CN114512637A - Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof - Google Patents
Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof Download PDFInfo
- Publication number
- CN114512637A CN114512637A CN202210063418.1A CN202210063418A CN114512637A CN 114512637 A CN114512637 A CN 114512637A CN 202210063418 A CN202210063418 A CN 202210063418A CN 114512637 A CN114512637 A CN 114512637A
- Authority
- CN
- China
- Prior art keywords
- lithium
- dimensional
- lithium metal
- conductive substrate
- temperature
- 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.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 150
- 239000011165 3D composite Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 84
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims abstract description 60
- 229960002799 stannous fluoride Drugs 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 44
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 29
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 13
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 46
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 45
- 239000004917 carbon fiber Substances 0.000 claims description 45
- 239000004744 fabric Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 239000002028 Biomass Substances 0.000 claims description 9
- 239000002238 carbon nanotube film Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 45
- 239000000243 solution Substances 0.000 description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 238000000151 deposition Methods 0.000 description 25
- 235000012431 wafers Nutrition 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002844 melting Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910010710 LiFePO Inorganic materials 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002905 metal composite material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910005282 Li13Sn5 Inorganic materials 0.000 description 1
- 229910007600 Li2Sn5 Inorganic materials 0.000 description 1
- 229910010766 Li5Sn2 Inorganic materials 0.000 description 1
- 229910011205 Li7Sn2 Inorganic materials 0.000 description 1
- 229910011217 Li7Sn3 Inorganic materials 0.000 description 1
- 229910012381 LiSn Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Images
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
- H01M4/134—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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention discloses a three-dimensional composite lithium metal cathode with a multifunctional interface layer, which comprises a three-dimensional conductive substrate, the multifunctional interface layer and loaded lithium metal; the multifunctional interface layer comprises lithium tin alloy and lithium fluoride. The three-dimensional conductive substrate is combined with an interface modification layer which has high ionic conductivity and is stable to electrolyte, stannous fluoride is loaded on the three-dimensional conductive substrate, and then the three-dimensional composite lithium metal cathode is prepared by utilizing high-temperature molten lithium, so that the construction of a lithium tin alloy and lithium fluoride at the interface between a lithium layer and the three-dimensional conductive substrate can be synchronously realized, and the problems of lithium affinity of the three-dimensional substrate and the problems of ionic transmission and interface stability of an electrode are solved; and the related preparation method is simple, convenient to operate and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a three-dimensional composite lithium metal cathode with a multifunctional interface layer and a preparation method thereof.
Background
With the widespread use of consumer electronics, electric bicycles, electric automobiles, and the like in life, the demand of people for the mass/volume energy density of energy storage battery devices has gradually increased, and the energy density of the current commercial lithium ion battery systems has basically reached the bottleneck, so that the exploration of next-generation novel energy storage materials and the development of battery systems with high energy density are urgent. In recent years, metallic lithium has been used for its high theoretical specific capacity (3860mAh g)-1) Low electrode potential (-3.04V compared to standard hydrogen electrode) and low density (0.534g cm)-3) And the like, and the characteristics attract the attention of battery researchers again.
However, the application of lithium metal batteries still has some bottlenecks, which limit the commercial application thereof. In particular, uneven deposition/stripping of lithium metal during charging and discharging may cause growth of lithium dendrites, which may pierce the separator, causing short-circuiting of the battery and even causing serious explosion problems; secondly, the problems of high reactivity of lithium metal and volume expansion during cyclic charge and discharge lead to continuous consumption of active lithium and electrolyte, so that the problems of low coulombic efficiency, short cycle life and the like are caused, and the practical application of the lithium metal battery is seriously hindered. With respect to the above challenges, the current research can be roughly classified into 2 types: i.e., surface conditioning and substrate modification. Common strategies to start with from the surface are: 1) optimizing electrolyte components, introducing electrolyte additives and the like to stabilize the surface layer (SEI layer) of the electrode/electrolyte; 2) an artificial protective layer, such as an inorganic carbon layer, an organic polymer layer, etc., is artificially coated on the surface of the metal lithium. The strategies for substrate modification are mainly: 1) a three-dimensional current collector (porous copper, carbon cloth and the like) is adopted as a carrier of the lithium metal to buffer the volume expansion of the lithium metal in the charge and discharge processes; 2) and (3) constructing a vertical nano-pore channel on the surface of a two-dimensional current collector such as a copper foil and the like to regulate the deposition of lithium.
The lithium metal negative electrode is a body-less electrode, and when the electrode undergoes a sharp volume change, the interfacial film constructed by the surface conditioning strategy is not strong and stable enough to inhibit dendrite growth. Most of the three-dimensional composite electrodes constructed by only modifying the substrate are lithium-phobic, the three-dimensional composite electrodes are difficult to be directly used as carriers of metal lithium for pre-storing and storing lithium, and the surfaces of the electrodes lack stable solid electrolyte membranes, so that the electrodes are easy to generate side reactions with electrolyte, and the capacity of the battery is attenuated. Therefore, the three-dimensional composite negative electrode which can regulate and control the deposition of lithium ions, inhibit the growth of dendritic crystals and buffer the volume change of the electrode is further explored and optimized so as to effectively solve the problems of lithium dendritic crystals, volume expansion and the like caused by the uneven deposition of lithium, and has important research and application significance.
Disclosure of Invention
The invention mainly aims to solve the problems and the defects in the prior art, and provides a three-dimensional composite lithium metal cathode with a multifunctional interface layer.
In order to achieve the purpose, the invention adopts the technical scheme that:
a three-dimensional composite lithium metal negative electrode with a multifunctional interface layer comprises a three-dimensional conductive substrate, the multifunctional interface layer (the interface layer between the three-dimensional conductive substrate and the lithium metal) and the lithium metal filled in the gaps of the three-dimensional conductive substrate and/or loaded on the surface of the multifunctional interface layer; the multifunctional interface layer comprises lithium tin alloy and lithium fluoride.
In the above scheme, the lithium tin alloy is Li2Sn5、LiSn、Li7Sn3、Li5Sn2、Li13Sn5、Li7Sn2And the like.
In the scheme, the three-dimensional composite lithium metal cathode is prepared by loading stannous fluoride on the surface of a three-dimensional conductive substrate, and then performing high-temperature molten lithium deposition and cooling to synchronously prepare the three-dimensional composite lithium metal cathode; when the three-dimensional conductive substrate is filled with high-temperature molten lithium, the loaded stannous fluoride can react with the contacted lithium at high temperature to generate lithium tin alloy and lithium fluoride, and then the multifunctional interface structure and the surface lithium layer are formed.
Preferably, in the step of depositing the high-temperature molten lithium, part of lithium fluoride obtained by the reaction further migrates to the surface of lithium, and the part of lithium fluoride formed on the surface can effectively reduce side reactions between lithium and the electrolyte solution, so that the interface stability of lithium/electrolyte solution is improved, and the growth of lithium dendrites is inhibited.
In the scheme, the temperature adopted in the high-temperature melting lithium deposition step is 200-250 ℃ and the time is 30-90 s.
In the scheme, the three-dimensional conductive substrate can be carbon fiber cloth, foam carbon, graphene foam, a carbon nanotube film, a biomass carbon film or the like.
Preferably, the three-dimensional conductive substrate can be in the shape of a circular sheet with the diameter of 8-12 mm.
The preparation method of the three-dimensional composite lithium metal negative electrode with the multifunctional interface layer comprises the following steps:
1) heating and dissolving stannous fluoride in a polar solvent to prepare a stannous fluoride solution;
2) adding a stannous fluoride solution into the three-dimensional conductive substrate for soaking treatment, cooling, taking out the soaked three-dimensional conductive substrate, and drying to obtain a stannous fluoride-loaded three-dimensional conductive substrate;
3) and carrying out high-temperature melting lithium deposition on the stannous fluoride-loaded three-dimensional conductive substrate in a protective atmosphere to fill a lithium layer into the three-dimensional conductive substrate, and naturally cooling to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
In the scheme, the three-dimensional conductive substrate is washed (alcohol washing and water washing) and dried (60-80 ℃ and 8-12 hours) before being used.
In the above scheme, the protective atmosphere may be nitrogen or argon.
In the scheme, the concentration of the stannous fluoride solution is 20-80 mmol/L.
In the scheme, the heating and dissolving temperature in the step 1) is 100-120 ℃, and the time is 1-2 hours.
In the above scheme, the polar solvent may be selected from dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Tetrahydrofuran (THF), or the like.
In the scheme, the soaking treatment step in the step 2) adopts a heating soaking process, the adopted temperature is 100-120 ℃, and the time is 2-4 hours.
In the scheme, the temperature adopted in the high-temperature molten lithium deposition step is 200-250 ℃, and preferably 210 ℃; the time is 30-90 s.
In the above scheme, the high-temperature molten lithium deposition step includes: adding the stannous fluoride-loaded three-dimensional conductive substrate obtained in the step 2) into molten lithium, and standing and depositing for 30-90 s.
In the above scheme, the molten lithium is obtained by heating and melting a lithium simple substance.
In the scheme, the drying temperature in the step 2) is 40-60 ℃, and the time is 4-6 h.
In the scheme, in the high-temperature molten lithium deposition process in the step 3), when the three-dimensional conductive substrate is filled with molten lithium, the loaded stannous fluoride reacts with the contacted lithium under the action of high temperature to be converted into a multifunctional interface layer containing lithium-tin alloy and lithium fluoride near the interface, and then the multifunctional interface layer is naturally cooled to room temperature, so that the three-dimensional composite lithium metal cathode with the multifunctional interface layer is obtained.
The three-dimensional composite lithium metal negative electrode with the multifunctional interface layer prepared according to the scheme can form the multifunctional interface layer (containing lithium tin alloy and lithium fluoride) on the three-dimensional conductive substrate, is favorable for manufacturing rich electrochemical active sites, forms a stable electrolyte/lithium metal interface in a circulating process, induces lithium to be uniformly deposited/stripped, effectively inhibits the growth of lithium dendrites, improves the volume effect, and further improves the circulating stability of the three-dimensional composite material as the lithium metal negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, a commercialized low-cost three-dimensional conductive substrate such as carbon fiber cloth is selected as a carrier of the lithium metal cathode, the conductivity is excellent, the specific surface area is large, the volume change of lithium in the deposition/stripping process can be effectively buffered, the local current density can be reduced, and the growth of lithium dendrites can be inhibited;
2) according to the invention, stannous fluoride is loaded on the three-dimensional conductive substrate, and then the high-temperature molten lithium and the stannous fluoride are reacted to generate the multifunctional interface layer containing the tin alloy and the lithium fluoride, so that the lithium-melting wettability of the three-dimensional conductive substrate can be effectively improved, and the uniform deposition of the molten lithium on the three-dimensional conductive substrate is promoted; the formed lithium-tin alloy has a high ion diffusion coefficient, can promote the transmission of lithium ions in metal lithium, and reduces the nucleation overpotential of lithium to guide the uniform deposition of lithium; the generated partial lithium fluoride can further migrate to the surface of lithium, has higher ion diffusion coefficient and is an electronic insulator, can effectively prevent the growth of lithium dendrites in an SEI film, improves the interface stability of the lithium to liquid electrolyte and plays a role in interface protection; the invention adopts a simple one-step lithium deposition composite process, can synchronously realize the construction of tin alloy and lithium fluoride at the interface of a lithium layer and a three-dimensional conductive substrate, and can simultaneously solve the problems of lithium affinity of the three-dimensional substrate and the problems of ion transmission and interface stability of an electrode;
3) according to the invention, the three-dimensional conductive substrate is combined with the interface modification layer which has high ionic conductivity and is stable to the electrolyte, so that the problems of dendritic crystal growth and volume expansion of the lithium metal battery can be effectively solved, and the practical application of the lithium metal battery can be further promoted;
4) the preparation method provided by the invention is simple, convenient to operate and suitable for popularization and application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a carbon fiber cloth used in example 1 of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of a three-dimensional composite lithium metal negative electrode with a multifunctional interfacial layer prepared in example 1 of the present invention;
FIG. 3 is a comparison graph of X-ray diffraction (XRD) patterns of carbon fiber cloth, and commercial stannous fluoride loaded with stannous fluoride in example 1 of the present invention;
fig. 4 is an X-ray diffraction (XRD) comparison pattern of the three-dimensional composite lithium metal negative electrode (example 1) obtained in example 1 of the present invention and the carbon fiber cloth-deposited lithium negative electrode (comparative example 1);
FIG. 5 shows that the three-dimensional lithium metal composite anode obtained in example 1 of the present invention and the anode obtained in comparative example 1 were used separately from lithium iron phosphate (LiFePO)4) Comparing the cycle performance of the full cell obtained by assembling the positive electrode;
FIG. 6 shows a three-dimensional lithium metal composite anode and lithium iron phosphate (LiFePO) obtained in example 1 of the present invention4) A multiplying power performance diagram of the whole battery obtained by assembling the positive electrode;
FIG. 7 shows a three-dimensional lithium metal composite anode obtained in example 2 of the present invention and a lithium iron phosphate (LiFePO) anode obtained in comparative example 14) Comparing the cycle performance of the full cell obtained by assembling the positive electrode;
FIG. 8 shows that the three-dimensional lithium metal composite anode obtained in example 3 of the present invention and the anode obtained in comparative example 1 were used separately from lithium iron phosphate (LiFePO)4) Comparing the cycle performance of the full cell obtained by assembling the positive electrode;
FIG. 9 shows a three-dimensional lithium metal composite anode obtained in example 4 of the present invention and a cathode obtained in comparative example 1, which are respectively mixed with lithium iron phosphate (LiFePO)4) Comparing the cycle performance of the full cell obtained by assembling the positive electrode;
FIG. 10 shows a three-dimensional composite lithium metal negative electrode obtained in example 5 of the present invention and a negative electrode obtained in comparative example 1, which are respectively mixed with lithium iron phosphate (LiFePO)4) Comparing the cycle performance of the full cell obtained by assembling the positive electrode;
FIG. 11 shows a three-dimensional lithium metal composite anode obtained in example 6 of the present invention and a cathode obtained in comparative example 1, which are respectively mixed with lithium iron phosphate (LiFePO)4) And comparing the cycle performance of the full cell obtained by assembling the positive electrode.
Detailed Description
The following examples are presented to further illustrate the present invention in order to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting a three-dimensional conductive substrate material carbon fiber cloth into a wafer with the diameter of 8mm, putting the wafer into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surface, and putting the wafer into a vacuum drying oven to dry for 8-12 h at the temperature of 60 ℃ for later use;
2) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), adding 39.2mg of stannous fluoride into 5mL of DMSO, placing the DMSO on an intelligent magnetic stirrer, stirring and heating (the heating temperature is 120 ℃) to completely dissolve the stannous fluoride to form a solution, preparing a stannous fluoride solution with the concentration of 50mM, and stopping stirring; adding the carbon fiber cloth cleaned in the step 1) into the obtained stannous fluoride solution, preserving the temperature, soaking the mixture for two hours (at 120 ℃), stopping heating, taking out the carbon fiber cloth after the solution is naturally cooled to room temperature, and drying the carbon fiber cloth on a heating table at a low temperature of 60 ℃ for 6 hours for later use;
3) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), the fully dried carbon fiber cloth loaded with stannous fluoride in the step 2) is weighed, the temperature of a heating table is set to be 210 ℃, a proper amount of lithium sheets are placed in a crucible to be melted, after the lithium sheets are completely melted, the carbon fiber cloth loaded with stannous fluoride is clamped by a sharp forceps and placed in molten lithium to be deposited for 30s, after the carbon fiber cloth is not completely cooled, the surface is flattened by a rolling device, and after the carbon fiber cloth is naturally cooled to room temperature, the three-dimensional composite lithium metal cathode with the multifunctional interface layer can be prepared.
Comparative example 1
A three-dimensional composite lithium metal negative electrode is prepared by the following steps:
1) cutting the three-dimensional conductive substrate material carbon fiber cloth into a wafer with the aperture of 8mm, cleaning according to the step 1) in the embodiment 1 to remove surface impurities, and drying for later use;
2) the procedure as in step 3) of example 1 was followed except that the heating stage was set to a temperature of 320 c (increasing the temperature increases the wettability of the simple substrate to molten lithium), to prepare the negative electrode.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the carbon fiber cloth used in example 1, and fig. 2 is a Scanning Electron Microscope (SEM) image of the three-dimensional composite lithium metal negative electrode having a multifunctional interface layer prepared in example 1. As can be seen from the comparison between the figure 1 and the figure 2, after the lithium is deposited on the three-dimensional carbon fiber cloth modified by the process, the carbon fiber of the three-dimensional carbon fiber cloth is fully infused by the molten lithium, which shows that the surface modification of the three-dimensional conductive carbon fiber cloth can effectively induce the lithium to be uniformly deposited and improve the problem of dendritic crystal growth.
FIG. 3 is a comparison graph of X-ray diffraction (XRD) of the carbon fiber cloth loaded with stannous fluoride obtained in step 2) of example 1 of the present invention, the carbon fiber cloth and commercial stannous fluoride. As can be seen from fig. 3, characteristic peaks of stannous fluoride appear at 19.761 °, 25.049 °, 27.857 ° and the like, which proves that the stannous fluoride is successfully loaded on the three-dimensional conductive carbon fiber cloth.
Fig. 4 is an X-ray diffraction (XRD) comparison pattern of the three-dimensional composite lithium metal negative electrode having a multifunctional interface layer prepared in example 1 of the present invention, the negative electrode prepared in comparative example 1, and a carbon fiber cloth. As can be seen from FIG. 4, the products obtained in example 1 exhibited lithium-tin alloys (Li) at 25.818 °, 29.198 °, 32.039 °, 59.878 ° and the like7Sn2) The characteristic peaks of lithium fluoride (LiF) appear at 44.996 degrees, 65.494 degrees and the like (partial lithium fluoride is formed in the obtained three-dimensional composite lithium metal negative electrode), which indicates that a multifunctional interface layer is formed, and the characteristic peaks of lithium (Li) appear at 36.190 degrees, 51.973 degrees, 64.980 degrees, 87.887 degrees and the like, which indicates that lithium is uniformly deposited on the carbon fiber cloth, and stannous fluoride loaded by the three-dimensional conductive carbon fiber cloth manufacturer can fully react with the contacted lithium to generate the multifunctional interface layer containing lithium tin alloy and lithium fluoride.
FIG. 5 shows that the three-dimensional composite lithium metal cathode with multifunctional interface layer prepared in example 1 of the present invention and the cathode obtained in comparative example 1 are respectively combined with lithium iron phosphate (LiFePO)4) Comparative cycle electrical performance of the positive assembled full cell. The figure shows that at 0.5C (1C 170mAh g)-1) The first discharge specific capacity of the full cell assembled with the negative electrode obtained in example 1 was 143.7mAh g during low rate cycling-1The reversible specific capacity can be maintained at 144.1mAh g after 100 cycles-1. And the three obtained in comparative example 1The specific first discharge capacity of the dimension conductive carbon fiber cloth deposited lithium as a negative electrode is 122.1mAh g-1After short-term circulation, the specific capacity is obviously attenuated, and the three-dimensional composite lithium metal cathode with the multifunctional interface layer, which is prepared by the invention, can be seen to show good circulation stability while improving the lithium storage performance of the battery.
Fig. 6 shows a three-dimensional composite lithium metal negative electrode with a multifunctional interface layer and lithium iron phosphate (LiFePO) prepared in example 1 of the present invention4) Rate performance plot of the positive assembled full cell. As can be seen from the graph, the specific discharge capacities of the full cells prepared in example 1 were 156mAh g at 0.2C, 0.5C, 1C, 2C, 3C, 4C, and 5C, respectively-1，145mAh g-1，131.5mAh g-1，120.6mAh g-1，107.8mAh g-1，98mAh g-1，81.7mAh g-1When the cycling rate returns to 0.2C, the specific discharge capacity of the full cell prepared in example 1 can be maintained at 155mAh g-1The result shows that the material has excellent cycle rate performance.
Example 2
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting a three-dimensional conductive substrate material carbon fiber cloth into a wafer with the diameter of 8mm, putting the wafer into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surface, and putting the wafer into a vacuum drying oven to dry for 8-12 h at the temperature of 60 ℃ for later use;
2) adding 16mg of stannous fluoride into 5mLDMSO in an argon glove box (the water content is less than 0.01ppm and the oxygen content is less than 0.01ppm), placing the mixture on an intelligent magnetic stirrer, stirring and heating the mixture (the heating temperature is 120 ℃) to completely dissolve the mixture to form a solution, preparing a stannous fluoride solution with the concentration of 20mM, and stopping stirring; adding the carbon fiber cloth cleaned in the step 1) into the obtained stannous fluoride solution, preserving the temperature, soaking the mixture for two hours (at 120 ℃), stopping heating, taking out the carbon fiber cloth after the solution is naturally cooled to room temperature, and drying the carbon fiber cloth on a heating table at a low temperature of 60 ℃ for 6 hours for later use;
3) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), the fully dried carbon fiber cloth loaded with stannous fluoride in the step 2) is weighed, the temperature of a heating table is set to be 210 ℃, a proper amount of lithium sheets are placed in a crucible to be melted, after the lithium sheets are completely melted, the carbon fiber cloth loaded with stannous fluoride is clamped by a sharp forceps and placed in molten lithium to be deposited for 30s, the carbon fiber cloth is taken out, after the carbon fiber cloth is not completely cooled, the surface is flattened by a rolling device, and after the carbon fiber cloth is naturally cooled to the room temperature, the three-dimensional composite lithium metal cathode with the multifunctional interface layer can be prepared.
Example 3
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting a three-dimensional conductive substrate material carbon fiber cloth into a wafer with the diameter of 8mm, putting the wafer into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surface, and putting the wafer into a vacuum drying oven to dry for 8-12 h at the temperature of 60 ℃ for later use;
2) adding 62.7mg of stannous fluoride into 5mLDMSO in an argon glove box (the water content is less than 0.01ppm, and the oxygen content is less than 0.01ppm), placing the mixture on an intelligent magnetic stirrer, stirring and heating (the heating temperature is 120 ℃) to completely dissolve the mixture to form a solution, preparing a stannous fluoride solution with the solution concentration of 80mM, stopping stirring, adding the carbon fiber cloth cleaned in the step 1) into the obtained stannous fluoride solution, preserving the temperature, soaking (120 ℃) for two hours, stopping heating, taking out the carbon fiber cloth after the solution is naturally cooled to room temperature, and drying the carbon fiber cloth on a heating table at the low temperature of 60 ℃ for 6 hours for later use;
3) weighing the carbon fiber cloth attached with stannous fluoride fully dried in the step 2) in an argon glove box (water content is less than 0.01ppm and oxygen content is less than 0.01ppm), setting the temperature of a heating table to be 210 ℃, and putting a proper amount of lithium sheets into a crucible for melting. And (3) when the lithium sheet is completely melted, clamping the carbon fiber cloth loaded with stannous fluoride by using a sharp forceps, putting the carbon fiber cloth into the melted lithium, depositing for 30s, taking out, flattening the surface by using a rolling device when the carbon fiber cloth is not completely cooled, and naturally cooling to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
Example 4
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting the three-dimensional conductive self-supporting graphene paper into round pieces with the diameter of 8mm, putting the round pieces into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the round pieces for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surface, and putting the round pieces into a vacuum drying oven to dry for 8-12 h at the temperature of 60 ℃ for later use;
2) adding 39.2mg of stannous fluoride into 5mL of DMSO (dimethyl sulfoxide) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), placing the mixture on an intelligent magnetic stirrer, stirring and heating (the heating temperature is 120 ℃) to completely dissolve the mixture to form a solution, preparing a stannous fluoride solution with the concentration of 50mM, stopping stirring, adding the cleaned three-dimensional conductive self-supporting graphene paper in the step 1) into the obtained stannous fluoride solution, preserving the temperature and soaking (the temperature is 120 ℃) for two hours, stopping heating, taking out the three-dimensional conductive self-supporting graphene paper after the solution is naturally cooled to room temperature, and drying the three-dimensional conductive self-supporting graphene paper on a heating table at the low temperature of 60 ℃ for 6 hours for later use;
3) weighing the fully dried three-dimensional conductive self-supporting graphene paper attached with stannous fluoride in the step 2) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), setting the temperature of a heating table to be 210 ℃, putting a proper amount of lithium sheets into a crucible for melting, clamping the three-dimensional conductive self-supporting graphene paper loaded with the stannous fluoride by using a sharp forceps, putting the three-dimensional conductive self-supporting graphene paper into molten lithium for deposition for 30s, taking out the three-dimensional conductive self-supporting graphene paper, flattening the surface by using a rolling device after the three-dimensional conductive self-supporting graphene paper is not completely cooled, and naturally cooling the three-dimensional conductive self-supporting graphene paper to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
Example 5
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting the three-dimensional conductive carbon nanotube film into a wafer with the diameter of 8mm, putting the wafer into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the wafer for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surface, and putting the wafer into a vacuum drying oven to dry the wafer for 8-12 h at the temperature of 60 ℃ for later use;
2) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), adding 39.2mg of stannous fluoride into 5ml of DMSO, putting the mixture on an intelligent magnetic stirrer, stirring and heating (the heating temperature is 120 ℃) to completely dissolve the stannous fluoride to form a solution, preparing a stannous fluoride solution with the concentration of 50mM, and stopping stirring; adding the cleaned three-dimensional conductive carbon nanotube film in the step 1) into the obtained stannous fluoride solution, preserving the temperature, soaking the stannous fluoride solution for two hours (at 120 ℃), stopping heating, taking out the three-dimensional conductive carbon nanotube film when the solution is naturally cooled to room temperature, and drying the three-dimensional conductive carbon nanotube film on a heating table at a low temperature of 60 ℃ for 6 hours for later use;
3) weighing the fully dried three-dimensional conductive carbon nanotube film attached with stannous fluoride in the step 2) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), setting the temperature of a heating table to be 210 ℃, putting a proper amount of lithium sheets into a crucible for melting, clamping the three-dimensional conductive carbon nanotube film loaded with stannous fluoride by using a sharp forceps, putting the three-dimensional conductive carbon nanotube film into molten lithium for deposition for 30s, taking out, flattening the surface by using a rolling device after incomplete cooling, and naturally cooling to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
Example 6
A three-dimensional composite lithium metal negative electrode with a multifunctional interface layer is prepared by adopting a solution heating soaking method and a high-temperature melting lithium deposition method, and specifically comprises the following preparation steps:
1) cutting the three-dimensional conductive biomass carbon film into wafers with the diameter of 8mm, putting the wafers into an ultrasonic cleaning instrument, alternately and ultrasonically cleaning the wafers for 3 times by using ethanol and deionized water in sequence, wherein each time is 10min to remove impurities on the surfaces of the wafers, and putting the wafers into a vacuum drying oven to dry the wafers for 8-12 h at the temperature of 60 ℃ for later use;
2) adding 39.2mg of stannous fluoride into 5mL of DMSO (dimethyl sulfoxide) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), placing the mixture on an intelligent magnetic stirrer, stirring and heating (the heating temperature is 120 ℃) to completely dissolve the mixture to form a solution, preparing a stannous fluoride solution with the concentration of 50mM, stopping stirring, adding the three-dimensional conductive biomass carbon film cleaned in the step 1) into the obtained stannous fluoride solution, preserving the temperature and soaking (120 ℃) for two hours, stopping heating, taking out the three-dimensional conductive biomass carbon film after the solution is naturally cooled to room temperature, drying the three-dimensional conductive biomass carbon film on a heating table at the low temperature of 60 ℃ for 6 hours for later use;
3) weighing the fully dried three-dimensional conductive biomass carbon film attached with stannous fluoride in the step 2) in an argon glove box (the water content is less than 0.01ppm, the oxygen content is less than 0.01ppm), setting the temperature of a heating table to be 210 ℃, putting a proper amount of lithium sheets into a crucible for melting, clamping the three-dimensional conductive biomass carbon film loaded with stannous fluoride by using a sharp forceps, putting the three-dimensional conductive biomass carbon film into molten lithium for deposition for 30s, taking out, flattening the surface by using a rolling device after incomplete cooling, and naturally cooling to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
FIGS. 7 to 11 show three-dimensional composite lithium metal cathodes with multifunctional interfacial layers according to examples 2 to 6 of the present invention and the cathodes obtained in comparative example 1, respectively, and lithium iron phosphate (LiFePO)4) Comparative cycle electrical performance of the positive assembled full cell.
The results show that: when the battery is cycled at low rate of 0.5C, the first discharge specific capacity of the full battery assembled by the negative electrodes obtained in the embodiments 2-6 is obviously higher than that of the full battery assembled by the negative electrode obtained in the comparative example 1 by using the three-dimensional conductive carbon fiber cloth deposited lithium as the negative electrode, the cycling stability is also obviously better than that of the comparative example 1, the specific capacity of the comparative example 1 is obviously attenuated after the short-term cycling, and the three-dimensional composite lithium metal negative electrode with the multifunctional interface layer prepared by the invention has excellent electrochemical cycling performance.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A three-dimensional composite lithium metal cathode with a multifunctional interface layer is characterized by comprising a three-dimensional conductive substrate, the multifunctional interface layer and loaded lithium metal; the multifunctional interface layer comprises lithium tin alloy and lithium fluoride.
2. The three-dimensional composite lithium metal cathode as claimed in claim 1, wherein the three-dimensional composite lithium metal cathode is prepared by loading stannous fluoride on the surface of a three-dimensional conductive substrate, and then performing high-temperature molten lithium deposition and cooling.
3. The three-dimensional composite lithium metal negative electrode according to claim 2, wherein the high-temperature molten lithium deposition step is performed at a temperature of 200-250 ℃ for 30-90 seconds.
4. The three-dimensional composite lithium metal anode of claim 1, wherein the three-dimensional conductive substrate is a carbon fiber cloth, carbon foam, graphene foam, carbon nanotube film, or biomass carbon film.
5. The method for preparing the three-dimensional composite lithium metal negative electrode with the multifunctional interface layer as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
1) heating and dissolving stannous fluoride in a polar solvent to prepare a stannous fluoride solution;
2) adding a stannous fluoride solution into the three-dimensional conductive substrate for soaking treatment, cooling, taking out the soaked three-dimensional conductive substrate, and drying to obtain a stannous fluoride-loaded three-dimensional conductive substrate;
3) and carrying out high-temperature fused lithium deposition on the three-dimensional conductive substrate loaded with stannous fluoride in a protective atmosphere, pouring fused lithium into a three-dimensional conductive frame of the three-dimensional conductive substrate, and naturally cooling to room temperature to obtain the three-dimensional composite lithium metal cathode with the multifunctional interface layer.
6. The preparation method according to claim 1, wherein the concentration of the stannous fluoride solution is 20-80 mmol/L.
7. The preparation method according to claim 1, wherein the heating and dissolving temperature in the step 1) is 100 to 120 ℃ and the time is 1 to 2 hours.
8. The method according to claim 1, wherein the polar solvent is dimethyl sulfoxide, N-dimethylformamide or tetrahydrofuran.
9. The preparation method according to claim 1, wherein the soaking step in the step 2) adopts a heating soaking process, the adopted temperature is 100-120 ℃, and the time is 2-4 hours.
10. The preparation method of claim 1, wherein the drying temperature in the step 2) is 40-60 ℃ and the drying time is 4-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210063418.1A CN114512637A (en) | 2022-01-20 | 2022-01-20 | Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210063418.1A CN114512637A (en) | 2022-01-20 | 2022-01-20 | Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114512637A true CN114512637A (en) | 2022-05-17 |
Family
ID=81550261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210063418.1A Pending CN114512637A (en) | 2022-01-20 | 2022-01-20 | Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114512637A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
| CN110299512A (en) * | 2019-06-25 | 2019-10-01 | 西安交通大学 | A kind of preparation method of the lithium metal battery cathode of carbon/tin multiple base support |
| CN110660968A (en) * | 2019-09-17 | 2020-01-07 | 天津大学 | Composite lithium metal negative electrode and preparation method thereof |
| CN111952567A (en) * | 2020-08-18 | 2020-11-17 | 武汉工程大学 | Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof |
| CN112151759A (en) * | 2020-09-24 | 2020-12-29 | 清华大学深圳国际研究生院 | Lithium metal cathode, preparation method and lithium ion battery |
| CN112909234A (en) * | 2021-01-20 | 2021-06-04 | 合肥工业大学 | Preparation method and application of lithium cathode or sodium cathode |
| CN113380993A (en) * | 2021-04-25 | 2021-09-10 | 厦门大学 | Preparation method of three-dimensional conductive framework, lithium metal composite negative electrode and surface protection layer |
| CN113629236A (en) * | 2021-07-15 | 2021-11-09 | 华中科技大学 | Composite metal lithium cathode and preparation method and application thereof |
-
2022
- 2022-01-20 CN CN202210063418.1A patent/CN114512637A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
| CN110299512A (en) * | 2019-06-25 | 2019-10-01 | 西安交通大学 | A kind of preparation method of the lithium metal battery cathode of carbon/tin multiple base support |
| CN110660968A (en) * | 2019-09-17 | 2020-01-07 | 天津大学 | Composite lithium metal negative electrode and preparation method thereof |
| CN111952567A (en) * | 2020-08-18 | 2020-11-17 | 武汉工程大学 | Organic lithium-philic composite cathode taking three-dimensional conductive carbon material as substrate and preparation method thereof |
| CN112151759A (en) * | 2020-09-24 | 2020-12-29 | 清华大学深圳国际研究生院 | Lithium metal cathode, preparation method and lithium ion battery |
| CN112909234A (en) * | 2021-01-20 | 2021-06-04 | 合肥工业大学 | Preparation method and application of lithium cathode or sodium cathode |
| CN113380993A (en) * | 2021-04-25 | 2021-09-10 | 厦门大学 | Preparation method of three-dimensional conductive framework, lithium metal composite negative electrode and surface protection layer |
| CN113629236A (en) * | 2021-07-15 | 2021-11-09 | 华中科技大学 | Composite metal lithium cathode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
| CN112736251B (en) | Three-dimensional porous material containing lithium alloy skeleton network, composite lithium negative electrode material and preparation method thereof | |
| CN109449376B (en) | Composite lithium metal electrode and preparation method thereof | |
| CN111370791A (en) | Formation method of lithium-sulfur battery and lithium-sulfur battery prepared by formation method | |
| CN114122332A (en) | Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives | |
| CN115663393B (en) | Chlorine-end-group MXene ink-based diaphragm for lithium metal battery and preparation method thereof | |
| CN108987673B (en) | Lithium negative electrode containing conductive protection film and preparation method and application thereof | |
| CN113451547B (en) | Composite metal lithium cathode and lithium ion battery comprising same | |
| CN113629231B (en) | Magnetically induced cobalt fiber/metallic lithium composite electrode material, and preparation method and application thereof | |
| CN115911263A (en) | Lithium metal composite pole piece and preparation method and application thereof | |
| CN115732783A (en) | Composite metal lithium cathode with artificial solid electrolyte interface layer and preparation method and application thereof | |
| CN114512637A (en) | Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof | |
| CN112216809B (en) | Metal cathode, preparation method thereof and lithium ion battery | |
| CN109301200B (en) | Preparation method of aluminum-doped zinc oxide modified three-dimensional copper/lithium metal negative electrode material | |
| WO2021179220A1 (en) | Anode pole piece, battery using same, and electronic device | |
| CN113903889A (en) | Lithium metal negative electrode and preparation method and application thereof | |
| CN115000412B (en) | Preparation method and application of surface modified carbon cloth 3D framework | |
| CN105826542B (en) | A kind of copper-antimony alloy-antimony nucleocapsid structure material and its application | |
| CN113097482B (en) | Negative electrode material, preparation method thereof and lithium battery with negative electrode material | |
| CN113410451B (en) | Lithium metal negative electrode flexible protection material and preparation method thereof | |
| CN114242956B (en) | Polymer negative electrode protective layer and preparation method and application thereof | |
| CN115663167B (en) | High-plasticity biphase alkali metal alloy material, thin film processing method thereof and application of secondary battery | |
| CN115528213B (en) | Lithium metal composite anode material and preparation method thereof | |
| CN115360356B (en) | Modified lithium cladding structure and preparation method and application thereof | |
| CN114335559B (en) | Lithium metal battery current collector 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 |