WO2024055444A1 - Three-dimensional lithium negative electrode and preparation method therefor, and lithium battery - Google Patents
Three-dimensional lithium negative electrode and preparation method therefor, and lithium battery Download PDFInfo
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- WO2024055444A1 WO2024055444A1 PCT/CN2022/137792 CN2022137792W WO2024055444A1 WO 2024055444 A1 WO2024055444 A1 WO 2024055444A1 CN 2022137792 W CN2022137792 W CN 2022137792W WO 2024055444 A1 WO2024055444 A1 WO 2024055444A1
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- lithium
- negative electrode
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 158
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 7
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910016509 CuF 2 Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 238000009718 spray deposition Methods 0.000 claims description 7
- 229910000733 Li alloy Inorganic materials 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 239000001989 lithium alloy Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 229910008449 SnF 2 Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 3
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 3
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 3
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 claims description 3
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 239000002322 conducting polymer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001540 jet deposition Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 poly(ethylene glycol) Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009941 weaving 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
-
- 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
Definitions
- the present invention relates to the technical field of lithium batteries, and in particular to a method for preparing a three-dimensional lithium negative electrode by pulse droplet spray deposition, a three-dimensional lithium negative electrode and a lithium secondary battery.
- lithium-ion batteries have entered a development trend of transitioning from traditional graphite anodes to lithium metal anodes.
- the use of lithium metal in the negative electrode can provide higher specific capacity and lower potential than the currently commercially dominant graphite negative electrode or the increasingly commercial silicon-carbon negative electrode.
- lithium metal anodes have unparalleled energy density advantages, practical applications still face many huge challenges such as poor cycle performance and potential safety risks.
- lithium metal anodes are still in small-scale trial production mainly for basic laboratory research purposes. They usually use the rolling process and have not been promoted commercially on a large scale.
- the mainstream products are limited to pure lithium foil, lithium (magnesium, aluminum) alloy foil, etc. types, and the thicknesses are all above 20 ⁇ m.
- they face problems such as low production efficiency and high cost.
- they lack key links such as three-dimensional morphology, thickness control, surface treatment and interface modification, making it difficult to meet their high-performance large-scale applications.
- Patent CN108807851A discloses a method for preparing a lithium metal battery negative electrode and a protective layer and composite electrolyte of the lithium metal electrode.
- the protective layer of the lithium metal electrode described in the patent has uniform current density and mechanical properties during lithium deposition. nature.
- the protective layer of the lithium metal electrode includes a plurality of composite particles: a particle core and an ion conductive oligomer containing an ion conductive unit and an ion conductive polymer containing an ion conductive unit arranged on at least a part of the particle core.
- a coating of at least one ion-conducting material is required to the ion conductive material.
- the ion conductive material poly(ethylene glycol) diacrylate (PEGDA) needs to self-polymerize, and the operation process is cumbersome and complex, making it difficult to achieve industrial production.
- PEGDA poly(ethylene glycol) diacrylate
- Patent CN112216811A discloses a method for preparing an ultra-thin lithium metal negative electrode. This method uses electrostatic interaction to weave a layer of electrochemically stable hybrid lithiophilic fibers on the copper surface to achieve stable and uniform lithium deposition, strengthen the lithium anode, and inhibit the growth of lithium metal dendrites.
- this preparation method is complex and time-consuming (14 hours for stirring the dispersion, 14 hours for weaving, 12 hours for drying, and 1 hour for electroplating), and it is also unable to achieve industrial production.
- the purpose of the present invention is to overcome the above technical problems and provide a preparation method and surface coating technology for a highly stable and high-performance three-dimensional lithium metal negative electrode.
- the present invention provides a method for preparing a three-dimensional lithium negative electrode.
- a method for preparing a three-dimensional lithium negative electrode comprising:
- Pulse droplet spray deposition is performed on the surface of the substrate to form a thin layer of lithium metal with a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode.
- the pulse droplet ejection deposition is as follows: using a high-frequency pulse controller, the molten lithium is ejected through a porous nozzle array to form filaments and/or droplets, which are then dropped on the surface of the substrate.
- the substrate is metal foil.
- the lithium is metallic lithium or lithium alloy
- the lithium alloy includes but is not limited to lithium silicon, lithium tin, lithium aluminum, lithium indium, lithium magnesium, and lithium zinc alloy.
- the substrate is a copper foil current collector
- the thickness of the lithium metal thin layer is ⁇ 20 ⁇ m.
- the present invention provides a three-dimensional lithium negative electrode.
- a three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention is a three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention.
- the present invention provides a lithium secondary battery.
- a lithium secondary battery the battery includes the three-dimensional lithium negative electrode described in the second aspect of the present invention.
- the present invention provides a surface coating method for a three-dimensional lithium negative electrode.
- a surface coating method for a three-dimensional lithium negative electrode includes coating a PAALi solution on the surface of a three-dimensional lithium negative electrode by spraying, spin coating or scraping, and heating to remove the solvent to obtain a PAALi-coated three-dimensional lithium negative electrode.
- the method further includes a PAALi coating layer combined with a lithiophilic inorganic filler to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure;
- the lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
- the present invention provides a PAALi-coated three-dimensional lithium negative electrode.
- a PAALi-coated three-dimensional lithium negative electrode prepared according to the surface coating method of a three-dimensional lithium negative electrode according to the fourth aspect of the present invention is provided.
- the present invention provides another lithium secondary battery.
- a lithium secondary battery the battery is a PAALi surface-coated three-dimensional lithium negative electrode according to the fifth aspect of the present invention.
- the three-dimensional lithium negative electrode provided by the present invention realizes the construction of a three-dimensional microstructure of lithium metal by using pulsed droplet spray deposition of molten lithium to reduce the local current density, inhibit the dendritic growth of lithium and buffer the dendrite growth of lithium metal during the cycle.
- the preparation method of volume deformation and simultaneous spray deposition is beneficial to finely control the deposition amount of lithium layer and realize the preparation of ultra-thin lithium metal layer.
- the three-dimensional lithium negative electrode and its preparation method and lithium battery provided by the present invention can achieve fine control of the thickness of the lithium metal layer and prepare an ultra-thin lithium metal layer (thickness ⁇ 20 ⁇ m) by regulating the pulse droplet ejection deposition process parameters. .
- discrete island-like lithium nanoparticles can be simultaneously obtained on a substrate (such as a copper current collector).
- a substrate such as a copper current collector.
- This three-dimensional porous structure of lithium metal layer can reduce local current density and buffer lithium metal. The volume deformation during cycling inhibits the dendrite growth of lithium.
- the surface coating method of the three-dimensional lithium negative electrode provided by the present invention uses spraying, spin coating or scraping to wrap the PAALi solution on the surface of the three-dimensional lithium metal, and removes the solvent after heating and drying to obtain a three-dimensional lithium metal thin layer coated on the PAALi surface. .
- the PAALi coating layer can also be combined with lithiophilic inorganic fillers to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure; lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
- the PAALi polymer layer can well block electrons from passing through, inhibiting lithium ions from obtaining electrons on the polymer surface and causing disordered reduction deposition.
- this artificial SEI layer can also physically isolate lithium metal. Direct contact with liquid electrolyte or solid electrolyte prevents the consumption of active lithium and the formation of dead lithium caused by the frequent generation and rupture of the native SEI layer, thereby preventing the growth of lithium dendrites while improving the Coulombic efficiency, and ultimately achieving a lithium metal interface of stabilization.
- the method for preparing three-dimensional lithium anodes by pulse droplet spray deposition, the three-dimensional lithium anodes and the lithium secondary batteries provided by the present invention provide a new path for the rapid preparation of three-dimensional lithium metal anodes with high interfacial stability, and promote the high performance of lithium metal anodes. application.
- the advantages of the three-dimensional lithium negative electrode and its preparation method and lithium battery provided by the present invention are:
- Three-dimensional lithium metal anode has high stability and high performance.
- Figure 1 shows the surface morphology of a three-dimensional porous lithium layer prepared by a pulse droplet jet deposition process in Example 1 provided by the present invention
- Figure 2 shows the surface morphology of the three-dimensional porous lithium negative electrode coated with the PAALi artificial lithium-conducting SEI layer in Example 2 provided by the present invention
- Figure 3 shows the surface morphology of the commercial lithium sheet without surface coating in the comparative example provided by the present invention
- Figure 4 is a comparison of cycle performance in the form of lithium symmetrical batteries provided by the present invention.
- the present invention provides a method for preparing a three-dimensional lithium negative electrode.
- a method for preparing a three-dimensional lithium negative electrode comprising:
- Pulse droplet spray deposition is performed on the surface of the substrate to form a thin layer of lithium metal with a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode.
- the pulsed droplet ejection deposition is as follows: using a high-frequency pulse controller, molten lithium is ejected through a porous nozzle array to form filaments and/or droplets, which drip onto the surface of the substrate.
- the substrate is metal foil.
- the lithium is metallic lithium or lithium alloy
- the lithium alloy includes but is not limited to lithium silicon, lithium tin, lithium aluminum, lithium indium, lithium magnesium, and lithium zinc alloy.
- the substrate is a copper foil current collector
- the thickness of the lithium metal thin layer is ⁇ 20 ⁇ m.
- the present invention provides a three-dimensional lithium negative electrode.
- a three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention is a three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention.
- the present invention provides a lithium secondary battery.
- a lithium secondary battery the battery includes the three-dimensional lithium negative electrode described in the second aspect of the present invention.
- the present invention provides a surface coating method for a three-dimensional lithium negative electrode.
- a surface coating method for a three-dimensional lithium negative electrode includes coating a PAALi solution on the surface of a three-dimensional lithium negative electrode by spraying, spin coating or scraping, and heating to remove the solvent to obtain a PAALi-coated three-dimensional lithium negative electrode.
- the method further includes a PAALi coating layer combined with a lithiophilic inorganic filler to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure;
- the lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
- the present invention provides a PAALi-coated three-dimensional lithium negative electrode.
- a PAALi-coated three-dimensional lithium negative electrode prepared according to the surface coating method of a three-dimensional lithium negative electrode according to the fourth aspect of the present invention is provided.
- the present invention provides another lithium secondary battery.
- a lithium secondary battery the battery is a PAALi surface-coated three-dimensional lithium negative electrode according to the fifth aspect of the present invention.
- molten lithium heated to above 182°C is ejected through a porous nozzle array to form filaments or droplets, which then drip on the copper foil current collector to form a three-dimensional structure.
- Thin layer of lithium metal is ejected through a porous nozzle array to form filaments or droplets, which then drip on the copper foil current collector to form a three-dimensional structure.
- the distance between the nozzle and the copper foil current collector is about 50 cm, and the droplet pulse frequency is 1500 times/min.
- the size of the lithium metal particles deposited on the copper current collector is about 3 ⁇ 5 ⁇ m, and the overall thickness is about 15 ⁇ m.
- the coating method is spin coating (2000 rpm), the PAALi solution concentration is 0.5 mol/L, the drying temperature is 80 degrees, and the drying time is 5 h. Under these conditions, the thickness of the organic coating layer It is about 10 ⁇ m. Increasing the spin coating speed or reducing the PAALi solution concentration can slightly reduce the thickness of the coating layer, and vice versa.
- the comparison example is a commercially available conventional lithium metal disc with a thickness of 500 ⁇ m and a diameter of 15 mm.
- the uncoated three-dimensional porous lithium anode of Example 1, the three-dimensional porous lithium anode of Example 2 coated with a PAALi lithium-conducting artificial SEI organic layer on the surface, and the untreated commercial lithium sheet of the comparative example are in lithium Comparison of cycle performance of lithium symmetric battery forms.
- any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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- 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 present invention relates to the technical field of lithium batteries, and in particular, to a method for preparing a three-dimensional lithium negative electrode by means of pulse-type droplet spraying deposition, a three-dimensional lithium negative electrode, and a lithium secondary battery. A method for preparing a three-dimensional lithium negative electrode. The method comprises: providing a conductive material as a substrate; and performing pulse-type droplet spraying deposition on the surface of the substrate to form a lithium metal thin layer having a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode. The present invention has the advantages of: (1) preparing an ultra-thin lithium metal foil layer having a thickness less than 20 μm; (2) quickly constructing a lithium metal negative electrode having a three-dimensional structure; (3) the stable coating of lithium-conducting polymer-based artificial SEI on the surface of lithium metal; and (4) the three-dimensional lithium metal negative electrode having high stability and high performance.
Description
本发明涉及锂电池技术领域，尤其涉及一种脉冲式液滴喷射沉积制备三维锂负极的方法、三维锂负极以及锂二次电池。The present invention relates to the technical field of lithium batteries, and in particular to a method for preparing a three-dimensional lithium negative electrode by pulse droplet spray deposition, a three-dimensional lithium negative electrode and a lithium secondary battery.
鉴于对更高能量密度的追求，锂离子电池进入了由传统石墨负极过渡到锂金属负极的发展趋势。负极锂金属的使用，能提供比目前商用主导的石墨负极或逐渐商用的硅碳负极更高的比容量和更低的电势。尽管锂金属负极拥有无可比拟的能量密度优势，但实际应用还面临循环性能差、潜在安全风险等诸多巨大挑战。In view of the pursuit of higher energy density, lithium-ion batteries have entered a development trend of transitioning from traditional graphite anodes to lithium metal anodes. The use of lithium metal in the negative electrode can provide higher specific capacity and lower potential than the currently commercially dominant graphite negative electrode or the increasingly commercial silicon-carbon negative electrode. Although lithium metal anodes have unparalleled energy density advantages, practical applications still face many huge challenges such as poor cycle performance and potential safety risks.
锂枝晶在铜集流体表面的不均匀成核与生长容易刺穿隔膜造成内部短路与热失控，叠加金属锂对液态电解质和固态电解质极高的反应活性容易造成表面活性锂的消耗与死锂的形成，都极易增大电池内阻并降低库伦效率，最终缩短电池循环寿命并造成安全性问题，这些都成为限制锂金属负极高性能应用的障碍。The uneven nucleation and growth of lithium dendrites on the surface of copper current collectors can easily pierce the separator and cause internal short circuits and thermal runaway. The extremely high reactivity of superimposed metallic lithium on liquid electrolytes and solid electrolytes can easily cause the consumption of surface active lithium and dead lithium. The formation of ions can easily increase the internal resistance of the battery and reduce the Coulombic efficiency, ultimately shortening the battery cycle life and causing safety issues. These have become obstacles that limit the high-performance application of lithium metal anodes.
当前锂金属负极仍处于满足实验室基础研究用途为主的小规模试生产，通常采用压延工艺，并未大规模商业化推广，主流产品仅限于纯锂箔、锂(镁、铝)合金箔等种类，且厚度均在20μm以上，同时面临生产效率低、成本高等问题，技术上缺乏三维形貌、厚度控制、表面处理与界面改性等关键环节，难以满足其高性能大规模应用。At present, lithium metal anodes are still in small-scale trial production mainly for basic laboratory research purposes. They usually use the rolling process and have not been promoted commercially on a large scale. The mainstream products are limited to pure lithium foil, lithium (magnesium, aluminum) alloy foil, etc. types, and the thicknesses are all above 20 μm. At the same time, they face problems such as low production efficiency and high cost. Technically, they lack key links such as three-dimensional morphology, thickness control, surface treatment and interface modification, making it difficult to meet their high-performance large-scale applications.
专利CN108807851A公开了一种用于制备锂金属电池负极及所述锂金属电极的保护层和复合电解质的方法，该专利所述的锂金属电极的保护层在锂沉积时具有均匀的电流密度和机械性质。其锂金属电极的保护层包括多个复合颗粒：颗粒芯和设置在所述颗粒芯的至少一部分上的选自包含离子传导单元的离子传导低聚物和包含离子传导单元的离子传导聚合物的至少一种离子传导材料的包覆层。但是，其中的离子传导材料聚(乙二醇)二丙烯酸酯(PEGDA)需要自聚，操作繁琐过程复杂，难以实现工业化生产。Patent CN108807851A discloses a method for preparing a lithium metal battery negative electrode and a protective layer and composite electrolyte of the lithium metal electrode. The protective layer of the lithium metal electrode described in the patent has uniform current density and mechanical properties during lithium deposition. nature. The protective layer of the lithium metal electrode includes a plurality of composite particles: a particle core and an ion conductive oligomer containing an ion conductive unit and an ion conductive polymer containing an ion conductive unit arranged on at least a part of the particle core. A coating of at least one ion-conducting material. However, the ion conductive material poly(ethylene glycol) diacrylate (PEGDA) needs to self-polymerize, and the operation process is cumbersome and complex, making it difficult to achieve industrial production.
专利CN112216811A公开了一种超薄锂金属负极的制备方法。此方法采用静电作用，在铜表面纺织一层电化学稳定的杂化亲锂纤维来实现稳定、均匀的锂沉积，坚固锂负极，具有抑制锂金属枝晶生长的作用。但是此制备方法复杂、耗时长(分散液搅拌14h，纺织需14h，干燥需12h，电镀1h)，同样无法实现工业化生产。Patent CN112216811A discloses a method for preparing an ultra-thin lithium metal negative electrode. This method uses electrostatic interaction to weave a layer of electrochemically stable hybrid lithiophilic fibers on the copper surface to achieve stable and uniform lithium deposition, strengthen the lithium anode, and inhibit the growth of lithium metal dendrites. However, this preparation method is complex and time-consuming (14 hours for stirring the dispersion, 14 hours for weaving, 12 hours for drying, and 1 hour for electroplating), and it is also unable to achieve industrial production.
本发明的目的在于克服上述技术问题，提供一种高稳定性、高性能三维锂金属负极的制备方法和表面包覆技术。The purpose of the present invention is to overcome the above technical problems and provide a preparation method and surface coating technology for a highly stable and high-performance three-dimensional lithium metal negative electrode.
为实现上述目的，本发明采用的技术方案如下。In order to achieve the above object, the technical solutions adopted by the present invention are as follows.
第一方面，本发明提供一种三维锂负极的制备方法。In a first aspect, the present invention provides a method for preparing a three-dimensional lithium negative electrode.
一种三维锂负极的制备方法，所述的方法包括：A method for preparing a three-dimensional lithium negative electrode, the method comprising:
提供作为基底的导电材料；以及providing an electrically conductive material as a substrate; and
于所述基底表面进行脉冲式液滴喷射沉积，在所述基底表面形成三维结构的锂金属薄层，从而形成所述三维锂负极。Pulse droplet spray deposition is performed on the surface of the substrate to form a thin layer of lithium metal with a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode.
进一步的，所述的脉冲式液滴喷射沉积为：通过高频脉冲控制器，把熔融锂经过具有多孔的喷头阵列喷出形成细丝和/或液滴，滴落在基底表面。Further, the pulse droplet ejection deposition is as follows: using a high-frequency pulse controller, the molten lithium is ejected through a porous nozzle array to form filaments and/or droplets, which are then dropped on the surface of the substrate.
进一步的，所述的基底为金属箔。Further, the substrate is metal foil.
进一步的，所述的锂为金属锂或锂合金；Further, the lithium is metallic lithium or lithium alloy;
所述的锂合金包括但不限于锂硅、锂锡、锂铝、锂铟、锂镁、锂锌合金。The lithium alloy includes but is not limited to lithium silicon, lithium tin, lithium aluminum, lithium indium, lithium magnesium, and lithium zinc alloy.
进一步的，所述的基底为铜箔集流体；Further, the substrate is a copper foil current collector;
所述的锂金属薄层的厚度<20μm。The thickness of the lithium metal thin layer is <20 μm.
第二方面，本发明提供一种三维锂负极。In a second aspect, the present invention provides a three-dimensional lithium negative electrode.
根据本发明第一方面所述三维锂负极的制备方法制备的三维锂负极。A three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention.
第三方面，本发明提供一种锂二次电池。In a third aspect, the present invention provides a lithium secondary battery.
一种锂二次电池，所述的电池包含本发明第二方面所述的三维锂负极。A lithium secondary battery, the battery includes the three-dimensional lithium negative electrode described in the second aspect of the present invention.
第四方面，本发明提供一种三维锂负极的表面包覆方法。In a fourth aspect, the present invention provides a surface coating method for a three-dimensional lithium negative electrode.
一种三维锂负极的表面包覆方法，所述的方法包括将PAALi溶液用喷涂或旋涂或刮涂包裹于三维锂负极表面，加热去除溶剂得到PAALi包覆的三维锂负极。A surface coating method for a three-dimensional lithium negative electrode. The method includes coating a PAALi solution on the surface of a three-dimensional lithium negative electrode by spraying, spin coating or scraping, and heating to remove the solvent to obtain a PAALi-coated three-dimensional lithium negative electrode.
在一个具体的实施例中，所述的方法还包括PAALi包覆层结合亲锂无机填料构筑有机-无机复合的人工导锂SEI层包覆结构；In a specific embodiment, the method further includes a PAALi coating layer combined with a lithiophilic inorganic filler to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure;
所述的亲锂无机填料包括但不限于Cu
2S、Cu
7S
4、CuF
2、Cu
3P、SnS
2、Cu
3N、AlN、CuF
2、SnSe、Cu
2Se、CuSe、CuSe
2、SnF
2、SbF
3、LiF、MgF
2和Li
3N。
The lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
第五方面，本发明提供一种PAALi包覆的三维锂负极。In a fifth aspect, the present invention provides a PAALi-coated three-dimensional lithium negative electrode.
根据本发明第四方面所述三维锂负极的表面包覆方法制备的PAALi包覆的三维锂负极。A PAALi-coated three-dimensional lithium negative electrode prepared according to the surface coating method of a three-dimensional lithium negative electrode according to the fourth aspect of the present invention.
第六方面，本发明提供另一种锂二次电池。In a sixth aspect, the present invention provides another lithium secondary battery.
一种锂二次电池，所述的电池本发明第五方面所述的PAALi表面包覆的三维锂负极。A lithium secondary battery, the battery is a PAALi surface-coated three-dimensional lithium negative electrode according to the fifth aspect of the present invention.
本发明提供的三维锂负极，通过采用熔融锂脉冲式液滴喷射沉积的方式实现锂金属三维微结构的构筑，以降低局部电流密度抑制锂的枝晶状生长并缓冲锂金属在循环过程中的体积形变，同时喷射沉积的制备方式利于精细控制锂层沉积量，实现超薄锂金属层的制备。The three-dimensional lithium negative electrode provided by the present invention realizes the construction of a three-dimensional microstructure of lithium metal by using pulsed droplet spray deposition of molten lithium to reduce the local current density, inhibit the dendritic growth of lithium and buffer the dendrite growth of lithium metal during the cycle. The preparation method of volume deformation and simultaneous spray deposition is beneficial to finely control the deposition amount of lithium layer and realize the preparation of ultra-thin lithium metal layer.
本发明提供的三维锂负极及其制备方法和锂电池，通过调控脉冲式液滴喷射沉积工艺参数，可以实现锂金属层厚薄的精细控制，并制备超薄的锂金属层(厚度<20 μm)。The three-dimensional lithium negative electrode and its preparation method and lithium battery provided by the present invention can achieve fine control of the thickness of the lithium metal layer and prepare an ultra-thin lithium metal layer (thickness <20 μm) by regulating the pulse droplet ejection deposition process parameters. .
采用脉冲式液滴喷射沉积工艺，可以在基底(如铜集流体)上同步得到离散型岛状分布的锂纳米颗粒，这种三维多孔结构的锂金属层，可以降低局部电流密度并缓冲锂金属在循环过程中的体积形变，抑制锂的枝晶状生长。Using a pulsed droplet jet deposition process, discrete island-like lithium nanoparticles can be simultaneously obtained on a substrate (such as a copper current collector). This three-dimensional porous structure of lithium metal layer can reduce local current density and buffer lithium metal. The volume deformation during cycling inhibits the dendrite growth of lithium.
本发明提供的三维锂负极的表面包覆方法，利用喷涂、旋涂或刮涂等方式将PAALi溶液包裹于三维锂金属表面，经过加温干燥去除溶剂得到PAALi表面包覆的三维锂金属薄层。PAALi包覆层还可以结合亲锂无机填料构筑有机-无机复合的人工导锂SEI层包覆结构；亲锂无机填料包括但不限于Cu
2S、Cu
7S
4、CuF
2、Cu
3P、SnS
2、Cu
3N、AlN、CuF
2、SnSe、Cu
2Se、CuSe、CuSe
2、SnF
2、SbF
3、LiF、MgF
2和Li
3N。
The surface coating method of the three-dimensional lithium negative electrode provided by the present invention uses spraying, spin coating or scraping to wrap the PAALi solution on the surface of the three-dimensional lithium metal, and removes the solvent after heating and drying to obtain a three-dimensional lithium metal thin layer coated on the PAALi surface. . The PAALi coating layer can also be combined with lithiophilic inorganic fillers to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure; lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
PAALi聚合物层在保证锂离子快速传导的同时，可很好地阻挡电子穿过，抑制锂离子在聚合物表面得到电子而发生无序的还原沉积，此外此人工SEI层还可以物理隔绝锂金属与液态电解液或固态电解质的直接接触，杜绝原生SEI层的频繁生成与破裂而导致的活性锂消耗与死锂形成，从而在阻止锂枝晶生长的同时，提高库伦效率，最终实现锂金属界面的稳定化。While ensuring rapid conduction of lithium ions, the PAALi polymer layer can well block electrons from passing through, inhibiting lithium ions from obtaining electrons on the polymer surface and causing disordered reduction deposition. In addition, this artificial SEI layer can also physically isolate lithium metal. Direct contact with liquid electrolyte or solid electrolyte prevents the consumption of active lithium and the formation of dead lithium caused by the frequent generation and rupture of the native SEI layer, thereby preventing the growth of lithium dendrites while improving the Coulombic efficiency, and ultimately achieving a lithium metal interface of stabilization.
本发明提供的脉冲式液滴喷射沉积制备三维锂负极的方法、三维锂负极以及锂二次电池为高界面稳定性的三维锂金属负极快速制备提供了新的路径，助力锂金属负极的高性能应用。The method for preparing three-dimensional lithium anodes by pulse droplet spray deposition, the three-dimensional lithium anodes and the lithium secondary batteries provided by the present invention provide a new path for the rapid preparation of three-dimensional lithium metal anodes with high interfacial stability, and promote the high performance of lithium metal anodes. application.
与现有技术相比，本发明提供的三维锂负极及其制备方法和锂电池的优点在于：Compared with the existing technology, the advantages of the three-dimensional lithium negative electrode and its preparation method and lithium battery provided by the present invention are:
(1)制备厚度<20μm的超薄锂金属箔层。(1) Prepare an ultra-thin lithium metal foil layer with a thickness of <20 μm.
(2) 快捷构建三维结构锂金属负极。(2) Quickly construct a three-dimensional structure lithium metal anode.
(3) 锂金属表面导锂聚合物基人工SEI的稳定包覆。(3) Stable coating of lithium metal surface conductive lithium polymer-based artificial SEI.
(4) 三维锂金属负极稳定性高、性能高。(4) Three-dimensional lithium metal anode has high stability and high performance.
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：The above and other aspects, features and advantages of embodiments of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
图1为本发明提供的实施例1通过脉冲式液滴喷射沉积工艺制备的三维多孔锂层表面形貌；Figure 1 shows the surface morphology of a three-dimensional porous lithium layer prepared by a pulse droplet jet deposition process in Example 1 provided by the present invention;
图2为本发明提供的实施例2表面PAALi人工导锂SEI层包覆的三维多孔锂负极表面形貌；Figure 2 shows the surface morphology of the three-dimensional porous lithium negative electrode coated with the PAALi artificial lithium-conducting SEI layer in Example 2 provided by the present invention;
图3为本发明提供的对比例中未表面包覆的商业化锂片表面形貌；Figure 3 shows the surface morphology of the commercial lithium sheet without surface coating in the comparative example provided by the present invention;
图4为本发明提供的锂对称电池形态下循环性能的对比。Figure 4 is a comparison of cycle performance in the form of lithium symmetrical batteries provided by the present invention.
为使本领域的技术人员更好地理解本发明的技术方案，以下实施例对本发明的作进一步详细描述，以下实施例仅用于说明发明，但不用来限制本发明的范围。In order for those skilled in the art to better understand the technical solutions of the present invention, the following examples further describe the present invention in detail. The following examples are only used to illustrate the invention, but are not used to limit the scope of the present invention.
第一方面，本发明提供一种三维锂负极的制备方法。In a first aspect, the present invention provides a method for preparing a three-dimensional lithium negative electrode.
一种三维锂负极的制备方法，所述的方法包括：A method for preparing a three-dimensional lithium negative electrode, the method comprising:
提供作为基底的导电材料；以及providing an electrically conductive material as a substrate; and
于所述基底表面进行脉冲式液滴喷射沉积，在所述基底表面形成三维结构的锂金属薄层，从而形成所述三维锂负极。Pulse droplet spray deposition is performed on the surface of the substrate to form a thin layer of lithium metal with a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode.
进一步的，所述的脉冲式液滴喷射沉积为：通过高频脉冲控制器，把熔融锂经过具有多孔的喷头阵列喷出形成细丝和/或液滴，滴落在基底表面。Further, the pulsed droplet ejection deposition is as follows: using a high-frequency pulse controller, molten lithium is ejected through a porous nozzle array to form filaments and/or droplets, which drip onto the surface of the substrate.
进一步的，所述的基底为金属箔。Further, the substrate is metal foil.
进一步的，所述的锂为金属锂或锂合金；Further, the lithium is metallic lithium or lithium alloy;
所述的锂合金包括但不限于锂硅、锂锡、锂铝、锂铟、锂镁、锂锌合金。The lithium alloy includes but is not limited to lithium silicon, lithium tin, lithium aluminum, lithium indium, lithium magnesium, and lithium zinc alloy.
进一步的，所述的基底为铜箔集流体；Further, the substrate is a copper foil current collector;
所述的锂金属薄层的厚度<20μm。The thickness of the lithium metal thin layer is <20 μm.
第二方面，本发明提供一种三维锂负极。In a second aspect, the present invention provides a three-dimensional lithium negative electrode.
根据本发明第一方面所述三维锂负极的制备方法制备的三维锂负极。A three-dimensional lithium negative electrode prepared according to the method for preparing a three-dimensional lithium negative electrode according to the first aspect of the present invention.
第三方面，本发明提供一种锂二次电池。In a third aspect, the present invention provides a lithium secondary battery.
一种锂二次电池，所述的电池包含本发明第二方面所述的三维锂负极。A lithium secondary battery, the battery includes the three-dimensional lithium negative electrode described in the second aspect of the present invention.
第四方面，本发明提供一种三维锂负极的表面包覆方法。In a fourth aspect, the present invention provides a surface coating method for a three-dimensional lithium negative electrode.
一种三维锂负极的表面包覆方法，所述的方法包括将PAALi溶液用喷涂或旋涂或刮涂包裹于三维锂负极表面，加热去除溶剂得到PAALi包覆的三维锂负极。A surface coating method for a three-dimensional lithium negative electrode. The method includes coating a PAALi solution on the surface of a three-dimensional lithium negative electrode by spraying, spin coating or scraping, and heating to remove the solvent to obtain a PAALi-coated three-dimensional lithium negative electrode.
在一个具体的实施例中，所述的方法还包括PAALi包覆层结合亲锂无机填料构筑有机-无机复合的人工导锂SEI层包覆结构；In a specific embodiment, the method further includes a PAALi coating layer combined with a lithiophilic inorganic filler to construct an organic-inorganic composite artificial lithium-conducting SEI layer coating structure;
所述的亲锂无机填料包括但不限于Cu
2S、Cu
7S
4、CuF
2、Cu
3P、SnS
2、Cu
3N、AlN、CuF
2、SnSe、Cu
2Se、CuSe、CuSe
2、SnF
2、SbF
3、LiF、MgF
2和Li
3N。
The lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
第五方面，本发明提供一种PAALi包覆的三维锂负极。In a fifth aspect, the present invention provides a PAALi-coated three-dimensional lithium negative electrode.
根据本发明第四方面所述三维锂负极的表面包覆方法制备的PAALi包覆的三维锂负极。A PAALi-coated three-dimensional lithium negative electrode prepared according to the surface coating method of a three-dimensional lithium negative electrode according to the fourth aspect of the present invention.
第六方面，本发明提供另一种锂二次电池。In a sixth aspect, the present invention provides another lithium secondary battery.
一种锂二次电池，所述的电池本发明第五方面所述的PAALi表面包覆的三维锂负极。A lithium secondary battery, the battery is a PAALi surface-coated three-dimensional lithium negative electrode according to the fifth aspect of the present invention.
实施例1Example 1
结合图1所示，通过高频脉冲控制器，把加热到182℃以上的熔融锂经过具有多孔的喷头阵列喷出形成细丝或液滴，进而滴落在铜箔集流体上形成三维结构的锂金属薄层。As shown in Figure 1, through a high-frequency pulse controller, molten lithium heated to above 182°C is ejected through a porous nozzle array to form filaments or droplets, which then drip on the copper foil current collector to form a three-dimensional structure. Thin layer of lithium metal.
铜箔集流体宽度为9 μm，宽度为200 mm，运行速度为10 cm/min，喷头直径为φ=0.7 mm，高频脉冲控制器中熔融锂注入速率为0.3 mL/min，温度维持在190度左右，喷口距离铜箔集流体约50 cm，液滴脉冲频率1500 次/min。在此实验条件下，在铜集流体上沉积的锂金属颗粒大小约为3~5 μm，整体厚度约为15 μm。The width of the copper foil current collector is 9 μm, the width is 200 mm, the operating speed is 10 cm/min, the nozzle diameter is φ=0.7 mm, the molten lithium injection rate in the high-frequency pulse controller is 0.3 mL/min, and the temperature is maintained at 190 The distance between the nozzle and the copper foil current collector is about 50 cm, and the droplet pulse frequency is 1500 times/min. Under this experimental condition, the size of the lithium metal particles deposited on the copper current collector is about 3~5 μm, and the overall thickness is about 15 μm.
实施例2Example 2
结合图2所示，涂布方式为旋涂（2000转/min），PAALi溶液浓度为0.5 mol/L，烘干温度为80度，干燥时长为5 h，在此条件下有机包覆层厚度大概为10 μm，增加旋涂转速，或减小PAALi溶液浓度，均可稍微减小包覆层厚度，反之亦然。As shown in Figure 2, the coating method is spin coating (2000 rpm), the PAALi solution concentration is 0.5 mol/L, the drying temperature is 80 degrees, and the drying time is 5 h. Under these conditions, the thickness of the organic coating layer It is about 10 μm. Increasing the spin coating speed or reducing the PAALi solution concentration can slightly reduce the thickness of the coating layer, and vice versa.
实施例3Example 3
结合图3所示，对比例为现成的市售常规锂金属圆片，规格为厚度500 μm，直径为15 mm。As shown in Figure 3, the comparison example is a commercially available conventional lithium metal disc with a thickness of 500 μm and a diameter of 15 mm.
实施例4Example 4
结合图4所示，实施例1未表面包覆的三维多孔锂负极、实施例2表面PAALi导锂人工SEI有机层包覆的三维多孔锂负极，和对比例未处理的商业化锂片在锂锂对称电池形态下循环性能的对比。As shown in Figure 4, the uncoated three-dimensional porous lithium anode of Example 1, the three-dimensional porous lithium anode of Example 2 coated with a PAALi lithium-conducting artificial SEI organic layer on the surface, and the untreated commercial lithium sheet of the comparative example are in lithium Comparison of cycle performance of lithium symmetric battery forms.
结果显示，实施例2极化电压明显更小，循环寿命明显提升，显示其良好的电化学性能。The results show that the polarization voltage of Example 2 is significantly smaller and the cycle life is significantly improved, indicating its good electrochemical performance.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种变换，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various transformations can be made to the technical solution of the present invention. These simple variations are all belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征和步骤，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that each of the specific technical features and steps described in the above-mentioned specific embodiments can be combined in any suitable manner without conflict. In order to avoid unnecessary repetition, the present invention includes various Possible combinations are not specified further.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
Claims (11)
- 一种三维锂负极的制备方法，其特征在于，所述制备方法包括：A method for preparing a three-dimensional lithium negative electrode, characterized in that the preparation method includes:提供作为基底的导电材料；以及providing an electrically conductive material as a substrate; and于所述基底表面进行脉冲式液滴喷射沉积，在所述基底表面形成三维结构的锂金属薄层，从而形成所述三维锂负极。Pulse droplet spray deposition is performed on the surface of the substrate to form a thin layer of lithium metal with a three-dimensional structure on the surface of the substrate, thereby forming the three-dimensional lithium negative electrode.
- 根据权利要求1所述的一种三维锂负极的制备方法，其特征在于，所述的脉冲式液滴喷射沉积为：通过高频脉冲控制器，把熔融锂经过具有多孔的喷头阵列喷出形成细丝和/或液滴，滴落在基底。A method for preparing a three-dimensional lithium negative electrode according to claim 1, characterized in that the pulsed droplet ejection deposition is formed by ejecting molten lithium through a porous nozzle array through a high-frequency pulse controller. Filaments and/or droplets that drip onto the substrate.
- 根据权利要求1所述的一种三维锂负极的制备方法，其特征在于，所述的基底为金属箔。The method for preparing a three-dimensional lithium negative electrode according to claim 1, wherein the substrate is a metal foil.
- 根据权利要求1所述的一种三维锂负极的制备方法，其特征在于，所述的锂为金属锂或锂合金；The method for preparing a three-dimensional lithium negative electrode according to claim 1, wherein the lithium is metallic lithium or a lithium alloy;所述的锂合金包括锂硅、锂锡、锂铝、锂铟、锂镁、锂锌合金中的至少一种。The lithium alloy includes at least one of lithium silicon, lithium tin, lithium aluminum, lithium indium, lithium magnesium and lithium zinc alloy.
- 根据权利要求1所述的一种三维锂负极的制备方法，其特征在于，所述的基底为铜箔集流体；The method for preparing a three-dimensional lithium negative electrode according to claim 1, wherein the substrate is a copper foil current collector;所述的锂金属薄层的厚度<20μm。The thickness of the lithium metal thin layer is <20 μm.
- 一种根据权利要求1~5任一项所述的制备方法制备的三维锂负极。A three-dimensional lithium negative electrode prepared according to the preparation method according to any one of claims 1 to 5.
- 一种锂二次电池，其特征在于：所述锂二次电池包含权利要求6所述的三维锂负极。A lithium secondary battery, characterized in that: the lithium secondary battery includes the three-dimensional lithium negative electrode of claim 6.
- 一种三维锂负极的表面包覆方法，其特征在于：所述表面包覆方法包括将PAALi溶液用喷涂或旋涂或刮涂包裹于三维锂负极表面，加热去除溶剂得到PAALi包覆的三维锂负极。A surface coating method for a three-dimensional lithium negative electrode, characterized in that: the surface coating method includes coating the PAALi solution on the surface of the three-dimensional lithium negative electrode by spraying, spin coating or scraping, and heating to remove the solvent to obtain PAALi-coated three-dimensional lithium. negative electrode.
- 根据权利要求8所述的一种三维锂负极的表面包覆方法，其特征在于：所述表面包覆方法还包括PAALi包覆层结合亲锂无机填料构筑有机-无机复合的人工导锂SEI层包覆结构；A surface coating method for a three-dimensional lithium negative electrode according to claim 8, characterized in that: the surface coating method further includes a PAALi coating layer combined with a lithiophilic inorganic filler to construct an organic-inorganic composite artificial lithium-conducting SEI layer cladding structure;所述的亲锂无机填料包括但不限于Cu 2S、Cu 7S 4、CuF 2、Cu 3P、SnS 2、Cu 3N、AlN、CuF 2、SnSe、Cu 2Se、CuSe、CuSe 2、SnF 2、SbF 3、LiF、MgF 2和Li 3N。 The lithiophilic inorganic fillers include but are not limited to Cu 2 S, Cu 7 S 4 , CuF 2 , Cu 3 P, SnS 2 , Cu 3 N, AlN, CuF 2 , SnSe, Cu 2 Se, CuSe, CuSe 2 , SnF 2 , SbF 3 , LiF, MgF 2 and Li 3 N.
- 一种根据权利要求8或9所述表面包覆方法制备的PAALi包覆的三维锂负极。A PAALi-coated three-dimensional lithium negative electrode prepared according to the surface coating method of claim 8 or 9.
- 一种锂二次电池，其特征在于：所述锂二次电池包含权利要求10所述的PAALi表面包覆的三维锂负极。A lithium secondary battery, characterized in that: the lithium secondary battery includes the PAALi surface-coated three-dimensional lithium negative electrode according to claim 10.
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