CN114284501B - Lithium metal negative electrode of hollow carbon sphere loaded with silver particles and solid-state battery - Google Patents
Lithium metal negative electrode of hollow carbon sphere loaded with silver particles and solid-state battery Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 88
- 239000004332 silver Substances 0.000 title claims abstract description 88
- 239000002245 particle Substances 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 102000004310 Ion Channels Human genes 0.000 abstract description 2
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 21
- 239000007784 solid electrolyte Substances 0.000 description 16
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000010534 mechanism of action Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WUALQPNAHOKFBR-UHFFFAOYSA-N lithium silver Chemical compound [Li].[Ag] WUALQPNAHOKFBR-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- ARPFTOUOGGAVCY-UHFFFAOYSA-M benzene hexadecyl(trimethyl)azanium bromide Chemical compound C1=CC=CC=C1.[Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C ARPFTOUOGGAVCY-UHFFFAOYSA-M 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000012613 in situ experiment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A lithium metal negative electrode of a hollow carbon sphere loaded with silver particles and a solid-state battery, wherein the carbon wall of the hollow carbon sphere is formed by amorphous carbon, the thickness of the carbon wall is 6-15 nm, the diameter of a hollow inner cavity of the hollow carbon sphere is 400-700 nm, the silver particles are loaded on the inner wall of the hollow carbon sphere, and the diameter of the silver particles is 5-20 nm. Silver particles are loaded on amino-functionalized silica spheres, resorcinol and formaldehyde are used as carbon source precursors, phenolic resin coating is carried out, finally calcination is carried out, and a silica sphere template is removed through hydrofluoric acid etching, so that a preparation product is obtained. The hollow carbon sphere loaded with silver particles, serving as a three-dimensional framework, provides an electronic ion channel, can effectively ensure reversibility of lithium ion intercalation and deintercalation, does not generate inactive lithium, and then plays a role in stress buffering in a solid-state battery circulation process, so that volume expansion in the solid-state battery circulation process is effectively limited, and the safety of the battery is improved.
Description
Technical Field
The invention relates to the field of solid lithium metal battery materials, in particular to a lithium metal negative electrode of a hollow carbon sphere loaded with silver particles and a solid battery.
Background
With the development of advanced energy storage technology, compared with the traditional liquid lithium metal battery, the lithium metal solid-state battery adopts nonflammable solid electrolyte as electrolyte, adopts lithium metal as a negative electrode, has high energy density and high safety, and is expected to replace the traditional liquid lithium ion battery. The solid-state electrolyte, which serves as a medium for lithium ion migration, is the core of the solid-state battery. The solid electrolyte can be divided into polymer systems having a room temperature conductivity of about 10 -7 ～10 -5 S/cm; oxide system having a conductivity of 10 at room temperature -6 ～10 -3 S/cm; sulfide systems having conductivities of about 10 at room temperature -3 ～10 -2 S/cm. And garnet type Li 7 La 3 Zr 2 O 12 The (LLZO) electrolyte has high lithium ion conductivity and is stable to lithium metal, and shows great application value.
In solid-state battery research based on garnet-type solid electrolyte, the interface between the solid-state electrolyte and an electrode has the challenges of limited solid-solid contact area, stress failure, interface side reaction and the like, the coulomb efficiency, cycle, multiplying power and other performances of the battery are seriously influenced, and the interface problem mainly comes from the uneven contact between the electrolyte and the electrode, so that lithium dendrite growth and battery short circuit are caused.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a lithium metal negative electrode of a hollow carbon sphere loaded with silver particles and a solid-state battery, which improve wettability and interface contact between a solid-state electrolyte and the negative electrode in the solid-state battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the hollow carbon sphere loaded with silver particles, wherein the carbon wall of the hollow carbon sphere is formed by amorphous carbon, the thickness of the carbon wall is 6-15 nm, the diameter of a hollow inner cavity of the hollow carbon sphere is 400-700 nm, the silver particles are loaded on the inner wall of the hollow carbon sphere, and the diameter of the silver particles is 5-20 nm.
The thickness of the carbon wall is 8-12 nm, the diameter of the hollow cavity of the hollow carbon sphere is 550-650 nm, and the diameter of the silver particle is 8-12 nm.
The preparation method of the hollow carbon sphere loaded with silver particles comprises the following steps:
1) Performing amino functionalization by taking the silica spheres as templates;
2) Doping the aminated silica spheres and silver nanoparticle sol, centrifuging, and cleaning to obtain silica spheres SiO loaded with silver particles 2 @Ag；
3) Silica sphere SiO loaded with silver particles by using resorcinol and formaldehyde solution as precursors of carbon 2 Carrying out phenolic resin coating reaction on @ Ag to obtain silica spheres SiO coated with amorphous carbon layer loaded with silver particles 2 @Ag@C；
4) SiO the silicon dioxide ball 2 Calcining and carbonizing the @ Ag @ C in a high-temperature furnace, and etching the product by using hydrofluoric acid solution to remove the silica sphere template, thus obtaining the hollow carbon spheres loaded with silver particles.
The silica spheres in step 1) are prepared as follows: and adding tetraethyl orthosilicate into the mixed solution of isopropanol and water for hydrolysis and polycondensation reaction, adding ammonia water, stirring, centrifuging, washing and separating to obtain the silica spheres.
The silica spheres were amino-functionalized in step 1) using isopropanol and an aminosilane coupling agent.
In the step 2), the volume ratio of the aminated silicon dioxide spheres to the silver nanoparticle sol is 1 (1-1.7), and in the doping process, the mixed solution is magnetically stirred at room temperature and then ultrasonically centrifuged.
In step 3), the conditions for calcination and carbonization in the high temperature furnace are as follows: under the inert gas atmosphere, the temperature is raised to 450-600 ℃ at the speed of 1-2 ℃/h, and the reaction is kept for 2-4 h.
The concentration of the hydrofluoric acid solution is 10-15 wt%; the hydrofluoric acid and SiO 2 The mass ratio of @ Ag @ C is 115-170:7-8.
The hollow carbon spheres loaded with silver particles are used for lithium metal cathodes.
The hollow carbon sphere loaded with silver particles is used for a lithium metal negative electrode of a solid-state battery.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the amorphous hollow carbon spheres loaded with silver particles are used as a layer of three-dimensional carbon-based framework, an electronic ion channel is provided, the reversibility of lithium ion intercalation and deintercalation can be effectively ensured, and no inactive lithium (namely 'dead' lithium) is generated.
2. The amorphous hollow carbon spheres loaded with silver particles serve as a layer of three-dimensional carbon-based framework to play a role in stress buffering in the battery cycle process, and the effect is mainly that ions are preferentially and rapidly transmitted along the carbon wall of the hollow carbon spheres, so that lithium dendrites cannot generate a large amount of deposition around the solid electrolyte, and the reverse 'puncturing' of the lithium dendrites is effectively inhibited.
3. The hollow carbon sphere loaded with silver particles is used as a layer of three-dimensional carbon-based framework, lithium metal gradually fills the inner cavity of the hollow framework, so that the volume expansion of the solid-state battery in the circulation process can be effectively limited, and the safety of the battery is improved.
4. The preparation process and the process of the hollow carbon sphere loaded with silver particles are simple, the material cost is low, and the hollow carbon sphere loaded with silver particles is a solid-state battery lithium metal anode material with commercial potential.
Drawings
FIG. 1 is a schematic flow chart of the preparation of silver particle-loaded hollow carbon spheres according to the present invention;
FIG. 2 is a graph showing the morphology characterization of the silver particle-loaded hollow carbon spheres prepared in example 1;
FIG. 3 is an in situ transmission characterization of the mechanism of action of hollow carbon spheres loaded with silver particles in a solid state battery of example 2;
fig. 4 is an in situ transmission characterization of the mechanism of action of hollow communicating carbon spheres loaded with silver particles in a solid state battery of example 3;
FIG. 5 is a schematic and topographical representation of a solid state battery of example 4;
fig. 6 is an in situ scan of example 4 characterizing the mechanism of action of hollow carbon spheres loaded with silver particles in a solid state battery.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
The diameter of the hollow inner cavity of the amorphous hollow carbon sphere is 400-700 nm, the thickness is 6-15 nm, the carbon wall of the amorphous hollow carbon sphere is of an amorphous structure, silver nano particles are attached to the inner wall of the amorphous hollow carbon sphere, and the diameter of the silver nano particles is 5-20 nm. Preferably, the inner diameter of the amorphous hollow carbon sphere is 550-650 nm, the thickness is 8-12 nm, the diameter of the silver nano particles is 8-12 nm, the number of the silver nano particles is enough, the ionic conductivity of the material can be effectively improved, a super-lithium interface with the solid electrolyte is formed, and lithium is effectively guided to be preferentially deposited in the hollow space inside the amorphous hollow carbon sphere.
The preparation method of the hollow carbon sphere loaded with silver particles, as shown in figure 1, comprises the following steps:
1) Adding tetraethyl orthosilicate into a mixed solution of isopropyl alcohol and water for hydrolysis polycondensation reaction to obtain silicon dioxide balls;
2) Using the silica spheres as a template, and performing amino functionalization on the silica spheres in the step 1 by using isopropanol and an aminosilane coupling agent to obtain aminated silica spheres;
3) Preparing silver nano sol;
4) Doping the aminated silica spheres obtained in the step 2 and the silver nanoparticle sol obtained in the step 3, centrifuging the spheres, and finally cleaning to obtain the silica spheres SiO loaded with silver nanoparticles 2 @Ag；
5) The precursor of resorcinol and formaldehyde solution as carbon is used for preparing the SiO of the silicon dioxide ball loaded with silver nano particles 2 Carrying out phenolic resin coating reaction on @ Ag to obtain silica spheres SiO coated with amorphous carbon layer loaded with silver nano particles 2 @Ag@C；
6) And calcining and carbonizing the silicon dioxide ball coated with the phenolic resin on the surface in a high-temperature furnace, and etching the product by using hydrofluoric acid to remove a silicon dioxide ball template to prepare the silver-doped hollow carbon ball.
Specifically, in the step 1), the hydrolysis and polycondensation reaction is carried out by adding tetraethyl orthosilicate into a mixed solution of isopropanol and water for stirring and hydrolyzing, then adding ammonia water, continuously stirring for 1-3 h at room temperature, centrifugally cleaning and separating, obtaining solid which is monodisperse silica spheres, and dispersing all solid particles in isopropanol. More specifically, the volume ratio of water of tetraethyl orthosilicate to isopropanol is 1 (9.5-10.5) (1-2); the volume ratio of the water to the ammonia water is (1-2): 1.
Specifically, 3-aminopropyl triethoxysilane is added to the isopropanol suspension of the dispersed silica spheres in the step 2), magnetic stirring is carried out for 8-13 h at 50-70 ℃, then centrifugal cleaning is carried out, solid particles are collected, and all the particles are dispersed in 15-25 mL of deionized water. More specifically, the amount of 3-aminopropyl triethoxysilane used is 0.08 to 0.1mL relative to 1mL of the isopropanol suspension of silica spheres.
Specifically, the silver nano sol in the step 3) is prepared by the following steps: adding silver nitrate solution into a mixed solution of absolute ethyl alcohol and water, carrying out intense magnetic stirring at 70-80 ℃, reacting for 5-6 min, adding polyvinylpyrrolidone aqueous solution, continuing magnetic stirring, reacting for 18-25 min, and adding sodium hydroxide aqueous solution. After the addition is completed, the mixed solution is taken out and cooled to the room temperature, and then magnetically stirred and reacted for 2 to 3 hours at the room temperature. More specifically, the concentrations of the silver nitrate solution, the polyvinylpyrrolidone aqueous solution, and the sodium hydroxide aqueous solution were 0.05M, 0.0025M, and 0.1M, respectively; the volume ratio of the absolute ethyl alcohol to the deionized water to the silver nitrate solution is (9-11): 4-6): 1.
Specifically, in the step 5), the phenolic resin coating is to use resorcinol and formaldehyde as carbon sources to coat the silica sphere SiO loaded with silver nano particles 2 Adding Ag into water, adding hexadecyl trimethyl ammonium benzene bromide as surfactant, adding concentrated ammonia water, magnetically stirring at room temperature for 10-12 min, and sequentially adding m-phenylene diamineReacting phenol with formaldehyde for 8-12 h, centrifuging, cleaning and drying to obtain SiO 2 @ Ag @ RF. Specifically, the dosage of the silica spheres loaded with silver nano particles is that of water, cetyl trimethyl ammonium bromide, resorcinol and formaldehyde is (1.8-2.2) g (22-25) mL (0.7-0.9) mL: (28-32) mg (40-44) mu L;
specifically, in the step 6), siO2@Ag@RF is placed in a high temperature tube furnace for calcination under the protection of inert gas Ar, the temperature is increased to 450-600 ℃ at the speed of 1-2 ℃/h, and the reaction is kept for 2-4 h, so that SiO is obtained 2 @ Ag @ C. More specifically, the SiO is prepared 2 Adding @ Ag@C into a mixed solution of isopropanol and deionized water, and carrying out centrifugal cleaning and drying after the reaction for 5-8 hours, wherein the dosage of hydrofluoric acid solution with the concentration of 10-15 wt% is 12-14 mL relative to 0.8g of carbonized silicon dioxide spheres coated with phenolic resin on the surfaces, so as to obtain the silver-loaded hollow carbon spheres.
Example 1
The specific preparation process of the hollow carbon sphere loaded with silver particles in this embodiment is as follows:
1) Preparing a silicon dioxide template: 8mL of tetraethyl orthosilicate (TEOS) is added into a mixed solution of 80mL of isopropanol and 12mL of deionized water, 8mL of ammonia water (the mass fraction is 25% and the same applies below) is added for reaction for 2 hours when the solution is vigorously stirred at room temperature, centrifugal cleaning and separation are carried out, the obtained solid is subjected to three times of centrifugal cleaning through isopropanol/deionized water, and a sample is collected, so that the silica spheres with good dispersibility and the diameter of about 440nm are obtained.
2) Amino-functionalized silica sphere preparation: the silica spheres obtained in step 1) were taken and dispersed in 100mL of isopropanol, then 1mL of 3-aminopropyl triethoxysilane (mass fraction 99%, the same applies hereinafter) was added and stirred in a 60 ℃ water bath for 10 hours, after which the obtained solid was centrifugally washed with isopropanol/deionized water, and the solid was collected and dispersed in 20mL of deionized water.
3) Silver nano sol preparation: 100mL of silver nitrate solution (0.05M) is added to a mixed solution of 100mL of ethanol and 50mL of deionized water, the mixture is vigorously stirred magnetically for 5min in a water bath at 75 ℃, then 20mL of polyvinylpyrrolidone aqueous solution (0.0025M) is added, the mixture is continuously stirred magnetically for 20min in the water bath at 75 ℃, then 5mL of sodium hydroxide solution (0.1M) is added, after the addition is completed, the mixed solution is taken out and cooled to room temperature, and then the mixture is reacted magnetically for 2h at room temperature.
4) Preparation of silver particle-loaded silica spheres (SiO 2 @ Ag): taking 140mL of silver nanoparticle colloid suspension in the step 3), dividing the silver nanoparticle colloid suspension into equal 7 parts, mixing 20mL of silver nanoparticle colloid suspension with the amino-functionalized silica sphere solution obtained in the step 2 in each batch, stirring at room temperature, centrifugally separating spheres, repeating the operation for 7 times, and centrifugally cleaning the spheres by using isopropanol/deionized water after the last batch of centrifugally separating spheres to obtain the silica spheres carrying silver particles.
5) Preparing a silica sphere with silver particles coated with phenolic resin on the surface: dispersing all the solid obtained in the step 4) in 240mL of deionized water, and carrying out ultrasonic dispersion treatment for 20 min. Then 8mL of cetyltrimethyl ammonium bromide (0.01M) and 0.8mL of ammonia were added and magnetically stirred at room temperature for 10min. Then 300mg of resorcinol and 420 mu L of formaldehyde solution (37% by mass) are added, stirred at room temperature for 8 hours, then deionized water/isopropanol is used for cleaning, a sample is collected, and the sample is placed in a 60 ℃ oven for drying for 8 hours, so that the silica spheres with the surfaces coated with the silver particles of the phenolic resin are obtained.
6) Carbonization and etching: grinding the solid obtained in the step 5), placing the ground solid in a high-temperature tube furnace under the protection of inert gas Ar for calcination, raising the temperature to 600 ℃ at the rate of 1 ℃/h, and reacting for 2 hours while maintaining the temperature to obtain SiO 2 @ Ag @ C. And adding the obtained calcined product into a mixed solution of isopropanol and deionized water, dissolving in a hydrofluoric acid solution with the concentration of 10wt%, magnetically stirring for reaction for 6 hours, and performing centrifugal cleaning and drying to obtain the silver doped hollow carbon sphere which is marked as Ag@C.
The hollow carbon spheres of the silver-loaded particles were characterized by Transmission Electron Microscopy (TEM), the results of which are shown in fig. 2. Fig. 2 (a) is a morphology diagram of a hollow carbon sphere loaded with silver particles under a Transmission Electron Microscope (TEM). The grey-black particles shown in the figure are silver nanoparticles and the grey tubular portions are amorphous carbon sphere walls. Fig. 2 (b) is a high angle annular dark field image (HADDF) of silver particle loaded carbon spheres under a Transmission Electron Microscope (TEM). The white bright spots are silver nano particles, and the other shiny tubular parts are amorphous carbon spherical walls. Fig. 2 (c) is a graph of carbon sphere wall at high magnification of transmission electron microscope.
Example 2
In-situ transmission characterizes the action mechanism of hollow carbon spheres Ag@C loaded with silver particles in a solid-state battery, the lithium dendrite deposition behavior is guided, a Cu electrode is used for constructing an anode by an in-situ transmission platform, a large amount of lithium is adhered to the Cu electrode, and garnet-type solid electrolyte Li with particles semi-embedded in the lithium is adhered to the Cu electrode 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) the negative electrode adopts a W electrode, the hollow carbon sphere Ag@C carrying silver particles prepared in example 1 is adhered at the W electrode as a three-dimensional carbon-based framework material, a power supply is externally connected, a closed loop is formed, a certain voltage is applied, and garnet type solid electrolyte Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) provides a transmission channel of lithium ions, and electrons are obtained after the transmission channel reaches the three-dimensional carbon-based framework layer to deposit lithium metal. The mechanism of action is shown in figure 3:
(1) As shown in fig. 3a, one side of the hollow carbon sphere loaded with silver particles is contacted with garnet-type solid electrolyte-lithium, and the other side is contacted with a tungsten (W) electrode, and after the garnet-type solid electrolyte-lithium is applied with forward bias, lithium ions in lithium metal start to deposit from the solid electrolyte through the solid electrolyte.
(2) As shown in fig. 3b, lithium ions passing through the solid electrolyte contact the amorphous hollow carbon spheres carrying silver particles and deposited lithium begins to enter the carbon spheres and fill the cavities of the carbon spheres.
(3) As shown in fig. 3c, the silver particles coated on the wall of the carbon sphere are gradually lithiated by the diffused lithium, and the lithium gradually fills the sphere cavity of the whole carbon sphere.
Example 3
The embodiment is a specific preparation process and in-situ transmission mechanism characterization of the hollow communicated carbon sphere loaded with silver particles:
silver particle-loaded hollow carbon spheres were prepared as in example 1, except that in step 1) the silica template was prepared, 8mL of tetraethyl orthosilicate (TEOS) was added to a mixed solution of 80mL of isopropyl alcohol and 12mL of deionized water, at which time stirring was not vigorous, 8mL of aqueous ammonia was added to react for 1.5 hours, unlike 2 hours in example 1, and the resulting solid was separated by centrifugal washing three times with isopropyl alcohol/deionized water, and samples were collected to obtain silica spheres having a general dispersibility of about 500nm in diameter.
The rest steps are the same as in example 1, and finally the hollow communicating carbon sphere loaded with silver particles is obtained.
In-situ transmission characterizes the action mechanism of the hollow communicating carbon sphere loaded with silver particles in the solid-state battery, so that the lithium dendrite deposition behavior is guided, and an in-situ transmission platform is built as described in the embodiment 2. The mechanism of action is shown in figure 4:
(1) As shown in fig. 4a, one side of the hollow communicating carbon sphere loaded with silver particles is contacted with garnet-type solid electrolyte-lithium, and the other side is contacted with a W electrode, and after the garnet-type solid electrolyte-lithium is applied with forward bias, lithium ions in lithium metal pass through the solid electrolyte to start deposition behavior from the solid electrolyte.
(2) As shown in fig. 4b, lithium ions passing through the solid electrolyte are in contact with the silver particles on the right side in the hollow communicated carbon spheres carrying silver particles, an alloying reaction occurs, the silver particles are lithiated to expand in volume, and deposited lithium starts to enter the carbon spheres by taking the particles as nucleation sites, and the cavities of the carbon spheres on the right side are filled.
(3) As shown in fig. 4c to 4i, lithium fills the sphere cavity of the right-side whole carbon sphere, starts to diffuse to the left-side carbon sphere, and gradually fills the sphere cavity of the left-side whole carbon sphere. To this end, the deposited lithium fills the communicating bi-carbon spheres.
Example 4
The embodiment is an in-situ Scanning (SEM) mechanism characterization when the hollow carbon sphere loaded with silver particles is used as a cathode material in a solid-state battery, and through in-situ electrodeposition, the direct observation of the deposition behavior of an electrode|solid electrolyte interface is of great significance for understanding the dendritic penetration phenomenon. In situ scanning experiments were performed in SEM (Zeiss Sigma) using a home-made experimental setup. Current output and impedance analysis were performed using an electrochemical workstation (CHI 660E).
As shown in fig. 5a, a schematic diagram of a solid-state battery is shown, the positive electrode material adopts lithium iron phosphate (LFP), and the negative electrode is a hollow carbon sphere lithium metal negative electrode loaded with silver particles. Each LLZTO electrolyte sheet in the self-made experimental apparatus was subjected to fine polishing leaving only a small amount of nano-scale scratches, using lithium metal as a lithium source, and adhering lithium in a molten state to one side of the LLZTO electrolyte sheet at 300 c to form an llzto|li interface, as shown in fig. 5b,
and a layer of hollow carbon spheres loaded with silver particles is uniformly coated on the other side surface of the LLZTO to serve as an important interface layer for improving wettability and contact, and the asymmetric battery is assembled to finally form Ag@C|LLZTO|Li. During in-situ experiments, electron beams of a certain intensity are applied to the observation area, the current density is given to the observation area, and the deposition behavior of the LLZTO surface is directly observed through a scanning electron microscope.
As shown in fig. 6a, the high energy electron beam is focused on the surface of the LLZTO surface coated with the silver particle-loaded hollow carbon spheres.
As shown in fig. 6b to h, li metal starts to grow outwards from the irradiation region, lithium permeates from the lithium source side to the upper silver particle-loaded hollow carbon sphere layer to perform uniform deposition, and the silver particle-loaded hollow carbon sphere layer undergoes significant volume expansion.
As shown in fig. 6i, eventually, a uniform interface is formed.
The interface functions to effectively guide lithium metal deposited from the three-dimensional carbon-based skeleton layer so that the lithium metal can be filled in the hollow inner cavity and can be deposited at a gap position of a carbon-based skeleton joint, thereby avoiding nanoscale or atomic defects on the LLZO electrolyte as unnecessary deposition hot spots, the three-dimensional carbon sphere skeleton prevents lithium dendrites from penetrating the solid electrolyte during the charge of the solid-state battery to cause internal short circuit of the battery, and eliminates inactive lithium generated during the discharge of the battery, thereby improving the coulomb efficiency and cycle life of the battery operation.
The invention provides a method for encapsulating lithium metal by using hollow carbon spheres loaded with silver nanoparticles. Compared with a common carbon sphere without silver nano particles, the silver particles loaded on the inner wall of the carbon sphere can induce lithium to deposit on the inner cavity and the outer wall of the carbon sphere, so that lithium dendrite deposition at a garnet-type solid electrolyte interface can be better avoided, and the cycle performance of the battery is further optimized. The heterogeneous silver nano particles can also be used as seed crystals for inducing lithium deposition, and react with lithium metal to form lithium silver alloy, and the lithium metal is deposited by taking the lithium silver alloy as a nucleation point and continuously fills the carbon sphere cavity.
The above examples are all preferred embodiments of the inventor on the basis of the experience of the analysis through sufficient arrangement in the research process, and other simple modifications can be made within the scope of other reasonable principles by other persons of ordinary skill without departing from the spirit and application concept of the invention.
Claims (7)
1. An application of a hollow carbon sphere loaded with silver particles, which is characterized in that: the hollow carbon spheres loaded with silver particles are used for lithium metal cathodes of solid-state batteries; the carbon wall of the hollow carbon sphere is formed by amorphous carbon, the thickness of the carbon wall is 6-15 nm, the diameter of the hollow inner cavity of the hollow carbon sphere is 400-700 nm, silver particles are loaded on the inner wall of the hollow carbon sphere, and the diameter of the silver particles is 5-20 nm;
the preparation method of the hollow carbon sphere loaded with silver particles comprises the following steps:
1) Performing amino functionalization by taking the silica sphere as a template;
2) Doping the aminated silica spheres and silver nanoparticle sol, centrifuging, and cleaning to obtain silica spheres SiO loaded with silver particles 2 @Ag；
3) Silica sphere SiO loaded with silver particles by using resorcinol and formaldehyde solution as precursors of carbon 2 Carrying out phenolic resin coating reaction on @ Ag to obtain silica spheres SiO coated with amorphous carbon layer loaded with silver particles 2 @Ag@C；
4) SiO the silicon dioxide ball 2 Calcining and carbonizing @ Ag @ C in a high-temperature furnaceAnd etching the product by using hydrofluoric acid solution to remove the silicon dioxide sphere template, thus obtaining the hollow carbon spheres loaded with silver particles.
2. Use of a hollow carbon sphere loaded with silver particles according to claim 1, wherein: the thickness of the carbon wall is 8-12 nm, the diameter of the hollow inner cavity of the hollow carbon sphere is 550-650 nm, and the diameter of the silver particle is 8-12 nm.
3. Use of a hollow carbon sphere loaded with silver particles according to claim 1, characterized in that the silica sphere in step 1) is prepared as follows: and adding tetraethyl orthosilicate into the mixed solution of isopropanol and water for hydrolysis and polycondensation reaction, adding ammonia water, stirring, centrifuging, washing and separating to obtain the silica spheres.
4. Use of a hollow carbon sphere loaded with silver particles according to claim 1, characterized in that in step 1) the silica sphere is amino-functionalized with isopropanol and an aminosilane coupling agent.
5. Use of a hollow carbon sphere loaded with silver particles according to claim 1, wherein: in the step 2), the volume ratio of the aminated silicon dioxide spheres to the silver nanoparticle sol is 1 (1-1.7), and in the doping process, the mixed solution is magnetically stirred at room temperature, and then ultrasonic centrifugation is carried out.
6. Use of a hollow carbon sphere loaded with silver particles according to claim 1, characterized in that in step 4) the conditions of calcination and carbonization in the high temperature furnace are: and in an inert gas atmosphere, heating to 450-600 ℃ at a speed of 1-2 ℃/h, and carrying out heat preservation reaction for 2-4 h.
7. Use of a hollow carbon sphere loaded with silver particles according to claim 1, wherein: the concentration of the hydrofluoric acid solution is 10-wt wt%; the hydrofluoric acid and SiO 2 @ Ag @ CThe mass ratio is (115-170) to (7-8).
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