7A Active CN114551813B (en) | 2022-02-28 | 2022-02-28 | Metal lithium composite electrode, preparation method, application and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114551813B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114937561B (en) * | 2022-06-01 | 2024-02-20 | 河北工业大学 | Tungsten nitride/molybdenum nitride composite material with layered staggered structure and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915604A (en) * | 2012-12-28 | 2014-07-09 | 财团法人工业技术研究院 | Protected active metal electrode, lithium metal electrode and element having such electrode |
| CN106654232A (en) * | 2017-01-20 | 2017-05-10 | 北京航空航天大学 | Preparation method of laminar composite for negative electrode of secondary metal lithium battery |
| CN108777294A (en) * | 2018-05-28 | 2018-11-09 | 福州大学 | A kind of porous spherical MoN that the carbon being made of nanometer sheet is supported and its application as negative material in lithium battery |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| CN111490252A (en) * | 2019-01-29 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Lithium metal protective layer, preparation method thereof and battery with same |
| CN111786019A (en) * | 2019-04-04 | 2020-10-16 | 中南大学 | Electrolyte for stabilizing metal lithium deposition and application of electrolyte in lithium metal battery |
| CN113321192A (en) * | 2021-05-21 | 2021-08-31 | 湖北工程学院 | Preparation method and application of cubic molybdenum nitride |
| WO2022000292A1 (en) * | 2020-06-30 | 2022-01-06 | 宁德时代新能源科技股份有限公司 | Composite lithium metal negative electrode, preparation method therefor, and secondary lithium battery and device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190393496A1 (en) * | 2018-06-21 | 2019-12-26 | Nanotek Instruments, Inc. | Method of extending cycle-life of a lithium metal secondary battery |
-
2022
- 2022-02-28 CN CN202210189864.7A patent/CN114551813B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915604A (en) * | 2012-12-28 | 2014-07-09 | 财团法人工业技术研究院 | Protected active metal electrode, lithium metal electrode and element having such electrode |
| CN106654232A (en) * | 2017-01-20 | 2017-05-10 | 北京航空航天大学 | Preparation method of laminar composite for negative electrode of secondary metal lithium battery |
| CN108777294A (en) * | 2018-05-28 | 2018-11-09 | 福州大学 | A kind of porous spherical MoN that the carbon being made of nanometer sheet is supported and its application as negative material in lithium battery |
| CN111490252A (en) * | 2019-01-29 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Lithium metal protective layer, preparation method thereof and battery with same |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| CN111786019A (en) * | 2019-04-04 | 2020-10-16 | 中南大学 | Electrolyte for stabilizing metal lithium deposition and application of electrolyte in lithium metal battery |
| WO2022000292A1 (en) * | 2020-06-30 | 2022-01-06 | 宁德时代新能源科技股份有限公司 | Composite lithium metal negative electrode, preparation method therefor, and secondary lithium battery and device |
| CN113321192A (en) * | 2021-05-21 | 2021-08-31 | 湖北工程学院 | Preparation method and application of cubic molybdenum nitride |
Non-Patent Citations (1)
| Title |
|---|
| "Lithiophilic Mo3N2/MoN as multifunctional interlayer for dendrite-free and ultra-stable lithium metal batteries";Xiaojuan Zhang等;《Journal of Colloid and Interface Science》;第612卷;第332-341页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114551813A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105098138B (en) | Negative electrode for lithium ion battery piece and preparation method thereof | |
| CN110808179B (en) | Nitrogen-oxygen co-doped biomass hard carbon material and preparation method and application thereof | |
| KR20200142562A (en) | Lithium ion secondary battery negative electrode material, and manufacturing method and application thereof | |
| CN113479860B (en) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material | |
| Xu et al. | Facile synthesis of Fe 3 O 4/NiFe 2 O 4 nanosheets with enhanced Lithium-ion storage by one-step chemical dealloying | |
| CN112968174B (en) | Lithium-philic alloy modification layer, composite lithium negative electrode material, and preparation methods and applications of lithium-philic alloy modification layer and composite lithium negative electrode material | |
| CN114267841B (en) | Preparation method and application of surface-fully-coated high-nickel single crystal ternary material | |
| CN114665058A (en) | Preparation method of lithium ion battery anode material lithium iron manganese phosphate | |
| Gao et al. | Lithiophilic Zn-doped CuO/ZnO nanoarrays modified 3D scaffold inducing lithium lateral plating achieving highly stable lithium metal anode | |
| CN113871702A (en) | Preparation of Geranite type solid electrolyte and all-solid-state battery application thereof | |
| CN114551813B (en) | Metal lithium composite electrode, preparation method, application and battery | |
| Luo et al. | State-of-art progress and perspectives on alloy-type anode materials for potassium-ion batteries | |
| CN113410459A (en) | Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application | |
| WO2020199869A1 (en) | Titanium dioxide-coated molybdenum trioxide material, preparation method therefor and use thereof | |
| Cheng et al. | Investigation of electrochemical performance on SnSe2 and SnSe nanocrystals as anodes for lithium ions batteries | |
| CN111747449A (en) | Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof | |
| CN109167026B (en) | Silicon-cobalt composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN112750989A (en) | Method for modifying lithium ion battery electrode material by using lithium ion conductor | |
| CN115703651B (en) | Oxide type lithium ion battery anode material containing high-valence variable-valence metal and preparation method thereof | |
| CN115304104A (en) | Manganese series lithium supplement additive and preparation method and application thereof | |
| CN114597369A (en) | Carbon-tin nano composite material and preparation method and application thereof | |
| CN114243007A (en) | Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof | |
| CN113506867A (en) | MoS for lithium ion battery2N/N doped composite material and preparation method thereof | |
| Liu et al. | Vanadium nitride nanoparticles as anode material for lithium ion hybrid capacitor applications | |
| CN107394177B (en) | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |