CN114284468B - MOF@rGO aerogel solid-state lithium air battery anode and preparation method - Google Patents
MOF@rGO aerogel solid-state lithium air battery anode and preparation method Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013208 UiO-67 Substances 0.000 claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 47
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 17
- 239000007784 solid electrolyte Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000007547 defect Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012917 MOF crystal Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000005486 organic electrolyte Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention is suitable for the technical field of metal air batteries, and provides a metal-air battery anode and a preparation method thereof, wherein the air battery anode is of a three-dimensional porous structure with closely-connected spherical-like nano particles, the MOF comprises MOFs with ion conduction capability such as UiO-67, the spherical-like nano particles comprise one or more of spherical nano particles and octahedral nano particles without edges and corners, and the porous structure is provided by a conductive substrate with excellent conductivity such as graphene aerogel. The MOF@rGO aerogel solid-state lithium air battery anode provided by the invention has high ion conductivity, high electron conductivity and good chemical/electrochemical/air stability, solves the problems of the existing air anode solid-state electrolyte material and conductive material that the combination is not tight, the ion/electron conductivity is poor, the chemical/electrochemical/air stability is poor and the like, and opens up a new direction for novel solid-state metal air batteries and other energy storage systems.
Description
Technical Field
The invention belongs to the technical field of metal-air batteries, and particularly relates to an anode of a MOF@rGO aerogel solid-state lithium-air battery and a preparation method thereof.
Background
In the great background of global carbon neutralization, the development of clean, renewable electrochemical energy storage technologies is urgent. In electrochemical energy storage systems, metal-air cells with high specific energy, long life, high safety are prominent. The metal-air battery has the characteristics of a lithium battery and a fuel battery, is formed by combining a metal negative electrode with reactivity and an air electrode, and shows extremely high mass specific energy and volume specific energy. Among them, lithium air batteries are favored due to their ultra-high theoretical energy density, which is one of the most potential electrochemical energy storage systems in the future. However, the development of lithium air batteries still faces many key scientific challenges.
Currently, solid electrolytes can be largely classified into inorganic solid electrolytes and organic polymer electrolytes. However, the organic polymer electrolyte has low room temperature conductivity, and cannot meet the requirement of the solid-state battery on the ionic conductivity of the electrolyte at room temperature; inorganic electrolytes, although having relatively high conductivity, have core problems such as high brittleness and poor stability to air. In the current common air anode, the catalyst, the ion conductor and the pore are in unordered distribution state, so that the key electrochemical performances such as battery performance, capacity, cycle life and the like are restricted.
For solid-state lithium-air batteries, the current research difficulty mainly lies in slow solid-solid phase interface reaction kinetics in the electrochemical reaction process and in the interface optimization problem of the anode and the cathode with electrolyte respectively. In addition, another core difficulty of solid-state lithium-air batteries is meeting the requirements of solid-state air anodes for both electron conductivity, ion conductivity and rich porosity to transport gas active species. The current common preparation method is to mix the catalyst material, the conductive carbon material and the solid electrolyte powder to prepare the positive electrode. The three-phase interface constructed by the preparation method is very limited and has small contact area, and the poor solid-solid contact interface between the electrode and the electrolyte ensures that an ion channel is discontinuous, the ion transmission is blocked greatly and the transmission efficiency is low. And the existing anode material has poor performance, so that the electrochemical performance is not ideal, and the development of the solid-state lithium air battery is seriously hindered.
Disclosure of Invention
The embodiment of the invention aims to provide an anode of a MOF@rGO aerogel solid lithium air battery and a preparation method thereof, and aims to solve the problems that an ion channel is discontinuous, ion transmission is blocked greatly and transmission efficiency is low due to poor solid-solid contact interface between an electrode and an electrolyte of the existing solid air battery. And the existing anode material has poor performance, so that the electrochemical performance is not ideal, and the development of the solid-state lithium air battery is seriously hindered.
The MOF@rGO aerogel solid lithium air battery anode is characterized by being of a three-dimensional porous structure tightly connected by spherical-like nanoparticles, wherein the MOF comprises one or more of spherical-like nanoparticles and octahedral-like nanoparticles without edges and corners, the spherical-like nanoparticles comprise one or more of the MOFs with ion conducting capability, the porous structure is provided by a conductive substrate with excellent conductivity, such as graphene aerogel, and the graphene aerogel has excellent gas diffusion capability.
According to a further technical scheme, the diameter of the spherical-like nano particles is 100-200 nm, the pore diameter of the porous structure is 10-500 mu m, and the pore diameter of the porous structure is adjustable.
The embodiment of the invention also aims at providing a preparation method of the anode of the MOF@rGO aerogel solid-state lithium air battery, which is characterized by comprising the following steps of:
step 1: preparing metal organic framework UiO-67 (Zr) nano-particles with defects and high specific surface area;
step 2: dissolving lithium salt in an organic electrolyte, and stirring to dissolve the lithium salt to obtain a lithium salt solution with the concentration of 1M;
step 3: adding the UiO-67 (Zr) nano particles obtained in the step 1 into the lithium salt solution obtained in the step 2, fully stirring, standing, centrifuging, washing and drying to obtain the UiO-67 (Zr) nano particles containing movable lithium ions;
step 4: preparing a three-dimensional loose porous graphene aerogel conductive substrate;
step 5: and (3) in-situ growing the UiO-67 (Zr) nano particles containing the movable lithium ions prepared in the step (3) on the graphene aerogel conductive substrate prepared in the step (4), and washing and drying to obtain the MOF@rGO aerogel solid-state lithium air battery anode.
According to a further technical scheme, in the step 1, the specific steps for preparing the defect-containing metal organic framework UiO-67 (Zr) nano-particles comprise the following steps:
step 1.1: zirconium chloride and 2,2 '-bipyridine-5, 5' -dicarboxylic acid were mixed in 1:1 is dissolved in N, N-dimethylformamide, triethylamine and acetic acid are added to regulate and control the growth of MOF crystals, the MOF crystals are transferred to a reaction kettle after being stirred uniformly, and the MOF crystals are kept at the temperature of 80-100 ℃ for 20-24 h, centrifuged, washed and dried to obtain white powder;
step 1.2: soaking the white powder obtained in the step 1.1 in hydrochloric acid solution at room temperature to obtain UiO-67 (Zr) nano-particles containing ligand defects;
step 1.3: the acid-treated UiO-67 (Zr) nanoparticles were centrifuged and washed sequentially with water, N-dimethylformamide and methanol, followed by vacuum drying to obtain activated UiO-67 (Zr) nanoparticles having unsaturated Zr sites.
According to a further technical scheme, the hydrothermal reaction temperature is preferably 80-100 ℃, more preferably 85 ℃;
the time of the hydrothermal reaction is preferably 20 to 24 h, more preferably 24 h;
the drying temperature is preferably 80-100 ℃, more preferably 80 ℃;
the drying time is preferably 10 to 12 h, more preferably 12 h;
the concentration of the hydrochloric acid is preferably 0.5-1M, more preferably 1M;
the time for soaking the hydrochloric acid is preferably 30-60 min, more preferably 30 min;
the temperature of the vacuum drying is preferably 200 to 350 ℃, more preferably 350 ℃.
The lithium salt in the step 2 comprises one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bistrifluoromethylsulfonylimide.
The organic solvent in the organic electrolyte in the step 2 comprises one or more of tetraethylene glycol dimethyl ether, ethylene carbonate, diethyl carbonate or dimethyl carbonate.
In a further technical scheme, in the step 2, the lithium salt is lithium hexafluorophosphate, and the organic electrolyte is tetraethyleneglycol dimethyl ether.
According to a further technical scheme, in the step 4, the specific steps for preparing the three-dimensional loose porous graphene aerogel conductive substrate comprise:
step 4.1: fully stirring and transferring the graphene dispersion liquid into a reaction kettle, and keeping the temperature at 100-150 ℃ for 20-24 h;
step 4.2: and freeze-drying the prepared graphene monomer to obtain the graphene aerogel with excellent mechanical strength.
Further technical solutions, the in-situ growth method in step 5 includes a seed crystal auxiliary method, a microwave method and a hydrothermal method.
According to a further technical scheme, the specific steps for preparing the anode of the MOF@rGO aerogel solid-state lithium air battery by the hydrothermal method comprise the following steps:
step 5.1: dispersing the solid electrolyte nano particles prepared in the step 3 and the graphene aerogel substrate prepared in the step 4 in an ethanol solution together, and carrying out ultrasonic treatment;
step 5.2: transferring to a reaction kettle, maintaining at 100-150 ℃ for 4-6 hours, and washing and drying to obtain the MOF@rGO aerogel solid lithium air battery anode.
In a third aspect, the invention also provides a MOF@MOF@rGO aerogel electrode-electrolyte integrated material; the MOF@MOF@rGO aerogel electrode-electrolyte integrated material comprises a MOF@rGO aerogel solid-state lithium air battery anode and a compact MOF solid-state electrolyte layer;
the thickness of the electrolyte layer is 10-20 mu m;
the electron conductivity of the electrode-electrolyte integrated material can reach 3 multiplied by 10 −3 S cm −1 ；
The electrode-electrolyte integrated material has a rich gas diffusion channel.
In a fourth aspect, the invention also provides a preparation method of the MOF@MOF@rGO aerogel electrode-electrolyte integrated material, which comprises the following steps:
step 6: dispersing the UiO-67 (Zr) nano particles containing movable lithium ions obtained in the step 3 into an alcohol water solution, adding a Nafion solution, and then performing ultrasonic treatment to obtain an electrolyte dispersion;
step 7: uniformly coating the solution dispersion on one side of a MOF@rGO aerogel electrode, and drying to obtain a MOF@MOF@rGO aerogel electrode-electrolyte integrated material;
the volume ratio of the alcohol aqueous solution to the water is 1: 10-10: 1, a step of;
the volume ratio of the Nafion solution to the water is 1: 10-10: 1, a step of;
the mass concentration of the Nafion solution is 5-10 wt%;
preferably, the obtained dispersion is coated on a MOF@rGO aerogel electrode, and then the obtained dispersion is dried under a xenon lamp to obtain the MOF@MOF@rGO aerogel electrode-electrolyte integrated material.
In a fifth aspect, the invention also provides a lithium air battery, which comprises the MOF@MOF@rGO aerogel electrode-electrolyte integrated material prepared by the preparation method according to any one of the technical schemes.
Preferably, the solid-state lithium air battery comprises a positive electrode-electrolyte integrated material and a negative electrode lithium sheet;
the diameter of the MOF@MOF@rGO aerogel electrode-electrolyte integrated material is 12 mm; the lithium sheet diameter was 14 mm.
The lithium air battery is an all-solid-state lithium air battery.
The MOF@rGO aerogel solid-state lithium air battery anode and the preparation method provided by the embodiment of the invention have the following beneficial effects:
(1) The MOF@rGO aerogel solid-state lithium air battery anode has high ion conductivity, high electron conductivity and good chemical/electrochemical/air stability, and solves the problems of the existing air anode solid-state electrolyte material and conductive material that the combination is not tight, the ion/electron conductivity is poor, the chemical/electrochemical/air stability is poor and the like;
(2) According to the in-situ growth method for preparing the air anode, the growth thickness and the density of electrolyte nano particles and conductive substrate graphene aerogel can be adjusted, so that a rich three-phase reaction interface is obtained, namely, reaction sites are increased. The discharge capacity of the solid lithium air battery can be improved by more than 2 times.
The problem of few three-phase interfaces of the existing solid-state lithium air battery is effectively solved;
(3) The MOF@MOF@rGO aerogel electrode-electrolyte integrated material disclosed by the invention constructs a highly stable electrode/electrolyte interface with low interface resistance. The problem of large interface impedance of the existing solid-state lithium air battery is effectively solved, and a new direction is opened up for the novel solid-state metal air battery and other energy storage systems.
Drawings
FIG. 1 is a scanning electron microscope picture of the MOF solid electrolyte prepared in example 1 of the present invention;
FIG. 2 is an ion conductivity test curve of the MOF solid electrolyte prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope picture of the positive electrode of the MOF@rGO aerogel solid state lithium air battery prepared in example 2 of the invention;
FIG. 4 is an electron conductivity diagram of the positive electrode of the MOF@rGO aerogel solid lithium air battery prepared in example 2 of the invention;
FIG. 5 is a top scanning electron microscope image of the MOF@MOF@rGO aerogel electrode-electrolyte integrated material prepared in example 3 of the present invention;
FIG. 6 is a cross-sectional scanning electron microscope picture of MOF@MOF@rGO aerogel electrode-electrolyte integrated material prepared in example 3 of the present invention;
FIG. 7 is a graph showing the comparison of capacity test of a solid-state lithium air battery with graphene nanoplatelets mixed electrolyte positive electrode in example 4 of the present invention;
FIG. 8 is a graph showing the cycle performance of a solid-state lithium air battery according to example 4 of the present invention, in which graphene nanoplatelets are used as the positive electrode of the mixed electrolyte;
FIG. 9 is a scanning electron microscope picture of the MOF/MOF/rGO aerogel electrode-electrolyte integrated material prepared in comparative example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Example 1
Preparation of UiO-67 (Zr) solid electrolyte:
1. 45 mg of 2,2 '-bipyridine-5, 5' -dicarboxylic acid were taken as 1:1 in N, N-dimethylformamide;
2. adding 0.36 mL triethylamine and 2.25 mL acetic acid, uniformly stirring, transferring to a reaction kettle, keeping 24 h at 85 ℃, centrifuging, washing and drying to obtain white powder;
3. soaking the obtained white powder in 1M hydrochloric acid solution for 30 min at room temperature to obtain UiO-67 (Zr) nanoparticles containing ligand defects;
4. centrifuging the acid-treated UiO-67 (Zr) nano-particles, washing the UiO-67 (Zr) nano-particles with water, N-dimethylformamide and methanol in sequence, and then drying the UiO-67 (Zr) nano-particles in vacuum at 350 ℃ to obtain a UiO-67 (Zr) solid electrolyte;
the solid state electrolyte of UiO-67 (Zr) prepared in example 1 of the present invention was characterized.
As can be seen from FIG. 1, the UiO-67 (Zr) solid electrolyte prepared by the present invention has a microscopic morphology of spheres and octahedra without corners.
Performance tests were performed on the UiO-67 (Zr) solid electrolyte prepared in example 1 of the present invention.
The UiO-67 (Zr) solid electrolyte was pressed into a disk with a diameter of 16 mm, and both sides were coated with silver paste for ion conductivity test.
As can be calculated from the graph of FIG. 2, the ionic conductivity of the UiO-67 (Zr) solid state electrolyte was 0.64 mS cm-1.
Example 2
Preparing a solid lithium air battery anode of UiO-67 (Zr) @ rGO aerogel:
1. the graphene dispersion was thoroughly stirred and transferred to a reaction kettle and kept at 24 h at 120 ℃;
2. freeze-drying the prepared graphene monomer to obtain graphene aerogel with excellent mechanical strength;
3. dispersing UiO-67 (Zr) solid electrolyte nano particles and a graphene aerogel substrate in an ethanol solution together, and carrying out ultrasonic treatment on the mixture 1 and h;
4. transferring to a reaction kettle, keeping the temperature at 120 ℃ for 4 h, and washing and drying to obtain the anode of the MOF@rGO aerogel solid lithium air battery.
Characterization was performed on the solid lithium air battery anode of UiO-67 (Zr) @ rGO aerogel prepared in example 2 of the present invention.
As can be seen from fig. 3, the solid electrolyte of the positive electrode of the UiO-67 (Zr) @ rGO aerogel solid lithium air battery prepared by the present invention has a three-dimensional porous structure, and the surface of the solid electrolyte is uniformly coated with the solid electrolyte having ion conducting capability.
Therefore, the multi-hollow solid anode prepared by the method has rich three-phase sites.
Performance detection is carried out on the anode of the UiO-67 (Zr) @ rGO aerogel solid-state lithium air battery prepared in the embodiment 2 of the invention.
The positive electrode was subjected to an electron conductivity test. Referring to fig. 4, the result of the electron conductivity test of the positive electrode of the solid lithium air battery of UiO-67 (Zr) @ rGO aerogel prepared in example 2 is in accordance with ohm's law.
From the test curve of FIG. 4, it can be calculated that the electronic conductivity of the anode of the UiO-67 (Zr) @ rGO aerogel solid state lithium air battery is 3X 10 −3 S cm −1 。
Example 3
Preparing a UiO-67 (Zr) @ UiO-67 (Zr) @ rGO aerogel electrode-electrolyte integrated material:
1. the UiO-67 (Zr) nanoparticles were dispersed to ethanol to water volume ratio of 1:1, continuously adding 5 wt% of Nafion solution into the alcohol water solution, and then carrying out ultrasonic treatment to obtain electrolyte dispersion;
2. and uniformly coating the solution dispersion on one side of the MOF@rGO aerogel electrode, and drying under a xenon lamp to obtain the UiO-67 (Zr) @UiO-67 (Zr) @rGO aerogel electrode-electrolyte integrated material.
Characterization was performed on the solid lithium air battery anode of UiO-67 (Zr) @ rGO aerogel prepared in example 2 of the present invention.
Referring to fig. 5, fig. 5 is a scanning electron microscope picture of the positive electrode of the UiO-67 (Zr) @ rGO aerogel solid-state lithium air battery prepared in example 3.
As can be seen from FIG. 5, the top of the UiO-67 (Zr) @ UiO-67 (Zr) @ rGO aerogel electrode-electrolyte integrated material prepared by the method still maintains a three-dimensional porous structure.
Referring to fig. 6, fig. 6 is a cross-sectional scanning electron microscope picture of the positive electrode of the UiO-67 (Zr) @ rGO aerogel solid-state lithium air battery prepared in example 3.
As can be seen from FIG. 6, the thickness of the electrolyte layer of the UiO-67 (Zr) @ UiO-67 (Zr) @ rGO aerogel electrode-electrolyte integrated material prepared by the method is 10-20 μm.
Example 4
Solid-state lithium air battery assembled by UiO-67 (Zr) @ UiO-67 (Zr) @ rGO aerogel electrode-electrolyte integrated material: the battery comprises a metallic lithium anode, uiO-67 (Zr) @ UiO-67 (Zr) @ rGO aerogel electrode-electrolyte integrated material.
The discharge performance test is carried out on the all-solid-state lithium air battery prepared in the embodiment 4 of the invention, and the test conditions are as follows: room temperature, current density 200 mA g −1 The cut-off voltage was 2V.
Referring to fig. 7, fig. 7 is a graph showing discharge performance comparison of the solid lithium air battery prepared in example 4 and the solid lithium air battery prepared in comparative example 2.
As can be seen from FIG. 7, example 4 was conducted at 200 mA g −1 Has larger discharge capacity at current density of 6891 mAh g −1 。
Referring to fig. 8, fig. 8 is a cycle performance comparison of the solid lithium air battery prepared in example 4 and the solid lithium air battery prepared in comparative example 2.
As can be seen from FIG. 8, example 4 was conducted at 100 mA g −1 And a current density of 500 mAh g −1 Has a longer cycle life of up to 115 cycles at the limited capacity.
Comparative example 1
Preparing a UiO-67 (Zr)/UiO-67 (Zr)/rGO electrolyte-electrode integrated material:
1. the weight ratio is 7:2:1, a solid state electrolyte of UiO-67 (Zr) and a polyvinylidene fluoride binder are ground to 0.5 h;
2. subsequently, the UiO-67 (Zr)/UiO-67 (Zr)/rGO electrolyte-electrode integrated material is prepared by a mechanical lamination compaction method.
Referring to fig. 9, fig. 9 is a topographical characterization of the positive electrode of comparative example 1.
As can be seen from comparing fig. 3 and 9, the air positive electrode layer prepared in comparative example 1 by means of mechanical mixing lacks a three-dimensional interconnected porous structure. Thus, during the electrochemical reaction, a three-phase reaction interface may be absent.
Comparative example 2
Solid state lithium air battery assembled with UiO-67 (Zr)/rGO electrolyte-electrode integrated material: the battery comprises a metallic lithium negative electrode, and a UiO-67 (Zr)/UiO-67 (Zr)/rGO electrolyte-electrode integrated material.
Referring to fig. 7, the discharge capacity of the battery of comparative example 2 was only 3370 mAh g-1.
Referring to fig. 8, the battery of comparative example 2 had a cycle life of only 53 cycles.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A mof@rgo aerogel solid state lithium air battery anode, characterized in that the air battery anode is a three-dimensional porous structure tightly connected by spheroidal nanoparticles, the MOF comprising UiO-67, the spheroidal nanoparticles comprising one or more of spherical nanoparticles and octahedral nanoparticles without edges and corners, the porous structure being provided by graphene aerogel;
the preparation method of the anode of the MOF@rGO aerogel solid-state lithium air battery comprises the following steps:
step 1: preparing metal organic framework UiO-67 (Zr) nano-particles with defects and high specific surface area;
step 2: dissolving lithium salt in an organic electrolyte, and stirring to dissolve the lithium salt to obtain a lithium salt solution with the concentration of 1M;
step 3: adding the UiO-67 (Zr) nano-particles obtained in the step 1 into the lithium salt solution obtained in the step 2, fully stirring, standing, centrifuging, washing and drying to obtain the UiO-67 (Zr) nano-particles containing movable lithium ions;
step 4: preparing a three-dimensional loose porous graphene aerogel conductive substrate;
step 5: growing the UiO-67 (Zr) nano particles containing the movable lithium ions prepared in the step 3 on the graphene aerogel conductive substrate prepared in the step 4 in situ, and washing and drying to obtain the MOF@rGO aerogel solid lithium air battery anode;
in the step 1, the specific steps for preparing the defect-containing metal organic framework UiO-67 (Zr) nano-particles comprise the following steps:
step 1.1: zirconium chloride and 2,2 '-bipyridine-5, 5' -dicarboxylic acid were mixed in an amount of 1:1 is dissolved in N, N-dimethylformamide, triethylamine and acetic acid are added to regulate and control the growth of MOF crystals, the MOF crystals are transferred to a reaction kettle after being stirred uniformly, and the MOF crystals are kept at the temperature of 80-100 ℃ for 20-24 h, centrifuged, washed and dried to obtain white powder;
step 1.2: soaking the white powder obtained in the step 1.1 in hydrochloric acid solution at room temperature to obtain UiO-67 (Zr) nano-particles containing ligand defects;
step 1.3: the acid-treated UiO-67 (Zr) nanoparticles were centrifuged and washed sequentially with water, N-dimethylformamide and methanol, followed by vacuum drying to obtain activated UiO-67 (Zr) nanoparticles having unsaturated Zr sites.
2. The positive electrode of the mof@rgo aerogel solid state lithium air battery according to claim 1, wherein the diameter of the spheroid-like nano particles is 100-200 nm, the pore diameter of the porous structure is 10-500 μm, and the pore diameter of the porous structure is adjustable.
3. The mof@rgo aerogel solid state lithium air battery positive electrode of claim 1, wherein the lithium salt in step 2 comprises one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bistrifluoromethylsulfonylimide.
4. The mof@rgo aerogel solid state lithium air battery positive electrode of claim 1, wherein the organic solvent in the organic electrolyte in step 2 comprises one or more of tetraethylene glycol dimethyl ether, ethylene carbonate, diethyl carbonate, or dimethyl carbonate.
5. The positive electrode of the mof@rgo aerogel solid lithium air battery according to claim 3, wherein the concentration of the hydrochloric acid solution in the step 1.2 is 0.5-1M, and the time of hydrochloric acid soaking is 30-60 min.
6. The positive electrode of the mof@rgo aerogel solid state lithium air battery according to claim 1, wherein in the step 4, the specific step of preparing the three-dimensional porous graphene aerogel conductive substrate comprises:
step 4.1: fully stirring and transferring the graphene dispersion liquid into a reaction kettle, and keeping the temperature at 100-150 ℃ for 20-24 h;
step 4.2: and freeze-drying the prepared graphene monomer to obtain the graphene aerogel with excellent mechanical strength.
7. The mof@rgo aerogel solid state lithium air battery cathode of claim 1, wherein the in-situ growth method in step 5 comprises a seed assisted method, a microwave method and a hydrothermal method.
8. The positive electrode of the MOF@rGO aerogel solid lithium air battery according to claim 7, wherein the specific steps of preparing the positive electrode of the MOF@rGO aerogel solid lithium air battery by a hydrothermal method comprise the following steps:
step 5.1: dispersing the solid electrolyte nano particles prepared in the step 3 and the graphene aerogel substrate prepared in the step 4 in an ethanol solution together, and carrying out ultrasonic treatment;
step 5.2: transferring to a reaction kettle, maintaining at 100-150 ℃ for 4-6 hours, and washing and drying to obtain the MOF@rGO aerogel solid lithium air battery anode.
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